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TW201732423A - Active-light-sensitive or radiation-sensitive composition, resist film in which same is used, pattern formation method, and method for manufacturing electronic device - Google Patents

Active-light-sensitive or radiation-sensitive composition, resist film in which same is used, pattern formation method, and method for manufacturing electronic device Download PDF

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Publication number
TW201732423A
TW201732423A TW105129897A TW105129897A TW201732423A TW 201732423 A TW201732423 A TW 201732423A TW 105129897 A TW105129897 A TW 105129897A TW 105129897 A TW105129897 A TW 105129897A TW 201732423 A TW201732423 A TW 201732423A
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group
compound
formula
acid
sensitive composition
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TW105129897A
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Naoya Shimoju
Hidehiro Mochizuki
Shuji Hirano
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Fujifilm Corp
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    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/62—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
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    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/78—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
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    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
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    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
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    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/26—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of rings other than six-membered aromatic rings
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    • C07C327/48—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to carbon atoms of six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
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    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
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    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/26—Sulfur atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
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Abstract

Provided is an active-light-sensitive or radiation-sensitive composition that contains (A) a compound having two or more of the structures represented by general formula (1), the compound not having an acid crosslinking group, and (B) a resin, said composition making it possible to form a pattern having exceptional sensitivity, resolution, roughness performance, and pattern cross-section shape, particularly when ultrafine patterns (e.g., having a line width of 50 nm or less) are formed. Also provided are a resist film in which the active-light-sensitive or radiation-sensitive composition is used, a pattern formation method, and a method for manufacturing an electronic device. In the formula, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a monovalent organic group. *represents a bond.

Description

組成物以及使用其的抗蝕劑膜、圖案形成方法及電子元件的製造方法Composition, resist film using the same, pattern forming method, and method of manufacturing electronic component

本發明是有關於一種感光化射線或感放射線性組成物以及使用其的抗蝕劑膜、圖案形成方法及電子元件的製造方法。 更詳細而言，本發明是有關於一種於積體電路（Integrated Circuit，IC）等的半導體製造步驟、液晶及熱能頭（thermal head）等的電路基板的製造、進而其他光刻加工（photofabrication）的微影步驟等中使用的感光化射線或感放射線性組成物以及使用其的抗蝕劑膜、圖案形成方法及電子元件的製造方法。The present invention relates to a sensitized ray or a radiation sensitive composition, a resist film using the same, a pattern forming method, and a method of producing an electronic component. More specifically, the present invention relates to a semiconductor manufacturing process such as an integrated circuit (IC), a circuit substrate such as a liquid crystal or a thermal head, and further photolithography. A sensitized ray or a radiation sensitive composition used in a lithography step or the like, a resist film using the same, a pattern forming method, and a method of producing an electronic component.

以前，於IC（Integrated Circuit，積體電路）或大規模積體電路（Large Scale Integrated circuit，LSI）等的半導體元件的製造製程中，一直藉由使用光阻劑（photoresist）組成物的微影來進行微細加工。 伴隨著積體電路的高積體化，逐漸要求形成次微米（submicron）區域或四分之一微米（quarter micron）區域的超微細圖案。伴隨於此，曝光波長亦如自g射線至i射線、進而至準分子雷射光（KrF、ArF）般可見短波長化的傾向。進而，目前除了準分子雷射光以外，亦正在開發使用電子束或X射線、或者極紫外線（Extreme Ultra Violet，EUV）光的微影。 於此種現狀下，關於抗蝕劑組成物，已提出了各種構成，例如除了樹脂及光酸產生劑以外含有特定添加劑的抗蝕劑組成物亦已為人所知（參照專利文獻1）。 [現有技術文獻] 專利文獻In the past, in the manufacturing process of a semiconductor element such as an IC (Integrated Circuit) or a Large Scale Integrated Circuit (LSI), lithography using a photoresist composition has been used. For micro processing. Along with the high integration of integrated circuits, it is increasingly required to form ultra-fine patterns of submicron regions or quarter micron regions. Along with this, the exposure wavelength tends to be shorter than that of the z-ray to the i-ray and further to the excimer laser light (KrF, ArF). Further, in addition to excimer laser light, lithography using electron beam or X-ray or Extreme Ultra Violet (EUV) light is currently being developed. In the present state of the art, various compositions have been proposed for the resist composition. For example, a resist composition containing a specific additive in addition to a resin and a photoacid generator is known (refer to Patent Document 1). [Prior Art Literature] Patent Literature

專利文獻1：日本專利第5644764號Patent Document 1: Japanese Patent No. 5644764

[發明所欲解決之課題] 然而，如今對各種電子設備要求進一步的高功能化，於此種情況下，要求製作更微細的配線，伴隨於此，謀求進一步提高感度、解析性、粗糙度性能及圖案剖面形狀等各種性能。 因此，本發明的目的在於提供一種尤其可於形成超微細（例如線寬50 nm以下）的圖案時，形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案的感光化射線或感放射線性組成物以及使用其的抗蝕劑膜、圖案形成方法及電子元件的製造方法。 [用以解決課題之手段][Problems to be Solved by the Invention] However, various electronic devices are required to be further highly functional. In this case, it is required to produce finer wiring, and further improvement in sensitivity, resolution, and roughness performance is required. And various properties such as pattern cross-sectional shape. Accordingly, it is an object of the present invention to provide a sensitized ray or a sensation of a pattern which is excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape, particularly when forming a pattern of ultrafine (for example, a line width of 50 nm or less). A radiation linear composition, a resist film using the same, a pattern forming method, and a method of producing an electronic component. [Means to solve the problem]

本發明者等人進行了潛心研究，結果發現，藉由含有特定化合物的感光化射線或感放射線性組成物而達成所述目的。The inventors of the present invention conducted intensive studies and found that the object is achieved by a sensitizing ray or a radiation sensitive composition containing a specific compound.

即，本發明如下。That is, the present invention is as follows.

[1] 一種感光化射線或感放射線性組成物，含有：（A）具有兩個以上的下述通式（1）所表示的結構且不具有酸交聯性基的化合物、以及藉由光化射線或放射線而產生酸的化合物， [化1]式中，X表示氧原子或硫原子，R表示氫原子或一價有機基；*表示結合鍵。 [2] 如[1]所記載的感光化射線或感放射線性組成物，其中所述通式（1）中的多個R中的至少一個為氫原子。 [3] 如[1]或[2]所記載的感光化射線或感放射線性組成物，其中所述化合物（A）具有下述通式（2）所表示的結構作為所述通式（1）所表示的結構， [化2]式中，X及R分別與所述通式（1）中的X及R為相同含意；A表示-NR'-或氧原子；R'表示氫原子或一價有機基；*表示結合鍵。 [4] 如[1]至[3]中任一項所記載的感光化射線或感放射線性組成物，其中所述化合物（A）的分子量為450以上。 [5] 如[1]至[4]中任一項所記載的感光化射線或感放射線性組成物，其中所述化合物（A）具有芳香族基。 [6] 如[1]至[5]中任一項所記載的感光化射線或感放射線性組成物，其中所述化合物（A）的共軛酸的pKa為1以下。 [7] 如[1]至[6]中任一項所記載的感光化射線或感放射線性組成物，其中所述化合物（A）不具有極性基經藉由酸的作用發生分解而脫離的脫離基保護的結構。 [8] 如[1]至[7]中任一項所記載的感光化射線或感放射線性組成物，其中所述化合物（A）具有3個以上的所述通式（1）所表示的結構。 [9] 如[8]所記載的感光化射線或感放射線性組成物，其中所述化合物（A）為下述通式（a）所表示的化合物， [化3]L表示三價連結基，Y1 、Y2 及Y3 分別獨立地表示具有所述通式（1）所表示的結構的一價有機基。 [10] 如[1]至[9]中任一項所記載的感光化射線或感放射線性組成物，其中所述化合物（A）為聚合物。 [11] 如[1]至[10]中任一項所記載的感光化射線或感放射線性組成物，更含有樹脂（B），相對於所述樹脂（B）的含量，所述化合物（A）的含量為1質量%～30質量%。 [12] 如[1]至[11]中任一項所記載的感光化射線或感放射線性組成物，更含有樹脂（B），所述樹脂（B）具有芳香族基。 [13] 如[1]至[12]中任一項所記載的感光化射線或感放射線性組成物，更含有交聯劑（C）。 [14] 如[1]至[13]中任一項所記載的感光化射線或感放射線性組成物，更含有疏水性樹脂（D）。 [15] 一種抗蝕劑膜，其是藉由如[1]至[14]中任一項所記載的感光化射線或感放射線性組成物所形成。 [16] 一種圖案形成方法，包括：對如[15]所記載的抗蝕劑膜照射光化射線或放射線；以及對經所述光化射線或放射線照射的膜進行顯影。 [17] 如[16]所記載的圖案形成方法，其中藉由含有有機溶劑的顯影液對經所述光化射線或放射線照射的膜進行顯影，形成負型圖案。 [18] 一種電子元件的製造方法，包括如[16]或[17]所記載的圖案形成方法。 [發明的效果][1] A photosensitive ray or a radiation-sensitive linear composition comprising: (A) a compound having two or more structures represented by the following formula (1) and having no acid crosslinkable group, and light-receiving a compound that produces an acid by radiation or radiation, [Chemical 1] In the formula, X represents an oxygen atom or a sulfur atom, R represents a hydrogen atom or a monovalent organic group; * represents a bond. [2] The sensitized ray or the radiation sensitive composition according to [1], wherein at least one of the plurality of R in the formula (1) is a hydrogen atom. [3] The sensitized ray or the radiation sensitive composition according to [1] or [2], wherein the compound (A) has a structure represented by the following formula (2) as the formula (1) ) the structure represented, [Chemical 2] In the formula, X and R each have the same meaning as X and R in the above formula (1); A represents -NR'- or an oxygen atom; R' represents a hydrogen atom or a monovalent organic group; * represents a bond. [4] The sensitized ray or the radiation sensitive composition according to any one of [1] to [3] wherein the compound (A) has a molecular weight of 450 or more. [5] The actinic ray or radiation sensitive composition according to any one of [1] to [4] wherein the compound (A) has an aromatic group. [6] The sensitized ray or the radiation sensitive composition according to any one of [1] to [5] wherein the conjugate acid of the compound (A) has a pKa of 1 or less. [7] The sensitized ray or radiation sensitive composition according to any one of [1] to [6] wherein the compound (A) does not have a polar group which is decomposed by decomposition of an acid to be detached. Detached from the structure of the base protection. [8] The sensitized ray or the radiation sensitive composition according to any one of [1], wherein the compound (A) has three or more of the formula (1). structure. [9] The sensitized ray or the radiation-sensitive composition according to [8], wherein the compound (A) is a compound represented by the following formula (a), [Chem. 3] L represents a trivalent linking group, and Y 1 , Y 2 and Y 3 each independently represent a monovalent organic group having a structure represented by the above formula (1). [10] The sensitized ray or radiation sensitive composition according to any one of [1] to [9] wherein the compound (A) is a polymer. [11] The sensitized ray or the radiation sensitive composition according to any one of [1] to [10] further comprising a resin (B), the compound (the content of the resin (B)) The content of A) is from 1% by mass to 30% by mass. [12] The sensitized ray or the radiation sensitive composition according to any one of [1] to [11] further comprising a resin (B) having an aromatic group. [13] The sensitized ray or the radiation sensitive composition according to any one of [1] to [12] further comprising a crosslinking agent (C). [14] The sensitized ray or the radiation sensitive composition according to any one of [1] to [13], further comprising a hydrophobic resin (D). [15] A resist film formed by the sensitized ray or the radiation sensitive composition according to any one of [1] to [14]. [16] A pattern forming method comprising: irradiating a resist film according to [15] with actinic rays or radiation; and developing a film irradiated with the actinic rays or radiation. [17] The pattern forming method according to [16], wherein the film irradiated with the actinic ray or the radiation is developed by a developing solution containing an organic solvent to form a negative pattern. [18] A method of producing an electronic component, comprising the pattern forming method according to [16] or [17]. [Effects of the Invention]

根據本發明，提供一種尤其可於形成超微細（例如線寬50 nm以下）的圖案時，形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案的感光化射線或感放射線性組成物以及使用其的抗蝕劑膜、圖案形成方法及電子元件的製造方法。According to the present invention, there is provided a sensitized ray or a radiation-sensitive composition which forms a pattern excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape particularly when a pattern of ultrafine (for example, a line width of 50 nm or less) is formed. And a resist film using the same, a pattern forming method, and a method of manufacturing an electronic component.

以下，對用以實施本發明的形態的一例加以說明。 於本說明書中的基團（原子團）的表述中，未記載經取代及未經取代的表述包含不具有取代基的基團，並且亦包含具有取代基的基團。例如所謂「烷基」，不僅是指不具有取代基的烷基（未經取代的烷基），而且亦包含具有取代基的烷基（經取代的烷基）。 所謂本說明書中的「光化射線」或「放射線」，例如是指水銀燈的明線光譜、準分子雷射所代表的遠紫外線、極紫外線（EUV光）、X射線、電子束（Electron Beam，EB）等。另外，本發明中所謂光，是指光化射線或放射線。 另外，所謂本說明書中的「曝光」，只要無特別說明，則不僅是指利用水銀燈、準分子雷射所代表的遠紫外線、極紫外線、X射線、EUV光等的曝光，利用電子束、離子束等粒子束的描畫亦包括在曝光中。 本說明書中，樹脂的重量平均分子量（Mw）、數量平均分子量（Mn）及分散度（Mw/Mn）是以由利用凝膠滲透層析（Gel Permeation Chromatography，GPC）裝置（東曹（Tosoh）製造的HLC-8120GPC）的GPC測定（溶劑：四氫呋喃，流量（樣本注入量）：10 μl，管柱：東曹（Tosoh）公司製造的TSK gel Multipore HXL-M（×4根），管柱溫度：40℃，流速：1.0 mL/min，檢測器：示差折射率（Refractive Index，RI）檢測器）所得的聚苯乙烯換算值的形式而定義。Hereinafter, an example of a form for carrying out the present invention will be described. In the expression of the group (atomic group) in the present specification, it is not described that the substituted and unsubstituted expression includes a group having no substituent, and also includes a group having a substituent. For example, the term "alkyl" means not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The term "actinic ray" or "radiation" in the present specification means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, and an electron beam (Electron Beam, EB) and so on. Further, the term "light" as used in the present invention means actinic ray or radiation. In addition, the term "exposure" in the present specification means not only exposure by far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps or excimer lasers, but also electron beams and ions, unless otherwise specified. The drawing of a beam of equal beams is also included in the exposure. In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (Mw/Mn) of the resin are determined by a gel permeation chromatography (GPC) device (Tosoh). GPC measurement of manufactured HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μl, column: TSK gel Multipore HXL-M (×4) manufactured by Tosoh Corporation, column temperature : 40 ° C, flow rate: 1.0 mL / min, detector: Refractive Index (RI) detector) defined in the form of polystyrene-converted values.

本發明的感光化射線或感放射線性組成物含有：（A）具有兩個以上的下述通式（1）所表示的結構且不具有酸交聯性基的化合物、以及藉由光化射線或放射線而產生酸的化合物。The sensitized ray or the radiation sensitive composition of the present invention contains: (A) a compound having two or more structures represented by the following formula (1) and having no acid crosslinkable group, and an actinic ray Or a compound that emits radiation to produce an acid.

[化4] [Chemical 4]

式中，X表示氧原子或硫原子，R表示氫原子或一價有機基。*表示結合鍵。In the formula, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a monovalent organic group. * indicates a bond.

藉此，尤其於形成超微細（例如線寬50 nm以下）的圖案時，可形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案，其原因雖不確定，但推定如下。Therefore, in particular, when a pattern of ultrafine (for example, a line width of 50 nm or less) is formed, a pattern excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape can be formed. The reason is not certain, but it is estimated as follows.

首先，所述通式（1）中的NC(=X)所表示的結構由於存在氮原子等，故例如與酯鍵相比較而極性更高。另外，化合物（A）具有兩個以上的此種高極性的結構。 因此可認為，於所形成的圖案中，化合物（A）提供多個極性非常高的部位，結果樹脂彼此經由此種高極性部位而相互作用，由此形成包含化合物（A）與本發明的感光化射線或感放射線性組成物可含有的樹脂（B）的疑似交聯結構。 而且推測，藉由所述疑似交聯結構，構成圖案的成分的凝聚性提高，藉此於超微細（例如線寬50 nm以下）的圖案中亦不易發生圖案的破壞等，解析性提高，圖案剖面形狀更優異。 另外推測，由於圖案中的樹脂（B）的凝聚性提高，化學增幅型抗蝕劑膜的曝光部中產生的酸過度擴散至未曝光部中的情況得到抑制，結果粗糙度性能優異。 另外，如上文所述，化合物（A）呈現出非常高的極性。結果化合物（A）與基板更牢固地密接，藉此圖案與基板的密接性提高，更不易發生圖案的倒塌，可認為這一情況亦是解析性提高的原因。 另外，曝光部中，所述擬交聯被局部破壞，添加劑成為樹脂的塑化劑。推測其結果為曝光部內的酸的擴散速度提高，感度提高。 進而，化合物（A）不具有酸交聯性基。藉此，於形成正型的圖案時亦不會負型化。另外可認為，因不易生成分解物，故不會發生由樹脂（B）的過疏化所致的Tg降低，進一步發揮所述擬交聯的效果。First, the structure represented by NC (=X) in the above formula (1) has a higher polarity because it has a nitrogen atom or the like, for example, compared with an ester bond. Further, the compound (A) has two or more such highly polar structures. Therefore, it is considered that in the formed pattern, the compound (A) provides a plurality of sites having a very high polarity, and as a result, the resins interact with each other via such a highly polar site, thereby forming the photosensitive compound containing the compound (A) and the present invention. The suspected crosslinked structure of the resin (B) which the ray or the radiation sensitive composition may contain. In addition, it is estimated that the cohesiveness of the components constituting the pattern is improved by the suspected crosslinked structure, whereby the pattern is less likely to be broken in the ultrafine (for example, a line width of 50 nm or less), and the resolution is improved. The cross-sectional shape is more excellent. In addition, it is estimated that the cohesiveness of the resin (B) in the pattern is improved, and the acid generated in the exposed portion of the chemically amplified resist film is excessively diffused into the unexposed portion, and the roughness performance is excellent. In addition, as described above, the compound (A) exhibits a very high polarity. As a result, the compound (A) adheres more strongly to the substrate, whereby the adhesion between the pattern and the substrate is improved, and the pattern collapse is less likely to occur, which is considered to be a cause of improvement in resolution. Further, in the exposed portion, the pseudo-crosslinking is partially broken, and the additive becomes a plasticizer of the resin. It is estimated that the diffusion rate of the acid in the exposed portion is improved, and the sensitivity is improved. Further, the compound (A) does not have an acid crosslinkable group. Thereby, it is not negatively formed when a positive pattern is formed. Further, it is considered that since the decomposition product is less likely to be formed, the decrease in Tg due to over-reduction of the resin (B) does not occur, and the effect of the pseudo-crosslinking is further exhibited.

＜感光化射線或感放射線性組成物＞ 繼而，對本發明的圖案形成方法中所用的感光化射線或感放射線性組成物加以說明。 本發明的感光化射線或感放射線性組成物較佳為ArF準分子雷射、電子束或極紫外線曝光用。 本發明的感光化射線或感放射線性組成物較佳為抗蝕劑組成物，可為正型的抗蝕劑組成物，亦可為負型的抗蝕劑組成物，另外，可為鹼性顯影用的抗蝕劑組成物，亦可為有機溶劑顯影用的抗蝕劑組成物。 另外，本發明的感光化射線或感放射線性組成物典型而言為化學增幅型的抗蝕劑組成物。<Photosensitive ray or radiation sensitive composition> Next, the sensitized ray or the radiation sensitive composition used in the pattern forming method of the present invention will be described. The sensitized ray or the radiation sensitive composition of the present invention is preferably an ArF excimer laser, an electron beam or an extreme ultraviolet ray exposure. The sensitized ray or radiation sensitive composition of the present invention is preferably a resist composition, and may be a positive resist composition, or may be a negative resist composition, and may be alkaline. The resist composition for development may be a resist composition for developing an organic solvent. Further, the sensitized ray or the radiation sensitive composition of the present invention is typically a chemically amplified resist composition.

以下，對本發明的感光化射線或感放射線性組成物中的各成分加以詳細說明。Hereinafter, each component in the sensitized ray or the radiation sensitive composition of the present invention will be described in detail.

＜（A）具有兩個以上的通式（1）所表示的結構且不具有酸交聯性基的化合物＞ 如上文所述，本發明的感光化射線或感放射線性組成物含有（A）具有兩個以上的下述通式（1）所表示的結構且不具有酸交聯性基的化合物（以下亦稱為化合物（A））。<(A) A compound having two or more structures represented by the formula (1) and having no acid crosslinkable group> As described above, the sensitized ray or the radiation sensitive composition of the present invention contains (A) A compound having two or more structures represented by the following formula (1) and having no acid crosslinkable group (hereinafter also referred to as compound (A)).

[化5] [Chemical 5]

式中，X表示氧原子或硫原子，R表示氫原子或一價有機基。*表示結合鍵。In the formula, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a monovalent organic group. * indicates a bond.

如上所述，化合物（A）不具有酸交聯性基。即，化合物（A）並非交聯劑，不相當於後述的交聯劑（C）。此處，酸交聯性基可列舉公知的基團，具代表性的是可列舉羥基甲基及烷氧基甲基。 因此，於本發明的感光化射線或感放射線性組成物含有樹脂（B）的情形時，化合物（A）不藉由酸的作用而與樹脂（B）交聯。As described above, the compound (A) does not have an acid crosslinkable group. That is, the compound (A) is not a crosslinking agent and does not correspond to the crosslinking agent (C) described later. Here, the acid crosslinkable group may, for example, be a known group, and a hydroxymethyl group and an alkoxymethyl group are exemplified. Therefore, when the photosensitive ray or the radiation sensitive composition of the present invention contains the resin (B), the compound (A) is not crosslinked with the resin (B) by the action of an acid.

另外，較佳為通式（1）中的多個R中的至少一個為氫原子。 藉由多個R中的至少一個為氫原子，通式（1）所表示的結構的高極性不易受損，可充分地發揮本發明的效果。Further, it is preferred that at least one of the plurality of R in the formula (1) is a hydrogen atom. When at least one of the plurality of R is a hydrogen atom, the high polarity of the structure represented by the formula (1) is not easily impaired, and the effects of the present invention can be sufficiently exerted.

作為R的一價有機基較佳為碳數1～30，例如可列舉烷基、環烷基、芳基、芳烷基、烯基等。該些基團亦可更具有取代基。 取代基例如可列舉：烷基（碳數1～4）、鹵素原子、羥基、烷氧基（碳數1～4）、羧基、烷氧基羰基（碳數2～6）等，較佳為碳數8以下。The monovalent organic group of R is preferably a carbon number of 1 to 30, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may also have more substituents. Examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, an alkoxycarbonyl group (having a carbon number of 2 to 6), and the like. The carbon number is 8 or less.

作為R的一價有機基較佳為烷基，更佳為碳數1～20的直鏈及分支烷基。烷基亦可於烷基鏈中具有氧原子、硫原子、氮原子。The monovalent organic group as R is preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl group may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain.

化合物（A）較佳為不具有藉由酸的作用而產生鹼的基團。The compound (A) preferably has no group which generates a base by the action of an acid.

化合物（A）較佳為具有下述通式（2）所表示的結構作為通式（1）所表示的結構的化合物。The compound (A) is preferably a compound having a structure represented by the following formula (2) as a structure represented by the formula (1).

[化6] [Chemical 6]

式中，X及R分別與所述通式（1）中的X及R為相同含意。A表示-NR'-或氧原子。R'表示氫原子或一價有機基。*表示結合鍵。In the formula, X and R each have the same meaning as X and R in the above formula (1). A represents -NR'- or an oxygen atom. R' represents a hydrogen atom or a monovalent organic group. * indicates a bond.

作為R'的一價有機基的具體例及較佳例與上文中關於作為R的一價有機基所述的具體例及較佳例相同。Specific examples and preferred examples of the monovalent organic group as R' are the same as the specific examples and preferred examples described above as the monovalent organic group as R.

化合物（A）較佳為具有醯胺基（於通式（1）中X表示氧原子）、脲基（於通式（2）中X表示氧原子，A表示-NR'-）或胺基甲酸酯基（於通式（2）中X表示氧原子，A表示-氧原子）作為通式（1）或通式（2）所表示的結構。The compound (A) preferably has a mercaptoamine group (wherein X represents an oxygen atom in the formula (1)), a urea group (wherein X represents an oxygen atom in the formula (2), and A represents -NR'-) or an amine group. The formate group (wherein X represents an oxygen atom in the formula (2), and A represents an -oxygen atom) is a structure represented by the formula (1) or the formula (2).

化合物（A）的共軛酸的pKa較佳為1以下。其原因在於：藉此，曝光部中由光酸產生劑所產生的酸不易被化合物（A）中和，基於酸的作用的所需反應充分地進行，故感度不易降低。The pKa of the conjugate acid of the compound (A) is preferably 1 or less. This is because the acid generated by the photoacid generator in the exposed portion is not easily neutralized by the compound (A), and the desired reaction by the action of the acid is sufficiently performed, so that the sensitivity is not easily lowered.

化合物（A）亦較佳為具有芳香族基，藉此，有構成圖案的成分的凝聚性進一步提高，解析性或粗糙度性能變得更良好的傾向。 於該情形時，化合物（A）可於通式（1）或通式（2）所表示的結構內具有芳香族基，亦可於通式（1）或通式（2）所表示的結構外具有芳香族基。前者的情形時，芳香族基分別包含於通式（1）的R、以及通式（2）的R及R'的至少一者中。It is also preferred that the compound (A) has an aromatic group, whereby the cohesiveness of the component constituting the pattern is further improved, and the analytical property or the roughness property tends to be further improved. In this case, the compound (A) may have an aromatic group in the structure represented by the formula (1) or the formula (2), or may be a structure represented by the formula (1) or the formula (2). It has an aromatic group outside. In the former case, the aromatic group is contained in at least one of R of the formula (1) and R and R' of the formula (2).

另外，尤其於形成正型圖案的情形時，亦較佳為通式（1）的R、以及通式（2）的R及R'的至少一者為具有拉電子性基的一價有機基。其原因在於：藉此，於曝光部中有通式（1）或通式（2）所表示的結構中的-NR-與-CX-間的鍵被由光酸產生劑所產生的酸切斷，構成抗蝕劑膜的成分的凝聚被解除的傾向，容易對曝光部進行顯影。Further, particularly in the case of forming a positive pattern, it is also preferred that at least one of R of the formula (1) and R and R' of the formula (2) is a monovalent organic group having an electron withdrawing group . The reason for this is that, in the exposed portion, the bond between -NR- and -CX- in the structure represented by the general formula (1) or the general formula (2) is acid-cut by the photoacid generator. The aggregation of the components constituting the resist film is released, and the exposed portion is easily developed.

拉電子性基較佳為哈米特定律（Hammett's rule）的σp值為0以上的基團。σp值為正的取代基可列舉：氟（0.06）、氯（0.30）、溴（0.27）、碘（0.30）等鹵素原子，-CHO（0.22）、-COCH3 （0.50）、-COC6 H5 （0.46）、-CONH2 （0.36）、-COO-（0.30）、-COOH（0.41）、-COOCH3 （0.39）、-COOC2 H5 （0.45）等具有羰基的基團，-SOCH3 （0.49）、-SO2 CH3 （0.72）、-SO2 C6 H5 （0.68）、-SO2 CF3 （0.93）、-SO2 NH2 （0.57）、-SO2 OC6 H5 （0.23）、-SO3 -（0.09）、-SO3 H（0.50）等具有磺醯基或亞磺醯基的基團，-CN（0.66）、-NO2 （0.78）、-N(CH3 )3 + （0.82）、-N(CF3 )2 （0.53）等含氮取代基，-CCl3 （0.46）、-CH2 Cl（0.18）、-CHCl2 （0.32）、-CF3 （0.54）等經鹵素原子取代的烷基。此處，括弧內的數值為σp值。 哈米特的σp值例如亦記載於C.哈馳（C.Harsch）等人的「藥物化學期刊（J. Med. Chem.）」（16，1207（1973））、「藥物化學期刊（J. Med. Chem.）」（20，304（1977））及「化學研究（Chem. Rev.）」（91，165（1991））等中。The electron withdrawing group is preferably a group having a σp value of 0 or more in Hammett's rule. Examples of the substituent having a positive σp value include halogen atoms such as fluorine (0.06), chlorine (0.30), bromine (0.27), and iodine (0.30), -CHO (0.22), -COCH 3 (0.50), and -COC 6 H. a group having a carbonyl group such as 5 (0.46), -CONH 2 (0.36), -COO-(0.30), -COOH (0.41), -COOCH 3 (0.39), -COOC 2 H 5 (0.45), -SOCH 3 (0.49), -SO 2 CH 3 (0.72), -SO 2 C 6 H 5 (0.68), -SO 2 CF 3 (0.93), -SO 2 NH 2 (0.57), -SO 2 OC 6 H 5 ( a group having a sulfonyl group or a sulfinyl group such as -3 3 ), -SO 3 -(0.09), -SO 3 H(0.50), -CN(0.66), -NO 2 (0.78), -N(CH 3 a nitrogen-containing substituent such as 3 + (0.82), -N(CF 3 ) 2 (0.53), -CCl 3 (0.46), -CH 2 Cl (0.18), -CHCl 2 (0.32), -CF 3 (0.54 An alkyl group substituted with a halogen atom. Here, the value in parentheses is the σp value. The σp value of Hammett is also described, for example, in C. Harsch et al., J. Med. Chem. (16, 1207 (1973)), Journal of Medicinal Chemistry (J). Med. Chem.)" (20, 304 (1977)) and "Chem. Rev." (91, 165 (1991)).

另外，化合物（A）可具有極性基經藉由酸的作用發生分解而脫離的脫離基保護的結構（酸分解性基），亦可不具有該結構（酸分解性基），尤其於形成負型圖案的情形時，化合物（A）較佳為不具有酸分解性基。其原因在於：藉此，於曝光部中有化合物（A）不因由光酸產生劑所產生的酸而分解，構成圖案的成分的凝聚性不降低的傾向，容易獲得優異的解析性及粗糙度性能。Further, the compound (A) may have a structure (acid-decomposable group) protected by a leaving group in which a polar group is decomposed by decomposition by an action of an acid, or may have no such structure (acid-decomposable group), particularly in forming a negative type. In the case of a pattern, the compound (A) preferably does not have an acid-decomposable group. The reason for this is that the compound (A) is decomposed in the exposed portion by the acid generated by the photo-acid generator, and the cohesiveness of the components constituting the pattern does not decrease, and excellent resolution and roughness are easily obtained. performance.

化合物（A）亦較佳為具有3個以上的通式（1）所表示的結構。It is also preferred that the compound (A) has three or more structures represented by the formula (1).

於該情形時，化合物（A）較佳為下述通式（a）所表示的化合物。In this case, the compound (A) is preferably a compound represented by the following formula (a).

[化7] [Chemistry 7]

L表示三價連結基，Y1 、Y2 及Y3 分別獨立地表示具有所述通式（1）所表示的結構的一價有機基。L represents a trivalent linking group, and Y 1 , Y 2 and Y 3 each independently represent a monovalent organic group having a structure represented by the above formula (1).

作為Y1 、Y2 及Y3 的一價有機基較佳為碳數1～30，例如可列舉烷基、環烷基、芳基、芳烷基、烯基、烷氧基、芳氧基等。該些基團亦可更具有取代基。 取代基例如可列舉烷基（碳數1～4）、鹵素原子、羥基、烷氧基（碳數1～4）、羧基、烷氧基羰基（碳數2～6）等，較佳為碳數8以下。The monovalent organic group of Y 1 , Y 2 and Y 3 preferably has a carbon number of 1 to 30, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, and an aryloxy group. Wait. These groups may also have more substituents. Examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, an alkoxycarbonyl group (having a carbon number of 2 to 6), and the like, and preferably a carbon. The number is 8 or less.

具有通式（1）所表示的結構的一價有機基典型而言於基團中具有通式（1）所表示的結構，於該情形時，所述一價有機基的具體例是將構成一價有機基的原子（典型而言為碳原子）替換為通式（1）所表示的結構而成。The monovalent organic group having the structure represented by the general formula (1) typically has a structure represented by the general formula (1) in the group, and in this case, a specific example of the monovalent organic group will constitute The atom of the monovalent organic group (typically a carbon atom) is replaced by the structure represented by the general formula (1).

作為L的三價連結基的具體例可列舉：自所述作為Y1 、Y2 及Y3 的一價有機基的具體例中進一步去掉兩個氫原子而成的基團。Specific examples of the trivalent linking group of L include a group in which two hydrogen atoms are further removed from the specific examples of the monovalent organic group of Y 1 , Y 2 and Y 3 .

化合物（A）可為低分子化合物的形態，亦可為聚合物的形態（組入至聚合物（典型而言為聚合物的一部分）中的形態）。另外，亦可將低分子化合物的形態與聚合物的形態併用。 於化合物（A）為低分子化合物的形態的情形時，較佳為實質上不具有分子量分佈。 另外，於化合物（A）為低分子化合物的形態的情形時，就抑制顯影缺陷的產生等觀點而言，較佳為分子量為3000以下，更佳為分子量為2000以下，進而佳為1500以下，最佳為1000以下。另外，就抑制化合物（A）的揮發等觀點而言，化合物（A）的分子量較佳為450以上。The compound (A) may be in the form of a low molecular compound or may be in the form of a polymer (a form incorporated into a polymer (typically a part of a polymer)). Further, the form of the low molecular compound may be used in combination with the form of the polymer. When the compound (A) is in the form of a low molecular compound, it is preferred that the compound has substantially no molecular weight distribution. In the case where the compound (A) is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,500 or less, from the viewpoint of suppressing generation of development defects. The best is below 1000. In addition, the molecular weight of the compound (A) is preferably 450 or more from the viewpoint of suppressing volatilization of the compound (A).

化合物（A）可列舉：胺甲酸酯系化合物（具有胺甲酸酯鍵的化合物）、脲系化合物（具有脲鍵的化合物）、醯胺系化合物（具有醯胺鍵的化合物）、巴比妥酸系化合物（具有巴比妥酸結構的化合物）、醯亞胺系化合物（具有醯亞胺鍵的化合物）、氰脲酸系化合物（具有氰脲酸結構的化合物）。Examples of the compound (A) include an urethane-based compound (a compound having a urethane bond), a urea-based compound (a compound having a urea bond), a guanamine-based compound (a compound having a guanamine bond), and Babi A tonic acid compound (a compound having a barbituric acid structure), a quinone imine compound (a compound having a quinone bond), and a cyanuric acid compound (a compound having a cyanuric acid structure).

以下示出化合物（A）的具體例，但本發明不限定於此。Specific examples of the compound (A) are shown below, but the present invention is not limited thereto.

[胺甲酸酯系化合物][Amine compound]

[化8] [化8]

[化9] [Chemistry 9]

[脲系化合物][urea compound]

[化10] [化10]

[醯胺系化合物][Amidoxime compound]

[化11] [11]

[巴比妥酸系化合物][barbituric acid compound]

[化12] [化12]

[醯亞胺系化合物][醯imino compound]

[化13] [Chemistry 13]

[氰脲酸系化合物][cyanuric acid compound]

[化14] [Chemistry 14]

以下，對化合物（A）的具代表性的具體例示出分子量及pKa。Hereinafter, a specific example of the compound (A) is shown as a molecular weight and a pKa.

[表1] （各化合物的分子量及pKa） *pKa過低故無法測定[Table 1] (Molecular weight and pKa of each compound) *pKa is too low to be measured

於合物（A）為聚合物的形態的情形時，化合物（A）亦可組入至後述樹脂（B）中。 於化合物（A）為聚合物的形態的情形時，化合物（A）亦較佳為具有下述通式（I）或通式（II）所表示的重複單元。When the compound (A) is in the form of a polymer, the compound (A) may be incorporated into the resin (B) to be described later. When the compound (A) is in the form of a polymer, the compound (A) is preferably a repeating unit represented by the following formula (I) or formula (II).

[化15] [化15]

通式（I）中， Xa1 表示氫原子、可具有取代基的烷基。 T表示單鍵或二價連結基。多個T可彼此相同亦可不同。 A表示具有所述通式（1）所表示的結構的基團。In the formula (I), Xa 1 represents a hydrogen atom and an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. A plurality of Ts may be the same or different from each other. A represents a group having the structure represented by the above formula (1).

Xa1 所表示的可具有取代基的烷基例如可列舉甲基或-CH2 -R11 所表示的基團。R11 表示鹵素原子（氟原子等）、羥基或一價有機基，例如可列舉碳數5以下的烷基、碳數5以下的醯基，較佳為碳數3以下的烷基，進而佳為甲基。Xa1 於一態樣中較佳為氫原子、甲基、三氟甲基或羥基甲基等。 T的二價連結基可列舉伸烷基、-COO-Rt-基、-O-Rt-基等。式中，Rt表示伸烷基或伸環烷基。 T較佳為單鍵或-COO-Rt-基。Rt較佳為碳數1～5的伸烷基，更佳為-CH2 -基、-(CH2 )2 -基、-(CH2 )3 -基。The alkyl group which may have a substituent represented by Xa 1 is, for example, a group represented by a methyl group or -CH 2 -R 11 . R 11 represents a halogen atom (fluorine atom), a hydroxyl group or a monovalent organic group include an alkyl group having a carbon number of 5 or less, 5 or less carbon atoms, acyl, preferably an alkyl group having a carbon number of 3 or less, and further good Is a methyl group. Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group in one aspect. The divalent linking group of T may, for example, be an alkyl group, a -COO-Rt- group or a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkyl group. T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH 2 - group, a -(CH 2 ) 2 - group or a -(CH 2 ) 3 - group.

通式（II）中， R61 、R62 及R63 分別獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基或烷氧基羰基。其中，R62 亦可與Ar6 鍵結而形成環，該情形的R62 表示單鍵或伸烷基。 X6 表示單鍵、-COO-或-CONR64 -。R64 表示氫原子或烷基。多個X6 可彼此相同亦可不同。 L6 表示單鍵或伸烷基。 Ar6 表示（n＋1）價的芳香環基，於與R62 鍵結而形成環的情形時表示（n＋2）價的芳香環基。 A表示具有所述通式（1）所表示的結構的基團。 n表示1～4的整數。於n為2以上的整數的情形時，多個A可彼此相同亦可不同。In the formula (II), R 61 , R 62 and R 63 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R 62 may also bond with Ar 6 to form a ring, and in this case, R 62 represents a single bond or an alkylene group. X 6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group. The plurality of X 6 may be the same or different from each other. L 6 represents a single bond or an alkyl group. Ar 6 represents an (n+1)-valent aromatic ring group, and when it is bonded to R 62 to form a ring, it represents an (n+2)-valent aromatic ring group. A represents a group having the structure represented by the above formula (1). n represents an integer of 1 to 4. In the case where n is an integer of 2 or more, a plurality of A's may be the same or different from each other.

所述各基團亦可具有取代基，取代基例如可列舉烷基（碳數1～4）、鹵素原子、羥基、烷氧基（碳數1～4）、羧基、烷氧基羰基（碳數2～6）等，較佳為碳數8以下。Each of the groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxycarbonyl group (carbon). The number is 2 to 6), etc., preferably 8 or less.

化合物（A）可組入至聚合物的主鏈中，亦可組入至聚合物的側鏈中，若將化合物（A）組入至聚合物的側鏈中，則有可更可靠地發揮「尤其可於形成超微細（例如線寬50 nm以下）的圖案時，形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案」等本案發明的效果的傾向，故較佳。The compound (A) may be incorporated into the main chain of the polymer or may be incorporated into the side chain of the polymer. If the compound (A) is incorporated into the side chain of the polymer, the compound (A) can be more reliably used. In particular, it is preferable to form an ultrafine (for example, a line width of 50 nm or less) pattern to form an effect of the present invention such as a pattern having excellent sensitivity, resolution, roughness performance, and pattern cross-sectional shape.

相對於聚合物的所有重複單元，具有通式（1）所表示的結構的重複單元（例如通式（I）或通式（II）所表示的重複單元）的含量較佳為1 mol%～30 mol%，更佳為5 mol%～30 mol%，進而佳為10 mol%～25 mol%。The content of the repeating unit having the structure represented by the general formula (1) (for example, the repeating unit represented by the general formula (I) or the general formula (II)) is preferably 1 mol% with respect to all the repeating units of the polymer. 30 mol%, more preferably 5 mol% to 30 mol%, and further preferably 10 mol% to 25 mol%.

以下，示出化合物（A）為聚合物的形態的化合物（A）的具體例。Specific examples of the compound (A) in which the compound (A) is in the form of a polymer are shown below.

[胺甲酸酯系化合物][Amine compound]

[化16] [Chemistry 16]

[脲系化合物][urea compound]

[化17] [化17]

[醯胺系化合物][Amidoxime compound]

[化18] [化18]

[巴比妥酸系化合物][barbituric acid compound]

[化19] [Chemistry 19]

[醯亞胺系化合物][醯imino compound]

[化20] [Chemistry 20]

[氰脲酸系化合物][cyanuric acid compound]

[化21] [Chem. 21]

尤其於化合物（A）為低分子化合物的形態的情形時，相對於後述樹脂（B）的含量，化合物（A）的含量較佳為1質量%～30質量%，更佳為5質量%～30質量%，進而佳為10質量%～25質量%。In particular, when the compound (A) is in the form of a low molecular compound, the content of the compound (A) is preferably from 1% by mass to 30% by mass, and more preferably 5% by mass based on the content of the resin (B) to be described later. 30% by mass, and more preferably 10% by mass to 25% by mass.

尤其於化合物（A）為低分子化合物的形態的情形時，相對於感光化射線或感放射線性組成物的總固體成分，化合物（A）的含量較佳為1質量%～30質量%，更佳為3質量%～25質量%，進而佳為5質量%～20質量%。In particular, when the compound (A) is in the form of a low molecular compound, the content of the compound (A) is preferably from 1% by mass to 30% by mass based on the total solid content of the sensitized ray or the radiation sensitive composition. It is preferably from 3% by mass to 25% by mass, and more preferably from 5% by mass to 20% by mass.

尤其於化合物（A）為聚合物的形態的情形時，相對於感光化射線或感放射線性組成物的總固體成分，化合物（A）的含量較佳為50質量%～99.9質量%，更佳為60質量%～99.0質量%。 另外，於化合物（A）為聚合物的形態的情形時，化合物（A）的重量平均分子量以由GPC法所得的聚苯乙烯換算值計，較佳為1,000～200,000，進而佳為3,000～20,000，最佳為5,000～15,000。關於化合物（A）的分散度（分子量分佈），使用通常為1～5、較佳為1～3、進而佳為1.2～3.0、尤佳為1.1～2.0的範圍的分散度（分子量分佈）。In particular, when the compound (A) is in the form of a polymer, the content of the compound (A) is preferably 50% by mass to 99.9% by mass, more preferably the total solid content of the sensitized ray or the radiation sensitive composition. It is 60% by mass to 99.0% by mass. In the case where the compound (A) is in the form of a polymer, the weight average molecular weight of the compound (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, based on the polystyrene equivalent value obtained by the GPC method. The best is 5,000 to 15,000. The degree of dispersion (molecular weight distribution) in the range of usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.1 to 2.0 is used for the degree of dispersion (molecular weight distribution) of the compound (A).

＜（B）樹脂＞ 感光化射線或感放射線性組成物較佳為含有樹脂（B），樹脂（B）較佳為具有芳香族基。 樹脂（B）可含有後述各種重複單元。<(B) Resin> The photosensitive ray or the radiation sensitive composition preferably contains the resin (B), and the resin (B) preferably has an aromatic group. The resin (B) may contain various repeating units described below.

[具有芳香環基的重複單元（a）] 樹脂（B）於較佳一實施形態中，含有具有芳香環基的重複單元（a）。 具有芳香環基的重複單元（a）可較佳地列舉具有酚性羥基的重複單元。 本說明書中，所謂酚性羥基，是指芳香環基的氫原子經羥基取代而成的基團。該芳香環基的芳香環為單環或多環的芳香環，可列舉苯環或萘環等。[Repeating unit (a) having an aromatic ring group] The resin (B), in a preferred embodiment, contains a repeating unit (a) having an aromatic ring group. The repeating unit (a) having an aromatic ring group is preferably a repeating unit having a phenolic hydroxyl group. In the present specification, the phenolic hydroxyl group means a group in which a hydrogen atom of an aromatic ring group is substituted with a hydroxyl group. The aromatic ring of the aromatic ring group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring or a naphthalene ring.

尤其於感光化射線或感放射線性組成物為電子束或極紫外線曝光用的情形、或含有後述交聯劑的情形（例如感光化射線或感放射線性組成物為鹼性顯影用的負型感光化射線或感放射線性組成物的情形）時，樹脂（B）較佳為含有具有酚性羥基的重複單元。In particular, when the sensitized ray or the radiation sensitive composition is used for electron beam or extreme ultraviolet ray exposure, or when a crosslinking agent to be described later is contained (for example, the sensitized ray or the radiation sensitive composition is a negative sensitization for alkaline development). In the case of a ray or a radiation sensitive composition, the resin (B) preferably contains a repeating unit having a phenolic hydroxyl group.

具有酚性羥基的重複單元例如可列舉下述通式（I）或通式（I-1）所表示的重複單元。The repeating unit having a phenolic hydroxyl group may, for example, be a repeating unit represented by the following formula (I) or formula (I-1).

[化22] [化22]

[化23] [化23]

式中， R41 、R42 及R43 分別獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基或烷氧基羰基。其中，R42 亦可與Ar4 鍵結而形成環，該情形的R42 表示單鍵或伸烷基。 X4 表示單鍵、-COO-或-CONR64 -，R64 表示氫原子或烷基。 L4 分別獨立地表示單鍵或二價連結基。 Ar4 表示（n＋1）價的芳香環基，於與R42 鍵結而形成環的情形時表示（n＋2）價的芳香環基。 n表示1～5的整數。 為了使通式（I）或通式（I-1）的重複單元高極性化，亦較佳為n為2以上的整數，或者X4 為-COO-或-CONR64 -。In the formula, R 41 , R 42 and R 43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R 42 may also bond with Ar 4 to form a ring, and in this case, R 42 represents a single bond or an alkylene group. X 4 represents a single bond, -COO- or -CONR 64 -, and R 64 represents a hydrogen atom or an alkyl group. L 4 each independently represents a single bond or a divalent linking group. Ar 4 represents a (n + 1) valent aromatic group, represented by (n + 2) valent aromatic group and when R 42 to be bonded to form a ring of the case. n represents an integer of 1 to 5. In order to increase the polarity of the repeating unit of the formula (I) or the formula (I-1), n is preferably an integer of 2 or more, or X 4 is -COO- or -CONR 64 -.

通式（I）及通式（I-1）中的R41 、R42 、R43 的烷基較佳可列舉：可具有取代基的甲基、乙基、丙基、異丙基、正丁基、第二丁基、己基、2-乙基己基、辛基、十二烷基等碳數20以下的烷基，更佳可列舉碳數8以下的烷基，尤佳可列舉碳數3以下的烷基。The alkyl group of R 41 , R 42 and R 43 in the formula (I) and the formula (I-1) is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group which may have a substituent. The alkyl group having a carbon number of 20 or less, such as a butyl group, a second butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, and particularly preferably a carbon number. An alkyl group of 3 or less.

通式（I）及通式（I-1）中的R41 、R42 、R43 的環烷基可為單環型，亦可為多環型。較佳可列舉：可具有取代基的環丙基、環戊基、環己基等碳數3個～8個且單環型的環烷基。 通式（I）及通式（I-1）中的R41 、R42 、R43 的鹵素原子可列舉氟原子、氯原子、溴原子及碘原子，尤佳為氟原子。 通式（I）及通式（I-1）中的R41 、R42 、R43 的烷氧基羰基所含的烷基較佳為與所述R41 、R42 、R43 的烷基相同的烷基。The cycloalkyl group of R 41 , R 42 and R 43 in the formula (I) and the formula (I-1) may be a monocyclic type or a polycyclic type. Preferable examples thereof include a cycloalkyl group having a substituent such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group having 3 to 8 carbon atoms and a monocyclic ring group. The halogen atom of R 41 , R 42 and R 43 in the general formula (I) and the general formula (I-1) may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom. The alkyl group contained in the alkoxycarbonyl group of R 41 , R 42 and R 43 in the formula (I) and the formula (I-1) is preferably an alkyl group with the above R 41 , R 42 and R 43 . The same alkyl group.

所述各基團的較佳取代基例如可列舉：烷基、環烷基、芳基、胺基、醯胺基、醯脲基、胺基甲酸酯基、羥基、羧基、鹵素原子、烷氧基、硫醚基、醯基、醯氧基、烷氧基羰基、氰基、硝基等，取代基的碳數較佳為8以下。Preferred substituents of the respective groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a guanidino group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, and an alkyl group. The oxy group, the thioether group, the decyl group, the decyloxy group, the alkoxycarbonyl group, the cyano group, the nitro group or the like has a carbon number of the substituent of preferably 8 or less.

Ar4 表示（n＋1）價的芳香環基。於n為1的情形時的二價芳香環基亦可具有取代基，例如可列舉以下基團作為較佳例：伸苯基、甲伸苯基、伸萘基、伸蒽基等碳數6～18的伸芳基，或例如含有噻吩、呋喃、吡咯、苯并噻吩、苯并呋喃、苯并吡咯、三嗪、咪唑、苯并咪唑、三唑、噻二唑、噻唑等雜環的芳香環基。Ar 4 represents an (n+1)-valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, and examples thereof include the following groups: a phenyl group, a methylphenyl group, a naphthyl group, a fluorenyl group and the like. a aryl group of -18 or a heterocyclic ring containing, for example, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, etc. Ring base.

於n為2以上的整數的情形時的（n＋1）價的芳香環基的具體例可較佳地列舉：自二價芳香環基的所述具體例中去掉（n－1）個任意的氫原子而成的基團。 （n＋1）價的芳香環基亦可更具有取代基。Specific examples of the (n+1)-valent aromatic ring group in the case where n is an integer of 2 or more can be preferably exemplified by removing (n-1) arbitrary hydrogens from the specific example of the divalent aromatic ring group. A group of atoms. The (n+1)-valent aromatic ring group may also have a more substituent.

上文所述的烷基、環烷基、烷氧基羰基及（n＋1）價的芳香環基可具有的取代基例如可列舉：通式（I）中的R41 、R42 、R43 中列舉的烷基；甲氧基、乙氧基、羥基乙氧基、丙氧基、羥基丙氧基、丁氧基等烷氧基；苯基等芳基等。 X4 所表示的-CONR64 -（R64 表示氫原子、烷基）中的R64 的烷基較佳可列舉：可具有取代基的甲基、乙基、丙基、異丙基、正丁基、第二丁基、己基、2-乙基己基、辛基、十二烷基等碳數20以下的烷基，更佳可列舉碳數8以下的烷基。 X4 較佳為單鍵、-COO-、-CONH-，更佳為單鍵、-COO-。The substituent which the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group and (n+1)-valent aromatic ring group may have, for example, may be exemplified by R 41 , R 42 and R 43 in the formula (I). The alkyl group exemplified is an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group or a butoxy group; an aryl group such as a phenyl group; and the like. The alkyl group of R 64 in -CONR 64 - (R 64 represents a hydrogen atom or an alkyl group) represented by X 4 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a group which may have a substituent. An alkyl group having a carbon number of 20 or less, such as a butyl group, a second butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms. X 4 is preferably a single bond, -COO-, -CONH-, more preferably a single bond, -COO-.

作為L4 的二價連結基較佳為伸烷基，伸烷基較佳可列舉：可具有取代基的亞甲基、伸乙基、伸丙基、伸丁基、伸己基、伸辛基等碳數1個～8個的基團。 Ar4 更佳為可具有取代基的碳數6～18的芳香環基，尤佳為苯環基、萘環基、聯苯環基。 通式（I）所表示的重複單元較佳為具備羥基苯乙烯結構。即，Ar4 較佳為苯環基。The divalent linking group as L 4 is preferably an alkylene group, and the alkylene group is preferably a methylene group which may have a substituent, an exoethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group. A group having 1 to 8 carbon atoms. Ar 4 is more preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a benzene ring group, a naphthalene ring group or a biphenyl ring group. The repeating unit represented by the formula (I) preferably has a hydroxystyrene structure. That is, Ar 4 is preferably a benzene ring group.

樹脂（B）所含有的具有酚性羥基的重複單元較佳可列舉下述通式（p1）所表示的重複單元。The repeating unit having a phenolic hydroxyl group contained in the resin (B) is preferably a repeating unit represented by the following formula (p1).

[化24] [Chem. 24]

通式（p1）中的R表示氫原子、鹵素原子或具有1個～4個碳原子的直鏈或分支的烷基。多個R可分別相同亦可不同。通式（p1）中的R尤佳為氫原子。R in the formula (p1) represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different. R in the formula (p1) is particularly preferably a hydrogen atom.

通式（p1）中的Ar表示芳香族環，例如可列舉：苯環、萘環、蒽環、茀環、菲環等可具有碳數6～18的取代基的芳香族烴環，或含有例如噻吩環、呋喃環、吡咯環、苯并噻吩環、苯并呋喃環、苯并吡咯環、三嗪環、咪唑環、苯并咪唑環、三唑環、噻二唑環、噻唑環等雜環的芳香環雜環。其中，最佳為苯環。In the general formula (p1), Ar represents an aromatic ring, and examples thereof include an aromatic hydrocarbon ring which may have a substituent having a carbon number of 6 to 18, such as a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring or a phenanthrene ring, or a For example, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, a thiazole ring, etc. Ring aromatic ring heterocycle. Among them, the best is a benzene ring.

通式（p1）中的m表示1～5的整數，較佳為1。m in the formula (p1) represents an integer of 1 to 5, preferably 1.

以下示出樹脂（B）所含有的具有酚性羥基的重複單元的具體例，但本發明不限定於此。式中，a表示1或2。Specific examples of the repeating unit having a phenolic hydroxyl group contained in the resin (B) are shown below, but the present invention is not limited thereto. Where a represents 1 or 2.

[化25] [化25]

[化26] [Chem. 26]

樹脂（B）可含有一種具有酚性羥基的重複單元（a），亦可含有兩種以上的具有酚性羥基的重複單元（a）。The resin (B) may contain a repeating unit (a) having a phenolic hydroxyl group, and may further contain two or more repeating units (a) having a phenolic hydroxyl group.

相對於樹脂（B）的所有重複單元，具有酚性羥基的重複單元（a）的含量較佳為10 mol%～95 mol%，更佳為20 mol%～90 mol%，進而佳為30 mol%～85 mol%。The content of the repeating unit (a) having a phenolic hydroxyl group is preferably from 10 mol% to 95 mol%, more preferably from 20 mol% to 90 mol%, and further preferably 30 mol, based on all the repeating units of the resin (B). % ~ 85 mol%.

具有芳香環基的重複單元（a）亦可為下述通式（X）所表示的重複單元。The repeating unit (a) having an aromatic ring group may also be a repeating unit represented by the following formula (X).

[化27] [化27]

通式（X）中， R61 、R62 及R63 分別獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基或烷氧基羰基。其中，R63 亦可與Ar鍵結而形成環，該情形的R62 表示單鍵或伸烷基。 Ar表示（n＋1）價的芳香環基，於與R62 鍵結而形成環的情形時表示（n＋2）價的芳香環基。 R7 分別獨立地表示碳數1～10的直鏈狀或分支狀或環狀的烷基、烷氧基或醯氧基、氰基、硝基、胺基、鹵素原子、酯基（-OCOR或-COOR：R為碳數1～6的烷基或氟化烷基）、或羧基。 n表示0以上的整數。In the formula (X), R 61 , R 62 and R 63 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R 63 may also be bonded to Ar to form a ring, and in this case, R 62 represents a single bond or an alkylene group. Ar represents an (n+1)-valent aromatic ring group, and when it is bonded to R 62 to form a ring, it represents an (n+2)-valent aromatic ring group. R 7 each independently represents a linear or branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or a decyloxy group, a cyano group, a nitro group, an amine group, a halogen atom, or an ester group (-OCOR) Or -COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group) or a carboxyl group. n represents an integer of 0 or more.

下述通式（X）亦較佳為下述通式（V）或下述通式（VI）所表示的重複單元。The following general formula (X) is also preferably a repeating unit represented by the following general formula (V) or the following general formula (VI).

[化28] [化28]

式中，n3表示0～4的整數。n4表示0～6的整數。 X4 為亞甲基、氧原子或硫原子。 R7 與所述通式（X）的R7 為相同含意。In the formula, n3 represents an integer of 0-4. N4 represents an integer of 0-6. X 4 is a methylene group, an oxygen atom or a sulfur atom. R 7 in the general formula (X) is of the same meaning as R 7.

以下示出通式（X）所表示的重複單元的具體例，但不限定於該些具體例。Specific examples of the repeating unit represented by the general formula (X) are shown below, but are not limited to these specific examples.

[化29] [化29]

[化30] [化30]

樹脂（B）可含有一種通式（X）所表示的重複單元（a），亦可含有兩種以上的通式（X）所表示的重複單元（a）。The resin (B) may contain one repeating unit (a) represented by the formula (X), or may contain two or more repeating units (a) represented by the formula (X).

相對於樹脂（B）的所有重複單元，通式（X）所表示的重複單元的含量較佳為5 mol%～50 mol%，更佳為5 mol%～40 mol%，進而佳為5 mol%～30 mol%。The content of the repeating unit represented by the general formula (X) is preferably from 5 mol% to 50 mol%, more preferably from 5 mol% to 40 mol%, and further preferably 5 mol, based on all the repeating units of the resin (B). % to 30 mol%.

另外，具有芳香環基的重複單元（a）亦可為後述具有極性基經藉由酸的作用發生分解而脫離的脫離基保護的結構的重複單元（c）中的具有芳香環基的重複單元。Further, the repeating unit (a) having an aromatic ring group may also be a repeating unit having an aromatic ring group in the repeating unit (c) of the structure having a leaving group which has a polar group which is decomposed by decomposition by an action of an acid. .

樹脂（B）可含有一種具有芳香環基的重複單元（a），亦可含有兩種以上的具有芳香環基的重複單元（a）。The resin (B) may contain a repeating unit (a) having an aromatic ring group, and may further contain two or more repeating units (a) having an aromatic ring group.

相對於樹脂（B）的所有重複單元，具有芳香環基的重複單元（a）的含量較佳為5 mol%～100 mol%，更佳為7 mol%～98 mol%，進而佳為8 mol%～96 mol%。The content of the repeating unit (a) having an aromatic ring group is preferably from 5 mol% to 100 mol%, more preferably from 7 mol% to 98 mol%, and even more preferably 8 mol, based on all the repeating units of the resin (B). % ~ 96 mol%.

[具有極性基經藉由酸的作用發生分解而脫離的脫離基保護的結構的重複單元（b）] 樹脂（B）於較佳一實施形態中，含有具有極性基經藉由酸的作用發生分解而脫離的脫離基保護的結構的重複單元（b）。 具有極性基經藉由酸的作用發生分解而脫離的脫離基保護的結構（酸分解性基）的重複單元（b）中的極性基可列舉羧基、醇性羥基、酚性羥基及磺酸基等。其中，極性基較佳為羧基、醇性羥基或酚性羥基，進而佳為羧基或酚性羥基。 另外，若樹脂（B）含有具有酸分解性基的重複單元，則藉由酸的作用而於鹼性顯影液中的溶解度增大，於有機溶劑中的溶解度減少。 因此，含有具有酸分解性基的重複單元的樹脂（B）可較佳地用於使用鹼性顯影液的正型圖案形成、或使用有機系顯影液的負型圖案形成中。[Repeating unit (b) having a structure in which a polar group is decomposed by decomposition by an acid to be decomposed and desorbed] Resin (B), in a preferred embodiment, containing a polar group by an action of an acid The repeating unit (b) of the structure that is decomposed and detached from the base protection. The polar group in the repeating unit (b) having a structure in which the polar group is decomposed and decomposed by the action of an acid (acid-decomposable group) can be exemplified by a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, and a sulfonic acid group. Wait. Among them, the polar group is preferably a carboxyl group, an alcoholic hydroxyl group or a phenolic hydroxyl group, and further preferably a carboxyl group or a phenolic hydroxyl group. Further, when the resin (B) contains a repeating unit having an acid-decomposable group, the solubility in the alkaline developing solution by the action of the acid increases, and the solubility in the organic solvent decreases. Therefore, the resin (B) containing a repeating unit having an acid-decomposable group can be preferably used in the formation of a positive pattern using an alkaline developer or in the formation of a negative pattern using an organic developer.

藉由酸的作用發生分解而脫離的脫離基例如可列舉式（Y1）～式（Y4）所表示的基團。 式（Y1）：-C(Rx1 )(Rx2 )(Rx3 ) 式（Y2）：-C(=O)OC(Rx1 )(Rx2 )(Rx3 ) 式（Y3）：-C(R36 )(R37 )(OR38 ) 式（Y4）：-C(Rn)(H)(Ar)Examples of the leaving group which is decomposed and decomposed by the action of an acid include a group represented by the formula (Y1) to the formula (Y4). Formula (Y1): -C(Rx 1 )(Rx 2 )(Rx 3 ) Formula (Y2): -C(=O)OC(Rx 1 )(Rx 2 )(Rx 3 ) Formula (Y3): -C (R 36 )(R 37 )(OR 38 ) Formula (Y4): -C(Rn)(H)(Ar)

式（Y1）、式（Y2）中，Rx1 ～Rx3 分別獨立地表示烷基（直鏈或分支）或環烷基（單環或多環）。其中，於Rx1 ～Rx3 全部為烷基（直鏈或分支）的情形時，較佳為Rx1 ～Rx3 中至少兩個為甲基。 更佳為Rx1 ～Rx3 分別獨立地表示直鏈或分支的烷基的重複單元，進而佳為Rx1 ～Rx3 分別獨立地表示直鏈烷基的重複單元。 Rx1 ～Rx3 的兩個亦可鍵結而形成單環或多環。 Rx1 ～Rx3 的烷基較佳為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基等碳數1～4的烷基。 Rx1 ～Rx3 的環烷基較佳為環戊基、環己基等單環的環烷基、降冰片基、四環癸基、四環十二烷基、金剛烷基等多環的環烷基。 Rx1 ～Rx3 的兩個鍵結而形成的環烷基較佳為環戊基、環己基等單環的環烷基、降冰片基、四環癸基、四環十二烷基、金剛烷基等多環的環烷基。尤佳為碳數5～6的單環的環烷基。 關於Rx1 ～Rx3 的兩個鍵結而形成的環烷基，例如構成環的一個亞甲基可經氧原子等雜原子、或羰基等具有雜原子的基團取代。 通式（Y1）、通式（Y2）所表示的重複單元例如較佳為Rx1 為甲基或乙基、Rx2 與Rx3 鍵結而形成所述環烷基的態樣。In the formula (Y1) and the formula (Y2), Rx 1 to Rx 3 each independently represent an alkyl group (straight chain or branched) or a cycloalkyl group (monocyclic or polycyclic). In the case where all of Rx 1 to Rx 3 are an alkyl group (straight chain or branched), at least two of Rx 1 to Rx 3 are preferably a methyl group. More preferably Rx 1 ~ Rx 3 each independently represent a repeating unit of a linear or branched alkyl group, and thus is good Rx 1 ~ Rx 3 each independently represent a linear alkyl group of repeating units. Two of Rx 1 to Rx 3 may also be bonded to form a single ring or multiple rings. The alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a t-butyl group. The cycloalkyl group of Rx 1 to Rx 3 is preferably a polycyclic ring such as a cyclopentyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group. alkyl. The cycloalkyl group formed by the two bonds of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclononyl group, a tetracyclododecyl group, or a diamond. A polycyclic cycloalkyl group such as an alkyl group. More preferably, it is a monocyclic cycloalkyl group having 5 to 6 carbon atoms. The cycloalkyl group formed by the two bonds of Rx 1 to Rx 3 may be substituted, for example, with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. The repeating unit represented by the formula (Y1) or the formula (Y2) is preferably, for example, a state in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to each other to form the cycloalkyl group.

式（Y3）中，R36 ～R38 分別獨立地表示氫原子或一價有機基。R37 與R38 亦可相互鍵結而形成環。一價有機基可列舉烷基、環烷基、芳基、芳烷基及烯基等，R36 亦較佳為氫原子。In the formula (Y3), R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group. R 37 and R 38 may also be bonded to each other to form a ring. The monovalent organic group may, for example, be an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, and R 36 is also preferably a hydrogen atom.

較佳的式（Y3）更佳為下述通式（Y3-1）所表示的結構。The preferred formula (Y3) is more preferably a structure represented by the following formula (Y3-1).

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此處，L1 及L2 分別獨立地表示氫原子、烷基、環烷基、芳基或將伸烷基與芳基組合而成的基團。 M表示單鍵或二價連結基。 Q表示烷基、可含有雜原子的環烷基、可含有雜原子的芳基、胺基、銨基、巰基、氰基或醛基。 L1 及L2 中的至少一個為氫原子，較佳為至少一個為烷基、環烷基、芳基或將伸烷基與芳基組合而成的基團。 Q、M、L1 的至少兩個亦可鍵結而形成環（較佳為5員環或6員環）。 就提高圖案倒塌性能的方面而言，較佳為L2 為二級烷基或三級烷基，更佳為三級烷基。二級烷基可列舉異丙基、環己基或降冰片基，三級烷基可列舉第三丁基或金剛烷。該些態樣中，因Tg或活化能量變高，故除了確保膜強度以外，可抑制灰霧。Here, L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a group in which an alkyl group and an aryl group are combined. M represents a single bond or a divalent linking group. Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amine group, an ammonium group, a fluorenyl group, a cyano group or an aldehyde group. At least one of L 1 and L 2 is a hydrogen atom, and preferably at least one is an alkyl group, a cycloalkyl group, an aryl group or a group in which an alkyl group and an aryl group are combined. At least two of Q, M, and L 1 may also be bonded to form a ring (preferably a 5-member ring or a 6-member ring). In terms of improving the pattern collapse property, L 2 is preferably a secondary alkyl group or a tertiary alkyl group, more preferably a tertiary alkyl group. The secondary alkyl group may, for example, be an isopropyl group, a cyclohexyl group or a norbornyl group, and the tertiary alkyl group may be a tertiary butyl group or adamantane. In these aspects, since the Tg or the activation energy becomes high, in addition to ensuring the film strength, fogging can be suppressed.

式（Y4）中，Ar表示芳香環基。Rn表示烷基、環烷基或芳基。Rn與Ar亦可相互鍵結而形成非芳香族環。Ar更佳為芳基。In the formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may also be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

樹脂（B）所含有的具有藉由酸的作用發生分解而產生極性基的基團的重複單元較佳為下述通式（AI）或通式（AII）所表示的重複單元。The repeating unit contained in the resin (B) having a group which is decomposed by an action of an acid to generate a polar group is preferably a repeating unit represented by the following formula (AI) or formula (AII).

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通式（AI）中， Xa1 表示氫原子、可具有取代基的烷基。 T表示單鍵或二價連結基。 Y表示藉由酸而脫離的基團。Y較佳為式（Y1）～式（Y4）。In the general formula (AI), Xa 1 represents a hydrogen atom and an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Y represents a group which is detached by an acid. Y is preferably a formula (Y1) to a formula (Y4).

Xa1 所表示的可具有取代基的烷基例如可列舉甲基或-CH2 -R11 所表示的基團。R11 表示鹵素原子（氟原子等）、羥基或一價有機基，例如可列舉碳數5以下的烷基、碳數5以下的醯基，較佳為碳數3以下的烷基，進而佳為甲基。Xa1 於一態樣中，較佳為氫原子、甲基、三氟甲基或羥基甲基等。 T的二價連結基可列舉伸烷基、-COO-Rt-基、-O-Rt-基等。式中，Rt表示伸烷基或伸環烷基。 T較佳為單鍵或-COO-Rt-基。Rt較佳為碳數1～5的伸烷基，更佳為-CH2 -基、-(CH2 )2 -基、-(CH2 )3 -基。The alkyl group which may have a substituent represented by Xa 1 is, for example, a group represented by a methyl group or -CH 2 -R 11 . R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and a fluorenyl group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms, and more preferably Is a methyl group. Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and the like. The divalent linking group of T may, for example, be an alkyl group, a -COO-Rt- group or a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkyl group. T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH 2 - group, a -(CH 2 ) 2 - group or a -(CH 2 ) 3 - group.

通式（AII）中， R61 、R62 及R63 分別獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基或烷氧基羰基。其中，R62 亦可與Ar6 鍵結而形成環，該情形的R62 表示單鍵或伸烷基。 X6 表示單鍵、-COO-或-CONR64 -。R64 表示氫原子或烷基。 L6 表示單鍵或伸烷基。 Ar6 表示（n＋1）價的芳香環基，於與R62 鍵結而形成環的情形時表示（n＋2）價的芳香環基。 於n≧2的情形時，Y2 分別獨立地表示氫原子或藉由酸的作用而脫離的基團。其中，Y2 的至少一個表示藉由酸的作用而脫離的基團。作為Y2 的藉由酸的作用而脫離的基團較佳為式（Y1）～式（Y4）。 n表示1～4的整數。In the formula (AII), R 61 , R 62 and R 63 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R 62 may also bond with Ar 6 to form a ring, and in this case, R 62 represents a single bond or an alkylene group. X 6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group. L 6 represents a single bond or an alkyl group. Ar 6 represents an (n+1)-valent aromatic ring group, and when it is bonded to R 62 to form a ring, it represents an (n+2)-valent aromatic ring group. In the case of n ≧ 2, Y 2 independently represents a hydrogen atom or a group which is detached by the action of an acid. Wherein at least one of Y 2 represents a group which is detached by the action of an acid. The group which is desorbed by the action of an acid as Y 2 is preferably a formula (Y1) to a formula (Y4). n represents an integer of 1 to 4.

所述各基團亦可具有取代基，取代基例如可列舉烷基（碳數1～4）、鹵素原子、羥基、烷氧基（碳數1～4）、羧基、烷氧基羰基（碳數2～6）等，較佳為碳數8以下。Each of the groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxycarbonyl group (carbon). The number is 2 to 6), etc., preferably 8 or less.

通式（AI）所表示的重複單元較佳為酸分解性(甲基)丙烯酸三級烷基酯系重複單元（Xa1 表示氫原子或甲基、且T表示單鍵的重複單元）。The repeating unit represented by the formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T represents a repeating unit of a single bond).

所述通式（AII）所表示的重複單元較佳為下述通式（AIII）所表示的重複單元。The repeating unit represented by the above formula (AII) is preferably a repeating unit represented by the following formula (AIII).

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通式（AIII）中，Ar3 表示芳香環基。 於n≧2的情形時，Y2 分別獨立地表示氫原子或藉由酸的作用而脫離的基團。其中，Y2 的至少一個表示藉由酸的作用而脫離的基團。作為Y2 的藉由酸的作用而脫離的基團較佳為式（Y1）～式（Y4）。 n表示1～4的整數。In the formula (AIII), Ar 3 represents an aromatic ring group. In the case of n ≧ 2, Y 2 independently represents a hydrogen atom or a group which is detached by the action of an acid. Wherein at least one of Y 2 represents a group which is detached by the action of an acid. The group which is desorbed by the action of an acid as Y 2 is preferably a formula (Y1) to a formula (Y4). n represents an integer of 1 to 4.

Ar6 及Ar3 所表示的芳香環基較佳為苯環基或萘環基，更佳為苯環基。The aromatic ring group represented by Ar 6 and Ar 3 is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

以下示出具有酸分解性基的重複單元的具體例，但本發明不限定於此。 具體例中，Rx表示氫原子、CH3 、CF3 或CH2 OH。Rxa、Rxb分別表示碳數1～4的烷基。Z表示含有極性基的取代基，於存在多個的情形時分別獨立。p表示0或正整數。Z所表示的含有極性基的取代基例如可列舉：具有羥基、氰基、胺基、烷基醯胺基或磺醯胺基的直鏈或分支的烷基、環烷基，較佳為具有羥基的烷基。分支狀烷基尤佳為異丙基。Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto. In a specific example, Rx represents a hydrogen atom, CH 3 , CF 3 or CH 2 OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent having a polar group, and is independent in the case where there are a plurality of cases. p represents 0 or a positive integer. The polar group-containing substituent represented by Z may, for example, be a linear or branched alkyl group having a hydroxyl group, a cyano group, an amine group, an alkylguanamine group or a sulfonylamino group, or a cycloalkyl group, preferably having An alkyl group of a hydroxyl group. The branched alkyl group is preferably an isopropyl group.

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所述具有酸分解性基的重複單元可為一種，亦可併用兩種以上。The repeating unit having an acid-decomposable group may be one type or two or more types may be used in combination.

相對於所述樹脂（B）中的所有重複單元，樹脂（B）中的具有酸分解性基的重複單元的含量（含有多種的情形時為其合計）較佳為5 mol%以上且80 mol%以下，更佳為5 mol%以上且75 mol%以下，進而佳為10 mol%以上且65 mol%以下。The content of the repeating unit having an acid-decomposable group in the resin (B) (in total of a plurality of cases) is preferably 5 mol% or more and 80 mol with respect to all the repeating units in the resin (B). % or less, more preferably 5 mol% or more and 75 mol% or less, and further preferably 10 mol% or more and 65 mol% or less.

另外，本案說明書中，具有酸分解性基及芳香環基的重複單元既相當於具有酸分解性基的重複單元，亦相當於具有芳香環基的重複單元。Further, in the present specification, the repeating unit having an acid-decomposable group and an aromatic ring group corresponds to a repeating unit having an acid-decomposable group and a repeating unit having an aromatic ring group.

[具有內酯基或磺內酯基的重複單元] 樹脂（B）亦較佳為含有具有內酯基或磺內酯（環狀磺酸酯）基的重複單元。內酯基或磺內酯基只要含有內酯結構或磺內酯結構，則可使用任意的基團，較佳為含有5員環～7員環內酯結構或磺內酯結構的基團，較佳為於5員環～7員環內酯結構或磺內酯結構上以形成雙環結構、螺環結構的形式縮環有其他環結構的基團。 更佳為含有具有如下基團的重複單元，所述基團具有下述通式（LC1-1）～通式（LC1-17）的任一個所表示的內酯結構或下述通式（SL1-1）～通式（SL1-3）的任一個所表示的磺內酯結構。另外，具有內酯結構或磺內酯結構的基團亦可直接鍵結於主鏈上。較佳的內酯結構或磺內酯結構為通式（LC1-1）、通式（LC1-4）、通式（LC1-5）、通式（LC1-6）、通式（LC1-13）、通式（LC1-14）所表示的基團。[Repeating unit having a lactone group or a sultone group] The resin (B) is also preferably a repeating unit having a lactone group or a sultone (cyclic sulfonate) group. The lactone group or the sultone group may be any group as long as it contains a lactone structure or a sultone structure, and preferably a group having a 5-membered ring to a 7-membered ring lactone structure or a sultone structure. It is preferred to condense a group having another ring structure in a form of a bicyclic structure or a spiro ring structure in a 5-membered to 7-membered ring lactone structure or a sultone structure. More preferably, it is a repeating unit having a group having a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-17) or the following formula (SL1) -1) - a sultone structure represented by any one of the formula (SL1-3). Further, a group having a lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structure or sultone structure is of the formula (LC1-1), formula (LC1-4), formula (LC1-5), formula (LC1-6), formula (LC1-13) ) a group represented by the formula (LC1-14).

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內酯結構部分或磺內酯結構部分可具有取代基（Rb2 ）亦可不具有取代基（Rb2 ）。較佳的取代基（Rb2 ）可列舉：碳數1～8的烷基、碳數4～7的環烷基、碳數1～8的烷氧基、碳數1～8的烷氧基羰基、羧基、鹵素原子、羥基、氰基、酸分解性基等。n2 表示0～4的整數。於n2 為2以上時，存在多個的Rb2 可相同亦可不同，另外，存在多個的Rb2 彼此亦可鍵結而形成環。The lactone moiety or the sultone moiety may have a substituent (Rb 2 ) or a substituent (Rb 2 ). Preferred examples of the substituent (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms. A carbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, or the like. n 2 represents an integer of 0 to 4. When n 2 is 2 or more, a plurality of Rb 2 may be the same or different, and a plurality of Rb 2 may be bonded to each other to form a ring.

含有具有通式（LC1-1）～通式（LC1-17）的任一個所表示的內酯結構或通式（SL1-1）～通式（SL1-3）的任一個所表示的磺內酯結構的基團的重複單元例如可列舉下述通式（AI）所表示的重複單元等。The sulphonate represented by any one of the lactone structure represented by any one of the formula (LC1-1) to the formula (LC1-17) or the formula (SL1-1) to the formula (SL1-3) The repeating unit of the group of the ester structure may, for example, be a repeating unit represented by the following formula (AI).

[化46] [Chem. 46]

通式（AI）中，Rb0 表示氫原子、鹵素原子或碳數1～4的烷基。 Rb0 的烷基可具有的取代基可列舉羥基、鹵素原子。 Rb0 的鹵素原子可列舉氟原子、氯原子、溴原子、碘原子。Rb0 較佳為氫原子或甲基。 Ab表示單鍵、伸烷基、具有單環或多環的脂環烴結構的二價連結基、醚基、酯基、羰基、羧基或將該些基團組合而成的二價基。較佳為單鍵、-Ab1 -CO2 -所表示的連結基。Ab1 為直鏈或分支伸烷基、單環或多環的伸環烷基，較佳為亞甲基、伸乙基、伸環己基、伸金剛烷基、伸降冰片基。 V表示通式（LC1-1）～通式（LC1-17）及通式（SL1-1）～通式（SL1-3）中的任一個所表示的基團。In the formula (AI), Rb 0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. The substituent which the alkyl group of Rb 0 may have includes a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group or a divalent group obtained by combining the groups. It is preferably a single bond or a linking group represented by -Ab 1 -CO 2 -. Ab 1 is a linear or branched alkyl, monocyclic or polycyclic cycloalkyl group, preferably a methylene group, an ethyl group, a cyclohexylene group, an adamantyl group, or a borneol group. V represents a group represented by any one of the formula (LC1-1) to the formula (LC1-17) and the formula (SL1-1) to the formula (SL1-3).

具有內酯基或磺內酯基的重複單元通常存在光學異構物，可使用任意的光學異構物。另外，可單獨使用一種光學異構物，亦可將多種光學異構物混合使用。於主要使用一種光學異構物的情形時，其光學純度（對映體過量（enantiomeric excess，ee））較佳為90%以上，更佳為95%以上。The repeating unit having a lactone group or a sultone group usually has an optical isomer, and any optical isomer can be used. Further, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. In the case where an optical isomer is mainly used, the optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more.

以下列舉具有內酯基或磺內酯基的重複單元的具體例，但本發明不限定於該些具體例。Specific examples of the repeating unit having a lactone group or a sultone group are listed below, but the present invention is not limited to these specific examples.

[化47] [化47]

[化48] [48]

相對於樹脂（B）中的所有重複單元，具有內酯基或磺內酯基的重複單元的含量較佳為1 mol%～30 mol%，更佳為5 mol%～25 mol%，進而佳為5 mol%～20 mol%。The content of the repeating unit having a lactone group or a sultone group is preferably from 1 mol% to 30 mol%, more preferably from 5 mol% to 25 mol%, based on all the repeating units in the resin (B). It is 5 mol% to 20 mol%.

[其他重複單元] 樹脂（B）可更含有以下重複單元作為其他重複單元：含有具有極性基的有機基的重複單元、特別是具有經極性基取代的脂環烴結構的重複單元。 藉此，基板密接性、顯影液親和性提高。經極性基取代的脂環烴結構的脂環烴結構較佳為金剛烷基、二金剛烷基、降冰片基。極性基較佳為羥基、氰基。以下列舉具有極性基的重複單元的具體例，但本發明不限定於該些具體例。[Other Repeating Units] The resin (B) may further contain the following repeating unit as another repeating unit: a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Thereby, the substrate adhesion and the developer affinity are improved. The alicyclic hydrocarbon structure of the polar group-substituted alicyclic hydrocarbon structure is preferably an adamantyl group, a diadamantyl group or a norbornyl group. The polar group is preferably a hydroxyl group or a cyano group. Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited to the specific examples.

[化49] [化49]

於樹脂（B）具有含有具有極性基的有機基的重複單元的情形時，相對於樹脂（B）中的所有重複單元，其含量較佳為1 mol%～30 mol%，更佳為5 mol%～25 mol%，進而佳為5 mol%～20 mol%。In the case where the resin (B) has a repeating unit containing an organic group having a polar group, the content thereof is preferably from 1 mol% to 30 mol%, more preferably 5 mol, based on all the repeating units in the resin (B). % to 25 mol%, and further preferably from 5 mol% to 20 mol%.

另外，樹脂（B）亦可含有具有藉由光化射線或放射線的照射而產生酸的基團（光酸產生基）的重複單元作為其他重複單元。於該情形時，可認為該具有光酸產生基的重複單元相當於後述藉由光化射線或放射線的照射而產生酸的化合物。 此種重複單元例如可列舉下述通式（4）所表示的重複單元。Further, the resin (B) may contain a repeating unit having a group (photoacid generating group) which generates an acid by irradiation with actinic rays or radiation as another repeating unit. In this case, it is considered that the repeating unit having a photoacid generating group corresponds to a compound which generates an acid by irradiation with actinic rays or radiation, which will be described later. Examples of such a repeating unit include a repeating unit represented by the following formula (4).

[化50] [化50]

R41 表示氫原子或甲基。L41 表示單鍵或二價連結基。L42 表示二價連結基。W表示藉由光化射線或放射線的照射發生分解而於側鏈上產生酸的結構部位。R 41 represents a hydrogen atom or a methyl group. L 41 represents a single bond or a divalent linking group. L 42 represents a divalent linking group. W represents a structural portion which is decomposed by irradiation with actinic rays or radiation to generate an acid on the side chain.

除此以外，通式（4）所表示的重複單元例如可列舉日本專利特開2014-041327號公報的段落[0094]～段落[0105]中記載的重複單元。In addition, the repeating unit represented by the formula (4) is, for example, a repeating unit described in paragraphs [0094] to [0105] of JP-A-2014-041327.

於樹脂（B）含有具有光酸產生基的重複單元的情形時，相對於樹脂（B）中的所有重複單元，具有光酸產生基的重複單元的含量較佳為1 mol%～40 mol%，更佳為5 mol%～35 mol%，進而佳為5 mol%～30 mol%。In the case where the resin (B) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably from 1 mol% to 40 mol% with respect to all the repeating units in the resin (B). More preferably, it is 5 mol% to 35 mol%, and further preferably 5 mol% to 30 mol%.

樹脂（B）亦可含有於側鏈上具有矽原子的重複單元。 於側鏈上具有矽原子的重複單元例如可列舉：具有矽原子的(甲基)丙烯酸酯系重複單元、具有矽原子的乙烯系重複單元等。於側鏈上具有矽原子的重複單元典型而言為於側鏈上具有含有矽原子的基團的重複單元，含有矽原子的基團例如可列舉：三甲基矽烷基、三乙基矽烷基、三苯基矽烷基、三環己基矽烷基、三(三甲基矽烷氧基)矽烷基、三(三甲基矽烷基)矽烷基、甲基雙(三甲基矽烷基)矽烷基、甲基雙(三甲基矽烷氧基)矽烷基、二甲基三甲基矽烷基矽烷基、二甲基三甲基矽烷氧基矽烷基或下述般的環狀或直鏈狀聚矽氧烷、或者籠型或梯型或無規型倍半矽氧烷結構等。式中，R及R1 分別獨立地表示一價取代基。*表示結合鍵。The resin (B) may also contain a repeating unit having a ruthenium atom in a side chain. Examples of the repeating unit having a ruthenium atom in the side chain include a (meth) acrylate-based repeating unit having a ruthenium atom, and an ethylene-based repeating unit having a ruthenium atom. The repeating unit having a halogen atom in the side chain is typically a repeating unit having a group containing a halogen atom in the side chain, and a group containing a halogen atom may, for example, be a trimethylsulfanyl group or a triethylsulfanyl group. , triphenyldecylalkyl, tricyclohexyldecylalkyl, tris(trimethyldecyloxy)decyl, tris(trimethyldecyl)decyl, methylbis(trimethyldecyl)decyl, A Bis(trimethyldecyloxy)decyl, dimethyltrimethyldecylalkyl, dimethyltrimethyldecyloxydecyl or a cyclic or linear polyoxyalkylene as described below Or cage or ladder or random sesquiterpene structure. In the formula, R and R 1 each independently represent a monovalent substituent. * indicates a bond.

[化51] [化51]

具有所述基團的重複單元例如可較佳地列舉：來源於具有所述基團的丙烯酸酯或甲基丙烯酸酯化合物的重複單元、或來源於具有所述基團與乙烯基的化合物的重複單元。The repeating unit having the group may, for example, preferably be a repeating unit derived from an acrylate or methacrylate compound having the group, or a repeating derived from a compound having the group and a vinyl group. unit.

於側鏈上具有矽原子的重複單元較佳為具有倍半矽氧烷結構的重複單元。 倍半矽氧烷結構例如可列舉籠型倍半矽氧烷結構、梯型倍半矽氧烷結構（ladder型倍半矽氧烷結構）、無規型倍半矽氧烷結構等。其中，較佳為籠型倍半矽氧烷結構。 此處，所謂籠型倍半矽氧烷結構，為具有籠狀骨架的倍半矽氧烷結構。籠型倍半矽氧烷結構可為完全籠型倍半矽氧烷結構，亦可為不完全籠型倍半矽氧烷結構，較佳為完全籠型倍半矽氧烷結構。 另外，所謂梯型倍半矽氧烷結構，為具有梯狀骨架的倍半矽氧烷結構。 另外，所謂無規型倍半矽氧烷結構，為骨架無規的倍半矽氧烷結構。The repeating unit having a halogen atom in the side chain is preferably a repeating unit having a sesquiterpene structure. Examples of the sesquioxane structure include a cage sesquiterpene oxide structure, a ladder sesquiterpene oxide structure (ladlad type sesquiterpene oxide structure), and a random sesquiterpene alkane structure. Among them, a cage type sesquiterpene oxide structure is preferred. Here, the cage sesquiterpene structure is a sesquiterpene structure having a cage skeleton. The cage sesquiterpene structure may be a completely caged sesquiterpene structure or an incomplete cage sesquiterpene structure, preferably a fully caged sesquiterpene structure. Further, the ladder type sesquiterpene oxide structure is a sesquiterpene oxide structure having a ladder skeleton. Further, the structure of the random sesquiterpene oxide is a skeleton sesquiterpene structure.

所述籠型倍半矽氧烷結構較佳為下述式（S）所表示的矽氧烷結構。The cage sesquiterpene oxide structure is preferably a oxoxane structure represented by the following formula (S).

[化52] [化52]

所述式（S）中，R表示一價有機基。多個R可相同亦可不同。 所述有機基並無特別限制，具體例可列舉：羥基、硝基、羧基、烷氧基、胺基、巰基、封端化巰基（例如經醯基封端（保護）的巰基）、醯基、醯亞胺基、膦基、氧膦基、矽烷基、乙烯基、可含有雜原子的烴基、含(甲基)丙烯酸基的基團及含環氧基的基團等。 所述可含有雜原子的烴基的雜原子例如可列舉氧原子、氮原子、硫原子、磷原子等。 所述可含有雜原子的烴基的烴基例如可列舉脂肪族烴基、芳香族烴基或將該些基團組合而成的基團等。 所述脂肪族烴基可為直鏈狀、分支鏈狀、環狀的任一種。所述脂肪族烴基的具體例可列舉：直鏈狀或分支狀的烷基（特別是碳數1～30）、直鏈狀或分支狀的烯基（特別是碳數2～30）、直鏈狀或分支狀的炔基（特別是碳數2～30）等。 所述芳香族烴基例如可列舉苯基、甲苯基、二甲苯基、萘基等碳數6～18的芳香族烴基等。In the formula (S), R represents a monovalent organic group. A plurality of Rs may be the same or different. The organic group is not particularly limited, and specific examples thereof include a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an amine group, a mercapto group, a blocked fluorenyl group (for example, a mercapto-terminated (protected) mercapto group), and a mercapto group. An anthracene group, a phosphino group, a phosphinyl group, a decyl group, a vinyl group, a hydrocarbon group which may contain a hetero atom, a group containing a (meth)acryl group, and an epoxy group-containing group. Examples of the hetero atom of the hydrocarbon group which may contain a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and the like. Examples of the hydrocarbon group of the hydrocarbon group which may contain a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining the groups. The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic group. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly, a carbon number of 1 to 30), a linear or branched alkenyl group (particularly, a carbon number of 2 to 30), and a straight Alkyl groups (especially 2 to 30 carbon atoms) in a chain or branched form. The aromatic hydrocarbon group may, for example, be an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group.

樹脂（B）可依照常法（例如自由基聚合）而合成。例如，通常的合成方法可列舉：使單體種及起始劑溶解於溶劑中並進行加熱，藉此進行聚合的總括聚合法；於加熱溶劑中用1小時～10小時滴加單體種及起始劑的溶液的滴加聚合法等，較佳為滴加聚合法。 反應溶劑例如可列舉：四氫呋喃、1,4-二噁烷、二異丙醚等醚類；甲基乙基酮、甲基異丁基酮等酮類；乙酸乙酯等酯溶劑；二甲基甲醯胺、二甲基乙醯胺等醯胺溶劑；後述丙二醇單甲醚乙酸酯、丙二醇單甲醚、環己酮等溶解感光化射線或感放射線性組成物的溶劑等。更佳為使用與感光化射線或感放射線性組成物中所用的溶劑相同的溶劑來進行聚合。藉此可抑制保存時的顆粒的產生。The resin (B) can be synthesized in accordance with a usual method (for example, radical polymerization). For example, a general synthesis method includes a polymerization method in which a monomer species and a starter are dissolved in a solvent and heated to carry out polymerization, and a monomer mixture is added dropwise in a heating solvent for 1 hour to 10 hours. The dropwise addition polymerization method of the solution of the initiator is preferably a dropping polymerization method. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; and dimethyl group. A guanamine solvent such as formamide or dimethylacetamide; a solvent such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or cyclohexanone which dissolves a sensitizing ray or a radiation sensitive composition. More preferably, the polymerization is carried out using the same solvent as that used in the photosensitive ray or the radiation sensitive composition. Thereby, generation of particles at the time of storage can be suppressed.

聚合反應較佳為於氮氣或氬氣等惰性氣體環境下進行。關於聚合起始劑，可使用市售的自由基起始劑（偶氮系起始劑、過氧化物等）來引發聚合。自由基起始劑較佳為偶氮系起始劑，較佳為具有酯基、氰基、羧基的偶氮系起始劑。較佳的起始劑可列舉偶氮雙異丁腈、偶氮雙(二甲基戊腈)、二甲基2,2'-偶氮雙(2-甲基丙酸酯)等。視需要追加、或分批添加起始劑，反應結束後，投入至溶劑中並以粉體或固體回收等方法回收所需的聚合物。反應的濃度為5質量%～50質量%，較佳為10質量%～45質量%。 反應溫度通常為10℃～150℃，較佳為30℃～120℃，進而佳為60℃～100℃。 純化可應用以下方法：藉由組合水洗或適當的溶劑而將殘留單體或寡聚物成分去除的液液萃取法；僅將特定的分子量以下者萃取去除的超濾等溶液狀態下的純化方法；或者藉由將樹脂溶液滴加至不良溶劑中而使樹脂於不良溶劑中凝固，藉此將殘留單體等去除的再沈澱法；或利用不良溶劑將經過濾分離的樹脂漿料進行清洗等固體狀態下的純化方法等通常的方法。The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, or the like) can be used to initiate polymerization. The radical initiator is preferably an azo initiator, and is preferably an azo initiator having an ester group, a cyano group or a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile, azobis(dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), and the like. The initiator is added as needed or in portions, and after completion of the reaction, it is introduced into a solvent and the desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is from 5% by mass to 50% by mass, preferably from 10% by mass to 45% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, and more preferably from 60 ° C to 100 ° C. For purification, the following method can be applied: a liquid-liquid extraction method in which residual monomer or oligomer component is removed by combining water washing or a suitable solvent; and a purification method in a solution state such as ultrafiltration in which only a specific molecular weight or less is extracted and removed. Or a reprecipitation method in which a resin is solidified in a poor solvent by solidifying a resin solution in a poor solvent, thereby removing residual monomers or the like; or cleaning the resin slurry separated by filtration using a poor solvent; A usual method such as a purification method in a solid state.

關於樹脂（B）的重量平均分子量，藉由GPC法以聚苯乙烯換算值計，較佳為1,000～200,000，進而佳為3,000～20,000，最佳為5,000～15,000。藉由將重量平均分子量設定為1,000～200,000，可防止耐熱性或耐乾式蝕刻性的劣化，且可防止顯影性劣化、或黏度變高而製膜性劣化的情況。 關於樹脂（B）的重量平均分子量的尤佳的其他形態，以由GPC法所得的聚苯乙烯換算值計而為3,000～9,500。 分散度（分子量分佈）通常為1～5，使用較佳為1～3、進而佳為1.2～3.0、尤佳為1.2～2.0的範圍的分散度（分子量分佈）。分散度越小，解析度、抗蝕劑形狀越優異，且抗蝕劑圖案的側壁光滑，粗糙度性優異。The weight average molecular weight of the resin (B) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15,000, in terms of polystyrene by the GPC method. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance or dry etching resistance can be prevented, and deterioration of developability or viscosity can be prevented, and film formability can be deteriorated. The other aspect of the weight average molecular weight of the resin (B) is preferably 3,000 to 9,500 in terms of polystyrene equivalent value obtained by the GPC method. The degree of dispersion (molecular weight distribution) is usually from 1 to 5, and a dispersion (molecular weight distribution) in a range of preferably from 1 to 3, more preferably from 1.2 to 3.0, particularly preferably from 1.2 to 2.0 is used. The smaller the degree of dispersion, the more excellent the resolution and the shape of the resist, and the side walls of the resist pattern are smooth and excellent in roughness.

感光化射線或感放射線性組成物中，樹脂（B）的含量於總固體成分中較佳為50質量%～99.9質量%，更佳為60質量%～99.0質量%。 另外，感光化射線或感放射線性組成物中，樹脂（B）可使用一種，亦可併用多種。In the photosensitive ray or the radiation sensitive composition, the content of the resin (B) is preferably 50% by mass to 99.9% by mass, and more preferably 60% by mass to 99.0% by mass, based on the total solid content. Further, in the photosensitive ray or the radiation sensitive composition, the resin (B) may be used alone or in combination of two or more.

＜藉由光化射線或放射線而產生酸的化合物＞ 感光化射線或感放射線性組成物含有藉由光化射線或放射線而產生酸的化合物（亦稱為「光酸產生劑（Photo Acid Generator，PAG）」）。 光酸產生劑可為低分子化合物的形態，亦可為組入至聚合物的一部分中的形態。另外，亦可將低分子化合物的形態與組入至聚合物的一部分中的形態併用。 於光酸產生劑為低分子化合物的形態的情形時，較佳為分子量為3000以下，更佳為2000以下，進而佳為1000以下。 於光酸產生劑為組入至聚合物的一部分中的形態的情形時，可組入至樹脂（B）的一部分中，亦可組入至與樹脂（B）不同的樹脂中。 本發明中，光酸產生劑較佳為低分子化合物的形態。 光酸產生劑只要為公知者，則並無特別限定，較佳為藉由光化射線或放射線、較佳為電子束或極紫外線的照射而產生有機酸、例如磺酸、雙(烷基磺醯基)醯亞胺或三(烷基磺醯基)甲基化物的至少任一種的化合物。 更佳可列舉下述通式（ZI）、通式（ZII）、通式（ZIII）所表示的化合物。<Compound which generates acid by actinic ray or radiation> The sensitized ray or the radiation sensitive composition contains a compound which generates an acid by actinic rays or radiation (also referred to as "Photo Acid Generator". PAG)"). The photoacid generator may be in the form of a low molecular compound or may be in a form incorporated into a part of the polymer. Further, the form of the low molecular compound may be used in combination with the form incorporated in a part of the polymer. When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. When the photoacid generator is in a form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (B) or may be incorporated into a resin different from the resin (B). In the present invention, the photoacid generator is preferably in the form of a low molecular compound. The photoacid generator is not particularly limited as long as it is known, and it is preferred to generate an organic acid such as a sulfonic acid or a bis(alkyl sulfonate) by irradiation with actinic rays or radiation, preferably an electron beam or extreme ultraviolet rays. A compound of at least one of fluorenyl imide or tris(alkylsulfonyl)methide. More preferably, it is a compound represented by the following general formula (ZI), general formula (ZII), and general formula (ZIII).

[化53] [化53]

所述通式（ZI）中， R201 、R202 及R203 分別獨立地表示有機基。 作為R201 、R202 及R203 的有機基的碳數通常為1～30，較佳為1～20。 另外，R201 ～R203 中的兩個亦可鍵結而形成環結構，亦可於環內含有氧原子、硫原子、酯鍵、醯胺鍵、羰基。R201 ～R203 中的兩個鍵結而形成的基團可列舉伸烷基（例如伸丁基、伸戊基）。 Z- 表示非親核性陰離子（引起親核反應的能力明顯低的陰離子）。In the above formula (ZI), R 201 , R 202 and R 203 each independently represent an organic group. The organic group of R 201 , R 202 and R 203 has a carbon number of usually 1 to 30, preferably 1 to 20. Further, two of R 201 to R 203 may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring. The group formed by bonding two of R 201 to R 203 may, for example, be an alkyl group (for example, a butyl group or a pentyl group). Z - represents a non-nucleophilic anion (an anion having a significantly lower ability to cause a nucleophilic reaction).

非親核性陰離子例如可列舉：磺酸根陰離子（脂肪族磺酸根陰離子、芳香族磺酸根陰離子、樟腦磺酸根陰離子等）、羧酸根陰離子（脂肪族羧酸根陰離子、芳香族羧酸根陰離子、芳烷基羧酸根陰離子等）、磺醯基醯亞胺陰離子、雙(烷基磺醯基)醯亞胺陰離子、三(烷基磺醯基)甲基化物陰離子等。Examples of the non-nucleophilic anion include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkyl group). a carboxylate anion or the like), a sulfonyl quinone imine anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl) methide anion, and the like.

脂肪族磺酸根陰離子及脂肪族羧酸根陰離子中的脂肪族部位可為烷基亦可為環烷基，較佳可列舉碳數1～30的直鏈或分支的烷基及碳數3～30的環烷基。The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number of 3 to 30. Cycloalkyl.

芳香族磺酸根陰離子及芳香族羧酸根陰離子中的芳香族基較佳可列舉碳數6～14的芳基，例如苯基、甲苯基、萘基等。The aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group or a naphthyl group.

所述列舉的烷基、環烷基及芳基亦可具有取代基。其具體例可列舉：硝基、氟原子等鹵素原子、羧基、羥基、胺基、氰基、烷氧基（較佳為碳數1～15）、環烷基（較佳為碳數3～15）、芳基（較佳為碳數6～14）、烷氧基羰基（較佳為碳數2～7）、醯基（較佳為碳數2～12）、烷氧基羰氧基（較佳為碳數2～7）、烷硫基（較佳為碳數1～15）、烷基磺醯基（較佳為碳數1～15）、烷基亞胺基磺醯基（較佳為碳數1～15）、芳氧基磺醯基（較佳為碳數6～20）、烷基芳氧基磺醯基（較佳為碳數7～20）、環烷基芳氧基磺醯基（較佳為碳數10～20）、烷氧基烷氧基（較佳為碳數5～20）、環烷基烷氧基烷氧基（較佳為碳數8～20）等。關於各基團所具有的芳基及環結構，可進一步列舉烷基（較佳為碳數1～15）作為取代基。The alkyl group, cycloalkyl group and aryl group exemplified may also have a substituent. Specific examples thereof include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3 to 3). 15) an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyloxy group. (preferably having a carbon number of 2 to 7), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), or an alkylimidosulfonyl group ( Preferred is a carbon number of 1 to 15), an aryloxysulfonyl group (preferably having a carbon number of 6 to 20), an alkylaryloxysulfonyl group (preferably having a carbon number of 7 to 20), or a cycloalkyl group. An oxysulfonyl group (preferably having a carbon number of 10 to 20), an alkoxyalkoxy group (preferably having a carbon number of 5 to 20), a cycloalkyl alkoxy alkoxy group (preferably having a carbon number of 8 to 8) 20) Wait. Further, as the aryl group and the ring structure of each group, an alkyl group (preferably having 1 to 15 carbon atoms) may be mentioned as a substituent.

芳烷基羧酸根陰離子中的芳烷基較佳可列舉碳數7～12的芳烷基，例如苄基、苯乙基、萘基甲基、萘基乙基、萘基丁基等。The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group or a naphthylbutyl group.

磺醯基醯亞胺陰離子例如可列舉糖精陰離子。Examples of the sulfonyl quinone imine anion include a saccharin anion.

雙(烷基磺醯基)醯亞胺陰離子、三(烷基磺醯基)甲基化物陰離子中的烷基較佳為碳數1～5的烷基。該些烷基的取代基可列舉：鹵素原子、經鹵素原子取代的烷基、烷氧基、烷硫基、烷氧基磺醯基、芳氧基磺醯基、環烷基芳氧基磺醯基等，較佳為氟原子或經氟原子取代的烷基。 另外，雙(烷基磺醯基)醯亞胺陰離子中的烷基亦可相互鍵結而形成環結構。藉此，酸強度增加。The alkyl group in the bis(alkylsulfonyl)phosphonium anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. The substituent of the alkyl group may, for example, be a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group or a cycloalkylaryloxysulfonate. The fluorenyl group or the like is preferably a fluorine atom or an alkyl group substituted by a fluorine atom. Further, the alkyl groups in the bis(alkylsulfonyl) quinone imine anion may be bonded to each other to form a ring structure. Thereby, the acid strength increases.

其他非親核性陰離子例如可列舉氟化磷（例如PF6 - ）、氟化硼（例如BF4 - ）、氟化銻（例如SbF6 - ）等。Examples of the other non-nucleophilic anion include phosphorus fluoride (for example, PF 6 - ), boron fluoride (for example, BF 4 - ), and cesium fluoride (for example, SbF 6 - ).

非親核性陰離子較佳為磺酸的至少α位經氟原子取代的脂肪族磺酸根陰離子、經氟原子或具有氟原子的基團取代的芳香族磺酸根陰離子、烷基經氟原子取代的雙(烷基磺醯基)醯亞胺陰離子、烷基經氟原子取代的三(烷基磺醯基)甲基化物陰離子。非親核性陰離子更佳為全氟脂肪族磺酸根陰離子（進而佳為碳數4～8）、具有氟原子的苯磺酸根陰離子，進而更佳為九氟丁磺酸根陰離子、全氟辛磺酸根陰離子、五氟苯磺酸根陰離子、3,5-雙(三氟甲基)苯磺酸根陰離子。The non-nucleophilic anion is preferably an aliphatic sulfonate anion having at least the α position of the sulfonic acid substituted by a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group substituted by a fluorine atom. A bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl) methide anion having an alkyl group substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (and more preferably a carbon number of 4 to 8), a benzenesulfonate anion having a fluorine atom, and more preferably a nonafluorobutanesulfonate anion or a perfluorooctanesulfonate. Acid anion, pentafluorobenzenesulfonate anion, 3,5-bis(trifluoromethyl)benzenesulfonate anion.

就酸強度的觀點而言，產生酸的pKa為-1以下的情況下感度提高，故較佳。From the viewpoint of acid strength, when the pKa of the generated acid is -1 or less, the sensitivity is improved, which is preferable.

另外，非親核性陰離子亦可列舉以下的通式（AN1）所表示的陰離子作為較佳態樣。Further, the non-nucleophilic anion may be an anion represented by the following general formula (AN1) as a preferred embodiment.

[化54] [54]

式中， Xf分別獨立地表示氟原子或經至少一個氟原子取代的烷基。 R1 、R2 分別獨立地表示氫原子、氟原子或烷基，存在多個的情形時的R1 、R2 可分別相同亦可不同。 L表示二價連結基，存在多個的情形時的L可相同亦可不同。 A表示環狀的有機基。 x表示1～20的整數，y表示0～10的整數，z表示0～10的整數。In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of cases, R 1 and R 2 may be the same or different. L represents a divalent linking group, and when there are a plurality of L, the L may be the same or different. A represents a cyclic organic group. x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

對通式（AN1）加以更詳細說明。 Xf的經氟原子取代的烷基中的烷基較佳為碳數1～10，更佳為碳數1～4。另外，Xf的經氟原子取代的烷基較佳為全氟烷基。 Xf較佳為氟原子或碳數1～4的全氟烷基。Xf的具體的可列舉：氟原子、CF3 、C2 F5 、C3 F7 、C4 F9 、CH2 CF3 、CH2 CH2 CF3 、CH2 C2 F5 、CH2 CH2 C2 F5 、CH2 C3 F7 、CH2 CH2 C3 F7 、CH2 C4 F9 、CH2 CH2 C4 F9 ，其中較佳為氟原子、CF3 。尤佳為兩個Xf為氟原子。The general formula (AN1) will be described in more detail. The alkyl group in the alkyl group substituted by a fluorine atom of Xf preferably has a carbon number of from 1 to 10, more preferably a carbon number of from 1 to 4. Further, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , CH 2 CH 2 C 4 F 9 , of which a fluorine atom or CF 3 is preferred. It is especially preferred that the two Xf are fluorine atoms.

R1 、R2 的烷基亦可具有取代基（較佳為氟原子），較佳為碳數1～4的基團。進而佳為碳數1～4的全氟烷基。R1 、R2 的具有取代基的烷基的具體例可列舉：CF3 、C2 F5 、C3 F7 、C4 F9 、C5 F11 、C6 F13 、C7 F15 、C8 F17 、CH2 CF3 、CH2 CH2 CF3 、CH2 C2 F5 、CH2 CH2 C2 F5 、CH2 C3 F7 、CH2 CH2 C3 F7 、CH2 C4 F9 、CH2 CH2 C4 F9 ，其中較佳為CF3 。 R1 、R2 較佳為氟原子或CF3 。The alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and is preferably a group having 1 to 4 carbon atoms. Further, it is preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , and C 7 F 15 . , C 8 F 17 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , CH 2 CH 2 C 4 F 9 , wherein CF 3 is preferred. R 1 and R 2 are preferably a fluorine atom or CF 3 .

x較佳為1～10，更佳為1～5。 y較佳為0～4，更佳為0。 z較佳為0～5，更佳為0～3。 L的二價連結基並無特別限定，可列舉-COO-、-OCO-、-CO-、-O-、-S-、-SO-、-SO2 -、伸烷基、伸環烷基、伸烯基或該些基團多個連結而成的連結基等，較佳為總碳數12以下的連結基。其中，較佳為-COO-、-OCO-、-CO-、-O-，更佳為-COO-、-OCO-。x is preferably from 1 to 10, more preferably from 1 to 5. y is preferably 0 to 4, more preferably 0. z is preferably from 0 to 5, more preferably from 0 to 3. The divalent linking group of L is not particularly limited, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO 2 -, an alkylene group, and a cycloalkyl group. The alkenyl group or a linking group in which a plurality of the groups are bonded to each other is preferably a linking group having a total carbon number of 12 or less. Among them, preferred are -COO-, -OCO-, -CO-, -O-, and more preferably -COO-, -OCO-.

A的環狀的有機基只要具有環狀結構，則並無特別限定，可列舉脂環基、芳基、雜環基（不僅為具有芳香族性的基團，亦包括不具有芳香族性的基團）等。 脂環基可為單環亦可為多環，較佳為環戊基、環己基、環辛基等單環的環烷基、降冰片基、三環癸基、四環癸基、四環十二烷基、金剛烷基等多環的環烷基。其中，降冰片基、三環癸基、四環癸基、四環十二烷基、金剛烷基等碳數7以上的具有大體積結構的脂環基可抑制曝光後加熱步驟中的膜中擴散性，就提高遮罩錯誤增強因子（Mask Error Enhancement Factor，MEEF）的觀點而言較佳。 芳基可列舉苯環、萘環、菲環、蒽環。 雜環基可列舉來源於呋喃環、噻吩環、苯并呋喃環、苯并噻吩環、二苯并呋喃環、二苯并噻吩環、吡啶環的基團。其中，較佳為來源於呋喃環、噻吩環、吡啶環的基團。The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (not only aromatic groups but also aromatic groups). Group) and so on. The alicyclic group may be a single ring or a polycyclic ring, preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, a norbornyl group, a tricyclic fluorenyl group, a tetracyclic fluorenyl group or a tetracyclic ring. A polycyclic cycloalkyl group such as dodecyl or adamantyl. Among them, an alicyclic group having a large volume structure having a carbon number of 7 or more, such as a norbornyl group, a tricyclic fluorenyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group, can be suppressed in the film in the post-exposure heating step. The diffusibility is preferred from the viewpoint of improving the Mask Error Enhancement Factor (MEEF). Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Examples of the heterocyclic group include a group derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, a group derived from a furan ring, a thiophene ring or a pyridine ring is preferred.

另外，環狀的有機基亦可列舉內酯結構，具體例可列舉上文所述的通式（LC1-1）～通式（LC1-17）所表示的內酯結構。Further, the cyclic organic group may be a lactone structure, and specific examples thereof include a lactone structure represented by the above formula (LC1-1) to formula (LC1-17).

所述環狀的有機基亦可具有取代基，所述取代基可列舉：烷基（可為直鏈、分支、環狀的任一種，較佳為碳數1～12）、環烷基（可為單環、多環、螺環的任一種，較佳為碳數3～20）、芳基（較佳為碳數6～14）、羥基、烷氧基、酯基、醯胺基、胺基甲酸酯基、醯脲基、硫醚基、磺醯胺基、磺酸酯基等。另外，構成環狀的有機基的碳（有助於形成環的碳）亦可為羰基碳。The cyclic organic group may have a substituent, and the substituent may, for example, be an alkyl group (which may be linear, branched or cyclic, preferably having a carbon number of 1 to 12) or a cycloalkyl group ( Any one of a monocyclic ring, a polycyclic ring and a spiro ring, preferably having a carbon number of 3 to 20), an aryl group (preferably having a carbon number of 6 to 14), a hydroxyl group, an alkoxy group, an ester group or an anthranyl group, A urethane group, a guanidino group, a thioether group, a sulfonylamino group, a sulfonate group or the like. Further, the carbon constituting the cyclic organic group (carbon which contributes to the formation of a ring) may also be a carbonyl carbon.

R201 、R202 及R203 的有機基可列舉芳基、烷基、環烷基等。 R201 、R202 及R203 中，較佳為至少一個為芳基，更佳為三個全部為芳基。芳基除了苯基、萘基等以外，亦可為吲哚殘基、吡咯殘基等雜芳基。R201 ～R203 的烷基及環烷基較佳可列舉碳數1～10的直鏈或分支烷基、碳數3～10的環烷基。烷基更佳可列舉甲基、乙基、正丙基、異丙基、正丁基等。環烷基更佳可列舉環丙基、環丁基、環戊基、環己基、環庚基等。該些基團亦可更具有取代基。該取代基可列舉：硝基、氟原子等鹵素原子、羧基、羥基、胺基、氰基、烷氧基（較佳為碳數1～15）、環烷基（較佳為碳數3～15）、芳基（較佳為碳數6～14）、烷氧基羰基（較佳為碳數2～7）、醯基（較佳為碳數2～12）、烷氧基羰氧基（較佳為碳數2～7）等，但不限定於該些基團。The organic group of R 201 , R 202 and R 203 may, for example, be an aryl group, an alkyl group or a cycloalkyl group. Of R 201 , R 202 and R 203 , preferably at least one is an aryl group, and more preferably all three are aryl groups. The aryl group may be a heteroaryl group such as an anthracene residue or a pyrrole residue, in addition to a phenyl group or a naphthyl group. The alkyl group and the cycloalkyl group of R 201 to R 203 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. More preferably, the alkyl group may be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. More preferably, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group. These groups may also have more substituents. Examples of the substituent include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3 to 3). 15) an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyloxy group. (preferably, carbon number is 2 to 7), etc., but it is not limited to these groups.

通式（ZII）、通式（ZIII）中， R204 ～R207 分別獨立地表示芳基、烷基或環烷基。In the general formula (ZII) and the general formula (ZIII), R 204 to R 207 each independently represent an aryl group, an alkyl group or a cycloalkyl group.

R204 ～R207 的芳基、烷基、環烷基與作為上文所述的化合物（ZI）中的R201 ～R203 的芳基、烷基、環烷基所說明的芳基相同。 R204 ～R207 的芳基、烷基、環烷基亦可具有取代基。該取代基亦可列舉上文所述的化合物（ZI）中的R201 ～R203 的芳基、烷基、環烷基可具有的取代基。R 204 ~ R 207 is an aryl group, an aryl group, a cycloalkyl group as described above with a compound of R (ZI) in 201 ~ R 203 is an aryl group, an alkyl group, a cycloalkyl group is the same as described. The aryl group, the alkyl group or the cycloalkyl group of R 204 to R 207 may have a substituent. The substituent may also be a substituent which the aryl group, the alkyl group or the cycloalkyl group of R 201 to R 203 in the compound (ZI) described above may have.

Z- 表示非親核性陰離子，可列舉與通式（ZI）中的Z- 的非親核性陰離子相同的陰離子。Z - represents a non-nucleophilic anion, and examples thereof include the same anion as the Z - non-nucleophilic anion in the formula (ZI).

通式（AN1）所表示的陰離子的A以外的部分、即- O3 S-{C(Xf)(Xf)}x-{(R1 )(R2 )}y-(L)z-所表示的基團的較佳例可列舉：- O3 S-CF2 -CH2 -OCO-、- O3 S-CF2 -CHF-CH2 -OCO-、- O3 S-CF2 -COO-、- O3 S-CF2 -CF2 -CH2 -及- O3 S-CF2 -CH(CF3 )-OCO-等。A portion other than A of the anion represented by the general formula (AN1), that is , -O 3 S-{C(Xf)(Xf)}x-{(R 1 )(R 2 )}y-(L)z- Preferred examples of the group represented are: - O 3 S-CF 2 -CH 2 -OCO-, - O 3 S-CF 2 -CHF-CH 2 -OCO-, - O 3 S-CF 2 -COO -, - O 3 S-CF 2 -CF 2 -CH 2 - and - O 3 S-CF 2 -CH(CF 3 )-OCO-.

本發明中，就抑制曝光中產生的酸向非曝光部中的擴散而使解析性良好的觀點而言，所述光酸產生劑較佳為藉由電子束或極紫外線的照射而產生體積為130 Å3 以上的大小的酸（更佳為磺酸）的化合物，更佳為產生體積為190 Å3 以上的大小的酸（更佳為磺酸）的化合物，進而佳為產生體積為270 Å3 以上的大小的酸（更佳為磺酸）的化合物，尤佳為產生體積為400 Å3 以上的大小的酸（更佳為磺酸）的化合物。其中，就感度或塗佈溶劑溶解性的觀點而言，所述體積較佳為2000 Å3 以下，進而佳為1500 Å3 以下。所述體積的值是使用富士通股份有限公司製造的「WinMOPAC」而求出。即，首先輸入各例的酸的化學結構，繼而將該結構作為初始結構，藉由使用MM3法的分子力場計算來確定各酸的最穩定立體構型，其後對該些最穩定立體構型進行使用PM3法的分子軌道計算，藉此可計算各酸的「佔有體積（accessible volume）」。 1 Å為1×10-10 m。In the present invention, the photoacid generator is preferably produced by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing diffusion of an acid generated during exposure to a non-exposed portion to improve the resolution. A compound having an acidity of more than 130 Å 3 ( more preferably a sulfonic acid), more preferably a compound having a volume of 190 Å 3 or more (more preferably a sulfonic acid), and preferably a volume of 270 Å. A compound having an acid of 3 or more in size (more preferably, a sulfonic acid) is particularly preferably a compound which produces an acid having a volume of 400 Å 3 or more (more preferably, a sulfonic acid). Among these, the volume is preferably 2,000 Å 3 or less, and more preferably 1,500 Å 3 or less from the viewpoint of sensitivity or solvent solubility of the coating solvent. The value of the volume was obtained by using "WinMOPAC" manufactured by Fujitsu Co., Ltd. That is, the chemical structure of the acid of each case is first input, and then the structure is taken as the initial structure, and the most stable stereo configuration of each acid is determined by using the molecular force field calculation of the MM3 method, and then the most stable stereostructure is The molecular orbital calculation using the PM3 method is performed, whereby the "accessible volume" of each acid can be calculated. 1 Å is 1 × 10 -10 m.

光酸產生劑可援用日本專利特開2014-41328號公報的段落[0368]～段落[0377]、日本專利特開2013-228681號公報的段落[0240]～段落[0262]（對應的美國專利申請公開第2015/004533號說明書的[0339]），將該些內容併入至本案說明書中。另外，較佳具體例可列舉以下的化合物，但不限定於該些化合物。The photoacid generator can be referred to paragraphs [0368] to [0377] of Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2013-228681, paragraph [0240] to paragraph [0262] (corresponding US patents) [0339] of the specification of the publication No. 2015/004533, the contents of which are incorporated herein by reference. Further, preferred examples thereof include the following compounds, but are not limited to these compounds.

[化55] [化55]

[化56] [化56]

[化57] [化57]

[化58] [化58]

光酸產生劑可單獨使用一種或組合使用兩種以上。 以組成物的總固體成分為基準，光酸產生劑於感光化射線或感放射線性組成物中的含量較佳為0.1質量%～50質量%，更佳為5質量%～50質量%，進而佳為8質量%～40質量%。尤其於電子束或極紫外線曝光時，為了兼具高感度化、高解析性，光酸產生劑的含有率越高越佳，進而佳為10質量%～40質量%，最佳為10質量%～35質量%。The photoacid generator may be used alone or in combination of two or more. The content of the photoacid generator in the sensitized ray or the radiation sensitive composition is preferably from 0.1% by mass to 50% by mass, more preferably from 5% by mass to 50% by mass, based on the total solid content of the composition. Preferably, it is 8 mass% to 40 mass%. In particular, in the case of electron beam or extreme ultraviolet light exposure, in order to achieve both high sensitivity and high resolution, the content of the photoacid generator is preferably as high as possible, and further preferably 10% by mass to 40% by mass, and most preferably 10% by mass. ~35 mass%.

＜（C）交聯劑＞ 本發明的感光化射線或感放射線性組成物可更含有交聯劑（以下亦稱為「化合物（C）」）。 此處，化合物（C）為與化合物（A）不同的成分。 於該情形時，本發明的感光化射線或感放射線性組成物通常為負型的感光化射線或感放射線性組成物。 交聯劑典型而言為藉由酸的作用而與樹脂（B）交聯的化合物，為具有酸交聯性基的化合物，且為於分子內含有兩個以上的羥基甲基或烷氧基甲基的化合物。另外，就提高粗糙度性能的觀點而言，較佳為交聯劑含有羥甲基。 化合物（C）可為低分子化合物的形態，亦可為組入至聚合物的一部分中的形態。另外，亦可將低分子化合物的形態與組入至聚合物的一部分中的形態併用。 於化合物（C）為低分子化合物的形態的情形時，較佳為分子量為3000以下，更佳為2000以下，進而佳為1000以下。<(C) Crosslinking Agent> The sensitized ray or the radiation sensitive composition of the present invention may further contain a crosslinking agent (hereinafter also referred to as "compound (C)"). Here, the compound (C) is a component different from the compound (A). In this case, the sensitized ray or the radiation-sensitive composition of the present invention is usually a negative-type sensitized ray or a radiation-sensitive composition. The crosslinking agent is typically a compound which is crosslinked with the resin (B) by the action of an acid, is a compound having an acid crosslinkable group, and contains two or more hydroxymethyl groups or alkoxy groups in the molecule. A compound of a methyl group. Further, from the viewpoint of improving the roughness performance, it is preferred that the crosslinking agent contains a methylol group. The compound (C) may be in the form of a low molecular compound or may be in a form incorporated into a part of the polymer. Further, the form of the low molecular compound may be used in combination with the form incorporated in a part of the polymer. When the compound (C) is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.

首先，對化合物（C）為低分子化合物的情形（以下亦稱為「化合物（C'）」）加以說明。化合物（C'）較佳可列舉：羥基甲基化或烷氧基甲基化酚化合物、烷氧基甲基化三聚氰胺系化合物、烷氧基甲基甘脲系化合物及烷氧基甲基化脲系化合物。尤佳的化合物（C'）可列舉：於分子內含有3個～5個苯環、進而合計具有兩個以上的羥基甲基或烷氧基甲基、且分子量為1200以下的酚衍生物或烷氧基甲基甘脲衍生物。 烷氧基甲基較佳為甲氧基甲基、乙氧基甲基。First, the case where the compound (C) is a low molecular compound (hereinafter also referred to as "compound (C')") will be described. The compound (C') is preferably a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethyl glycoluril compound, and an alkoxymethylated group. Urea compound. Particularly preferred compound (C') is a phenol derivative having three to five benzene rings in the molecule and further having two or more hydroxymethyl groups or alkoxymethyl groups and having a molecular weight of 1200 or less. Alkoxymethyl glycoluril derivatives. The alkoxymethyl group is preferably a methoxymethyl group or an ethoxymethyl group.

所述化合物（C'）的例子中，具有羥基甲基的酚衍生物可藉由使對應的不具有羥基甲基的酚化合物與甲醛於鹼觸媒下反應而獲得。另外，具有烷氧基甲基的酚衍生物可藉由使對應的具有羥基甲基的酚衍生物與醇於酸觸媒下反應而獲得。In the example of the compound (C'), a phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound having no hydroxymethyl group with formaldehyde under a base catalyst. Further, a phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol under an acid catalyst.

其他較佳的化合物（C'）的例子進而可列舉：烷氧基甲基化三聚氰胺系化合物、烷氧基甲基甘脲系化合物類及烷氧基甲基化脲系化合物般的具有N-羥基甲基或N-烷氧基甲基的化合物。Further, examples of the other preferable compound (C') include an alkoxymethylated melamine-based compound, an alkoxymethyl-glycoluride-based compound, and an alkoxymethylated urea-based compound having N- A compound of hydroxymethyl or N-alkoxymethyl.

此種化合物可列舉：六甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺、四甲氧基甲基甘脲、1,3-雙甲氧基甲基-4,5-雙甲氧基伸乙基脲、雙甲氧基甲基脲等，是揭示於EP0,133,216A號、西德專利第3,634,671號、西德專利第3,711,264號、EP0,212,482A號中。 以下列舉化合物（C'）的具體例中的尤佳者。Such compounds may be exemplified by hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl glycoluril, and 1,3-bismethoxymethyl-4,5-dimethoxy-properylene. The urea, bis-methoxymethyl urea, and the like are disclosed in EP 0,133,216 A, West German Patent No. 3,634,671, West German Patent No. 3,711,264, EP 0,212,482 A. The following is a list of specific examples of the compound (C').

[化59] [化59]

式中，L1 ～L8 分別獨立地表示羥基甲基或烷氧基甲基。 於本發明的一形態中，化合物（C'）較佳為下述通式（I）所表示的化合物。In the formula, L 1 to L 8 each independently represent a hydroxymethyl group or an alkoxymethyl group. In one embodiment of the present invention, the compound (C') is preferably a compound represented by the following formula (I).

[化60] [60]

通式（I）中， R1 及R6 分別獨立地表示氫原子或碳數5以下的烴基。 R2 及R5 分別獨立地表示烷基、環烷基、芳基或醯基。 R3 及R4 分別獨立地表示氫原子或碳數2以上的有機基。R3 及R4 亦可相互鍵結而形成環。In the formula (I), R 1 and R 6 each independently represent a hydrogen atom or a hydrocarbon group having 5 or less carbon atoms. R 2 and R 5 each independently represent an alkyl group, a cycloalkyl group, an aryl group or a fluorenyl group. R 3 and R 4 each independently represent a hydrogen atom or an organic group having 2 or more carbon atoms. R 3 and R 4 may also be bonded to each other to form a ring.

於本發明的一形態中，R1 及R6 較佳為碳數5以下的烴基，更佳為碳數4以下的烴基，尤佳可列舉甲基、乙基、丙基、異丙基。In one embodiment of the present invention, R 1 and R 6 are preferably a hydrocarbon group having 5 or less carbon atoms, more preferably a hydrocarbon group having 4 or less carbon atoms, and particularly preferably a methyl group, an ethyl group, a propyl group or an isopropyl group.

R2 及R5 所表示的烷基例如較佳為碳數1～6以下的烷基，環烷基例如較佳為碳數3～12的環烷基，芳基例如較佳為碳數6～12的芳基，醯基例如較佳為烷基部位的碳數為1～6的醯基。 於本發明的一形態中，R2 及R5 較佳為烷基，更佳為以碳數1～6的烷基為更佳，尤佳為甲基。The alkyl group represented by R 2 and R 5 is, for example, preferably an alkyl group having 1 to 6 carbon atoms, the cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and the aryl group is preferably, for example, a carbon number of 6 The aryl group of ～12 is preferably a fluorenyl group having 1 to 6 carbon atoms in the alkyl group. In one embodiment of the present invention, R 2 and R 5 are preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group.

R3 及R4 所表示的碳數2以上的有機基例如可列舉碳數2以上的烷基、環烷基、芳基等，另外，較佳為R3 及R4 相互鍵結形成而形成以下將詳述的環。Examples of the organic group having 2 or more carbon atoms represented by R 3 and R 4 include an alkyl group having 2 or more carbon atoms, a cycloalkyl group, and an aryl group. Further, it is preferred that R 3 and R 4 are bonded to each other to form a group. The ring will be detailed below.

R3 及R4 相互鍵結而形成的環例如可列舉：芳香族或非芳香族的烴環、芳香族或非芳香族的雜環、或將該些環的兩個以上組合而成的多環縮合環。Examples of the ring formed by bonding R 3 and R 4 to each other include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic hetero ring, or a combination of two or more of these rings. Ring condensation ring.

該些環亦可具有取代基，此種取代基例如可列舉：烷基、環烷基、烷氧基、羧基、芳基、烷氧基甲基、醯基、烷氧基羰基、硝基、鹵素或羥基等。The ring may have a substituent. Examples of such a substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, a decyl group, an alkoxycarbonyl group, and a nitro group. Halogen or hydroxyl groups, etc.

以下，列舉R3 及R4 相互鍵結而形成的環的具體例。式中的*表示與酚核的連結部位。Hereinafter, specific examples of the ring formed by bonding R 3 and R 4 to each other will be described. * in the formula indicates a linking site with a phenol nucleus.

[化61] [化61]

於本發明的一形態中，較佳為通式（I）中的R3 及R4 鍵結而形成含有苯環的多環縮合環，更佳為形成茀結構。 化合物（C'）例如較佳為通式（I）中的R3 及R4 鍵結而形成下述通式（I-a）所表示的茀結構。In one embodiment of the present invention, it is preferred that R 3 and R 4 in the formula (I) are bonded to each other to form a polycyclic condensed ring containing a benzene ring, and more preferably to form a fluorene structure. For example, the compound (C') is preferably bonded to R 3 and R 4 in the formula (I) to form a fluorene structure represented by the following formula (Ia).

[化62] [化62]

式中， R7 及R8 分別獨立地表示取代基。取代基例如可列舉烷基、環烷基、烷氧基、芳基、烷氧基甲基、醯基、烷氧基羰基、硝基、鹵素或羥基等。 n1及n2分別獨立地表示0～4的整數，較佳為表示0或1。 *表示與酚核的連結部位。In the formula, R 7 and R 8 each independently represent a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an alkoxymethyl group, a decyl group, an alkoxycarbonyl group, a nitro group, a halogen group or a hydroxyl group. N1 and n2 each independently represent an integer of 0 to 4, and preferably represent 0 or 1. * indicates the site of attachment to the phenol nucleus.

另外，於本發明的一形態中，化合物（C'）較佳為由下述通式（I-b）所表示。 [化63] Further, in one embodiment of the present invention, the compound (C') is preferably represented by the following formula (Ib). [化63]

式中， R1b 及R6b 分別獨立地表示碳數5以下的烷基。 R2b 及R5b 分別獨立地表示碳數6以下的烷基或碳數3～12的環烷基。 Z表示與式中的碳原子一起形成環所必需的原子組群。 關於Z與式中的碳原子一起形成的環，與上述通式（I）的說明中關於R3 及R4 相互鍵結而形成的環所說明的環相同。In the formula, R 1b and R 6b each independently represent an alkyl group having 5 or less carbon atoms. R 2b and R 5b each independently represent an alkyl group having 6 or less carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. Z represents a group of atoms necessary to form a ring together with a carbon atom in the formula. The ring formed by Z together with the carbon atom in the formula is the same as the ring described in the ring of the above formula (I) in which R 3 and R 4 are bonded to each other.

於本發明的一形態中，化合物（C'）較佳為於分子內具有4個以上的芳香環、及合計2個烷氧基甲基及/或羥基甲基的化合物。In one embodiment of the present invention, the compound (C') is preferably a compound having four or more aromatic rings in the molecule and a total of two alkoxymethyl groups and/or hydroxymethyl groups.

繼而，對通式（I）所表示的化合物（C'）的製造方法加以說明。 成為通式（I）所表示的化合物（C'）的母核的雙酚化合物通常是藉由使對應的2分子的酚化合物、與對應的1分子的酮於酸觸媒存在下進行脫水縮合反應而合成。Next, a method for producing the compound (C') represented by the formula (I) will be described. The bisphenol compound which is a mother nucleus of the compound (C') represented by the formula (I) is usually subjected to dehydration condensation by the corresponding two molecules of the phenol compound and the corresponding one molecule of the ketone in the presence of an acid catalyst. Synthesis by reaction.

利用三聚甲醛及二甲胺對所得的雙酚體進行處理，進行胺基甲基化，藉此獲得下述通式（I-C）所表示的中間體。繼而，經過乙醯基化、脫乙醯基化、烷基化而獲得目標酸交聯劑。The obtained bisphenol is treated with trioxane and dimethylamine to carry out aminomethylation, whereby an intermediate represented by the following formula (I-C) can be obtained. Then, the target acid crosslinking agent is obtained by acetylation, deacetylation, and alkylation.

[化64] [化64]

式中，R1 、R3 、R4 及R6 與通式（I）中的各基團為相同含意。In the formula, R 1 , R 3 , R 4 and R 6 have the same meanings as the respective groups in the formula (I).

該合成法與現有的在鹼性條件下經由羥基甲基體般的合成方法（例如日本專利特開2008-273844號公報）相比，不易生成寡聚物，故有抑制顆粒形成的效果。 以下示出通式（I）所表示的化合物（C'）的具體例。This synthesis method is less likely to form an oligomer than a conventional synthesis method by a hydroxymethyl group under a basic condition (for example, JP-A-2008-273844), and therefore has an effect of suppressing the formation of particles. Specific examples of the compound (C') represented by the formula (I) are shown below.

[化65] [化65]

本發明中，化合物（C'）可單獨使用，亦可組合使用兩種以上。就良好的圖案形狀的觀點而言，較佳為將兩種以上組合使用。In the present invention, the compound (C') may be used singly or in combination of two or more. From the viewpoint of a good pattern shape, it is preferred to use two or more types in combination.

於化合物（C）為組入至聚合物的一部分中的形態的情形時，可組入至樹脂（B）的一部分中，亦可組入至與樹脂（B）不同的樹脂中。When the compound (C) is in a form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (B) or may be incorporated into a resin different from the resin (B).

本發明的感光化射線或感放射線性組成物可含有化合物（C）亦可不含化合物（C），於含有化合物（C）的情形時，於感光化射線或感放射線性組成物的總固體成分中，化合物（C）的含量較佳為0.5質量%～30質量%，更佳為1質量%～15質量%。The photosensitive ray or the radiation sensitive composition of the present invention may contain the compound (C) or the compound (C), and in the case of containing the compound (C), the total solid content of the sensitized ray or the radiation sensitive composition The content of the compound (C) is preferably from 0.5% by mass to 30% by mass, more preferably from 1% by mass to 15% by mass.

＜溶劑＞ 本發明中所用的感光化射線或感放射線性組成物較佳為含有溶劑（亦稱為「抗蝕劑溶劑」）。該溶劑較佳為含有（M1）丙二醇單烷基醚羧酸酯與（M2）選自由丙二醇單烷基醚、乳酸酯、乙酸酯、烷氧基丙酸酯、鏈狀酮、環狀酮、內酯及碳酸伸烷基酯所組成的組群中的至少一種的至少一者。另外，該溶劑亦可更含有成分（M1）及成分（M2）以外的成分。<Solvent> The sensitized ray or the radiation sensitive composition used in the present invention preferably contains a solvent (also referred to as "resist solvent"). The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) is selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic At least one of at least one of the group consisting of a ketone, a lactone, and an alkylene carbonate. Further, the solvent may further contain components other than the component (M1) and the component (M2).

本發明者等人發現，藉由將此種溶劑與上文所述的樹脂組合使用，組成物的塗佈性提高，並且可形成顯影缺陷數少的圖案。其理由雖未必明確，但本發明者等人認為其原因在於：該些溶劑由於上文所述的樹脂的溶解性、沸點及黏度的平衡良好，故可抑制組成物膜的膜厚的不均一或旋塗中的析出物的產生等。The present inventors have found that by using such a solvent in combination with the above-described resin, the coating property of the composition is improved, and a pattern having a small number of development defects can be formed. The reason for this is not necessarily clear, but the inventors believe that the solvent is excellent in the solubility, the boiling point, and the viscosity of the resin described above, so that the film thickness of the film of the composition can be suppressed. Or the production of precipitates in spin coating, and the like.

成分（M1）較佳為選自由丙二醇單甲醚乙酸酯、丙二醇單甲醚丙酸酯及丙二醇單乙醚乙酸酯所組成的組群中的至少一種，尤佳為丙二醇單甲醚乙酸酯。The component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, and more preferably propylene glycol monomethyl ether acetate ester.

成分（M2）較佳為以下溶劑。 丙二醇單烷基醚較佳為丙二醇單甲醚或丙二醇單乙醚。 乳酸酯較佳為乳酸乙酯、乳酸丁酯或乳酸丙酯。 乙酸酯較佳為乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸異丁酯、乙酸丙酯、乙酸異戊酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯或乙酸3-甲氧基丁酯。 丁酸丁酯亦較佳。 烷氧基丙酸酯較佳為3-甲氧基丙酸甲酯（methyl 3-methoxy propionate，MMP）、或3-乙氧基丙酸乙酯（ethyl-3-ethoxypropionate，EEP）。 鏈狀酮較佳為1-辛酮、2-辛酮、1-壬酮、2-壬酮、丙酮、4-庚酮、1-己酮、2-己酮、二異丁基酮、苯基丙酮、甲基乙基酮、甲基異丁基酮、乙醯基丙酮、丙酮基丙酮、紫羅酮（ionone）、二丙酮醇、乙醯基原醇、苯乙酮、甲基萘基酮或甲基戊基酮。 環狀酮較佳為甲基環己酮、異佛爾酮或環己酮。 內酯較佳為γ-丁內酯。 碳酸伸烷基酯較佳為碳酸伸丙酯。The component (M2) is preferably the following solvent. The propylene glycol monoalkyl ether is preferably propylene glycol monomethyl ether or propylene glycol monoethyl ether. The lactate is preferably ethyl lactate, butyl lactate or propyl lactate. The acetate is preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or acetic acid. -Methoxybutyl ester. Butyl butyrate is also preferred. The alkoxypropionate is preferably methyl 3-methoxy propionate (MMP) or ethyl-3-ethoxypropionate (EEP). The chain ketone is preferably 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, benzene Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile acetone, acetone acetone, ionone, diacetone alcohol, acetyl primol, acetophenone, methyl naphthyl Ketone or methyl amyl ketone. The cyclic ketone is preferably methylcyclohexanone, isophorone or cyclohexanone. The lactone is preferably γ-butyrolactone. The alkylene carbonate is preferably a propyl carbonate.

成分（M2）更佳為丙二醇單甲醚、乳酸乙酯、3-乙氧基丙酸乙酯、甲基戊基酮、環己酮、乙酸丁酯、乙酸戊酯、γ-丁內酯或碳酸伸丙酯。The component (M2) is more preferably propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, amyl acetate, γ-butyrolactone or Propyl carbonate.

除了所述成分以外，較佳為使用碳原子數為7以上（較佳為7～14，更佳為7～12，進而佳為7～10）、且雜原子數為2以下的酯系溶劑。In addition to the above-mentioned components, an ester solvent having 7 or more (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and having 2 or less hetero atoms is preferably used. .

碳原子數為7以上且雜原子數為2以下的酯系溶劑的較佳例可列舉：乙酸戊酯、乙酸2-甲基丁酯、乙酸1-甲基丁酯、乙酸己酯、丙酸戊酯、丙酸己酯、丙酸丁酯、異丁酸異丁酯、丙酸庚酯、丁酸丁酯等，尤佳為使用乙酸異戊酯。Preferable examples of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include pentyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, and propionic acid. Amyl ester, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate, etc., particularly preferably isoamyl acetate.

成分（M2）較佳為使用著火點（以下亦稱為fp）為37℃以上的溶劑。此種成分（M2）較佳為丙二醇單甲醚（fp：47℃）、乳酸乙酯（fp：53℃）、3-乙氧基丙酸乙酯（fp：49℃）、甲基戊基酮（fp：42℃）、環己酮（fp：44℃）、乙酸戊酯（fp：45℃）、2-羥基異丁酸甲酯（fp：45℃）、γ-丁內酯（fp：101℃）或碳酸伸丙酯（fp：132℃）。該些溶劑中，進而佳為丙二醇單乙醚、乳酸乙酯、乙酸戊酯或環己酮，尤佳為丙二醇單乙醚或乳酸乙酯。另外，此處所謂「著火點」，是指東京化成工業股份有限公司或西格瑪-奧德里奇（Sigma-Aldrich）公司的試劑目錄中記載的值。The component (M2) is preferably a solvent having a point of ignition (hereinafter also referred to as fp) of 37 ° C or higher. Such a component (M2) is preferably propylene glycol monomethyl ether (fp: 47 ° C), ethyl lactate (fp: 53 ° C), ethyl 3-ethoxypropionate (fp: 49 ° C), methyl amyl group. Ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), amyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), γ-butyrolactone (fp : 101 ° C) or propyl carbonate (fp: 132 ° C). Among these solvents, further preferred is propylene glycol monoethyl ether, ethyl lactate, amyl acetate or cyclohexanone, and particularly preferably propylene glycol monoethyl ether or ethyl lactate. In addition, the "fire point" herein refers to a value described in the reagent catalogue of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.

溶劑較佳為含有成分（M1）。溶劑更佳為實質上僅包含成分（M1），或為成分（M1）與其他成分的混合溶劑。後者的情形時，溶劑進而佳為包含成分（M1）與成分（M2）兩者。The solvent preferably contains the component (M1). More preferably, the solvent contains only the component (M1), or a mixed solvent of the component (M1) and other components. In the latter case, the solvent further preferably contains both the component (M1) and the component (M2).

成分（M1）與成分（M2）之質量比較佳為在100：0至15：85的範圍內，更佳為在100：0至40：60的範圍內，進而佳為在100：0至60：40的範圍內。即，溶劑較佳為僅包含成分（M1），或包含成分（M1）與成分（M2）兩者且該些成分之質量比如下。即，後者的情形時，成分（M1）相對於成分（M2）之質量比較佳為15/85以上，更佳為40/60以上，進而佳為60/40以上。若採用此種構成，則可進一步減少顯影缺陷數。The mass of the component (M1) and the component (M2) is preferably in the range of 100:0 to 15:85, more preferably in the range of 100:0 to 40:60, and further preferably in the range of 100:0 to 60. :40 within range. That is, the solvent preferably contains only the component (M1), or both the component (M1) and the component (M2), and the mass of the components is as follows. That is, in the latter case, the mass of the component (M1) relative to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and still more preferably 60/40 or more. According to this configuration, the number of development defects can be further reduced.

另外，於溶劑包含成分（M1）與成分（M2）兩者的情形時，成分（M1）相對於成分（M2）之質量比例如是設定為99/1以下。In the case where the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is, for example, set to 99/1 or less.

如上所述，溶劑亦可更含有成分（M1）及成分（M2）以外的成分。該情形時，相對於溶劑的總量，成分（M1）及成分（M2）以外的成分的含量較佳為在5質量%至30質量%的範圍內。As described above, the solvent may further contain components other than the component (M1) and the component (M2). In this case, the content of the components other than the component (M1) and the component (M2) is preferably in the range of 5 mass% to 30 mass% with respect to the total amount of the solvent.

溶劑於感光化射線或感放射線性組成物中所佔的含量較佳為以所有成分的固體成分濃度成為0.5質量%～30質量%的方式設定，更佳為以成為1質量%～20質量%的方式設定。若如此，則可進一步提高感光化射線或感放射線性組成物的塗佈性。The content of the solvent in the sensitized ray or the radiation-sensitive composition is preferably set so that the solid content concentration of all the components is 0.5% by mass to 30% by mass, and more preferably 1% by mass to 20% by mass. Way to set. If so, the coatability of the sensitized ray or the radiation sensitive composition can be further improved.

＜（E）鹼性化合物＞ 為了減少自曝光至加熱為止的經時的性能變化，本發明的感光化射線或感放射線性組成物較佳為含有（E）鹼性化合物。 鹼性化合物較佳可列舉具有下述式（A）～式（E）所表示的結構的化合物。<(E) Basic Compound> The sensitized ray or the radiation sensitive composition of the present invention preferably contains (E) a basic compound in order to reduce the change in performance over time from exposure to heating. The basic compound preferably has a compound having the structure represented by the following formula (A) to formula (E).

[化66] [化66]

通式（A）及通式（E）中，R200 、R201 及R202 可相同亦可不同，表示氫原子、烷基（較佳為碳數1～20）、環烷基（較佳為碳數3～20）或芳基（較佳為碳數6～20），此處，R201 與R202 亦可相互鍵結而形成環。In the general formula (A) and the general formula (E), R 200 , R 201 and R 202 may be the same or different and each represent a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), or a cycloalkyl group. The carbon number is 3 to 20) or the aryl group (preferably, the carbon number is 6 to 20). Here, R 201 and R 202 may be bonded to each other to form a ring.

關於所述烷基，具有取代基的烷基較佳為碳數1～20的胺基烷基、碳數1～20的羥基烷基或碳數1～20的氰基烷基。 R203 、R204 、R205 及R206 可相同亦可不同，表示碳數1個～20個的烷基。 該些通式（A）及通式（E）中的烷基更佳為未經取代。The alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms. R 203 , R 204 , R 205 and R 206 may be the same or different and each represent an alkyl group having 1 to 20 carbon atoms. The alkyl groups in the general formula (A) and the general formula (E) are more preferably unsubstituted.

較佳的化合物可列舉：胍、胺基吡咯啶、吡唑、吡唑啉、哌嗪、胺基嗎啉、胺基烷基嗎啉、哌啶等，進而佳的化合物可列舉：具有咪唑結構、二氮雜雙環結構、氫氧化鎓結構、羧酸鎓鹽結構、三烷基胺結構、苯胺結構或吡啶結構的化合物，具有羥基及/或醚鍵的烷基胺衍生物，具有羥基及/或醚鍵的苯胺衍生物等。Preferred examples of the compound include hydrazine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc. Further preferred compounds include an imidazole structure. , a diazabicyclo structure, a ruthenium hydroxide structure, a ruthenium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, having a hydroxyl group and/or Or an aniline derivative of an ether bond or the like.

具有咪唑結構的化合物可列舉：咪唑、2,4,5-三苯基咪唑、苯并咪唑等。具有二氮雜雙環結構的化合物可列舉：1,4-二氮雜雙環[2,2,2]辛烷、1,5-二氮雜雙環[4,3,0]壬-5-烯、1,8-二氮雜雙環[5,4,0]十一-7-烯等。具有氫氧化鎓結構的化合物可列舉：氫氧化三芳基鋶、氫氧化苯甲醯甲基鋶、具有2-氧代烷基的氫氧化鋶、具體而言氫氧化三苯基鋶、氫氧化三(第三丁基苯基)鋶、氫氧化雙(第三丁基苯基)錪、氫氧化苯甲醯甲基噻吩、氫氧化2-氧代丙基噻吩等。具有羧酸鎓鹽結構的化合物為具有氫氧化鎓結構的化合物的陰離子部成為羧酸鹽的化合物，例如可列舉乙酸鹽、金剛烷-1-羧酸鹽、全氟烷基羧酸鹽等。具有三烷基胺結構的化合物可列舉三(正丁基)胺、三(正辛基)胺等。苯胺化合物可列舉：2,6-二異丙基苯胺、N,N-二甲基苯胺、N,N-二丁基苯胺、N,N-二己基苯胺等。具有羥基及/或醚鍵的烷基胺衍生物可列舉：乙醇胺、二乙醇胺、三乙醇胺、三(甲氧基乙氧基乙基)胺等。具有羥基及/或醚鍵的苯胺衍生物可列舉N,N-雙(羥基乙基)苯胺等。Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane and 1,5-diazabicyclo[4,3,0]non-5-ene. 1,8-diazabicyclo[5,4,0]undec-7-ene and the like. The compound having a ruthenium hydroxide structure may, for example, be a triarylphosphonium hydroxide, a benzamidine methylhydrazine hydroxide, a ruthenium hydroxide having a 2-oxoalkyl group, specifically, a triphenylphosphonium hydroxide or a hydroxide three. (Third butylphenyl) hydrazine, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methylthiophene hydroxide, 2-oxopropylthiophene hydroxide, and the like. The compound having a ruthenium carboxylate salt structure is a compound in which the anion portion of the compound having a ruthenium hydroxide structure is a carboxylate salt, and examples thereof include an acetate salt, an adamantane-1-carboxylate, and a perfluoroalkyl carboxylate. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine, tris(n-octyl)amine and the like. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. The alkylamine derivative having a hydroxyl group and/or an ether bond may, for example, be ethanolamine, diethanolamine, triethanolamine or tris(methoxyethoxyethyl)amine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

較佳的鹼性化合物進而可列舉具有苯氧基的胺化合物、具有苯氧基的銨鹽化合物。Further, preferred basic compounds include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.

胺化合物可使用一級、二級、三級的胺化合物，較佳為至少一個烷基鍵結於氮原子的胺化合物。胺化合物更佳為三級胺化合物。胺化合物只要至少一個烷基（較佳為碳數1～20）鍵結於氮原子，則除了烷基以外，環烷基（較佳為碳數3～20）或芳基（較佳為碳數6～12）亦可鍵結於氮原子。 另外，胺化合物較佳為於烷基鏈中具有氧原子而形成氧伸烷基。氧伸烷基的個數於分子內為一個以上，較佳為3個～9個，進而佳為4個～6個。氧伸烷基中，較佳為氧伸乙基（-CH2 CH2 O-）或氧伸丙基（-CH(CH3 )CH2 O-或-CH2 CH2 CH2 O-），進而佳為氧伸乙基。The amine compound may be a primary, secondary or tertiary amine compound, preferably an amine compound having at least one alkyl group bonded to a nitrogen atom. The amine compound is more preferably a tertiary amine compound. The amine compound is a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (preferably carbon) as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. The number 6 to 12) may also be bonded to a nitrogen atom. Further, the amine compound preferably has an oxygen atom in the alkyl chain to form an oxygen alkyl group. The number of the oxygen alkyl groups is one or more in the molecule, preferably from 3 to 9, and more preferably from 4 to 6. In the oxygen alkyl group, an oxygen extended ethyl group (-CH 2 CH 2 O-) or an oxygen extended propyl group (-CH(CH 3 )CH 2 O- or -CH 2 CH 2 CH 2 O-) is preferred. Further preferably, the oxygen is extended to the ethyl group.

銨鹽化合物可使用一級、二級、三級、四級的銨鹽化合物，較佳為至少一個烷基鍵結於氮原子的銨鹽化合物。銨鹽化合物只要至少一個烷基（較佳為碳數1～20）鍵結於氮原子，則除了烷基以外，環烷基（較佳為碳數3～20）或芳基（較佳為碳數6～12）亦可鍵結於氮原子。 銨鹽化合物較佳為於烷基鏈中具有氧原子而形成氧伸烷基。氧伸烷基的個數於分子內為一個以上，較佳為3個～9個，進而佳為4個～6個。氧伸烷基中，較佳為氧伸乙基（-CH2 CH2 O-）或氧伸丙基（-CH(CH3 )CH2 O-或-CH2 CH2 CH2 O-），進而佳為氧伸乙基。 銨鹽化合物的陰離子可列舉鹵素原子、磺酸鹽、硼酸鹽、磷酸鹽等，其中較佳為鹵素原子、磺酸鹽。鹵素原子尤佳為氯化物、溴化物、碘化物，磺酸鹽尤佳為碳數1～20的有機磺酸鹽。有機磺酸鹽可列舉碳數1～20的烷基磺酸鹽、芳基磺酸鹽。烷基磺酸鹽的烷基亦可具有取代基，取代基例如可列舉氟、氯、溴、烷氧基、醯基、芳基等。烷基磺酸鹽具體可列舉：甲磺酸鹽、乙磺酸鹽、丁磺酸鹽、己磺酸鹽、辛磺酸鹽、苄基磺酸鹽、三氟甲磺酸鹽、五氟乙磺酸鹽、九氟丁磺酸鹽等。芳基磺酸鹽的芳基可列舉苯環、萘環、蒽環。苯環、萘環、蒽環亦可具有取代基，取代基較佳為碳數1～6的直鏈或分支烷基、碳數3～6的環烷基。直鏈或分支烷基、環烷基具體可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正己基、環己基等。其他取代基可列舉：碳數1～6的烷氧基、鹵素原子、氰基、硝基、醯基、醯氧基等。The ammonium salt compound may be a primary, secondary, tertiary or tertiary ammonium salt compound, preferably an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom. The ammonium salt compound is preferably a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. The carbon number 6 to 12) may also be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain to form an oxygen alkyl group. The number of the oxygen alkyl groups is one or more in the molecule, preferably from 3 to 9, and more preferably from 4 to 6. In alkylene oxide, oxygen is preferably stretched ethyl (-CH 2 CH 2 O-) or oxygen extension propyl (-CH (CH 3) CH 2 O- or -CH 2 CH 2 CH 2 O-) , Further preferably, the oxygen is extended to the ethyl group. The anion of the ammonium salt compound may, for example, be a halogen atom, a sulfonate, a borate or a phosphate. Among them, a halogen atom or a sulfonate is preferred. The halogen atom is preferably a chloride, a bromide or an iodide, and a sulfonate is preferably an organic sulfonate having 1 to 20 carbon atoms. The organic sulfonate may, for example, be an alkylsulfonate or an arylsulfonate having 1 to 20 carbon atoms. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy, decyl, aryl and the like. Specific examples of the alkyl sulfonate include mesylate, ethanesulfonate, butanesulfonate, hexanosulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, and pentafluoroethane. Sulfonic acid salt, nonafluorobutanesulfonate and the like. The aryl group of the aryl sulfonate may, for example, be a benzene ring, a naphthalene ring or an anthracene ring. The benzene ring, the naphthalene ring and the anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and the cycloalkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-hexyl group, and a cyclohexyl group. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, a decyl group, and a decyloxy group.

所謂具有苯氧基的胺化合物、具有苯氧基的銨鹽化合物，為於胺化合物或銨鹽化合物的烷基的與氮原子為相反側的末端具有苯氧基的化合物。苯氧基亦可具有取代基。苯氧基的取代基例如可列舉：烷基、烷氧基、鹵素原子、氰基、硝基、羧基、羧酸酯基、磺酸酯基、芳基、芳烷基、醯氧基、芳氧基等。取代基的取代位可為2位～6位的任一個。取代基的個數可為1～5的範圍的任一個。The amine compound having a phenoxy group or an ammonium salt compound having a phenoxy group is a compound having a phenoxy group at the terminal of the alkyl group of the amine compound or the ammonium salt compound opposite to the nitrogen atom. The phenoxy group may also have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, a decyloxy group, and an aromatic group. Oxyl and the like. The substitution position of the substituent may be any of 2 to 6 positions. The number of substituents may be in the range of 1 to 5.

較佳為於苯氧基與氮原子之間具有至少一個氧伸烷基。氧伸烷基的個數於分子內為一個以上，較佳為3個～9個，進而佳為4個～6個。氧伸烷基中，較佳為氧伸乙基（-CH2 CH2 O-）或氧伸丙基（-CH(CH3 )CH2 O-或-CH2 CH2 CH2 O-），進而佳為氧伸乙基。It is preferred to have at least one oxygen-extended alkyl group between the phenoxy group and the nitrogen atom. The number of the oxygen alkyl groups is one or more in the molecule, preferably from 3 to 9, and more preferably from 4 to 6. In the oxygen alkyl group, an oxygen extended ethyl group (-CH 2 CH 2 O-) or an oxygen extended propyl group (-CH(CH 3 )CH 2 O- or -CH 2 CH 2 CH 2 O-) is preferred. Further preferably, the oxygen is extended to the ethyl group.

具有苯氧基的胺化合物可藉由以下方式獲得：將具有苯氧基的一級胺或二級胺與鹵化烷基醚加熱而使其反應後，添加氫氧化鈉、氫氧化鉀、四烷基銨等強鹼的水溶液後，利用乙酸乙酯、氯仿等有機溶劑進行萃取。或者可藉由以下方式獲得：將一級胺或二級胺與於末端具有苯氧基的鹵化烷基醚加熱而使其反應後，添加氫氧化鈉、氫氧化鉀、四烷基銨等強鹼的水溶液後，利用乙酸乙酯、氯仿等有機溶劑進行萃取。The amine compound having a phenoxy group can be obtained by heating a primary amine or a secondary amine having a phenoxy group and a halogenated alkyl ether, and then adding sodium hydroxide, potassium hydroxide or tetraalkyl. After an aqueous solution of a strong alkali such as ammonium is extracted with an organic solvent such as ethyl acetate or chloroform. Alternatively, it can be obtained by heating a primary amine or a secondary amine with a halogenated alkyl ether having a phenoxy group at the terminal and reacting it with a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. After the aqueous solution, extraction is carried out using an organic solvent such as ethyl acetate or chloroform.

（具有質子受體性官能基，且藉由光化射線或放射線的照射發生分解而產生質子受體性降低、消失、或由質子受體性變化為酸性的化合物的化合物（PA）） 本發明的組成物亦可更含有以下化合物作為鹼性化合物：具有質子受體性官能基，且藉由光化射線或放射線的照射發生分解而產生質子受體性降低、消失、或由質子受體性變化為酸性的化合物的化合物[以下亦稱為化合物（PA）]。(Compound (PA) having a proton-receptive functional group and decomposing by irradiation with actinic rays or radiation to cause a decrease in proton acceptor property, or a compound which is acidic by proton acceptor change) The composition may further contain a compound as a basic compound having a proton-receptive functional group and decomposing by irradiation with actinic rays or radiation to cause a decrease in proton acceptor property, disappearance, or proton acceptability. A compound which is changed to an acidic compound [hereinafter also referred to as a compound (PA)].

所謂質子受體性官能基，為可與質子發生靜電相互作用的基團或具有電子的官能基，且例如是指具有環狀聚醚等巨環結構的官能基、或含有具有無助於π共軛的非共價電子對的氮原子的官能基。所謂具有無助於π共軛的非共價電子對的氮原子，例如為具有下述通式所表示的部分結構的氮原子。The proton acceptor functional group is a group capable of electrostatically interacting with a proton or a functional group having an electron, and is, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or having a helpless π A functional group of a nitrogen atom of a conjugated non-covalent electron pair. The nitrogen atom having a non-covalent electron pair which does not contribute to π conjugate is, for example, a nitrogen atom having a partial structure represented by the following formula.

[化67] [67]

質子受體性官能基的較佳部分結構例如可列舉冠醚、氮雜冠醚、一級～三級胺、吡啶、咪唑、吡嗪結構等。Preferred partial structures of the proton acceptor functional group include crown ether, azacrown ether, first to tertiary amine, pyridine, imidazole, pyrazine structure and the like.

化合物（PA）藉由光化射線或放射線的照射發生分解而產生質子受體性降低、消失、或由質子受體性變化為酸性的化合物。此處，所謂質子受體性的降低、消失、或由質子受體性向酸性的變化，為由於對質子受體性官能基加成質子而引起的質子受體性的變化，具體而言是指由具有質子受體性官能基的化合物（PA）與質子生成質子加成物時，其化學平衡的平衡常數減少。The compound (PA) is decomposed by irradiation with actinic rays or radiation to cause a compound having reduced proton acceptability, disappearance, or acidity change from proton acceptor. Here, the decrease or disappearance of proton acceptor or the change from proton acceptor to acidity is a change in proton acceptor property due to the addition of a proton to a proton acceptor functional group, specifically When a proton-addition product is formed from a compound (PA) having a proton-receptive functional group and a proton, the equilibrium constant of the chemical equilibrium is reduced.

化合物（PA）的具體例例如可列舉下述化合物。進而，化合物（PA）的具體例例如可援用日本專利特開2014-41328號公報的段落0421～段落0428、日本專利特開2014-134686號公報的段落0108～段落0116中記載的化合物，將該些內容併入至本說明書中。Specific examples of the compound (PA) include the following compounds. Further, specific examples of the compound (PA) include, for example, the compounds described in paragraphs 0021 to 0, 026 of JP-A-2014-41328, and paragraphs 0108 to 0116 of JP-A-2014-134686. These are incorporated into this specification.

[化68] [化68]

[化69] [化69]

[化70] [化70]

該些鹼性化合物可單獨使用或將兩種以上一併使用。These basic compounds may be used singly or in combination of two or more.

以感光化射線或感放射線性組成物的固體成分為基準，鹼性化合物的使用量通常為0.001質量%～10質量%，較佳為0.01質量%～5質量%。The amount of the basic compound used is usually 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass based on the solid content of the sensitized ray or the radiation sensitive composition.

光酸產生劑與鹼性化合物於組成物中的使用比例較佳為光酸產生劑/鹼性化合物（莫耳比）＝2.5～300。即，就感度、解析度的方面而言，莫耳比較佳為2.5以上，就抑制由直至曝光後加熱處理為止的經時的抗蝕劑圖案的粗化所致的解析度降低的方面而言，較佳為300以下。光酸產生劑/鹼性化合物（莫耳比）更佳為5.0～200，進而佳為7.0～150。The ratio of use of the photoacid generator to the basic compound in the composition is preferably a photoacid generator/basic compound (mole ratio) = 2.5 to 300. In other words, in terms of sensitivity and resolution, it is preferable that the molar amount is 2.5 or more, and the aspect of the resolution of the resist pattern which has passed through the heat treatment after the post-exposure heat treatment is suppressed from being lowered. Preferably, it is 300 or less. The photoacid generator/basic compound (mole ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

鹼性化合物例如可使用日本專利特開2013-11833號公報的段落0140～段落0144中記載的化合物（胺化合物、含醯胺基的化合物、脲化合物、含氮雜環化合物等）。For the basic compound, for example, a compound (an amine compound, a guanamine group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, or the like) described in paragraphs 0140 to 0144 of JP-A-2013-11833 can be used.

＜（D）疏水性樹脂＞ 本發明的組成物亦可含有疏水性樹脂（以下亦稱為「疏水性樹脂（D）」或簡稱為「樹脂（D）」）。另外，疏水性樹脂（D）較佳為與樹脂（B）不同。 疏水性樹脂（D）較佳為以偏向存在於界面的方式設計，與界面活性劑不同，未必需要於分子內具有親水基，亦可對將極性物質/非極性物質均勻混合並無幫助。 添加疏水性樹脂的效果可列舉：抑制抗蝕劑膜表面對水的靜態/動態接觸角，提高液浸液追隨性，抑制逸氣等。<(D) Hydrophobic Resin> The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as "hydrophobic resin (D)" or simply "resin (D)"). Further, the hydrophobic resin (D) is preferably different from the resin (B). The hydrophobic resin (D) is preferably designed to exist in a biased manner at the interface. Unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule, and it is not necessary to uniformly mix the polar substance/nonpolar substance. The effect of adding a hydrophobic resin is to suppress the static/dynamic contact angle with respect to water on the surface of the resist film, to improve the followability of the liquid immersion liquid, and to suppress outgas.

就偏向存在於膜表層的觀點而言，疏水性樹脂（D）較佳為具有「氟原子」、「矽原子」及「含有於樹脂的側鏈部分中的CH3 部分結構」的任一種以上，進而佳為具有兩種以上。 於疏水性樹脂（D）含有氟原子及/或矽原子的情形時，疏水性樹脂（D）中的所述氟原子及/或矽原子可含有於樹脂的主鏈中，亦可含有於側鏈中。From the viewpoint of bias present in the film surface layer, the hydrophobic resin (D) preferably having "a fluorine atom,""Siatom" and "side chain portion of the resin contained in the CH 3 partial structure" refers to any one or more And then there are two or more. When the hydrophobic resin (D) contains a fluorine atom and/or a ruthenium atom, the fluorine atom and/or the ruthenium atom in the hydrophobic resin (D) may be contained in the main chain of the resin or may be contained on the side. In the chain.

於疏水性樹脂（D）含有氟原子的情形時，較佳為含有具有氟原子的烷基、具有氟原子的環烷基或具有氟原子的芳基作為具有氟原子的部分結構的樹脂。 具有氟原子的烷基（較佳為碳數1～10，更佳為碳數1～4）為至少一個氫原子經氟原子取代的直鏈或分支烷基，亦可更具有氟原子以外的取代基。 具有氟原子的環烷基及具有氟原子的芳基分別為一個氫原子經氟原子取代的環烷基及具有氟原子的芳基，亦可更具有氟原子以外的取代基。When the hydrophobic resin (D) contains a fluorine atom, it is preferably a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom or an aryl group having a fluorine atom as a partial structure having a fluorine atom. An alkyl group having a fluorine atom (preferably having a carbon number of 1 to 10, more preferably a carbon number of 1 to 4) is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may have a fluorine atom or the like. Substituent. The cycloalkyl group having a fluorine atom and the aryl group having a fluorine atom are each a cycloalkyl group in which one hydrogen atom is substituted with a fluorine atom and an aryl group having a fluorine atom, and may further have a substituent other than a fluorine atom.

具有氟原子的烷基、具有氟原子的環烷基及具有氟原子的芳基較佳可列舉下述通式（F2）～通式（F4）所表示的基團，但本發明不限定於此。The alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom are preferably a group represented by the following formula (F2) to formula (F4), but the invention is not limited thereto. this.

[化71] [71]

通式（F2）～通式（F4）中， R57 ～R68 分別獨立地表示氫原子、氟原子或烷基（直鏈或分支）。其中，R57 ～R61 的至少一個、R62 ～R64 的至少一個及R65 ～R68 的至少一個分別獨立地表示氟原子或至少一個氫原子經氟原子取代的烷基（較佳為碳數1～4）。 R57 ～R61 及R65 ～R67 較佳為全部為氟原子。R62 、R63 及R68 較佳為至少一個氫原子經氟原子取代的烷基（較佳為碳數1～4），進而佳為碳數1～4的全氟烷基。R62 與R63 亦可相互連結而形成環。In the general formulae (F2) to (F4), R 57 to R 68 each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched). Wherein at least one of R 57 to R 61 , at least one of R 62 to R 64 and at least one of R 65 to R 68 each independently represent a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably Carbon number 1 to 4). R 57 to R 61 and R 65 to R 67 are preferably all fluorine atoms. R 62 , R 63 and R 68 are preferably an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom (preferably having 1 to 4 carbon atoms), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R 62 and R 63 may also be bonded to each other to form a ring.

疏水性樹脂（D）亦可含有矽原子。較佳為具有烷基矽烷基結構（較佳為三烷基矽烷基）、或環狀矽氧烷結構作為具有矽原子的部分結構的樹脂。 具有氟原子或矽原子的重複單元的例子可列舉US2012/0251948A1[0519]中例示的重複單元。The hydrophobic resin (D) may also contain a ruthenium atom. It is preferably a resin having an alkyl fluorenylene structure (preferably a trialkyl decyl group) or a cyclic siloxane structure as a partial structure having a ruthenium atom. Examples of the repeating unit having a fluorine atom or a ruthenium atom include the repeating unit exemplified in US2012/0251948A1 [0519].

另外，如上所述，疏水性樹脂（D）亦較佳為於側鏈部分中含有CH3 部分結構。 此處，疏水性樹脂（D）中的側鏈部分所含有的CH3 部分結構（以下亦簡稱為「側鏈CH3 部分結構」）中，包含乙基、丙基等所具有的CH3 部分結構。 另一方面，直接鍵結於疏水性樹脂（D）的主鏈的甲基（例如具有甲基丙烯酸結構的重複單元的α-甲基）因主鏈的影響而對疏水性樹脂（D）偏向存在於表面的幫助小，故不包含在本發明的CH3 部分結構中。Further, as described above, the hydrophobic resin (D) preferably also has a CH 3 moiety structure in the side chain portion. Here, the structure of the side chain portion 3 partially hydrophobic resin (D) contained in the CH (hereinafter also referred to as "partial structure a side chain CH 3"), and comprises ethyl, propyl and the like has CH 3 part structure. On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, an α-methyl group having a repeating unit of a methacrylic acid structure) is biased toward the hydrophobic resin (D) due to the influence of the main chain The help present on the surface is small and is not included in the CH 3 partial structure of the present invention.

更具體而言，於疏水性樹脂（D）含有例如下述通式（M）所表示的重複單元等來源於具有含有碳-碳雙鍵的聚合性部位的單體的重複單元、且R11 ～R14 為CH3 「本身」的情形時，該CH3 不包含在本發明的側鏈部分所含有的CH3 部分結構中。 另一方面，自C-C主鏈經由任意的原子而存在的CH3 部分結構相當於本發明的CH3 部分結構。例如於R11 為乙基（CH2 CH3 ）的情形時，視為具有「一個」本發明的CH3 部分結構。More specifically, the hydrophobic resin (D) contains, for example, a repeating unit represented by the following formula (M), and a repeating unit derived from a monomer having a polymerizable moiety containing a carbon-carbon double bond, and R 11 When R 14 is a CH 3 "self", the CH 3 is not included in the CH 3 partial structure contained in the side chain portion of the present invention. On the other hand, since the partial structure CH 3 via any of the CC backbone atoms present in the partial structure corresponding to CH 3 of the present invention. For example, when R 11 is an ethyl group (CH 2 CH 3 ), it is considered to have a "one" structure of the CH 3 moiety of the present invention.

[化72] [化72]

所述通式（M）中， R11 ～R14 分別獨立地表示側鏈部分。 側鏈部分的R11 ～R14 可列舉氫原子、一價有機基等。 關於R11 ～R14 的一價有機基可列舉：烷基、環烷基、芳基、烷氧基羰基、環烷氧基羰基、芳氧基羰基、烷基胺基羰基、環烷基胺基羰基、芳基胺基羰基等，該些基團亦可更具有取代基。In the above formula (M), R 11 to R 14 each independently represent a side chain moiety. R 11 to R 14 in the side chain moiety include a hydrogen atom, a monovalent organic group and the like. The monovalent organic group of R 11 to R 14 may, for example, be an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group or a cycloalkylamine. The carbonyl group, the arylaminocarbonyl group and the like may further have a substituent.

疏水性樹脂（D）較佳為含有於側鏈部分中具有CH3 部分結構的重複單元的樹脂，更佳為含有下述通式（II）所表示的重複單元、及下述通式（III）所表示的重複單元中的至少一種重複單元（x）作為此種重複單元。The hydrophobic resin (D) is preferably a resin containing a repeating unit having a CH 3 partial structure in a side chain moiety, more preferably a repeating unit represented by the following formula (II), and the following formula (III) At least one of the repeating units represented by the repeating unit (x) is such a repeating unit.

以下，對通式（II）所表示的重複單元加以詳細說明。Hereinafter, the repeating unit represented by the formula (II) will be described in detail.

[化73] [化73]

所述通式（II）中，Xb1 表示氫原子、烷基、氰基或鹵素原子，R2 表示具有一個以上的CH3 部分結構的對於酸穩定的有機基。此處，對於酸穩定的有機基更具體而言，較佳為不具有酸分解性基（藉由酸的作用發生分解而產生羧基等極性基的基團）的有機基。In the above formula (II), X b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R 2 represents an acid-stable organic group having one or more CH 3 moiety structures. Here, more specifically, the acid-stable organic group is preferably an organic group which does not have an acid-decomposable group (a group which decomposes by an action of an acid to generate a polar group such as a carboxyl group).

Xb1 的烷基較佳為碳數1～4的烷基，可列舉甲基、乙基、丙基、羥基甲基或三氟甲基等，較佳為甲基。 Xb1 較佳為氫原子或甲基。 R2 可列舉具有一個以上的CH3 部分結構的烷基、環烷基、烯基、環烯基、芳基及芳烷基。所述環烷基、烯基、環烯基、芳基及芳烷基亦可更具有烷基作為取代基。 R2 較佳為具有一個以上的CH3 部分結構的烷基或經烷取代的環烷基。 作為R2 的具有一個以上的CH3 部分結構的對於酸穩定的有機基較佳為具有2個以上且10個以下的CH3 部分結構，更佳為具有2個以上且8個以下的CH3 部分結構。 以下列舉通式（II）所表示的重複單元的較佳具體例。另外，本發明不限定於此。The alkyl group of X b1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a methyl group is preferable. X b1 is preferably a hydrogen atom or a methyl group. R 2 may, for example, be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group having one or more CH 3 partial structures. The cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent. R 2 is preferably an alkyl group having one or more CH 3 moiety structures or an alkyl group substituted with an alkane. The acid-stable organic group having one or more CH 3 partial structures of R 2 preferably has two or more and ten or less CH 3 partial structures, more preferably two or more and eight or less CH 3 . Part of the structure. Preferred specific examples of the repeating unit represented by the formula (II) are listed below. In addition, the invention is not limited to this.

[化74] [化74]

通式（II）所表示的重複單元較佳為對於酸穩定的（非酸分解性的）重複單元，具體而言，較佳為不具有藉由酸的作用發生分解而產生極性基的基團的重複單元。 以下，對通式（III）所表示的重複單元加以詳細說明。The repeating unit represented by the formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, preferably a group which does not have a polar group by decomposition of an acid. Repeat unit. Hereinafter, the repeating unit represented by the formula (III) will be described in detail.

[化75] [化75]

所述通式（III）中，Xb2 表示氫原子、烷基、氰基或鹵素原子，R3 表示具有一個以上的CH3 部分結構的對於酸穩定的有機基，n表示1～5的整數。 Xb2 的烷基較佳為碳數1～4的烷基，可列舉甲基、乙基、丙基、羥基甲基或三氟甲基等，較佳為氫原子。 Xb2 較佳為氫原子。 R3 為對於酸穩定的有機基，故更具體而言，較佳為不具有酸分解性基的有機基。In the above formula (III), X b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R 3 represents an acid-stable organic group having one or more CH 3 moiety structures, and n represents an integer of 1 to 5 . The alkyl group of X b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a hydrogen atom is preferred. X b2 is preferably a hydrogen atom. R 3 is an organic group which is stable to an acid, and therefore, more specifically, an organic group having no acid-decomposable group is preferable.

R3 可列舉具有一個以上的CH3 部分結構的烷基。 作為R3 的具有一個以上的CH3 部分結構的對於酸穩定的有機基較佳為具有1個以上且10個以下的CH3 部分結構，更佳為具有1個以上且8個以下的CH3 部分結構，進而佳為具有1個以上且4個以下的CH3 部分結構。 n表示1～5的整數，更佳為表示1～3的整數，進而佳為表示1或2。R 3 may, for example, be an alkyl group having one or more CH 3 moiety structures. The acid-stable organic group having one or more CH 3 partial structures of R 3 preferably has one or more and ten or less CH 3 partial structures, more preferably one or more and eight or less CH 3 . The partial structure preferably further has one or more and four or less CH 3 partial structures. n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

以下列舉通式（III）所表示的重複單元的較佳具體例。另外，本發明不限定於此。Preferred specific examples of the repeating unit represented by the formula (III) are listed below. In addition, the invention is not limited to this.

[化76] [化76]

通式（III）所表示的重複單元較佳為對於酸穩定的（非酸分解性的）重複單元，具體而言，較佳為不具有藉由酸的作用發生分解而產生極性基的基團的重複單元。The repeating unit represented by the formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, preferably a group which does not have a polar group by decomposition of an acid. Repeat unit.

於疏水性樹脂（D）於側鏈部分中含有CH3 部分結構的情形時，進而尤其於不具有氟原子及矽原子的情形時，相對於疏水性樹脂（D）的所有重複單元，通式（II）所表示的重複單元及通式（III）所表示的重複單元中的至少一種重複單元（x）的含量較佳為90 mol%以上，更佳為95 mol%以上。相對於疏水性樹脂（D）的所有重複單元，含量通常為100 mol%以下。In the case where the hydrophobic resin (D) contains a CH 3 partial structure in the side chain portion, and further, particularly in the case of not having a fluorine atom and a ruthenium atom, the general formula with respect to all the repeating units of the hydrophobic resin (D) The content of at least one of the repeating unit represented by (II) and the repeating unit represented by the formula (III) is preferably 90 mol% or more, more preferably 95 mol% or more. The content is usually 100 mol% or less with respect to all the repeating units of the hydrophobic resin (D).

相對於疏水性樹脂（D）的所有重複單元，疏水性樹脂（D）以90 mol%以上而含有通式（II）所表示的重複單元及通式（III）所表示的重複單元中的至少一種重複單元（x），藉此疏水性樹脂（D）的表面自由能量增加。結果，疏水性樹脂（D）不易偏向存在於抗蝕劑膜的表面，可使抗蝕劑膜對水的靜態/動態接觸角可靠地增大，提高液浸液追隨性。The hydrophobic resin (D) contains at least 90 mol% or more of the repeating unit represented by the formula (II) and at least the repeating unit represented by the formula (III) with respect to all the repeating units of the hydrophobic resin (D). A repeating unit (x) whereby the surface free energy of the hydrophobic resin (D) is increased. As a result, the hydrophobic resin (D) is less likely to be biased on the surface of the resist film, and the static/dynamic contact angle of the resist film with respect to water can be reliably increased, and the liquid immersion liquid followability can be improved.

另外，疏水性樹脂（D）於（i）含有氟原子及/或矽原子的情形時、（ii）於側鏈部分中含有CH3 部分結構的情形時，亦可具有至少一個選自下述（x）～（z）的組群中的基團。 （x）酸基、 （y）藉由鹼性顯影液的作用發生分解而於鹼性顯影液中的溶解度增大的基團（以下亦稱為極性變換基）、 （z）藉由酸的作用發生分解的基團Further, when the hydrophobic resin (D) contains (i) a fluorine atom and/or a ruthenium atom, and (ii) a CH 3 moiety structure in the side chain portion, it may have at least one selected from the group consisting of A group in the group of (x) to (z). (x) an acid group, (y) a group which is decomposed by the action of an alkaline developing solution to increase solubility in an alkaline developing solution (hereinafter also referred to as a polar converting group), and (z) by an acid a group in which decomposition occurs

酸基（x）可列舉：酚性羥基、羧酸基、氟化醇基、磺酸基、磺醯胺基、磺醯基醯亞胺基、(烷基磺醯基)(烷基羰基)亞甲基、(烷基磺醯基)(烷基羰基)醯亞胺基、雙(烷基羰基)亞甲基、雙(烷基羰基)醯亞胺基、雙(烷基磺醯基)亞甲基、雙(烷基磺醯基)醯亞胺基、三(烷基羰基)亞甲基、三(烷基磺醯基)亞甲基等。 較佳的酸基可列舉氟化醇基（較佳為六氟異丙醇）、磺醯亞胺基、雙(烷基羰基)亞甲基。Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamino group, a sulfonyl fluorenylene group, or an alkylsulfonyl group (alkylcarbonyl group). Methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indenylene, bis(alkylsulfonyl) Methylene, bis(alkylsulfonyl) fluorenylene, tris(alkylcarbonyl)methylene, tris(alkylsulfonyl)methylene, and the like. Preferred acid groups include a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, and a bis(alkylcarbonyl)methylene group.

具有酸基（x）的重複單元可列舉：來源於丙烯酸、甲基丙烯酸的重複單元般的酸基直接鍵結於樹脂的主鏈上的重複單元，或者酸基經由連結基而鍵結於樹脂的主鏈上的重複單元等，進而亦可於聚合時使用具有酸基的聚合起始劑或鏈轉移劑而導入至聚合物鏈的末端，任一情形均較佳。具有酸基（x）的重複單元亦可含有氟原子及矽原子的至少任一個。 相對於疏水性樹脂（D）中的所有重複單元，具有酸基（x）的重複單元的含量較佳為1 mol%～50 mol%，更佳為3 mol%～35 mol%，進而佳為5 mol%～20 mol%。 以下示出具有酸基（x）的重複單元的具體例，但本發明不限定於此。式中，Rx表示氫原子、CH3 、CF3 或CH2 OH。The repeating unit having an acid group (x) may be a repeating unit in which an acid group derived from a repeating unit of acrylic acid or methacrylic acid is directly bonded to a main chain of the resin, or an acid group is bonded to the resin via a linking group. The repeating unit or the like on the main chain may be further introduced into the end of the polymer chain by using a polymerization initiator or a chain transfer agent having an acid group during polymerization, and any of them is preferred. The repeating unit having an acid group (x) may further contain at least one of a fluorine atom and a germanium atom. The content of the repeating unit having an acid group (x) is preferably from 1 mol% to 50 mol%, more preferably from 3 mol% to 35 mol%, based on all the repeating units in the hydrophobic resin (D), and further preferably 5 mol% to 20 mol%. Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH 3 , CF 3 or CH 2 OH.

[化77] [化77]

[化78] [化78]

藉由鹼性顯影液的作用發生分解而於鹼性顯影液中的溶解度增大的基團（y）較佳為具有內酯結構的基團、酸酐基或酸醯亞胺基，尤佳為具有內酯結構的基團。 含有該些基團的重複單元例如為來源於丙烯酸酯及甲基丙烯酸酯的重複單元等所述基團直接鍵結於樹脂的主鏈上的重複單元。或者，所述重複單元亦可為所述基團經由連結基而鍵結於樹脂的主鏈上的重複單元。或者，所述重複單元亦可於聚合時使用具有所述基團的聚合起始劑或鏈轉移劑來導入至樹脂的末端。 含有具有內酯結構的基團的重複單元例如可列舉：與上文中於樹脂P的項中說明的具有內酯結構的重複單元相同的重複單元。The group (y) which is decomposed by the action of the alkaline developing solution and which has an increased solubility in the alkaline developing solution is preferably a group having a lactone structure, an acid anhydride group or a phosphonium imide group, and particularly preferably a group having a lactone structure. The repeating unit containing such a group is, for example, a repeating unit derived from a repeating unit derived from an acrylate or a methacrylate, and the group is directly bonded to a main chain of the resin. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced to the end of the resin by using a polymerization initiator or a chain transfer agent having the group at the time of polymerization. The repeating unit containing a group having a lactone structure may, for example, be the same repeating unit as the repeating unit having a lactone structure described above in the item of the resin P.

以疏水性樹脂（D）中的所有重複單元為基準，具有藉由鹼性顯影液的作用發生分解而於鹼性顯影液中的溶解度增大的基團（y）的重複單元的含量較佳為1 mol%～100 mol%，更佳為3 mol%～98 mol%，進而佳為5 mol%～95 mol%。The content of the repeating unit of the group (y) having an increased solubility in the alkaline developing solution which is decomposed by the action of the alkaline developing solution is preferably based on all the repeating units in the hydrophobic resin (D). It is 1 mol% to 100 mol%, more preferably 3 mol% to 98 mol%, and further preferably 5 mol% to 95 mol%.

疏水性樹脂（D）中的具有藉由酸的作用發生分解的基團（z）的重複單元可列舉與樹脂P中列舉的具有酸分解性基的重複單元相同的重複單元。具有藉由酸的作用發生分解的基團（z）的重複單元亦可含有氟原子及矽原子的至少任一個。相對於樹脂（D）中的所有重複單元，疏水性樹脂（D）中的具有藉由酸的作用發生分解的基團（z）的重複單元的含量較佳為1 mol%～80 mol%，更佳為10 mol%～80 mol%，進而佳為20 mol%～60 mol%。 疏水性樹脂（D）亦可更含有與上文所述的重複單元不同的重複單元。The repeating unit having a group (z) which is decomposed by the action of an acid in the hydrophobic resin (D) may be the same repeating unit as the repeating unit having an acid-decomposable group exemplified in the resin P. The repeating unit having a group (z) which is decomposed by the action of an acid may further contain at least one of a fluorine atom and a ruthenium atom. The content of the repeating unit having a group (z) which is decomposed by the action of an acid in the hydrophobic resin (D) is preferably from 1 mol% to 80 mol%, based on all the repeating units in the resin (D). More preferably, it is 10 mol% to 80 mol%, and further preferably 20 mol% to 60 mol%. The hydrophobic resin (D) may further contain a repeating unit different from the repeating unit described above.

於疏水性樹脂（D）所含的所有重複單元中，含有氟原子的重複單元較佳為10 mol%～100 mol%，更佳為30 mol%～100 mol%。另外，於疏水性樹脂（D）所含的所有重複單元中，含有矽原子的重複單元較佳為10 mol%～100 mol%，更佳為20 mol%～100 mol%。The repeating unit containing a fluorine atom in all the repeating units contained in the hydrophobic resin (D) is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%. Further, in all the repeating units contained in the hydrophobic resin (D), the repeating unit containing a halogen atom is preferably from 10 mol% to 100 mol%, more preferably from 20 mol% to 100 mol%.

另一方面，尤其於疏水性樹脂（D）於側鏈部分中含有CH3 部分結構的情形時，亦較佳為疏水性樹脂（D）實質上不含氟原子及矽原子的形態。另外，疏水性樹脂（D）較佳為僅由如下重複單元實質上構成，所述重複單元是僅由選自碳原子、氧原子、氫原子、氮原子及硫原子中的原子所構成。On the other hand, in particular, when the hydrophobic resin (D) contains a CH 3 partial structure in the side chain portion, it is also preferred that the hydrophobic resin (D) is substantially free of fluorine atoms and germanium atoms. Further, the hydrophobic resin (D) is preferably constituted substantially only by a repeating unit composed of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom.

疏水性樹脂（D）的標準聚苯乙烯換算的重量平均分子量較佳為1,000～100,000，更佳為1,000～50,000。 另外，疏水性樹脂（D）可使用一種，亦可併用多種。相對於本發明的組成物中的總固體成分，疏水性樹脂（D）於組成物中的含量較佳為0.01質量%～10質量%，更佳為0.05質量%～8質量%。The standard polystyrene-equivalent weight average molecular weight of the hydrophobic resin (D) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000. Further, the hydrophobic resin (D) may be used alone or in combination of two or more. The content of the hydrophobic resin (D) in the composition is preferably 0.01% by mass to 10% by mass, and more preferably 0.05% by mass to 8% by mass based on the total solid content of the composition of the present invention.

疏水性樹脂（D）中，較佳為殘留單體或寡聚物成分為0.01質量%～5質量%，更佳為0.01質量%～3質量%。另外，分子量分佈（Mw/Mn，亦稱為分散度）較佳為1～5的範圍，更佳為1～3的範圍。In the hydrophobic resin (D), the residual monomer or oligomer component is preferably 0.01% by mass to 5% by mass, and more preferably 0.01% by mass to 3% by mass. Further, the molecular weight distribution (Mw/Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.

疏水性樹脂（D）可利用各種市售品，亦可藉由常法進行（例如自由基聚合）合成。The hydrophobic resin (D) can be used in various commercial products, and can also be synthesized by a usual method (for example, radical polymerization).

＜（F）界面活性劑＞ 本發明中所用的感光化射線或感放射線性組成物亦可更含有界面活性劑（F）。藉由含有界面活性劑，於利用波長為250 nm以下、特別是220 nm以下的曝光光源的情形時，能以良好的感度及解析度而形成密接性及顯影缺陷更少的圖案。 界面活性劑尤佳為使用氟系及/或矽系界面活性劑。 氟系及/或矽系界面活性劑例如可列舉美國專利申請公開第2008/0248425號說明書的[0276]中記載的界面活性劑。另外亦可使用：艾福拓（Eftop）EF301或艾福拓（Eftop）EF303（新秋田化成（股）製造）；弗洛德（Fluorad）FC430、弗洛德（Fluorad）FC431或弗洛德（Fluorad）FC4430（住友3M（股）製造）；美佳法（Megafac）F171、美佳法（Megafac）F173、美佳法（Megafac）F176、美佳法（Megafac）F189、美佳法（Megafac）F113、美佳法（Megafac）F110、美佳法（Megafac）F177、美佳法（Megafac）F120或美佳法（Megafac）R08（迪愛生（DIC）（股）製造）；沙福隆（Surflon）S-382、沙福隆（Surflon）SC101、沙福隆（Surflon）SC102、沙福隆（Surflon）SC103、沙福隆（Surflon）SC104、沙福隆（Surflon）SC 105或沙福隆（Surflon）SC 106（旭硝子（股）製造）；托利所（Troysol）S-366（特洛伊化學（Troy Chemical）（股）製造）；GF-300或GF-150（東亞合成化學（股）製造）；沙福隆（Surflon）S-393（清美化學（Seimi Chemical）（股）製造）；艾福拓（Eftop）EF121、艾福拓（Eftop）EF122A、艾福拓（Eftop）EF122B、艾福拓（Eftop）RF122C、艾福拓（Eftop）EF125M、艾福拓（Eftop）EF135M、艾福拓（Eftop）EF351、艾福拓（Eftop）EF352、艾福拓（Eftop）EF801、艾福拓（Eftop）EF802或艾福拓（Eftop）EF601（三菱材料電子化成（Jemco）（股）製造）；PF636、PF656、PF6320或PF6520（歐諾法（OMNOVA）公司製造）；或者FTX-204G、FTX-208G、FTX-218G、FTX-230G、FTX-204D、FTX-208D、FTX-212D、FTX-218D或FTX-222D（尼歐斯（股）（Neos）製造）。另外，聚矽氧烷聚合物KP-341（信越化學工業（股）製造）亦可用作矽系界面活性劑。<(F) Surfactant> The sensitized ray or the radiation sensitive composition used in the present invention may further contain a surfactant (F). By using a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used, a pattern having less adhesion and development defects can be formed with good sensitivity and resolution. It is especially preferable to use a fluorine-based and/or a lanthanoid surfactant as the surfactant. Examples of the fluorine-based and/or lanthanoid surfactants include the surfactants described in [0276] of the specification of U.S. Patent Application Publication No. 2008/0248425. Also available: Eftop EF301 or Eftop EF303 (new Akita Chemicals Co., Ltd.); Fluorad FC430, Fluorad FC431 or Frode (Fluorad) Fluorad) FC4430 (manufactured by Sumitomo 3M); Megafac F171, Megafac F173, Megafac F176, Megafac F189, Megafac F113, Megafa ( Megafac) F110, Megafac F177, Megafac F120 or Megafac R08 (made by Diane Health (DIC)); Surflon S-382, Sha Fulong ( Surflon) SC101, Surflon SC102, Surflon SC103, Surflon SC104, Surflon SC 105 or Surflon SC 106 (Asahi Glass) Manufactured; Troysol S-366 (manufactured by Troy Chemical); GF-300 or GF-150 (manufactured by East Asian Synthetic Chemicals); Surflon S- 393 (made by Seimi Chemical Co., Ltd.); Eftop EF121, Eftop EF122A, Eftop EF122B, Eftop RF122C, Eftop EF125M, Eftop EF135M, Aifutuo (Eftop) EF351, Eftop EF352, Eftop EF801, Eftop EF802 or Eftop EF601 (made by Mitsubishi Materials Electronics (Jemco)); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, FTX-208G, FTX-218G, FTX-230G, FTX-204D, FTX-208D, FTX-212D, FTX-218D Or FTX-222D (manufactured by Neos). Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

另外，界面活性劑除了上文所示般的公知的界面活性劑以外，亦可使用藉由短鏈聚合法（亦稱為短鏈聚合物法）或寡聚合法（亦稱為寡聚物法）所製造的氟脂肪族化合物來合成。具體而言，亦可將由該氟脂肪族化合物所衍生的具有氟脂肪族基的聚合物用作界面活性劑。該氟脂肪族化合物例如可藉由日本專利特開2002-90991號公報中記載的方法來合成。 另外，亦可使用美國專利申請公開第2008/0248425號說明書的[0280]中記載的氟系及/或矽系以外的界面活性劑。Further, in addition to the known surfactants as described above, the surfactant may also be used by a short-chain polymerization method (also referred to as a short-chain polymer method) or an oligomerization method (also referred to as an oligomer method). The fluoroaliphatic compound produced is synthesized. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can also be used as a surfactant. The fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991. Further, a surfactant other than the fluorine-based and/or lanthanide-based surfactants described in [0280] of the specification of the US Patent Application Publication No. 2008/0248425 can also be used.

該些界面活性劑可單獨使用一種，亦可組合使用兩種以上。These surfactants may be used alone or in combination of two or more.

於本發明中所用的感光化射線或感放射線性組成物含有界面活性劑的情形時，以組成物的總固體成分為基準，其含量較佳為0質量%～2質量%，更佳為0.0001質量%～2質量%，進而佳為0.0005質量%～1質量%。When the sensitized ray or the radiation sensitive composition used in the present invention contains a surfactant, the content thereof is preferably 0% by mass to 2% by mass, more preferably 0.0001% based on the total solid content of the composition. The mass% to 2% by mass, and more preferably 0.0005 mass% to 1 mass%.

＜其他添加劑＞ 本發明中所用的感光化射線或感放射線性組成物亦可更含有溶解抑制化合物、染料、塑化劑、光增感劑、光吸收劑及/或促進於顯影液中的溶解性的化合物（例如分子量1000以下的酚化合物、或者含有羧基的脂環族或脂肪族化合物）。<Other Additives> The sensitized ray or the radiation sensitive composition used in the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorbing agent, and/or promote dissolution in a developer. A compound (for example, a phenol compound having a molecular weight of 1,000 or less or an alicyclic or aliphatic compound having a carboxyl group).

本發明中所用的感光化射線或感放射線性組成物亦可更含有溶解抑制化合物。此處所謂「溶解抑制化合物」，為藉由酸的作用發生分解而於有機系顯影液中的溶解度減少的分子量3000以下的化合物。The sensitized ray or the radiation sensitive composition used in the present invention may further contain a dissolution inhibiting compound. Here, the "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less which is decomposed by the action of an acid and which has reduced solubility in an organic developing solution.

本發明中所用的感光化射線或感放射線性組成物亦較佳為含有有機酸。於該情形時，就經時穩定性的觀點而言，有機酸的量以多為佳，關於本發明的感光化射線性或感放射線性組成物中的有機酸的含有率，較佳為以相對於總固體成分而超過5質量%的方式添加。本發明的一形態中，以組成物中的總固體成分為基準，本發明的組成物中的有機酸的含有率更佳為多於5質量%且少於15質量%，進而佳為多於5質量%且少於10質量%。The sensitized ray or radiation sensitive composition used in the present invention preferably also contains an organic acid. In this case, the amount of the organic acid is preferably from the viewpoint of stability over time, and the content of the organic acid in the sensitizing ray-sensitive or radiation-sensitive composition of the present invention is preferably It is added so as to exceed 5% by mass based on the total solid content. In one aspect of the present invention, the content of the organic acid in the composition of the present invention is more preferably more than 5% by mass and less than 15% by mass based on the total solid content in the composition, and more preferably more than 5 mass% and less than 10 mass%.

就經時穩定性的觀點而言，有機酸較佳為pKa為0～10的範圍，更佳為2～8的範圍，進而佳為3～7的範圍。此處所謂pKa，表示水溶液中的pKa，例如為「化學便覽（II）」（修訂4版，1993年，日本化學會編，丸善股份有限公司）中所記載者，該值越低表示酸強度越大。水溶液中的pKa具體而言可藉由以下方式實際測定：使用無限稀釋水溶液，對25℃下的酸解離常數進行測定，另外，亦可使用下述軟體封包1，藉由計算而求出基於哈米特的取代基常數及公知文獻值的資料庫的值。本說明書中的pKa的值全部表示使用該軟體封包藉由計算而求出的值。軟體封包1：高級化學發展（Advanced Chemistry Development）（ACD/Labs）Solaris系統用軟體，版本8.14（Software V8.14 for Solaris）（1994-2007，ACD/Labs）。The organic acid preferably has a pKa of from 0 to 10, more preferably from 2 to 8, and even more preferably from 3 to 7, from the viewpoint of stability over time. Here, pKa is a pKa in an aqueous solution, and is described, for example, in "Chemical Fact (II)" (Revised 4th Edition, 1993, edited by Nippon Chemical Society, Maruzen Co., Ltd.). The lower the value, the acid strength. The bigger. Specifically, the pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C using an infinitely diluted aqueous solution, or by using the following soft package 1 and calculating it based on the calculation. The substituent constant of Mitt and the value of the database of well-known literature values. The values of pKa in the present specification all indicate values obtained by calculation using the software package. Software Encapsulation 1: Advanced Chemistry Development (ACD/Labs) Software for Solaris Systems, Version 8.14 (Software V8.14 for Solaris) (1994-2007, ACD/Labs).

就抑制樹脂與光酸產生劑之間發生的加成反應的觀點而言，有機酸的pKa較佳為低於樹脂的pKa，另外，較佳為高於由酸產生劑所產生的酸的pKa。本發明的一形態中，有機酸的pKa較佳為較樹脂（B）的pKa低3以上，更佳為低5以上。另外，其他形態中，有機酸的pKa較佳為較由光酸產生劑所產生的酸的pKa高2以上，更佳為高3以上。The pKa of the organic acid is preferably lower than the pKa of the resin from the viewpoint of suppressing the addition reaction occurring between the resin and the photoacid generator, and further preferably higher than the pKa of the acid produced by the acid generator. . In one embodiment of the present invention, the pKa of the organic acid is preferably 3 or more, more preferably 5 or less, lower than the pKa of the resin (B). Further, in other forms, the pKa of the organic acid is preferably 2 or more, more preferably 3 or more, higher than the pKa of the acid produced by the photoacid generator.

本發明中可使用的有機酸例如可列舉有機羧酸、有機磺酸等，其中較佳為有機羧酸。有機羧酸例如可列舉：芳香族有機羧酸、脂肪族羧酸、脂環式羧酸、不飽和脂肪族羧酸、氧基羧酸、烷氧基羧酸等。本發明的一形態中，有機酸較佳為有機羧酸，更佳為芳香族有機羧酸，進而佳為苯甲酸、水楊酸、2-羥基-3-萘甲酸、2-萘甲酸等，最佳為水楊酸。The organic acid which can be used in the present invention is, for example, an organic carboxylic acid, an organic sulfonic acid or the like, and among them, an organic carboxylic acid is preferred. Examples of the organic carboxylic acid include an aromatic organic carboxylic acid, an aliphatic carboxylic acid, an alicyclic carboxylic acid, an unsaturated aliphatic carboxylic acid, an oxycarboxylic acid, and an alkoxycarboxylic acid. In one embodiment of the present invention, the organic acid is preferably an organic carboxylic acid, more preferably an aromatic organic carboxylic acid, and further preferably benzoic acid, salicylic acid, 2-hydroxy-3-naphthoic acid or 2-naphthoic acid. The best is salicylic acid.

有機羧酸的pKa較佳為3.3以上。 另外，有機羧酸較佳為不具有羧基以外的酸基。The pKa of the organic carboxylic acid is preferably 3.3 or more. Further, the organic carboxylic acid preferably has no acid group other than the carboxyl group.

藉由感光化射線或感放射線性組成物含有有機羧酸，有機羧酸將感光化射線或感放射線性組成物中的鹼性化合物中和，由此防止樹脂（B）、疏水性樹脂（D）及組入至聚合物中的形態的化合物（A）的經時分解，有感光化射線或感放射線性組成物的經時穩定性提高的傾向。The photosensitive ray or the radiation-sensitive linear composition contains an organic carboxylic acid, and the organic carboxylic acid neutralizes the basic compound in the sensitized ray or the radiation-sensitive linear composition, thereby preventing the resin (B) and the hydrophobic resin (D). And the time-dependent decomposition of the compound (A) in the form of the composition incorporated in the polymer tends to improve the temporal stability of the sensitized ray or the radiation-sensitive composition.

以下示出有機羧酸的較佳具體例。Preferred specific examples of the organic carboxylic acid are shown below.

[化79] [化79]

＜抗蝕劑膜＞ 本發明亦是有關於一種藉由本發明的感光化射線或感放射線性組成物所形成的抗蝕劑膜，此種膜例如是藉由將本發明的組成物塗佈於基板等支撐體上而形成。該膜的厚度較佳為0.02 μm～0.1 μm。關於塗佈於基板上的方法，藉由旋塗、輥式塗佈、淋塗、浸漬塗佈、噴霧塗佈、刮刀塗佈等適當的塗佈方法塗佈於基板上，較佳為旋轉塗佈，其轉速較佳為1000 rpm～3000 rpm。將塗佈膜於60℃～150℃下預烘烤1分鐘～20分鐘，較佳為於80℃～120℃下預烘烤1分鐘～10分鐘而形成薄膜。 例如於半導體用晶圓的情形時，構成被加工基板及其最表層的材料可使用矽晶圓，成為最表層的材料的例子可列舉Si、SiO2 、SiN、SiON、TiN、WSi、硼磷矽玻璃（Boro-phospho-silicate Glass，BPSG）、旋塗玻璃（Spin on Glass，SOG）、有機抗反射膜等。<Resist film> The present invention also relates to a resist film formed by the sensitized ray or the radiation sensitive composition of the present invention, which film is applied, for example, by coating the composition of the present invention It is formed on a support such as a substrate. The thickness of the film is preferably from 0.02 μm to 0.1 μm. The method of applying to the substrate is applied to the substrate by a suitable coating method such as spin coating, roll coating, shower coating, dip coating, spray coating, blade coating, or the like, preferably spin coating. The cloth preferably has a rotation speed of 1000 rpm to 3000 rpm. The coating film is prebaked at 60 ° C to 150 ° C for 1 minute to 20 minutes, preferably at 80 ° C to 120 ° C for 1 minute to 10 minutes to form a film. For example, in the case of a semiconductor wafer, a tantalum wafer can be used as a material constituting the substrate to be processed and its outermost layer, and examples of the material of the outermost layer include Si, SiO 2 , SiN, SiON, TiN, WSi, and boron phosphorus. Boro-phospho-silicate glass (BPSG), spin on glass (SOG), organic anti-reflection film, and the like.

亦可於形成抗蝕劑膜之前，預先於基板上塗設抗反射膜。 抗反射膜可使用：鈦、二氧化鈦、氮化鈦、氧化鉻、碳、非晶矽等的無機膜型及包含吸光劑與聚合物材料的有機膜型的任一種。另外，亦可使用布魯爾科技（Brewer Science）公司製造的DUV30系列或DUV-40系列或者希普勵（Shipley）公司製造的AR-2、AR-3、AR-5等市售的有機抗反射膜來作為有機抗反射膜。An anti-reflection film may be applied to the substrate in advance before the formation of the resist film. As the antireflection film, any of an inorganic film type such as titanium, titanium oxide, titanium nitride, chromium oxide, carbon, or amorphous germanium, and an organic film type containing a light absorbing agent and a polymer material can be used. In addition, you can also use DUV30 series or DUV-40 series manufactured by Brewer Science or commercially available organic anti-AR-2, AR-3, AR-5 manufactured by Shipley. The reflective film serves as an organic anti-reflection film.

另外，本發明的圖案形成方法中，亦可於抗蝕劑膜的上層形成頂塗層。頂塗層較佳為不與抗蝕劑膜混合，進而可均勻地塗佈於抗蝕劑膜上層。 關於頂塗層，並無特別限定，可藉由現有公知的方法來形成現有公知的頂塗層，例如可根據日本專利特開2014-059543號公報的段落0072～段落0082的記載來形成頂塗層。 例如較佳為將日本專利特開2013-61648號公報中記載般的含有鹼性化合物的頂塗層形成於抗蝕劑膜上。頂塗層可含有的鹼性化合物的具體例與所述鹼性化合物（E）相同。 另外，頂塗層較佳為包含含有至少一個選自由醚鍵、硫醚鍵、羥基、硫醇基、羰基鍵及酯鍵所組成的組群中的基團或鍵的化合物。Further, in the pattern forming method of the present invention, a top coat layer may be formed on the upper layer of the resist film. The top coat layer is preferably not mixed with the resist film, and can be uniformly applied to the upper layer of the resist film. The top coat layer is not particularly limited, and a conventionally known top coat layer can be formed by a conventionally known method. For example, the top coat layer can be formed according to the description of paragraphs 0072 to 0082 of JP-A-2014-059543. Floor. For example, a top coat layer containing a basic compound as described in JP-A-2013-61648 is preferably formed on a resist film. Specific examples of the basic compound which the top coat layer may contain are the same as the basic compound (E). Further, the top coat layer preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

另外，頂塗層較佳為含有樹脂。頂塗層可含有的樹脂並無特別限定，可使用與感光化射線性或感放射線性組成物中可含有的疏水性樹脂相同的樹脂，可較佳地列舉所述疏水性樹脂（D）。 關於疏水性樹脂，可參照日本專利特開2013-61647號公報的[0017]～[0023]（對應的美國公開專利公報2013/244438號的[0017]～[0023]）、及日本專利特開2014-56194號公報的[0016]～[0165]的記載，將該些內容併入至本案說明書中。 頂塗層較佳為包含含有具有芳香環的重複單元的樹脂。藉由含有具有芳香環的重複單元，尤其於電子束或EUV曝光時，二次電子的產生效率、及自藉由光化射線或放射線而產生酸的化合物的酸產生效率提高，於形成圖案時可期待高感度化、高解析化的效果。Further, the top coat layer preferably contains a resin. The resin which may be contained in the top coat layer is not particularly limited, and a resin similar to the hydrophobic resin which can be contained in the sensitizing ray-sensitive or radiation-sensitive composition can be used, and the hydrophobic resin (D) can be preferably used. For the hydrophobic resin, refer to [0017] to [0023] of the Japanese Patent Laid-Open Publication No. 2013-61647 (corresponding to [0017] to [0023] of US Published Patent Publication No. 2013/244438), and Japanese Patent Laid-Open The descriptions of [0016] to [0165] of the Japanese Patent Publication No. 2014-56194 are incorporated herein by reference. The top coat layer preferably contains a resin containing a repeating unit having an aromatic ring. By containing a repeating unit having an aromatic ring, particularly when exposed to an electron beam or EUV, the efficiency of generating secondary electrons and the acid generating efficiency of a compound which generates an acid from actinic rays or radiation are improved when forming a pattern. High sensitivity and high resolution can be expected.

樹脂的重量平均分子量較佳為3000～100000，進而佳為3000～30000，最佳為5000～20000。於總固體成分中，頂塗層形成用組成物中的樹脂的調配量較佳為50質量%～99.9質量%，更佳為70質量%～99.7質量%，進而佳為80質量%～99.5質量%。The weight average molecular weight of the resin is preferably from 3,000 to 100,000, more preferably from 3,000 to 30,000, most preferably from 5,000 to 20,000. In the total solid content, the amount of the resin in the top coat layer-forming composition is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 99.7% by mass, and still more preferably 80% by mass to 99.5% by mass. %.

於頂塗層含有多種樹脂的情形時，較佳為含有至少一種具有氟原子及/或矽原子的樹脂（XA）。更佳為頂塗層組成物含有至少一種具有氟原子及/或矽原子的樹脂（XA）、以及氟原子及/或矽原子的含有率小於樹脂（XA）的樹脂（XB）。藉此，於形成頂塗層膜時，樹脂（XA）偏向存在於頂塗層膜的表面，故可改良顯影特性或液浸液追隨性等性能。In the case where the top coat layer contains a plurality of resins, it is preferred to contain at least one resin (XA) having a fluorine atom and/or a ruthenium atom. More preferably, the top coat composition contains at least one resin (XA) having a fluorine atom and/or a ruthenium atom, and a resin (XB) having a fluorine atom and/or ruthenium atom content lower than that of the resin (XA). Thereby, when the top coat film is formed, the resin (XA) is biased on the surface of the top coat film, so that performance such as development characteristics or liquid immersion followability can be improved.

以頂塗層組成物所含的總固體成分為基準，樹脂（XA）的含量較佳為0.01質量%～30質量%，更佳為0.1質量%～10質量%，進而佳為0.1質量%～8質量%，尤佳為0.1質量%～5質量%。以頂塗層組成物所含的總固體成分為基準，樹脂（XB）的含量較佳為50.0質量%～99.9質量%，更佳為60質量%～99.9質量%，進而佳為70質量%～99.9質量%，尤佳為80質量%～99.9質量%。The content of the resin (XA) is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass based on the total solid content of the top coat composition. 8% by mass, particularly preferably 0.1% by mass to 5% by mass. The content of the resin (XB) is preferably from 50.0% by mass to 99.9% by mass, more preferably from 60% by mass to 99.9% by mass, even more preferably 70% by mass based on the total solid content of the top coat composition. 99.9% by mass, particularly preferably 80% by mass to 99.9% by mass.

相對於樹脂（XA）的重量平均分子量，樹脂（XA）所含有的氟原子的較佳範圍較佳為5質量%～80質量%，更佳為10質量%～80質量%。 相對於樹脂（XA）的重量平均分子量，樹脂（XA）所含有的矽原子的較佳範圍較佳為2質量%～50質量%，更佳為2質量%～30質量%。The preferred range of the fluorine atom contained in the resin (XA) is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 80% by mass based on the weight average molecular weight of the resin (XA). The preferred range of the ruthenium atom contained in the resin (XA) is preferably from 2% by mass to 50% by mass, and more preferably from 2% by mass to 30% by mass based on the weight average molecular weight of the resin (XA).

樹脂（XB）較佳為實質上不含氟原子及矽原子的形態，於該情形時，具體而言，相對於樹脂（XB）中的所有重複單元，具有氟原子的重複單元及具有矽原子的重複單元的合計含量較佳為0 mol%～20 mol%，更佳為0 mol%～10 mol%，進而佳為0 mol%～5 mol%，尤佳為0 mol%～3 mol%，理想為0 mol%，即不含氟原子及矽原子。The resin (XB) is preferably in a form substantially free of a fluorine atom and a ruthenium atom. In this case, specifically, a repeating unit having a fluorine atom and a ruthenium atom with respect to all repeating units in the resin (XB) The total content of the repeating units is preferably from 0 mol% to 20 mol%, more preferably from 0 mol% to 10 mol%, further preferably from 0 mol% to 5 mol%, particularly preferably from 0 mol% to 3 mol%, It is ideally 0 mol%, that is, no fluorine atom or germanium atom.

頂塗層組成物總體中的樹脂的調配量於總固體成分中較佳為50質量%～99.9質量%，更佳為60質量%～99.0質量%。The blending amount of the resin in the entire top coat composition is preferably from 50% by mass to 99.9% by mass, and more preferably from 60% by mass to 99.0% by mass, based on the total solid content.

另外，頂塗層亦可含有酸產生劑、交聯劑及所述化合物（A）。該些各成分的具體例及較佳例如上文所述。Further, the top coat layer may further contain an acid generator, a crosslinking agent, and the compound (A). Specific examples of the respective components and preferred are as described above.

頂塗層典型而言是由頂塗層形成用組成物所形成。 頂塗層形成用組成物較佳為將各成分溶解於溶劑中，進行過濾器過濾。過濾器較佳為孔徑（pore size）0.1 μm以下、更佳為0.05 μm以下、進而佳為0.03 μm以下的聚四氟乙烯製、聚乙烯製、尼龍製的過濾器。另外，過濾器亦可將多種串聯或並聯連接而使用。另外，亦可將組成物過濾多次，過濾多次的步驟亦可為循環過濾步驟。進而，亦可於過濾器過濾的前後，對組成物進行脫氣處理等。本發明的頂塗層形成用組成物較佳為不含金屬等雜質。該些材料所含的金屬成分的含量較佳為10 ppm以下，更佳為5 ppm以下，進而佳為1 ppm以下，尤佳為實質上不含（測定裝置的檢測極限以下）。The top coat layer is typically formed of a top coat forming composition. The top coat layer-forming composition is preferably prepared by dissolving each component in a solvent and filtering the filter. The filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. In addition, the filter can also be used in a variety of series or parallel connections. Alternatively, the composition may be filtered a plurality of times, and the step of filtering a plurality of times may also be a circulation filtration step. Further, the composition may be subjected to a degassing treatment or the like before and after the filter is filtered. The top coat layer forming composition of the present invention preferably contains no impurities such as metal. The content of the metal component contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less, and particularly preferably substantially no (below the detection limit of the measuring device).

於將後述曝光設定為液浸曝光的情形時，頂塗層是配置於抗蝕劑膜與液浸液之間，亦作為不使抗蝕劑膜直接與液浸液接觸的層而發揮功能。於該情形時，頂塗層（頂塗層形成用組成物）具有的較佳特性為對抗蝕劑膜的塗佈適性、對放射線特別是193 nm的透明性、對液浸液（較佳為水）的難溶性。另外，頂塗層較佳為不與抗蝕劑膜混合，進而可均勻地塗佈於抗蝕劑膜的表面。 另外，為了不溶解抗蝕劑膜而將頂塗層形成用組成物均勻地塗佈於抗蝕劑膜的表面，頂塗層形成用組成物較佳為含有不溶解抗蝕劑膜的溶劑。不溶解抗蝕劑膜的溶劑進而佳為使用與下文將詳述的含有有機溶劑的顯影液（有機系顯影液）不同的成分的溶劑。When the exposure described later is set to the liquid immersion exposure, the top coat layer is disposed between the resist film and the liquid immersion liquid, and also functions as a layer that does not directly contact the resist film with the liquid immersion liquid. In this case, the top coat (the composition for forming a top coat layer) has preferable properties such as coating suitability to a resist film, transparency to radiation, particularly 193 nm, and liquid immersion liquid (preferably Insoluble in water). Further, the top coat layer is preferably not mixed with the resist film, and can be uniformly applied to the surface of the resist film. Further, in order to uniformly apply the top coat layer-forming composition to the surface of the resist film without dissolving the resist film, the top coat layer-forming composition preferably contains a solvent which does not dissolve the resist film. The solvent which does not dissolve the resist film is more preferably a solvent which uses a component different from the organic solvent-containing developing solution (organic developing solution) which will be described later.

頂塗層形成用組成物的塗佈方法並無特別限定，可使用現有公知的旋塗法、噴霧法、輥式塗佈法、浸漬法等。The coating method of the top coat layer forming composition is not particularly limited, and a conventionally known spin coating method, spray method, roll coating method, dipping method, or the like can be used.

頂塗層的膜厚並無特別限制，就對曝光光源的透明性的觀點而言，以通常5 nm～300 nm、較佳為10 nm～300 nm、更佳為20 nm～200 nm、進而佳為30 nm～100 nm的厚度而形成。 形成頂塗層後，視需要將基板加熱（Prebake，PB）。 就解析性的觀點而言，頂塗層的折射率較佳為接近抗蝕劑膜的折射率。 頂塗層較佳為不溶於液浸液中，更佳為不溶於水中。 關於頂塗層的後退接觸角，就液浸液追隨性的觀點而言，較佳為液浸液對頂塗層的後退接觸角（23℃）為50度～100度，更佳為80度～100度。 液浸曝光中，液浸液必須追隨於曝光頭在晶圓上高速掃描並形成曝光圖案的動作而於晶圓上移動，因此動態狀態下的液浸液對頂塗層的接觸角變重要，為了獲得更良好的抗蝕劑性能，較佳為具有所述範圍的後退接觸角。The film thickness of the top coat layer is not particularly limited, and is usually from 5 nm to 300 nm, preferably from 10 nm to 300 nm, more preferably from 20 nm to 200 nm, from the viewpoint of transparency of the exposure light source. It is preferably formed at a thickness of 30 nm to 100 nm. After forming the top coat, the substrate is heated (Prebake, PB) as needed. From the standpoint of analyticity, the refractive index of the top coat layer is preferably close to the refractive index of the resist film. The top coat layer is preferably insoluble in the liquid immersion liquid, and more preferably is insoluble in water. Regarding the receding contact angle of the top coat layer, from the viewpoint of the liquid immersion liquid followability, it is preferred that the receding contact angle (23 ° C) of the liquid immersion liquid to the top coat layer is 50 to 100 degrees, more preferably 80 degrees. ~100 degrees. In liquid immersion exposure, the liquid immersion liquid must follow the high-speed scanning of the exposure head on the wafer and form an exposure pattern to move on the wafer, so that the contact angle of the liquid immersion liquid to the top coating in the dynamic state becomes important. In order to obtain better resist properties, it is preferred to have a receding contact angle of the stated range.

於剝離頂塗層時，可使用有機系顯影液，亦可另行使用剝離劑。剝離劑較佳為對抗蝕劑膜的滲透小的溶劑。於可同時進行頂塗層的剝離與抗蝕劑膜的顯影等方面而言，頂塗層較佳為可藉由有機系顯影液而剝離。用於剝離的有機系顯影液只要可將抗蝕劑膜的低曝光部溶解去除，則並無特別限制。When the top coat is peeled off, an organic developer may be used, or a release agent may be separately used. The release agent is preferably a solvent which is less permeable to the resist film. The top coat layer is preferably peeled off by an organic developer in terms of simultaneous peeling of the top coat layer and development of the resist film. The organic developing solution for peeling is not particularly limited as long as it can dissolve and remove the low-exposure portion of the resist film.

就利用有機系顯影液進行剝離等觀點而言，頂塗層於有機系顯影液中的溶解速度較佳為1 nm/sec～300 nm/sec，更佳為10 nm/sec～100 nm/sec。 此處，所謂頂塗層於有機系顯影液中的溶解速度，為將頂塗層成膜後暴露於顯影液中時的膜厚減少速度，本發明中是指浸漬於23℃的乙酸丁酯中時的速度。 藉由將頂塗層於有機系顯影液中的溶解速度設定為1/sec秒以上、較佳為10 nm/sec以上，有減少將抗蝕劑膜顯影後的顯影缺陷產生的效果。另外，藉由將所述溶解速度設定為300 nm/sec以下、較佳為100 nm/sec，可能有以下效果：由於液浸曝光時的曝光不均一減少的影響，將抗蝕劑膜顯影後的圖案的線邊緣粗糙度變得更良好等。 頂塗層亦可使用其他公知的顯影液、例如鹼性水溶液等而去除。可使用的鹼性水溶液具體可列舉氫氧化四甲基銨的水溶液。The dissolution rate of the top coat layer in the organic developer is preferably from 1 nm/sec to 300 nm/sec, more preferably from 10 nm/sec to 100 nm/sec, from the viewpoint of peeling off using an organic developer. . Here, the dissolution rate of the top coat layer in the organic developer is the film thickness reduction rate when the top coat layer is formed into a film and then exposed to the developer, and in the present invention, it is butyl acetate immersed at 23 ° C. The speed of the time. When the dissolution rate of the top coat layer in the organic developer is set to 1/sec second or more, preferably 10 nm/sec or more, the effect of developing defects after development of the resist film is reduced. Further, by setting the dissolution rate to 300 nm/sec or less, preferably 100 nm/sec, there may be an effect that after the resist film is developed due to the influence of uneven exposure unevenness during immersion exposure The line edge roughness of the pattern becomes better and the like. The top coat layer can also be removed using other known developing solutions such as an alkaline aqueous solution. Specific examples of the alkaline aqueous solution which can be used include an aqueous solution of tetramethylammonium hydroxide.

＜圖案形成方法＞ 本發明是有關於一種圖案形成方法，其包括：對所述抗蝕劑膜照射光化射線或放射線（進行曝光）；以及對經所述光化射線或放射線照射的膜進行顯影。本發明中，所述曝光較佳為使用ArF準分子雷射、電子束或極紫外線來進行。<Pattern forming method> The present invention relates to a pattern forming method comprising: irradiating an actinic ray or radiation (exposure) to the resist film; and performing a film irradiated with the actinic ray or radiation development. In the present invention, the exposure is preferably carried out using an ArF excimer laser, an electron beam or an extreme ultraviolet ray.

於精密積體電路元件的製造等中，關於對抗蝕劑膜上的曝光（圖案形成步驟），較佳為首先對本發明的抗蝕劑膜以圖案狀進行ArF準分子雷射、電子束或極紫外線（EUV）照射。關於曝光量，ArF準分子雷射的情形時為1 mJ/cm2 ～100 mJ/cm2 左右，較佳為20 mJ/cm2 ～60 mJ/cm2 左右，電子束的情形時為0.1μC/cm2 ～20 μC/cm2 左右，較佳為3 μC/cm2 ～10 μC/cm2 左右，極紫外線的情形時為0.1 mJ/cm2 ～20 mJ/cm2 左右，較佳為3 mJ/cm2 ～15 mJ/cm2 左右，以成為如上曝光量的方式進行曝光。 繼而，於加熱板上，較佳為於60℃～150℃下進行5秒鐘～20分鐘的曝光後加熱（曝光後烘烤），更佳為於80℃～120℃下進行15秒鐘～10分鐘的曝光後加熱（曝光後烘烤），進而佳為於80℃～120℃下進行1分鐘～10分鐘的曝光後加熱（曝光後烘烤），繼而進行顯影、淋洗、乾燥，藉此形成圖案。此處，曝光後加熱是根據樹脂（B）中的具有酸分解性基的重複單元（b）的酸分解性而適當調整。於酸分解性低的情形時，曝光後加熱的溫度亦較佳為110℃以上，加熱時間亦較佳為45秒鐘以上。於樹脂（B）中的具有酸分解性基的重複單元（b）為式（AII）所表示的重複單元的情形時，曝光後加熱的溫度亦較佳為110℃以上，加熱時間亦較佳為45秒鐘以上。 顯影液是適宜選擇，較佳為使用鹼性顯影液（具代表性的是鹼性水溶液）或含有有機溶劑的顯影液（亦稱為有機系顯影液）。於顯影液為鹼性水溶液的情形時，利用氫氧化四甲基銨（Tetramethylammonium Hydroxide，TMAH）、氫氧化四丁基銨（Tetrabutylammonium hydroxide，TBAH）等的0.1質量%～5質量%、較佳為2質量%～3質量%的鹼性水溶液，藉由浸漬（dip）法、浸置（puddle）法、噴霧（spray）法等常法進行0.1分鐘～3分鐘、較佳為0.5分鐘～2分鐘的顯影。鹼性顯影液中，亦可添加適當量的醇類及/或界面活性劑。如此，於負型圖案的形成時，未曝光部分的膜溶解，經曝光的部分難以溶解於顯影液中，另外於正型圖案的形成時，經曝光的部分的膜溶解，未曝光部的膜難以溶解於顯影液中，藉此於基板上形成目標圖案。In the production of a precision integrated circuit element, etc., regarding the exposure (pattern forming step) on the resist film, it is preferred to first perform an ArF excimer laser, an electron beam or a pole on the resist film of the present invention in a pattern. Ultraviolet (EUV) irradiation. Regarding the amount of exposure, in the case of an ArF excimer laser, it is about 1 mJ/cm 2 to 100 mJ/cm 2 , preferably about 20 mJ/cm 2 to 60 mJ/cm 2 , and in the case of an electron beam, 0.1 μC. /cm 2 to 20 μC/cm 2 or so, preferably about 3 μC/cm 2 to 10 μC/cm 2 , and in the case of extreme ultraviolet rays, about 0.1 mJ/cm 2 to 20 mJ/cm 2 , preferably 3 The exposure is performed so as to have the above exposure amount, mJ/cm 2 to 15 mJ/cm 2 or so. Then, on the hot plate, it is preferably heated at 60 ° C to 150 ° C for 5 seconds to 20 minutes (post-exposure baking), more preferably at 80 ° C to 120 ° C for 15 seconds. After 10 minutes of post-exposure heating (post-exposure bake), it is preferred to perform post-exposure heating (post-exposure bake) at 80 ° C to 120 ° C for 1 minute to 10 minutes, followed by development, rinsing, and drying. This forms a pattern. Here, the post-exposure heating is appropriately adjusted depending on the acid decomposition property of the repeating unit (b) having an acid-decomposable group in the resin (B). In the case where the acid decomposition property is low, the temperature after the post-exposure heating is also preferably 110 ° C or more, and the heating time is also preferably 45 seconds or more. In the case where the repeating unit (b) having an acid-decomposable group in the resin (B) is a repeating unit represented by the formula (AII), the temperature after the post-exposure heating is also preferably 110 ° C or more, and the heating time is also preferably. It is more than 45 seconds. The developer is suitably selected, and an alkaline developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic developer) is preferably used. When the developer is an aqueous alkaline solution, it is preferably 0.1% by mass to 5% by mass, such as Tetramethylammonium Hydroxide (TMAH) or Tetrabutylammonium Hydroxide (TBAH). The alkaline aqueous solution of 2% by mass to 3% by mass is subjected to a usual method such as a dip method, a puddle method, or a spray method for 0.1 minute to 3 minutes, preferably 0.5 minute to 2 minutes. Development. An appropriate amount of an alcohol and/or a surfactant may be added to the alkaline developer. As described above, in the formation of the negative pattern, the film of the unexposed portion is dissolved, and the exposed portion is hardly dissolved in the developing solution, and when the positive pattern is formed, the exposed portion of the film is dissolved, and the film of the unexposed portion is dissolved. It is difficult to dissolve in the developer, thereby forming a target pattern on the substrate.

其中，本發明的圖案形成方法中，較佳為藉由含有有機溶劑的顯影液對經光化射線或放射線照射的膜進行顯影，形成負型圖案。In the pattern forming method of the present invention, it is preferred that the film irradiated with actinic rays or radiation is developed by a developing solution containing an organic solvent to form a negative pattern.

於本發明的圖案形成方法包括使用鹼性顯影液進行顯影的步驟的情形時，鹼性顯影液例如可使用：氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨水等無機鹼類，乙胺、正丙胺等一級胺類，二乙胺、二正丁胺等二級胺類，三乙胺、甲基二乙基胺等三級胺類，二甲基乙醇胺、三乙醇胺等醇胺類，氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化四戊基銨、氫氧化四己基銨、氫氧化四辛基銨、氫氧化乙基三甲基銨、氫氧化丁基三甲基銨、氫氧化甲基三戊基銨、氫氧化二丁基二戊基銨等氫氧化四烷基銨，氫氧化三甲基苯基銨、氫氧化三甲基苄基銨、氫氧化三乙基苄基銨、氫氧化二甲基雙(2-羥基乙基)銨等四級銨鹽，吡咯、哌啶等環狀胺類等的鹼性水溶液。 進而，亦可於所述鹼性水溶液中添加適當量的醇類、界面活性劑而使用。 鹼性顯影液的鹼濃度通常為0.1質量%～20質量%。 鹼性顯影液的pH值通常為10.0～15.0。 尤其較理想為氫氧化四甲基銨的2.38質量%的水溶液。In the case where the pattern forming method of the present invention includes the step of performing development using an alkaline developing solution, the alkaline developing solution may be, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, or ammonia. Such as inorganic bases, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, Alcoholamines such as triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraammonium hydroxide, tetrahexylammonium hydroxide, hydroxide Tetraalkylammonium hydroxide such as tetraoctyl ammonium, ethyl trimethyl ammonium hydroxide, butyl trimethyl ammonium hydroxide, methyl tripentyl ammonium hydroxide, dibutyl diamyl ammonium hydroxide, etc. a quaternary ammonium salt such as trimethylphenylammonium oxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide or dimethylbis(2-hydroxyethyl)ammonium hydroxide, pyrrole or piperidine An alkaline aqueous solution such as a cyclic amine. Further, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution to be used. The alkali concentration of the alkaline developer is usually from 0.1% by mass to 20% by mass. The pH of the alkaline developer is usually from 10.0 to 15.0. In particular, an aqueous solution of 2.38 mass% of tetramethylammonium hydroxide is preferred.

於鹼性顯影之後進行的淋洗處理中的淋洗液是使用純水，亦可添加適當量的界面活性劑而使用。 另外，可於顯影處理或淋洗處理之後，進行藉由超臨界流體將附著於圖案上的顯影液或淋洗液去除的處理。The eluent used in the rinsing treatment after the alkaline development is pure water, and an appropriate amount of a surfactant may be added and used. Further, after the development treatment or the rinsing treatment, the treatment for removing the developer or eluent adhering to the pattern by the supercritical fluid may be performed.

於本發明的圖案形成方法包括使用含有有機溶劑的顯影液進行顯影的步驟的情形時，該步驟中的該顯影液（以下亦稱為有機系顯影液）可使用酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑、醚系溶劑等極性溶劑及烴系溶劑。In the case where the pattern forming method of the present invention includes a step of performing development using a developing solution containing an organic solvent, the developer (hereinafter also referred to as an organic developing solution) in this step may be a ketone solvent or an ester solvent. A polar solvent such as an alcohol solvent, a guanamine solvent or an ether solvent, or a hydrocarbon solvent.

本發明中，所謂酯系溶劑為分子內具有酯基的溶劑，所謂酮系溶劑為分子內具有酮基的溶劑，所謂醇系溶劑為分子內具有醇性羥基的溶劑，所謂醯胺系溶劑為分子內具有醯胺基的溶劑，所謂醚系溶劑為分子內具有醚鍵的溶劑。該些溶劑中，亦存在一分子內具有多種所述官能基的溶劑，該情形時，亦相當於含有該溶劑所具有的官能基的任一溶劑種類。例如，二乙二醇單甲醚相當於所述分類中的醇系溶劑、醚系溶劑的任一種。另外，所謂烴系溶劑為不具有取代基的烴溶劑。 尤其較佳為含有選自酮系溶劑、酯系溶劑、醇系溶劑及醚系溶劑中的至少一種溶劑的顯影液。In the present invention, the ester-based solvent is a solvent having an ester group in the molecule, and the ketone-based solvent is a solvent having a ketone group in the molecule. The alcohol-based solvent is a solvent having an alcoholic hydroxyl group in the molecule, and the amide-based solvent is a solvent. A solvent having a guanamine group in the molecule, and the ether solvent is a solvent having an ether bond in the molecule. Among these solvents, a solvent having a plurality of such functional groups in one molecule is also present, and in this case, it corresponds to any solvent type containing a functional group possessed by the solvent. For example, diethylene glycol monomethyl ether corresponds to any of an alcohol solvent and an ether solvent in the classification. Further, the hydrocarbon solvent is a hydrocarbon solvent having no substituent. In particular, a developer containing at least one solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and an ether solvent is preferable.

就可抑制抗蝕劑膜的膨潤的方面而言，顯影液較佳為使用碳原子數為7以上（較佳為7～14，更佳為7～12，進而佳為7～10）、且雜原子數為2以下的酯系溶劑。 所述酯系溶劑的雜原子為碳原子及氫原子以外的原子，例如可列舉氧原子、氮原子、硫原子等。雜原子數較佳為2以下。 碳原子數為7以上且雜原子數為2以下的酯系溶劑的較佳例可列舉：乙酸戊酯、乙酸異戊酯、乙酸2-甲基丁酯、乙酸1-甲基丁酯、乙酸己酯、丙酸戊酯、丙酸己酯、丙酸庚酯、丁酸丁酯、異丁酸異丁酯等，尤佳為使用乙酸異戊酯或異丁酸異丁酯。In terms of suppressing swelling of the resist film, the developer preferably has a carbon number of 7 or more (preferably 7 to 14, more preferably 7 to 12, and still more preferably 7 to 10). An ester solvent having a number of hetero atoms of 2 or less. The hetero atom of the ester solvent is an atom other than a carbon atom or a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of hetero atoms is preferably 2 or less. Preferable examples of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, and acetic acid. Hexyl ester, amyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, isobutyl isobutyrate, etc., preferably using isoamyl acetate or isobutyl isobutyrate.

顯影液除了上文所述的碳原子數為7以上且雜原子數為2以下的酯系溶劑以外，亦可使用下述酯系溶劑及下述烴系溶劑的混合溶劑、或下述酮系溶劑及下述烴溶劑的混合溶劑。於該情形時，於抑制抗蝕劑膜的膨潤的方面有效果。 於將酯系溶劑與烴系溶劑組合使用的情形時，酯系溶劑較佳為使用乙酸異戊酯。另外，就製備抗蝕劑膜的溶解性等觀點而言，烴系溶劑較佳為使用飽和烴溶劑（例如辛烷、壬烷、癸烷、十二烷、十一烷、十六烷等）。 酮系溶劑例如可列舉：1-辛酮、2-辛酮、1-壬酮、2-壬酮、丙酮、2-庚酮（甲基戊基酮）、4-庚酮、1-己酮、2-己酮、二異丁基酮、2,5-二甲基-4-己酮、二異丁基酮、環己酮、甲基環己酮、苯基丙酮、甲基乙基酮、甲基異丁基酮、乙醯基丙酮、丙酮基丙酮、紫羅酮、二丙酮基醇、乙醯基原醇、苯乙酮、甲基萘基酮、異佛爾酮、碳酸伸丙酯等，尤佳為使用二異丁基酮、2,5-二甲基-4-己酮。 酯系溶劑例如可列舉：乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸異丙酯、乙酸戊酯（pentyl acetate）、乙酸異戊酯、乙酸戊酯（amyl acetate）、丙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯、乙基-3-乙氧基丙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯、丁酸丁酯、2-羥基異丁酸甲酯等。 醇系溶劑例如可列舉：甲醇、乙醇、正丙醇、異丙醇、正丁醇、第二丁醇、4-甲基-2-戊醇、第三丁醇、異丁醇、正己醇、正庚醇、正辛醇、正癸醇等醇，或乙二醇、二乙二醇、三乙二醇等二醇系溶劑，或乙二醇單甲醚、丙二醇單甲醚、乙二醇單乙醚、丙二醇單乙醚、二乙二醇單甲醚、三乙二醇單乙醚、甲氧基甲基丁醇等二醇醚系溶劑等。 醚系溶劑例如除了所述二醇醚系溶劑以外，可列舉苯甲醚、二噁烷、四氫呋喃等。 醯胺系溶劑例如可使用：N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、六甲基磷醯三胺、1,3-二甲基-2-咪唑啶酮等。 烴系溶劑例如可列舉：甲苯、二甲苯等芳香族烴系溶劑，戊烷、己烷、辛烷、癸烷、十一烷等脂肪族烴系溶劑。 另外，作為烴系溶劑的脂肪族烴系溶劑亦可為碳數相同且結構不同的化合物的混合物。例如於使用癸烷作為脂肪族烴系溶劑的情形時，作為碳數相同且結構不同的化合物的2-甲基壬烷、2,2-二甲基辛烷、4-乙基辛烷、異辛烷等亦可包含於脂肪族烴系溶劑中。 另外，所述碳數相同且結構不同的化合物可僅包含一種，亦可如上文所述般包含多種。 所述溶劑亦可混合多種，亦可與所述以外的溶劑或水混合而使用。其中，為了充分發揮本發明的效果，較佳為顯影液總體的含水率小於10質量%，更佳為實質上不含水分。 即，有機溶劑相對於有機系顯影液的使用量較佳為相對於顯影液的總量而為90質量%以上且100質量%以下，較佳為95質量%以上且100質量%以下。 尤其有機系顯影液較佳為含有選自由酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑及醚系溶劑所組成的組群中的至少一種有機溶劑的顯影液。In addition to the ester-based solvent having a carbon number of 7 or more and a hetero atom number of 2 or less, a mixed solvent of the following ester-based solvent and the following hydrocarbon-based solvent, or the following ketone system may be used. A solvent and a mixed solvent of the following hydrocarbon solvent. In this case, it is effective in suppressing swelling of the resist film. When the ester solvent is used in combination with a hydrocarbon solvent, the ester solvent is preferably isoamyl acetate. Further, from the viewpoint of solubility in the preparation of the resist film, etc., it is preferred to use a saturated hydrocarbon solvent (for example, octane, decane, decane, dodecane, undecane, hexadecane or the like) as the hydrocarbon solvent. . Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, and 1-hexanone. , 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone , methyl isobutyl ketone, acetyl ketone acetone, acetone acetone, ionone, diacetone alcohol, acetyl primol, acetophenone, methyl naphthyl ketone, isophorone, carbonic acid For esters and the like, it is preferred to use diisobutyl ketone or 2,5-dimethyl-4-hexanone. Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and propylene glycol monomethyl ether. Acid ester, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, Butyl butyrate, methyl 2-hydroxyisobutyrate, and the like. Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, 4-methyl-2-pentanol, tert-butanol, isobutanol, and n-hexanol. An alcohol such as n-heptanol, n-octanol or n-nonanol, or a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether or ethylene glycol A glycol ether solvent such as monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol. Examples of the ether solvent include, in addition to the glycol ether solvent, anisole, dioxane, tetrahydrofuran, and the like. The guanamine-based solvent can be, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine, 1 , 3-dimethyl-2-imidazolidinone and the like. Examples of the hydrocarbon-based solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane and undecane. Further, the aliphatic hydrocarbon solvent as the hydrocarbon solvent may be a mixture of compounds having the same carbon number and different structures. For example, when decane is used as the aliphatic hydrocarbon-based solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and the like are compounds having the same carbon number and different structures. Octane or the like may also be contained in an aliphatic hydrocarbon solvent. Further, the compounds having the same carbon number and different structures may include only one kind, and may also contain a plurality of kinds as described above. The solvent may be mixed in a plurality of types, or may be used in combination with a solvent or water other than the above. In order to fully exert the effects of the present invention, it is preferred that the total moisture content of the developer is less than 10% by mass, and more preferably substantially no moisture. In other words, the amount of the organic solvent to be used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and preferably 95% by mass or more and 100% by mass or less based on the total amount of the developer. In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

有機系顯影液的蒸氣壓於20℃下較佳為5 kPa以下，進而佳為3 kPa以下，尤佳為2 kPa以下。藉由將有機系顯影液的蒸氣壓設定為5 kPa以下，顯影液於基板上或顯影杯內的蒸發得到抑制，晶圓面內的溫度均勻性提高，結果晶圓面內的尺寸均勻性變良好。 具有5 kPa以下的蒸氣壓的具體例可列舉：1-辛酮、2-辛酮、1-壬酮、2-壬酮、2-庚酮（甲基戊基酮）、4-庚酮、2-己酮、二異丁基酮、環己酮、甲基環己酮、苯基丙酮、甲基異丁基酮等酮系溶劑；乙酸丁酯、乙酸戊酯、乙酸異戊酯、乙酸戊酯、丙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯、乙基-3-乙氧基丙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯等酯系溶劑；正丙醇、異丙醇、正丁醇、第二丁醇、第三丁醇、異丁醇、正己醇、正庚醇、正辛醇、正癸醇等醇系溶劑；乙二醇、二乙二醇、三乙二醇等二醇系溶劑；或乙二醇單甲醚、丙二醇單甲醚、乙二醇單乙醚、丙二醇單乙醚、二乙二醇單甲醚、三乙二醇單乙醚、甲氧基甲基丁醇等二醇醚系溶劑；四氫呋喃等醚系溶劑；N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺的醯胺系溶劑；甲苯、二甲苯等芳香族烴系溶劑；辛烷、癸烷等脂肪族烴系溶劑。 具有作為尤佳範圍的2 kPa以下的蒸氣壓的具體例可列舉：1-辛酮、2-辛酮、1-壬酮、2-壬酮、2-庚酮、4-庚酮、2-己酮、二異丁基酮、環己酮、甲基環己酮、苯基丙酮等酮系溶劑；乙酸丁酯、乙酸戊酯、丙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯、乙基-3-乙氧基丙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、乳酸乙酯、乳酸丁酯、乳酸丙酯等酯系溶劑；正丁醇、第二丁醇、第三丁醇、異丁醇、正己醇、正庚醇、正辛醇、正癸醇等醇系溶劑；乙二醇、二乙二醇、三乙二醇等二醇系溶劑；或乙二醇單甲醚、丙二醇單甲醚、乙二醇單乙醚、丙二醇單乙醚、二乙二醇單甲醚、三乙二醇單乙醚、甲氧基甲基丁醇等二醇醚系溶劑；N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺的醯胺系溶劑；二甲苯等芳香族烴系溶劑；辛烷、癸烷、十一烷等脂肪族烴系溶劑。The vapor pressure of the organic developer is preferably 5 kPa or less at 20 ° C, more preferably 3 kPa or less, and still more preferably 2 kPa or less. By setting the vapor pressure of the organic developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is changed. good. Specific examples of the vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), and 4-heptanone. a ketone solvent such as 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone; butyl acetate, amyl acetate, isoamyl acetate, acetic acid Amyl ester, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropyl Acid ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. An ester solvent; an alcohol solvent such as n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol or n-nonanol; a glycol solvent such as diol, diethylene glycol or triethylene glycol; or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, three Glycol ethers such as ethylene glycol monoethyl ether and methoxymethylbutanol An ether solvent such as tetrahydrofuran; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, amide-based solvent of N,N-dimethylformamide; toluene, xylene An aromatic hydrocarbon solvent; an aliphatic hydrocarbon solvent such as octane or decane. Specific examples of the vapor pressure of 2 kPa or less which is a particularly preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, and 2- a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone or phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Ester, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl An ester solvent such as -3-methoxybutyl acetate, ethyl lactate, butyl lactate or propyl lactate; n-butanol, second butanol, third butanol, isobutanol, n-hexanol, positive An alcohol solvent such as heptanol, n-octanol or n-decyl alcohol; a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; or ethylene glycol monomethyl ether, propylene glycol monomethyl ether or ethylene glycol a glycol ether solvent such as monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol; N-methyl-2-pyrrolidone, N, N - guanamine solvent of dimethylacetamide, N,N-dimethylformamide; And the like aromatic hydrocarbon solvents; octane, decane, undecane, and the like aliphatic hydrocarbon solvents.

有機系顯影液亦可含有鹼性化合物。本發明中所用的顯影液可含有的鹼性化合物的具體例及較佳例與上文所述的感光化射線或感放射線性組成物可含有的鹼性化合物的具體例及較佳例相同。The organic developer may also contain a basic compound. Specific examples and preferred examples of the basic compound which may be contained in the developer used in the present invention are the same as those of the basic compound and preferred examples which may be contained in the above-mentioned photosensitive radiation or radiation sensitive composition.

有機系顯影液中，視需要可添加適當量的界面活性劑。 界面活性劑並無特別限定，例如可使用離子性或非離子性的氟系及/或矽系界面活性劑等。該些氟及/或矽系界面活性劑例如可列舉：日本專利特開昭62-36663號公報、日本專利特開昭61-226746號公報、日本專利特開昭61-226745號公報、日本專利特開昭62-170950號公報、日本專利特開昭63-34540號公報、日本專利特開平7-230165號公報、日本專利特開平8-62834號公報、日本專利特開平9-54432號公報、日本專利特開平9-5988號公報、美國專利第5405720號說明書、美國專利第5360692號說明書、美國專利第5529881號說明書、美國專利第5296330號說明書、美國專利第5436098號說明書、美國專利第5576143號說明書、美國專利第5294511號說明書、美國專利第5824451號說明書中記載的界面活性劑，較佳為非離子性的界面活性劑。非離子性的界面活性劑並無特別限定，進而佳為使用氟系界面活性劑或矽系界面活性劑。 相對於顯影液的總量，界面活性劑的使用量較佳為0質量%～2質量%，進而佳為0.0001質量%～2質量%，尤佳為0.0005質量%～1質量%。In the organic developer, an appropriate amount of a surfactant may be added as needed. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. Examples of the fluorine- and/or lanthanum-based surfactants include, for example, Japanese Patent Laid-Open No. Sho 62-36663, Japanese Patent Laid-Open No. SHO 61-226746, Japanese Patent Laid-Open No. 61-226745, and Japanese Patent. JP-A-62-170950, JP-A-63-34540, JP-A-H07-230165, JP-A-H08-62834 Japanese Patent Laid-Open Publication No. Hei 9-5988, U.S. Patent No. 5,405, 720, U.S. Patent No. 5,360, 692, U.S. Patent No. 5,529, 881, U.S. Patent No. 5,296,330, U.S. Patent No. 5,436,098, U.S. Patent No. 5,576,143, The surfactant described in the specification, the specification of U.S. Patent No. 5,294,511, and the specification of U.S. Patent No. 5,824,451 is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, and a fluorine-based surfactant or a lanthanoid surfactant is preferably used. The amount of the surfactant to be used is preferably from 0% by mass to 2% by mass, more preferably from 0.0001% by mass to 2% by mass, even more preferably from 0.0005% by mass to 1% by mass, based on the total amount of the developer.

顯影方法例如可應用：將基板於充滿顯影液的槽中浸漬一定時間的方法（浸漬法）；藉由表面張力使顯影液於基板表面上堆積並靜止一定時間，藉此進行顯影的方法（浸置法）；對基板表面噴霧顯影液的方法（噴霧法）；一面以一定速度掃描顯影液噴出噴嘴，一面朝以一定速度旋轉的基板上連續噴出顯影液的方法（動態分配法）等。 於所述各種顯影方法包括自顯影裝置的顯影噴嘴向抗蝕劑膜噴出顯影液的步驟的情形時，所噴出的顯影液的噴出壓（所噴出的顯影液的每單位面積的流速）較佳為2 mL/sec/mm2 以下，更佳為1.5 mL/sec/mm2 以下，進而佳為1 mL/sec/mm2 以下。流速並不特別存在下限，若考慮到處理量（throughput），則較佳為0.2 mL/sec/mm2 以上。 藉由將噴出的顯影液的噴出壓設定為所述範圍，可顯著減少顯影後的來源於抗蝕劑殘渣的圖案的缺陷。 其詳細機制雖不確定，但恐怕可認為其原因在於：藉由將噴出壓設定為所述範圍，顯影液對抗蝕劑膜所賦予的壓力變小，可抑制抗蝕劑膜·圖案被無意中削去或破壞的情況。 另外，顯影液的噴出壓（mL/sec/mm2 ）為顯影裝置中的顯影噴嘴出口處的值。The developing method can be applied, for example, to a method of immersing a substrate in a bath filled with a developing solution for a certain period of time (dipping method); and developing the developing solution on the surface of the substrate by a surface tension for a certain period of time, thereby performing development (dipping) A method of spraying a developer onto a surface of a substrate (spray method); a method of continuously ejecting a developer onto a substrate rotating at a constant speed while scanning a developer discharge nozzle at a constant speed (dynamic method). In the case where the various developing methods include the step of ejecting the developing solution from the developing nozzle of the developing device to the resist film, the ejection pressure of the ejected developing solution (the flow rate per unit area of the ejected developing solution) is preferably It is 2 mL/sec/mm 2 or less, more preferably 1.5 mL/sec/mm 2 or less, and further preferably 1 mL/sec/mm 2 or less. The flow rate does not particularly have a lower limit, and is preferably 0.2 mL/sec/mm 2 or more in consideration of the throughput. By setting the discharge pressure of the discharged developing solution to the above range, the defects of the pattern derived from the resist residue after development can be remarkably reduced. Although the detailed mechanism is not certain, it is considered to be because the pressure applied to the resist film by the developer is reduced by setting the discharge pressure to the above range, and the resist film and pattern can be suppressed from being inadvertently The situation of being cut or destroyed. Further, the discharge pressure (mL/sec/mm 2 ) of the developer is a value at the exit of the developing nozzle in the developing device.

調整顯影液的噴出壓的方法例如可列舉：利用泵等來調整噴出壓的方法；或藉由自加壓罐（tank）的供給來調整壓力，藉此改變噴出壓的方法等。The method of adjusting the discharge pressure of the developing solution is, for example, a method of adjusting the discharge pressure by a pump or the like, or a method of adjusting the pressure by adjusting the pressure from the supply of a tank, thereby changing the discharge pressure.

另外，於使用含有有機溶劑的顯影液進行顯影的步驟之後，亦可實施一面替換為其他溶劑一面停止顯影的步驟。Further, after the step of performing development using a developing solution containing an organic solvent, a step of stopping development while replacing it with another solvent may be carried out.

於使用含有有機溶劑的顯影液進行顯影的步驟之後，亦可包括使用淋洗液進行清洗的步驟，就處理量（生產性）、淋洗液使用量等觀點而言，亦可不包括使用淋洗液進行清洗的步驟。After the step of performing development using a developing solution containing an organic solvent, the step of washing with an eluent may be included, and the elution amount may not be included in terms of the amount of processing (productivity), the amount of eluent used, and the like. The step of cleaning the liquid.

使用含有有機溶劑的顯影液進行顯影的步驟之後的淋洗步驟中所用的淋洗液只要不溶解抗蝕劑圖案，則並無特別限制，可使用含有通常的有機溶劑的溶液。所述淋洗液較佳為使用含有選自由烴系溶劑、酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑及醚系溶劑所組成的組群中的至少一種有機溶劑的淋洗液。 烴系溶劑、酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑及醚系溶劑的具體例可列舉與含有有機溶劑的顯影液中說明的具體例相同者，尤其可較佳地列舉乙酸丁酯及甲基異丁基原醇。 於使用含有有機溶劑的顯影液進行顯影的步驟之後，更佳為進行使用含有選自由酯系溶劑、醇系溶劑、烴系溶劑所組成的組群中的至少一種有機溶劑的淋洗液進行清洗的步驟，進而佳為以進行使用含有醇系溶劑或烴系溶劑的淋洗液進行清洗的步驟為宜。The eluent used in the rinsing step after the step of performing development using the developing solution containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a usual organic solvent can be used. The eluent is preferably rinsed with at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. liquid. Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent are the same as those described in the developer containing the organic solvent, and particularly preferred examples thereof Butyl acetate and methyl isobutyl orthoester. After the step of performing development using a developer containing an organic solvent, it is more preferable to carry out cleaning using an eluent containing at least one organic solvent selected from the group consisting of an ester solvent, an alcohol solvent, and a hydrocarbon solvent. Preferably, the step of washing with an eluent containing an alcohol solvent or a hydrocarbon solvent is preferably carried out.

有機溶劑中，淋洗液所含的有機溶劑亦較佳為使用烴系溶劑，更佳為使用脂肪族烴系溶劑。就其效果進一步提高等觀點而言，淋洗液中所用的脂肪族烴系溶劑較佳為碳數5以上的脂肪族烴系溶劑（例如戊烷、己烷、辛烷、癸烷、十一烷、十二烷、十六烷等），較佳為碳原子數為8以上的脂肪族烴系溶劑，更佳為碳原子數為10以上的脂肪族烴系溶劑。 另外，所述脂肪族烴系溶劑的碳原子數的上限值並無特別限定，例如可列舉16以下，較佳為14以下，更佳為12以下。 所述脂肪側烴系溶劑中，尤佳為癸烷、十一烷、十二烷，最佳為十一烷。 藉由如此般使用烴系溶劑（特別是脂肪族烴系溶劑）作為淋洗液中所含的有機溶劑，而進一步發揮以下效果：將顯影後稍許滲入至抗蝕劑膜中的顯影液沖洗去，進一步抑制膨潤，從而抑制圖案倒塌等。In the organic solvent, the organic solvent contained in the eluent is preferably a hydrocarbon solvent, and more preferably an aliphatic hydrocarbon solvent. The aliphatic hydrocarbon solvent used in the eluent is preferably an aliphatic hydrocarbon solvent having a carbon number of 5 or more (for example, pentane, hexane, octane, decane, eleven). An alkane, dodecane, hexadecane or the like is preferably an aliphatic hydrocarbon solvent having 8 or more carbon atoms, more preferably an aliphatic hydrocarbon solvent having 10 or more carbon atoms. In addition, the upper limit of the number of carbon atoms of the aliphatic hydrocarbon-based solvent is not particularly limited, and is, for example, 16 or less, preferably 14 or less, and more preferably 12 or less. Among the aliphatic side hydrocarbon solvents, decane, undecane and dodecane are preferred, and undecane is preferred. By using a hydrocarbon solvent (especially an aliphatic hydrocarbon solvent) as the organic solvent contained in the eluent, the following effects are further exerted: the developer which is slightly infiltrated into the resist film after development is washed away. Further suppressing swelling, thereby suppressing pattern collapse or the like.

所述各成分亦可混合多種，亦可與所述以外的有機溶劑混合而使用。The respective components may be mixed in a plurality of kinds, and may be used in combination with an organic solvent other than the above.

淋洗液中的含水率較佳為10質量%以下，更佳為5質量%以下，尤佳為3質量%以下。藉由將含水率設定為10質量%以下，可獲得良好的顯影特性。The water content in the eluent is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

於使用含有有機溶劑的顯影液進行顯影的步驟之後所用的淋洗液的蒸氣壓於20℃下較佳為0.05 kPa以上且5 kPa以下，進而佳為0.1 kPa以上且5 kPa以下，最佳為0.12 kPa以上且3 kPa以下。藉由將淋洗液的蒸氣壓設定為0.05 kPa以上且5 kPa以下，晶圓面內的溫度均勻性提高，進而由淋洗液的滲透所引起的膨潤得到抑制，晶圓面內的尺寸均勻性變良好。The vapor pressure of the eluent used after the step of performing development using the developer containing the organic solvent is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the eluent to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling caused by the penetration of the eluent is suppressed, and the wafer surface is uniform in size. Sex has changed.

淋洗液中，亦可添加適當量的界面活性劑而使用。An appropriate amount of a surfactant may be added to the eluent for use.

淋洗步驟中，使用所述含有有機溶劑的淋洗液對使用含有有機溶劑的顯影液進行了顯影的晶圓進行清洗處理。清洗處理的方法並無特別限定，例如可應用：將淋洗液連續噴出至以一定速度旋轉的基板上的方法（旋轉塗佈法）、將基板於充滿淋洗液的槽中浸漬一定時間的方法（浸漬法）、對基板表面噴霧淋洗液的方法（噴霧法）等，其中較佳為利用旋轉塗佈方法來進行清洗處理，於清洗後使基板以2000 rpm～4000 rpm的轉速旋轉，將淋洗液自基板上去除。另外，亦較佳為於淋洗步驟之後包括加熱步驟（後烘烤（Post Bake））。藉由烘烤將殘留於圖案間及圖案內部的顯影液及淋洗液去除。淋洗步驟之後的加熱步驟是於通常40℃～160℃、較佳為70℃～95℃下進行通常10秒鐘～3分鐘、較佳為30秒鐘～90秒鐘。In the rinsing step, the wafer subjected to development using a developing solution containing an organic solvent is subjected to a cleaning treatment using the organic solvent-containing eluent. The method of the cleaning treatment is not particularly limited, and for example, a method of continuously ejecting the eluent onto a substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a tank filled with the eluent for a certain period of time can be applied. The method (dipping method), the method of spraying the eluent onto the surface of the substrate (spraying method), etc., wherein the cleaning treatment is preferably performed by a spin coating method, and after the cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. The eluent is removed from the substrate. In addition, it is also preferred to include a heating step (Post Bake) after the rinsing step. The developer and the eluent remaining between the patterns and the inside of the pattern are removed by baking. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, preferably 70 ° C to 95 ° C for usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

於不包括使用淋洗液進行清洗的步驟的情形時，例如可採用日本專利特開2015-216403的段落[0014]～段落[0086]中記載的顯影處理方法。In the case where the step of washing with the eluent is not included, for example, the development processing method described in paragraphs [0014] to [0086] of JP-A-2015-216403 can be employed.

另外，本發明的圖案形成方法亦可包括使用有機系顯影液的顯影步驟、與使用鹼性顯影液的顯影步驟。藉由使用有機系顯影液的顯影，曝光強度弱的部分被去除，藉由進行使用鹼性顯影液的顯影，曝光強度強的部分亦被去除。藉由如此般進行多次顯影的多重顯影製程，可僅使中間曝光強度的區域不溶解而進行圖案形成，故可形成較通常更微細的圖案（與日本專利特開2008-292975號公報的段落[0077]相同的機制）。Further, the pattern forming method of the present invention may further include a developing step using an organic developing solution and a developing step using an alkaline developing solution. By developing using an organic developing solution, a portion having a weak exposure intensity is removed, and by performing development using an alkaline developing solution, a portion having a high exposure intensity is also removed. By the multiple development process in which the development is performed as many times as described above, the pattern of the intermediate exposure intensity can be formed only by insolubilization, so that a more fine pattern can be formed (with the paragraph of JP-A-2008-292975) [0077] The same mechanism).

本發明的感光化射線或感放射線性組成物、及本發明的圖案形成方法中使用的各種材料（例如抗蝕劑溶劑、顯影液、淋洗液、抗反射膜形成用組成物、頂塗層形成用組成物等）較佳為不含金屬、含鹵素的金屬鹽、酸、鹼、含硫原子或磷原子的成分等雜質。此處，含金屬原子的雜質可列舉Na、K、Ca、Fe、Cu、Mn、Mg、Al、Cr、Ni、Zn、Ag、Sn、Pb、Li或該些元素的鹽等。 該些材料所含的雜質的含量較佳為1 ppm以下，更佳為1 ppb以下，進而佳為100 ppt以下，尤佳為10 ppt以下，最佳為實質上不含（測定裝置的檢測極限以下）。 自各種材料中去除金屬等雜質的方法例如可列舉使用過濾器的過濾。關於過濾器孔徑，較佳為孔徑10 nm以下，更佳為5 nm以下，進而佳為3 nm以下。關於過濾器的材質，較佳為聚四氟乙烯製、聚乙烯製、尼龍製的過濾器。過濾器亦可為將該些材質與離子交換介質組合而成的複合材料。過濾器亦可使用預先經有機溶劑清洗的過濾器。於過濾器過濾步驟中，亦可將多種過濾器串聯或並聯連接而使用。於使用多種過濾器的情形時，亦可將孔徑及/或材質不同的過濾器組合而使用。另外，亦可將各種材料過濾多次，過濾多次的步驟亦可為循環過濾步驟。 另外，減少各種材料所含的金屬等雜質的方法可列舉：選擇金屬含量少的原料作為構成各種材料的原料；對構成各種材料的原料進行過濾器過濾；利用鐵氟龍（Teflon，註冊商標）對裝置內進行襯底（lining）等而於儘可能抑制污染（contamination）的條件下進行蒸餾等方法。對構成各種材料的原料進行的過濾器過濾的較佳條件與上文所述的條件相同。 除了過濾器過濾以外，亦可進行利用吸附材料的雜質去除，亦可將過濾器過濾與吸附材料組合使用。吸附材料可使用公知的吸附材料，例如可使用矽膠（silica gel）、沸石等無機系吸附材料、活性炭等有機系吸附材料。 另外，減少本發明的有機系處理液中所含的金屬等雜質的方法可列舉：選擇金屬含量少的原料作為構成各種材料的原料；對構成各種材料的原料進行過濾器過濾；利用鐵氟龍（註冊商標）對裝置內進行襯底等而於儘可能抑制污染的條件下進行蒸餾等方法。對構成各種材料的原料進行的過濾器過濾的較佳條件與上文所述的條件相同。 除了過濾器過濾以外，亦可進行利用吸附材料的雜質去除，亦可將過濾器過濾與吸附材料組合使用。吸附材料可使用公知的吸附材料，例如可使用矽膠、沸石等無機系吸附材料、活性炭等有機系吸附材料。Various materials used in the sensitized ray or radiation sensitive composition of the present invention and the pattern forming method of the present invention (for example, a resist solvent, a developing solution, an eluent, an antireflective film forming composition, and a top coat) The composition for formation, etc.) is preferably an impurity such as a metal-free, halogen-containing metal salt, an acid, a base, a component containing a sulfur atom or a phosphorus atom. Here, examples of the metal atom-containing impurities include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or a salt of these elements. The content of the impurities contained in the materials is preferably 1 ppm or less, more preferably 1 ppb or less, further preferably 100 ppt or less, and particularly preferably 10 ppt or less, and most preferably substantially no (detection limit of the measuring device) the following). A method of removing impurities such as metals from various materials may, for example, be filtration using a filter. Regarding the filter pore diameter, the pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon. The filter may also be a composite material in which these materials are combined with an ion exchange medium. The filter can also use a filter that has been previously cleaned with an organic solvent. In the filter filtration step, a plurality of filters may be used in series or in parallel. When a variety of filters are used, filters having different apertures and/or materials may be used in combination. In addition, various materials may be filtered multiple times, and the step of filtering a plurality of times may also be a circulation filtration step. In addition, as a method of reducing impurities such as metals contained in various materials, raw materials having a small metal content are selected as raw materials constituting various materials, and filters constituting various materials are subjected to filter filtration; and Teflon (registered trademark) is used. A method of performing distillation or the like under the conditions of lining or the like in the apparatus to suppress contamination as much as possible. The preferred conditions for filter filtration of the raw materials constituting the various materials are the same as those described above. In addition to filter filtration, impurity removal using adsorbent materials can also be performed, and filter filtration can also be used in combination with adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite or an organic adsorbent such as activated carbon can be used. In addition, a method of reducing impurities such as metals contained in the organic-based treatment liquid of the present invention is as follows: a raw material having a small metal content is selected as a raw material constituting various materials; a raw material constituting various materials is subjected to filter filtration; and Teflon is used; (Registered Trademark) A method in which a substrate or the like is placed in a device to perform distillation under conditions that suppress contamination as much as possible. The preferred conditions for filter filtration of the raw materials constituting the various materials are the same as those described above. In addition to filter filtration, impurity removal using adsorbent materials can also be performed, and filter filtration can also be used in combination with adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as tannin or zeolite, or an organic adsorbent such as activated carbon can be used.

＜收容容器＞ 關於可用於顯影液及淋洗液的有機溶劑（亦稱為「有機系處理液」），較佳為使用經保存於具有收容部的化學增幅型或非化學增幅型抗蝕劑膜的圖案化用有機系處理液的收容容器中的有機溶劑。該收容容器例如較佳為抗蝕劑膜的圖案化用有機系處理液的收容容器，該收容容器的收容部的與有機系處理液接觸的內壁是由與聚乙烯樹脂、聚丙烯樹脂及聚乙烯-聚丙烯樹脂的任一種不同的樹脂或實施有防銹·防金屬溶出處理的金屬所形成。可於該收容容器的所述收容部中收容用作抗蝕劑膜的圖案化用有機系處理液的預定的有機溶劑，於抗蝕劑膜的圖案化時中，使用自所述收容部中排出的有機溶劑。<Storage Container> The organic solvent (also referred to as "organic treatment liquid") which can be used for the developer and the eluent is preferably used in a chemically amplified or non-chemically amplified resist which is stored in the storage portion. The organic solvent in the storage container of the organic treatment liquid is used for patterning the film. The storage container is preferably a storage container for an organic processing liquid for patterning of a resist film, and an inner wall of the storage portion of the storage container that is in contact with the organic processing liquid is made of a polyethylene resin, a polypropylene resin, and Any of various polyethylene-polypropylene resins or metals which are subjected to rust and metal elution treatment. A predetermined organic solvent used as a patterning organic processing liquid for a resist film is accommodated in the accommodating portion of the accommodating container, and is used in the accommodating portion during patterning of the resist film. Exhausted organic solvent.

於所述收容容器更具有用以將所述收容部密閉的密封部的情形時，該密封部亦較佳為由與聚乙烯樹脂、聚丙烯樹脂及聚乙烯-聚丙烯樹脂所組成的組群中的一種以上的樹脂不同的樹脂或實施有防銹·防金屬溶出處理的金屬所形成。In the case where the storage container further has a sealing portion for sealing the receiving portion, the sealing portion is preferably a group composed of a polyethylene resin, a polypropylene resin, and a polyethylene-polypropylene resin. One or more resins having different resins or metals subjected to rust and metal elution treatment are formed.

此處，所謂密封部，是指可將收容部與外氣阻斷的構件，可較佳地列舉襯墊（packing）或O環等。Here, the sealing portion refers to a member that can block the housing portion from the outside air, and a packing or an O-ring or the like can be preferably used.

與選自由聚乙烯樹脂、聚丙烯樹脂及聚乙烯-聚丙烯樹脂所組成的組群中的一種以上的樹脂不同的樹脂較佳為全氟樹脂。The resin different from the one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.

全氟樹脂可列舉：四氟乙烯樹脂（聚四氟乙烯（Polytetrafluoroethylene，PTFE））、四氟乙烯-全氟烷基乙烯醚共聚物（Perfluoroalkoxy，PFA）、四氟乙烯-六氟丙烯共聚合樹脂（Fluorinated ethylene propylene，FEP）、四氟乙烯-乙烯共聚物樹脂（Ethylene Tetrafluoro Ethylene，ETFE）、三氟氯乙烯-乙烯共聚合樹脂（Ethylene-chlorotrifluoroethylene，ECTFE）、偏二氟乙烯樹脂（聚偏二氟乙烯（Polyvinylidene fluoride，PVDF））、三氟氯乙烯共聚合樹脂（聚三氟氯乙烯（Polychlorotrifluoroethylene，PCTFE））、氟乙烯樹脂（聚氟乙烯（Polyvinylfluoride，PVF））等。Examples of the perfluoro resin include: tetrafluoroethylene resin (polytetrafluoroethylene (PTFE)), tetrafluoroethylene-perfluoroalkoxy (PFA), tetrafluoroethylene-hexafluoropropylene copolymerized resin. (Fluorinated ethylene propylene, FEP), Ethylene Tetrafluoro Ethylene (ETFE), Ethylene-chlorotrifluoroethylene (ECTFE), vinylidene fluoride resin (Polyvinylidene) Polyvinylidene fluoride (PVDF), chlorotrifluoroethylene (PCT), fluoroethylene (polyvinylfluoride (PVF)), and the like.

尤佳的全氟樹脂可列舉：四氟乙烯樹脂、四氟乙烯-全氟烷基乙烯基醚共聚物、四氟乙烯-六氟丙烯共聚合樹脂。Particularly preferred perfluororesins include tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.

實施有防銹·防金屬溶出處理的金屬的金屬可列舉：碳鋼、合金鋼、鎳鉻鋼、鎳鉻鉬鋼、鉻鋼、鉻鉬鋼、錳鋼等。Examples of the metal which is subjected to the rust-preventing and metal-proof elution treatment include carbon steel, alloy steel, nickel-chromium steel, nickel-chromium-molybdenum steel, chrome steel, chrome-molybdenum steel, and manganese steel.

防銹·防金屬溶出處理較佳為應用皮膜技術。The anti-rust and metal-proof elution treatment is preferably a film coating technique.

皮膜技術中，大致分為金屬被覆（各種鍍敷）、無機被覆（各種化成處理、玻璃、混凝土、陶瓷等）及有機被覆（防銹油、塗料、橡膠、塑膠）此三種。The film technology is roughly classified into three types: metal coating (various plating), inorganic coating (various chemical conversion treatment, glass, concrete, ceramics, etc.) and organic coating (rustproof oil, paint, rubber, and plastic).

較佳的皮膜技術可列舉利用防銹油、防銹劑、腐蝕抑制劑、螯合化合物、可剝性塑膠、襯底劑的表面處理。Preferred film techniques include surface treatment using rust preventive oil, rust inhibitor, corrosion inhibitor, chelating compound, peelable plastic, and substrate agent.

其中，較佳為各種鉻酸鹽、亞硝酸鹽、矽酸鹽、磷酸鹽、油酸、二聚酸、環烷酸等羧酸、羧酸金屬皂、磺酸鹽、胺鹽、酯（高級脂肪酸的甘油酯或磷酸酯）等腐蝕抑制劑、乙二胺四乙酸、葡萄糖酸、氮川基三乙酸、羥基乙基乙二胺三乙酸、二乙三胺五作酸等螯合化合物及氟樹脂襯底。尤佳為磷酸鹽處理及氟樹脂襯底。Among them, various chromate, nitrite, citrate, phosphate, oleic acid, dimer acid, naphthenic acid and the like, carboxylic acid metal soap, sulfonate, amine salt, ester are preferred. Corrosion inhibitors such as fatty acid glycerides or phosphates, chelating compounds such as ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaic acid, and fluorine Resin substrate. It is especially preferred for phosphate treatment and fluororesin substrates.

另外，與直接的被覆處理相比較，亦較佳為不直接防銹，而採用作為防銹處理之前的階段的「前處理」來作為延長被覆處理的防銹期間的處理方法。Further, it is preferable to use "pretreatment" as a stage before the rust prevention treatment as a treatment method for extending the rust prevention period of the coating treatment as compared with the direct coating treatment.

此種前處理的具體例可較佳地列舉：藉由清洗或研磨將存在於金屬表面的氯化物或硫酸鹽等各種腐蝕因子去除的處理。Specific examples of such pretreatment include a treatment of removing various corrosion factors such as chloride or sulfate present on the metal surface by washing or grinding.

收容容器具體可列舉以下容器。Specific examples of the storage container include the following containers.

·英特格麗思（Entegris）公司製造的氟純淨（Fluoro Pure）PFA複合轉筒（接液內面：PFA樹脂襯底） ·JFE公司製造的鋼製轉筒缸（接液內面：磷酸鋅皮膜）· Fluoro Pure PFA composite drum manufactured by Entegris (liquid inner surface: PFA resin substrate) · Steel drum cylinder manufactured by JFE (liquid inner surface: phosphoric acid Zinc film)

另外，本發明中可使用的收容容器亦可列舉日本專利特開平11-021393號公報[0013]～[0030]、及日本專利特開平10-45961號公報[0012]～[0024]中記載的容器。In addition, the storage container which can be used in the present invention is also described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. container.

本發明的有機系處理液為了防止靜電帶電、或隨後發生的伴隨著靜電放電的化學藥液配管或各種部分（過濾器、O-環、管等）的故障，亦可添加導電性的化合物。導電性的化合物並無特別限制，例如可列舉甲醇。添加良並無特別限制，就維持較佳的顯影特性的觀點而言，較佳為10質量%以下，進而佳為5質量%以下。關於化學藥液配管的構件，可使用經SUS（不鏽鋼）或實施了抗靜電處理的聚乙烯、聚丙烯或氟樹脂（聚四氟乙烯、全氟烷氧基樹脂等）被覆的各種配管。關於過濾器或O-環，亦同樣地可使用實施了抗靜電處理的聚乙烯、聚丙烯或氟樹脂（聚四氟乙烯、全氟烷氧基樹脂等）。The organic-based treatment liquid of the present invention may be added with a conductive compound in order to prevent electrostatic charging or subsequent chemical chemical liquid piping or various parts (filters, O-rings, tubes, etc.) accompanying electrostatic discharge. The conductive compound is not particularly limited, and examples thereof include methanol. The addition is not particularly limited, and is preferably 10% by mass or less, and more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics. As the member of the chemical liquid chemical pipe, various pipes coated with SUS (stainless steel) or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, or the like) subjected to antistatic treatment can be used. As the filter or the O-ring, a polyethylene, a polypropylene or a fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin or the like) subjected to an antistatic treatment can also be used.

另外，通常顯影液及淋洗液是於使用後通過配管而收容於廢液罐中。此時，若使用烴系溶劑作為淋洗液，則為了防止溶解於顯影液中的抗蝕劑析出而附著於晶圓背面或配管側面等的情況，有再次使溶解抗蝕劑的溶劑於配管中通過的方法。於配管中通過的方法可列舉：於利用淋洗液的清洗後，利用溶解抗蝕劑的溶劑將基板的背面或側面等清洗而流動的方法；或不與抗蝕劑接觸而使溶解抗蝕劑的溶劑以於配管中通過的方式流動的方法。 於配管中通過的溶劑只要可溶解抗蝕劑，則並無特別限定，例如可列舉上文所述的有機溶劑，可使用丙二醇單甲醚乙酸酯（PGMEA）、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯、丙二醇單甲醚丙酸酯、丙二醇單乙醚丙酸酯、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、丙二醇單甲醚（PGME）、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、乙二醇單甲醚、乙二醇單乙醚、2-庚酮、乳酸乙酯、1-丙醇、丙酮等。其中，較佳為可使用PGMEA、PGME、環己酮。Further, usually, the developer and the eluent are stored in a waste liquid tank through a pipe after use. In this case, when a hydrocarbon-based solvent is used as the eluent, in order to prevent the resist dissolved in the developer from being deposited and adhering to the back surface of the wafer or the side surface of the pipe, the solvent for dissolving the resist is again supplied to the pipe. The method adopted in the middle. The method of passing through the piping may be a method in which the back surface or the side surface of the substrate is washed and flowed by a solvent in which the resist is dissolved after washing with the eluent, or the resist is dissolved without being in contact with the resist. A method in which a solvent of a solvent flows in a manner of passing through a pipe. The solvent to be used in the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the above-mentioned organic solvents, and propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate can be used. Propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone Wait. Among them, PGMEA, PGME, and cyclohexanone are preferably used.

可將藉由本發明的圖案形成方法所得的圖案用作遮罩，適當進行蝕刻處理及離子注入等，而製造半導體微細電路、壓印用模具結構體、光罩等。The pattern obtained by the pattern forming method of the present invention can be used as a mask, and an etching process, ion implantation, or the like can be suitably performed to produce a semiconductor fine circuit, a die structure for imprint, a photomask, and the like.

藉由所述方法所形成的圖案亦可用於定向自組裝（Directed Self-Assembly，DSA）中的導引圖案形成（例如參照ACS Nano Vol.4，No.8，4815頁-4823頁）。另外，藉由所述方法所形成的圖案例如可用作日本專利特開平3-270227及日本專利特開2013-164509號公報中揭示的間隔件製程的芯材（core）。The pattern formed by the method can also be used for guiding pattern formation in Directed Self-Assembly (DSA) (see, for example, ACS Nano Vol. 4, No. 8, pages 4815 - 4823). In addition, the pattern formed by the above-described method can be used, for example, as a core of a spacer process disclosed in Japanese Laid-Open Patent Publication No. Hei No. 3-270227 and Japanese Patent Laid-Open No. Hei No. 2013-164509.

另外，關於使用本發明的組成物來製作壓印用模具的情形的製程，例如是記載於日本專利第4109085號公報、日本專利特開2008-162101號公報及「奈米壓印的基礎與技術開發·應用展開－奈米壓印的基板技術與最新的技術展開－編輯：平井義彥（前沿（Frontier）出版）」中。In addition, the process of producing a stamping die using the composition of the present invention is described, for example, in Japanese Patent No. 4109085, Japanese Patent Laid-Open No. 2008-162101, and "Basic and Technology of Nano Imprinting". Development and application development - Nano-imprinted substrate technology and the latest technology development - edit: Hirai Yoshihiko (Frontier).

使用本發明的圖案形成方法所製造的光罩可為ArF準分子雷射等所用的光透過式遮罩，亦可為以EUV光作為光源的反射系微影中所用的光反射式遮罩。The photomask manufactured by the pattern forming method of the present invention may be a light transmissive mask used for an ArF excimer laser or the like, or may be a light reflective mask used in a reflection system lithography using EUV light as a light source.

另外，本發明亦是有關於一種電子元件的製造方法，其包括所述本發明的圖案形成方法。Further, the present invention relates to a method of manufacturing an electronic component comprising the pattern forming method of the present invention.

藉由本發明的電子元件的製造方法所製造的電子元件可較佳地搭載於電氣電子設備（家電、辦公用具（Office Appliance，OA）·媒體相關設備、光學用設備及通信設備等）。 [實施例]The electronic component manufactured by the method of manufacturing an electronic component of the present invention can be preferably mounted on an electric and electronic device (a home appliance, an office appliance (OA), a media-related device, an optical device, a communication device, or the like). [Examples]

以下，藉由實施例對本發明加以更具體說明，但本發明只要不超出其主旨，則不限定於以下的實施例。另外，只要無特別說明，則「份」、「%」為質量基準。Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, "parts" and "%" are quality standards unless otherwise specified.

＜合成例1：化合物（C-13）的合成＞ 於流通氮氣的1 L的三口燒瓶中添加0.1 L的乙酸丁酯、25 g（0.13 mol）的苯氧基乙醇，加溫至90℃。於所述燒瓶的內溫不超過110℃的溫度下滴加40.38 g（0.29 mol）的間二甲苯二異氰酸酯，進而於100℃下進行4小時熟化。其後，冷卻至60℃，添加10 mL的甲醇並攪拌15分鐘。進而，添加乙酸乙酯/甲醇/己烷＝50 mL/50 mL/200 mL的混合液並攪拌15分鐘。將析出的白色結晶過濾分離，以乙酸乙酯/甲醇/己烷＝50 mL/50 mL/200 mL的混合液來清洗該結晶，並進行減壓乾燥，由此合成目標化合物。<Synthesis Example 1: Synthesis of Compound (C-13)> 0.1 L of butyl acetate and 25 g (0.13 mol) of phenoxyethanol were added to a 1 L three-necked flask through which nitrogen gas was passed, and the mixture was heated to 90 °C. 40.38 g (0.29 mol) of m-xylene diisocyanate was added dropwise at a temperature at which the internal temperature of the flask did not exceed 110 ° C, and further aging was carried out at 100 ° C for 4 hours. Thereafter, it was cooled to 60 ° C, 10 mL of methanol was added and stirred for 15 minutes. Further, a mixture of ethyl acetate/methanol/hexane = 50 mL / 50 mL / 200 mL was added and stirred for 15 minutes. The precipitated white crystals were separated by filtration, and the crystals were washed with a mixture of ethyl acetate / methanol / hexane = 50 mL / 50 mL / 200 mL, and dried under reduced pressure to give the title compound.

與所述合成例1同樣地，其他化合物（A）亦是基於對應的異氰酸酯化合物、與對應的胺化合物或醇化合物的反應等而合成。Similarly to the above Synthesis Example 1, the other compound (A) is also synthesized based on the reaction of the corresponding isocyanate compound, the corresponding amine compound or the alcohol compound, and the like.

以下的實施例中，作為化合物（A），自上文中列舉的化合物C-1～C-36、U-1～U-16、A-1～A-22、BA-1～BA-14、I-1～I-14及CA-1～CA-10中適當選擇而使用。 關於組入至聚合物中的形態的化合物（A），使用具有下表所示的重複單元的組成比（莫耳比；自左向右依序對應）、重量平均分子量（Mw）及分散度（Mw/Mn）的化合物。In the following examples, as the compound (A), the compounds C-1 to C-36, U-1 to U-16, A-1 to A-22, BA-1 to BA-14, which are listed above, are used. I-1 to I-14 and CA-1 to CA-10 are appropriately selected and used. Regarding the compound (A) which is incorporated into the form of the polymer, the composition ratio (molar ratio; from left to right in order) having the repeating unit shown in the following table, weight average molecular weight (Mw) and dispersion degree are used. (Mw/Mn) compound.

[表2] [Table 2]

以下示出實施例及比較例中所用的樹脂、光酸產生劑、鹼性化合物、交聯劑、疏水性樹脂、界面活性劑、溶劑、顯影液及淋洗液。The resin, photoacid generator, basic compound, crosslinking agent, hydrophobic resin, surfactant, solvent, developer, and eluent used in the examples and comparative examples are shown below.

[樹脂] 將樹脂的結構、組成比（莫耳比）、重量平均分子量（Mw）、分散度（Mw/Mn）示於以下。Et表示乙基。[Resin] The structure, composition ratio (mole ratio), weight average molecular weight (Mw), and dispersity (Mw/Mn) of the resin are shown below. Et represents an ethyl group.

[化80] [化80]

[表3] [table 3]

[光酸產生劑][Photoacid generator]

[化81] [化81]

[鹼性化合物][alkaline compound]

[化82] [化82]

[交聯劑][crosslinking agent]

[化83] [化83]

[疏水性樹脂] 將疏水性樹脂的結構、組成比（莫耳比）、重量平均分子量（Mw）、分散度（Mw/Mn）示於以下。[Hydrophobic Resin] The structure, composition ratio (mole ratio), weight average molecular weight (Mw), and dispersity (Mw/Mn) of the hydrophobic resin are shown below.

[化84] [化84]

[表4] [Table 4]

[溶劑] PGMEA：丙二醇單甲醚乙酸酯（別名1-甲氧基-2-乙醯氧基丙烷） PGME：丙二醇單甲醚（別名1-甲氧基-2-丙醇） EL：乳酸乙酯 CyHx：環己酮[Solvent] PGMEA: propylene glycol monomethyl ether acetate (alias 1-methoxy-2-ethoxypropane propane) PGME: propylene glycol monomethyl ether (alias 1-methoxy-2-propanol) EL: lactic acid Ethyl ester CyHx: cyclohexanone

[實施例1-1～實施例1-30、比較例1-1～比較例1-5（電子束（EB）曝光；正型圖案形成）] （1）抗蝕劑組成物的塗液製備及塗設 使下述表1～表3中所示的成分溶解於下述表1～表3中所示的溶劑中，製備固體成分濃度4.0質量%的溶液，利用具有0.02 μm的孔徑的聚乙烯過濾器對其進行過濾，獲得實施例1-1～實施例1-30及比較例1-1～比較例1-5的抗蝕劑組成物溶液。此處，下述表1～表3的溶劑的數值是以質量%來表示相對於溶劑總量的含量。使用東京電子（Tokyo Electron）製造的旋塗機馬克（Mark）8將該些抗蝕劑組成物溶液塗佈於預先實施了六甲基二矽氮烷（HMDS）處理的6吋Si晶圓上，於100℃下於加熱板上乾燥60秒鐘，獲得膜厚150 nm的抗蝕劑膜。 此處，1吋為0.0254 m。 另外，即便將所述Si晶圓變更為鉻基板，亦可獲得與後述實施例相同的效果。[Example 1-1 to Example 1-30, Comparative Example 1-1 to Comparative Example 1-5 (Electron Beam (EB) Exposure; Positive Pattern Formation)] (1) Preparation of Coating Composition of Resist Composition And the components shown in the following Tables 1 to 3 were dissolved in the solvent shown in the following Tables 1 to 3 to prepare a solution having a solid concentration of 4.0% by mass, and a polycondensation having a pore diameter of 0.02 μm was used. This was filtered with an ethylene filter to obtain a resist composition solution of Examples 1-1 to 1-30 and Comparative Examples 1-1 to 1-5. Here, the numerical values of the solvents in the following Tables 1 to 3 are expressed by mass% with respect to the total amount of the solvent. These resist composition solutions were applied to a 6 吋 Si wafer previously treated with hexamethyldioxane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron. It was dried on a hot plate at 100 ° C for 60 seconds to obtain a resist film having a film thickness of 150 nm. Here, 1吋 is 0.0254 m. Further, even if the Si wafer is changed to a chromium substrate, the same effects as those of the embodiment described later can be obtained.

（2）EB曝光及顯影 使用電子束描畫裝置（日立製作所（股）製造的HL750，加速電壓50 KeV）對所述（1）中獲得的塗佈有抗蝕劑膜的晶圓進行圖案照射。此時，以形成1：1的線與間隙的方式進行描畫。電子束描畫後，於加熱板上於100℃下加熱60秒鐘後，浸置2.38質量%的氫氧化四甲基銨水溶液而顯影30秒鐘，以純水淋洗後，使晶圓以4000 rpm的轉速旋轉30秒鐘後，於95℃下進行60秒鐘加熱，藉此獲得線寬50 nm的1：1線與間隙圖案的抗蝕劑圖案。(2) EB exposure and development The resist film-coated wafer obtained in the above (1) was subjected to pattern irradiation using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage: 50 KeV). At this time, drawing is performed in such a manner as to form a line and a gap of 1:1. After electron beam drawing, the film was heated at 100 ° C for 60 seconds on a hot plate, and then immersed in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide for development for 30 seconds, and rinsed with pure water to make the wafer 4000. After rotating at a rotation speed of rpm for 30 seconds, heating was performed at 95 ° C for 60 seconds, thereby obtaining a resist pattern of a 1:1 line and gap pattern having a line width of 50 nm.

（3）抗蝕劑圖案的評價 使用掃描式電子顯微鏡（日立製作所（股）製造的S-9220），根據下述方法實施所得的抗蝕劑圖案的性能評價。將結果示於下述表4中。(3) Evaluation of resist pattern The performance of the obtained resist pattern was evaluated by the following method using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The results are shown in Table 4 below.

[感度] 使用掃描式電子顯微鏡（日立製作所（股）製造的S-4300）對所得的圖案的剖面形狀進行觀察。將解析線寬50 nm的1：1線與間隙的抗蝕劑圖案時的曝光量（電子束照射量）作為感度（Eop）。 其中，關於比較例1-1～比較例1-5，因無法解析線寬50 nm的1：1線與間隙圖案，故於比較例1-1中，將解析線寬67 nm的1：1線與間隙圖案時的曝光量（電子束照射量）作為感度（Eop），於比較例1-2中，將解析線寬68 nm的1：1線與間隙圖案時的曝光量（電子束照射量）作為感度（Eop），於比較例1-3～比較例1-5中，將解析線寬66 nm的1：1線與間隙圖案時的曝光量（電子束照射量）作為感度（Eop）。[Sensitivity] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount (electron beam irradiation amount) when the 1:1 line having a line width of 50 nm and the resist pattern of the gap were analyzed was taken as the sensitivity (Eop). In Comparative Example 1-1 to Comparative Example 1-5, since the 1:1 line and the gap pattern having a line width of 50 nm could not be analyzed, in Comparative Example 1-1, the analysis line width was 1:1 at 67 nm. The exposure amount (electron beam irradiation amount) at the time of the line and the gap pattern was taken as the sensitivity (Eop), and in Comparative Example 1-2, the exposure amount when the 1:1 line having a line width of 68 nm and the gap pattern were analyzed (electron beam irradiation) As the sensitivity (Eop), in Comparative Example 1-3 to Comparative Example 1-5, the exposure amount (electron beam irradiation amount) when the 1:1 line having a line width of 66 nm and the gap pattern were analyzed was used as the sensitivity (Eop). ).

[解析力] 將顯示出所述感度的曝光量（電子束照射量）下的極限解析力（線與間隙分離解析的最小線寬）作為解析力（nm）。[Resolution Force] The ultimate resolution (the minimum line width of the line and gap separation analysis) at which the exposure amount (electron beam irradiation amount) of the sensitivity is displayed is taken as the resolution (nm).

[線寬粗糙度（LWR）性能] 對於線寬50 nm的1：1線與間隙圖案的長度方向0.5 μm的任意50點，使用掃描式電子顯微鏡（日立製作所（股）製造的S-9220）來測量線寬，求出其標準偏差，算出3σ。值越小表示性能越良好。 其中，關於比較例1-1～比較例1-5，因無法解析線寬50 nm的1：1線與間隙圖案，故於比較例1-1中，對線寬67 nm的1：1線與間隙圖案求出所述距離的標準偏差，算出3σ，於比較例1-2中，對線寬68 nm的1：1線與間隙圖案求出所述距離的標準偏差，算出3σ，於比較例1-3～比較例1-5中，對線寬66 nm的1：1線與間隙圖案求出所述距離的標準偏差，算出3σ。[Line width roughness (LWR) performance] Scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.) is used for any 50 points of a line width of 50 nm and a gap of 0.5 μm in the longitudinal direction of the gap pattern. To measure the line width, find the standard deviation and calculate 3σ. A smaller value indicates better performance. In Comparative Example 1-1 to Comparative Example 1-5, since the 1:1 line and the gap pattern having a line width of 50 nm could not be resolved, in Comparative Example 1-1, the 1:1 line having a line width of 67 nm was used. The standard deviation of the distance was obtained from the gap pattern, and 3σ was calculated. In Comparative Example 1-2, the standard deviation of the distance was obtained from the 1:1 line of the line width of 68 nm and the gap pattern, and 3σ was calculated. In Examples 1-3 to 1-5, the standard deviation of the distance was obtained for a 1:1 line having a line width of 66 nm and a gap pattern, and 3σ was calculated.

[圖案剖面形狀] 使用掃描式電子顯微鏡（日立製作所（股）製造的S-9220）對線寬50 nm的1：1線與間隙的抗蝕劑圖案的剖面形狀進行觀察，進行「矩形」、「圓頂（round top）形狀（圖案剖面的上部帶弧度的形狀）」等的評價。 其中，關於比較例1-1～比較例1-5，因無法解析線寬50 nm的1：1線與間隙圖案，故於比較例1-1中，對線寬67 nm的1：1線與間隙圖案進行所述評價，於比較例1-2中，對線寬68 nm的1：1線與間隙圖案進行所述評價，於比較例1-3～比較例1-5中，對線寬66 nm的1：1線與間隙圖案進行所述評價。 圖案剖面形狀較佳為「矩形」。[Pattern section shape] A cross-sectional shape of a resist pattern having a line width of 50 nm and a 1:1 line and a gap was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), and a "rectangular shape" was observed. Evaluation of the "round top shape (the shape of the upper portion of the pattern cross section with a curvature)". In Comparative Example 1-1 to Comparative Example 1-5, since the 1:1 line and the gap pattern having a line width of 50 nm could not be resolved, in Comparative Example 1-1, the 1:1 line having a line width of 67 nm was used. The evaluation was performed with the gap pattern, and in Comparative Example 1-2, the 1:1 line and the gap pattern having a line width of 68 nm were subjected to the evaluation, and in Comparative Example 1-3 to Comparative Example 1-5, the line was aligned. The evaluation was performed with a 1:1 line and gap pattern of 66 nm wide. The cross-sectional shape of the pattern is preferably "rectangular".

[表5] 表1 [Table 5] Table 1

[表6] 表2 [Table 6] Table 2

[表7] 表3 [Table 7] Table 3

上表中，化合物H-1～化合物H-4如以下所示。另外，化合物H-4相當於具有酸交聯性基的化合物（交聯劑）。In the above table, the compounds H-1 to H-4 are as shown below. Further, the compound H-4 corresponds to a compound (crosslinking agent) having an acid crosslinkable group.

[化85] [化85]

[表8] 表4 [Table 8] Table 4

由上表得知，使用含有符合化合物（A）的化合物的抗蝕劑組成物的實施例1-1～實施例1-30與使用不含該化合物的抗蝕劑組成物的比較例1-1～比較例1-5相比較，於形成超微細的圖案時，可形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案。From the above table, Comparative Examples 1 to 1 to 30 using a resist composition containing the compound of the compound (A) and Comparative Example 1 using a resist composition containing no such compound were used. In comparison with Comparative Example 1-5, when an ultrafine pattern is formed, a pattern excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape can be formed.

[實施例2-1～實施例2-13、比較例2-1～比較例2-3（電子束（EB）曝光；負型圖案形成）] 使下述表5中所示的成分溶解於下述表5中所示的溶劑中，製備固體成分濃度2.7質量%的溶液，使用具有0.02 μm的孔徑的聚乙烯過濾器對其進行過濾，獲得實施例2-1～實施例2-13及比較例2-1～比較例2-3的抗蝕劑組成物溶液。此處，下述表5的溶劑的數值是以質量%來表示相對於溶劑總量的含量。除了使用該些抗蝕劑組成物以外，與實施例1-1同樣地實施抗蝕劑組成物的塗設、EB曝光及顯影、以及抗蝕劑圖案的評價。將結果示於下述表6中。[Example 2-1 to Example 2-13, Comparative Example 2-1 to Comparative Example 2-3 (Electron Beam (EB) Exposure; Negative Pattern Formation)] The components shown in Table 5 below were dissolved in In the solvent shown in the following Table 5, a solution having a solid concentration of 2.7% by mass was prepared, and the mixture was filtered using a polyethylene filter having a pore diameter of 0.02 μm to obtain Examples 2-1 to 2-13. The resist composition solutions of Comparative Examples 2-1 to 2-3. Here, the numerical values of the solvent of the following Table 5 are the mass % and the content with respect to the total amount of the solvent. Coating of the resist composition, EB exposure and development, and evaluation of the resist pattern were carried out in the same manner as in Example 1-1, except that the resist compositions were used. The results are shown in Table 6 below.

[表9] 表5 [Table 9] Table 5

[表10] 表6 [Table 10] Table 6

由上表得知，使用含有符合化合物（A）的化合物的抗蝕劑組成物的實施例2-1～實施例2-13與使用不含該化合物的抗蝕劑組成物的比較例2-1～比較例2-3相比較，於形成超微細的圖案時，可形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案。From the above table, Comparative Example 2 to Example 2-13 using a resist composition containing the compound of the compound (A) and Comparative Example 2 using a resist composition containing no compound In comparison with Comparative Example 2-3, when an ultrafine pattern is formed, a pattern excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape can be formed.

另外，所述實施例中，即便將顯影液、淋洗液變更為上文所述的有機溶劑來形成負型圖案，亦可獲得相同的效果。Further, in the above-described embodiment, the same effect can be obtained even if the developer and the eluent are changed to the above-described organic solvent to form a negative pattern.

[實施例3-1～實施例3-8、比較例3-1～比較例3-3（ArF準分子雷射曝光；負型圖案形成）] （1）抗蝕劑組成物的塗液製備及塗設 使下述表7中所示的成分溶解於下述表7中所示的溶劑中，製備固體成分濃度3.5質量%的溶液，使用具有0.04 μm的孔徑的聚乙烯過濾器對其進行過濾，獲得實施例3-1～實施例3-8及比較例3-1～比較例3-3的抗蝕劑組成物溶液。此處，下述表7的溶劑的數值是以質量%來表示相對於溶劑總量的含量。使用東京電子（Tokyo Electron）製造的旋塗機馬克（Mark）8將該些抗蝕劑組成物溶液塗佈於預先實施了六甲基二矽氮烷（HMDS）處理的6吋Si晶圓上，於100℃下於加熱板上乾燥60秒鐘，獲得膜厚120 nm的抗蝕劑膜。[Example 3-1 to Example 3-8, Comparative Example 3-1 to Comparative Example 3-3 (ArF excimer laser exposure; negative pattern formation)] (1) Preparation of coating liquid of resist composition And coating, the components shown in the following Table 7 were dissolved in the solvent shown in the following Table 7, and a solution having a solid concentration of 3.5% by mass was prepared, which was subjected to a polyethylene filter having a pore diameter of 0.04 μm. The solutions of the resist compositions of Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-3 were obtained by filtration. Here, the numerical values of the solvent of the following Table 7 are the mass % and the content with respect to the total amount of the solvent. These resist composition solutions were applied to a 6 吋 Si wafer previously treated with hexamethyldioxane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron. The film was dried on a hot plate at 100 ° C for 60 seconds to obtain a resist film having a film thickness of 120 nm.

（2）ArF曝光及顯影 對所述（1）中獲得的塗佈有抗蝕劑膜的晶圓使用ArF準分子雷射液浸掃描儀（ASML公司製造，XT1700i，數值孔徑（Numerical Aperture，NA）1.20，四極照明（C-Quad），外σ為0.900，內σ為0.790，Y偏向），介隔線寬50 nm的1：1線與間隙圖案的半色調遮罩進行圖案曝光。液浸液是使用超純水。其後，於90℃下進行60秒鐘加熱（曝光後烘烤（Post Exposure Bake，PEB））。繼而，利用乙酸丁酯浸置30秒鐘進行顯影，利用4-甲基-2-戊醇浸置30秒鐘進行淋洗。繼而，使晶圓以2000 rpm的轉速旋轉30秒鐘，藉此獲得線寬50 nm的1：1線與間隙圖案的抗蝕劑圖案。(2) ArF exposure and development The ArF excimer laser immersion scanner (XT1700i, Numerical Aperture, NA) was used for the resist film-coated wafer obtained in the above (1). ) 1.20, four-pole illumination (C-Quad), external σ is 0.900, internal σ is 0.790, Y-biased), and a 1:1 line with a line width of 50 nm and a halftone mask of the gap pattern are used for pattern exposure. The liquid immersion liquid is ultrapure water. Thereafter, heating was performed at 90 ° C for 60 seconds (Post Exposure Bake (PEB)). Then, development was carried out by immersing in butyl acetate for 30 seconds, and immersion was carried out by immersing in 4-methyl-2-pentanol for 30 seconds. Then, the wafer was rotated at 2000 rpm for 30 seconds, thereby obtaining a 1:1 line and gap pattern resist pattern having a line width of 50 nm.

（3）抗蝕劑圖案的評價 使用掃描式電子顯微鏡（日立製作所（股）製造的S-9220），根據下述方法來實施所得的抗蝕劑圖案的性能評價。將結果示於下述表8中。(3) Evaluation of resist pattern The performance evaluation of the obtained resist pattern was carried out by the following method using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The results are shown in Table 8 below.

[感度] 使用掃描式電子顯微鏡（日立製作所（股）製造的S-4300）對所得的圖案的剖面形狀進行觀察。將解析線寬50 nm的1：1線與間隙的抗蝕劑圖案時的曝光量作為感度（Eop）。 其中，關於比較例3-2～比較例3-3，因無法解析線寬50 nm的1：1線與間隙圖案，故於比較例3-2中，將解析線寬52 nm的1：1線與間隙圖案時的曝光量作為感度（Eop），於比較例3-3中，將解析線寬55 nm的1：1線與間隙圖案時的曝光量作為感度（Eop）。[Sensitivity] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount when the 1:1 line having a line width of 50 nm and the resist pattern of the gap were analyzed was taken as the sensitivity (Eop). In Comparative Example 3-2 to Comparative Example 3-3, since the 1:1 line and the gap pattern having a line width of 50 nm could not be analyzed, in Comparative Example 3-2, the 1:1 line width of the analysis was 52 nm. The exposure amount at the time of the line and the gap pattern was taken as the sensitivity (Eop). In Comparative Example 3-3, the exposure amount when the 1:1 line having a line width of 55 nm and the gap pattern were analyzed was used as the sensitivity (Eop).

[解析力] 將顯示出所述感度的曝光量下的極限解析力（線與間隙分離解析的最小線寬）作為解析力（nm）。[Resolution Force] The ultimate resolution (the minimum line width of the line and gap separation analysis) at the exposure amount of the sensitivity is shown as the resolution (nm).

[線寬粗糙度（LWR）性能] 對於線寬50 nm的1：1線與間隙圖案的長度方向0.5 μm的任意50點，使用掃描式電子顯微鏡（日立製作所（股）製造的S-9220）來測量線寬，求出其標準偏差，算出3σ。值越小表示性能越良好。 其中，關於比較例3-2～比較例3-3，因無法解析線寬50 nm的1：1線與間隙圖案，故於比較例3-2中，對線寬52 nm的1：1線與間隙圖案求出所述距離的標準偏差，算出3σ，於比較例3-3中，對線寬55 nm的1：1線與間隙圖案求出所述距離的標準偏差，算出3σ。[Line width roughness (LWR) performance] Scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.) is used for any 50 points of a line width of 50 nm and a gap of 0.5 μm in the longitudinal direction of the gap pattern. To measure the line width, find the standard deviation and calculate 3σ. A smaller value indicates better performance. In Comparative Example 3-2 to Comparative Example 3-3, since the 1:1 line and the gap pattern having a line width of 50 nm could not be resolved, in Comparative Example 3-2, the 1:1 line having a line width of 52 nm was used. The standard deviation of the distance was obtained from the gap pattern, and 3σ was calculated. In Comparative Example 3-3, the standard deviation of the distance was obtained from the 1:1 line having a line width of 55 nm and the gap pattern, and 3σ was calculated.

[圖案剖面形狀] 使用掃描式電子顯微鏡（日立製作所（股）製造的S-9220）對線寬50 nm的1：1線與間隙的抗蝕劑圖案的剖面形狀進行觀察，進行「矩形」、「圓頂形狀」等的評價。 其中，關於比較例3-2～比較例3-3，因無法解析線寬50 nm的1：1線與間隙圖案，故於比較例3-2中，對線寬52 nm的1：1線與間隙圖案進行所述評價，於比較例3-3中，對線寬55 nm的1：1線與間隙圖案進行所述評價。 圖案剖面形狀較佳為「矩形」。[Pattern section shape] A cross-sectional shape of a resist pattern having a line width of 50 nm and a 1:1 line and a gap was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), and a "rectangular shape" was observed. Evaluation of "dome shape" and the like. In Comparative Example 3-2 to Comparative Example 3-3, since the 1:1 line and the gap pattern having a line width of 50 nm could not be resolved, in Comparative Example 3-2, the 1:1 line having a line width of 52 nm was used. The evaluation was performed with the gap pattern, and in Comparative Example 3-3, the evaluation was performed on a 1:1 line and a gap pattern having a line width of 55 nm. The cross-sectional shape of the pattern is preferably "rectangular".

[表11] 表7 [Table 11] Table 7

[表12] 表8 [Table 12] Table 8

由上表得知，使用含有符合化合物（A）的化合物的抗蝕劑組成物的實施例3-1～實施例3-8與使用不含該化合物的抗蝕劑組成物的比較例3-1～比較例3-3相比較，於形成超微細的圖案時，可形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案。From the above table, Example 3-1 to Example 3-8 using a resist composition containing the compound according to the compound (A) and Comparative Example 3 using a resist composition containing no such compound were used. In comparison with Comparative Example 3-3, when an ultrafine pattern is formed, a pattern excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape can be formed.

[實施例4-1～實施例4-13、比較例4-1～比較例4-3（EUV曝光；負型圖案形成）] （1）抗蝕劑組成物的塗液製備及塗設 使下述表9中所示的成分溶解於下述表9中所示的溶劑中，製備固體成分濃度1.3質量%的溶液，使用具有0.03 μm的孔徑的聚乙烯過濾器對其進行過濾，獲得實施例4-1～實施例4-13及比較例4-1～比較例4-3的抗蝕劑組成物溶液。此處，下述表9的溶劑的數值是以質量%表示相對於溶劑總量的含量。使用東京電子（Tokyo Electron）製造的旋塗機馬克（Mark）8，將該些抗蝕劑組成物溶液塗佈於預先實施了六甲基二矽氮烷（HMDS）處理的6吋Si晶圓上，於100℃下於加熱板上乾燥60秒鐘，獲得膜厚40 nm的抗蝕劑膜。[Example 4-1 to Example 4-13, Comparative Example 4-1 to Comparative Example 4-3 (EUV exposure; negative pattern formation)] (1) Preparation and coating of the coating composition of the resist composition The components shown in the following Table 9 were dissolved in a solvent shown in the following Table 9, and a solution having a solid content concentration of 1.3% by mass was prepared, which was filtered using a polyethylene filter having a pore diameter of 0.03 μm to obtain an implementation. The resist composition solutions of Examples 4-1 to 4-13 and Comparative Examples 4-1 to 4-3. Here, the numerical values of the solvent of the following Table 9 are the mass % with respect to the total amount of the solvent. The resist composition solution was applied to a 6 吋 Si wafer previously treated with hexamethyldioxane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron. The film was dried on a hot plate at 100 ° C for 60 seconds to obtain a resist film having a film thickness of 40 nm.

（2）EUV曝光及顯影 對所述（1）中獲得的塗佈有抗蝕劑膜的晶圓使用EUV曝光裝置（艾科泰克（Exitech）公司製造的微曝光工具（Micro Exposure Tool），NA為0.3，四極（Quadrupole），外σ為0.68，內σ為0.36），使用曝光遮罩（線/間隙＝1/1）進行圖案曝光。曝光後，於加熱板上於100℃下進行90秒鐘加熱後，浸置乙酸異戊酯而顯影30秒鐘，使用十一烷進行淋洗後，使晶圓以4000 rpm的轉速旋轉30秒鐘後，於95℃下進行60秒鐘烘烤，藉此獲得線寬32 nm的1：1線與間隙圖案的抗蝕劑圖案。(2) EUV exposure and development The EUV exposure apparatus (Micro Exposure Tool, manufactured by Exetech), NA, was used for the wafer coated with the resist film obtained in the above (1). It is 0.3, Quadrupole, external σ is 0.68, internal σ is 0.36), and pattern exposure is performed using an exposure mask (line/gap=1/1). After the exposure, the film was heated at 100 ° C for 90 seconds on a hot plate, and then isopentyl acetate was immersed for development for 30 seconds. After rinsing with undecane, the wafer was rotated at 4000 rpm for 30 seconds. After the clock, baking was performed at 95 ° C for 60 seconds, thereby obtaining a resist pattern of a 1:1 line and gap pattern having a line width of 32 nm.

（3）抗蝕劑圖案的評價 使用掃描式電子顯微鏡（日立製作所（股）製造的S-9220），根據下述方法來實施所得的抗蝕劑圖案的性能評價。將結果示於下述表10中。(3) Evaluation of resist pattern The performance evaluation of the obtained resist pattern was carried out by the following method using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The results are shown in Table 10 below.

[感度] 使用掃描式電子顯微鏡（日立製作所（股）製造的S-4300）對所得的圖案的剖面形狀進行觀察。將解析線寬32 nm的1：1線與間隙的抗蝕劑圖案時的曝光量作為感度（Eop）。 其中，關於比較例4-1～比較例4-3，因無法解析線寬32 nm的1：1線與間隙圖案，故於比較例4-1及比較例4-3中，將解析線寬35 nm的1：1線與間隙圖案時的曝光量作為感度（Eop），於比較例4-2中，將解析線寬36 nm的1：1線與間隙圖案時的曝光量作為感度（Eop）。[Sensitivity] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount when the 1:1 line having a line width of 32 nm and the resist pattern of the gap were analyzed was taken as the sensitivity (Eop). In Comparative Example 4-1 to Comparative Example 4-3, since the 1:1 line and the gap pattern having a line width of 32 nm could not be analyzed, the analysis line width was analyzed in Comparative Example 4-1 and Comparative Example 4-3. The exposure amount at the time of the 1:1 line and the gap pattern of 35 nm was taken as the sensitivity (Eop), and in Comparative Example 4-2, the exposure amount when the 1:1 line of the line width of 36 nm and the gap pattern were analyzed was used as the sensitivity (Eop). ).

[解析力] 將顯示出所述感度的曝光量下的極限解析力（線與間隙分離解析的最小線寬）作為解析力（nm）。[Resolution Force] The ultimate resolution (the minimum line width of the line and gap separation analysis) at the exposure amount of the sensitivity is shown as the resolution (nm).

[線寬粗糙度（LWR）性能] 對於線寬32 nm的1：1線與間隙圖案的長度方向0.5 μm的任意50點，使用掃描式電子顯微鏡（日立製作所（股）製造的S-9220）來測量線寬，求出其標準偏差，算出3σ。值越小表示性能越良好。 其中，關於比較例4-1～比較例4-3，因無法解析線寬32 nm的1：1線與間隙圖案，故於比較例4-1及比較例4-3中，對線寬35 nm的1：1線與間隙圖案求出所述距離的標準偏差，算出3σ，於比較例4-2中，對線寬36 nm的1：1線與間隙圖案求出所述距離的標準偏差，算出3σ。[Line width roughness (LWR) performance] For a 1:1 line with a line width of 32 nm and an arbitrary 50 points of 0.5 μm in the longitudinal direction of the gap pattern, a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.) was used. To measure the line width, find the standard deviation and calculate 3σ. A smaller value indicates better performance. In Comparative Example 4-1 to Comparative Example 4-3, since the 1:1 line and the gap pattern having a line width of 32 nm could not be analyzed, in Comparative Example 4-1 and Comparative Example 4-3, the line width was 35. The standard deviation of the distance was obtained from the 1:1 line and gap pattern of nm, and 3σ was calculated. In Comparative Example 4-2, the standard deviation of the distance was obtained from the 1:1 line and the gap pattern of the line width of 36 nm. , calculate 3σ.

[圖案剖面形狀] 使用掃描式電子顯微鏡（日立製作所（股）製造的S-9220）對線寬32 nm的1：1線與間隙的抗蝕劑圖案的剖面形狀進行觀察，進行「矩形」、「圓頂形狀」等的評價。 其中，關於比較例4-1～比較例4-3，因無法解析線寬32 nm的1：1線與間隙圖案，故於比較例4-1及比較例4-3中，對線寬35 nm的1：1線與間隙圖案進行所述評價，於比較例4-2中，對線寬36 nm的1：1線與間隙圖案進行所述評價。 圖案剖面形狀較佳為「矩形」。[Pattern section shape] The cross-sectional shape of the resist pattern of the 1:1 line and the gap of the line width of 32 nm was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), and "rectangular" was observed. Evaluation of "dome shape" and the like. In Comparative Example 4-1 to Comparative Example 4-3, since the 1:1 line and the gap pattern having a line width of 32 nm could not be analyzed, in Comparative Example 4-1 and Comparative Example 4-3, the line width was 35. The evaluation was performed with a 1:1 line and gap pattern of nm, and in Comparative Example 4-2, the 1:1 line with a line width of 36 nm and the gap pattern were subjected to the evaluation. The cross-sectional shape of the pattern is preferably "rectangular".

[表13] 表9 [Table 13] Table 9

[表14] 表10 [Table 14] Table 10

由上表得知，使用含有符合化合物（A）的化合物的抗蝕劑組成物的實施例4-1～實施例4-13與使用不含該化合物的抗蝕劑組成物的比較例4-1～比較例4-3相比較，於形成超微細的圖案時，可形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案。From the above table, Comparative Example 4 to Example 4-13 using a resist composition containing the compound of the compound (A) and Comparative Example 4 using a resist composition containing no such compound were used. In comparison with Comparative Example 4-3, when an ultrafine pattern is formed, a pattern excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape can be formed.

於對表9的實施例的組成物進行EUV曝光時，即便將乙酸異戊酯調整為二異丁基酮與乙酸異戊酯的50質量份：50質量份的混合物，亦可獲得相同的效果。 於對表9的實施例的組成物進行EUV曝光時，即便將淋洗液設定為十一烷與二異丁基酮的40質量份：60質量份的混合物，亦可獲得相同的效果。When the composition of the examples of Table 9 was subjected to EUV exposure, the same effect was obtained even if isoamyl acetate was adjusted to a mixture of 50 parts by mass of 50 parts by mass of diisobutyl ketone and isoamyl acetate. . When the composition of the examples of Table 9 was subjected to EUV exposure, the same effect was obtained even if the eluent was set to a mixture of 40 parts by mass of:undecane and diisobutyl ketone: 60 parts by mass.

[實施例5-1～實施例5-13、比較例5-1～比較例5-2（電子束（EB）曝光；正型圖案形成）] 使下述表11中所示的成分溶解於下述表11中所示的溶劑中，製備固體成分濃度4.0質量%的溶液，使用具有0.02 μm的孔徑的聚乙烯過濾器對其進行過濾，獲得實施例5-1～實施例5-13及比較例5-1～比較例5-2的抗蝕劑組成物溶液。此處，下述表11的溶劑的數值是以質量%來表示相對於溶劑總量的含量。除了使用該些抗蝕劑組成物以外，與實施例1-1同樣地實施抗蝕劑組成物的塗設、EB曝光及顯影、以及抗蝕劑圖案的評價。將結果示於下述表12中。[Example 5-1 to Example 5-13, Comparative Example 5-1 to Comparative Example 5-2 (Electron Beam (EB) Exposure; Positive Pattern Formation)] The components shown in Table 11 below were dissolved in In the solvent shown in the following Table 11, a solution having a solid concentration of 4.0% by mass was prepared, which was filtered using a polyethylene filter having a pore diameter of 0.02 μm to obtain Examples 5-1 to 5-13. The resist composition solutions of Comparative Examples 5-1 to 5-2. Here, the numerical values of the solvent of the following Table 11 are the mass % and the content with respect to the total amount of the solvent. Coating of the resist composition, EB exposure and development, and evaluation of the resist pattern were carried out in the same manner as in Example 1-1, except that the resist compositions were used. The results are shown in Table 12 below.

[表15] 表11 [Table 15] Table 11

[表16] 表12 [Table 16] Table 12

由上表得知，使用含有符合化合物（A）的化合物的抗蝕劑組成物的實施例5-1～實施例5-13與使用不含該化合物的抗蝕劑組成物的比較例5-1～比較例5-2相比較，於形成超微細的圖案時，可形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案。From the above table, Example 5-1 to Example 5-13 using a resist composition containing the compound according to the compound (A) and Comparative Example 5 using a resist composition containing no such compound were used. In comparison with Comparative Example 5-2, when an ultrafine pattern is formed, a pattern excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape can be formed.

另外，所述實施例中，即便於上文所述的較佳範圍內變更顯影液、淋洗液，亦顯示出相同的性能。另外，即便將顯影液混合使用兩種以上、將淋洗液混合使用兩種以上，亦顯示出相同的性能。 另外，所述實施例中，即便於抗蝕劑膜上設置用以實施發明的形態中說明的頂塗層，亦可獲得相同的效果。 [產業上的可利用性]Further, in the above examples, the same performance was exhibited even if the developer and the eluent were changed within the above preferred range. Further, even if two or more kinds of developing solutions are used in combination, and two or more kinds of eluent liquids are used in combination, the same performance is exhibited. Further, in the above-described embodiment, the same effect can be obtained even if the top coat layer described in the embodiment for carrying out the invention is provided on the resist film. [Industrial availability]

根據本發明，可提供一種尤其可於形成超微細（例如線寬50 nm以下）的圖案時，形成感度、解析性、粗糙度性能及圖案剖面形狀全部優異的圖案的感光化射線或感放射線性組成物以及使用其的抗蝕劑膜、圖案形成方法及電子元件的製造方法。According to the present invention, it is possible to provide a sensitized ray or a radiation sensitizing pattern which is excellent in pattern, shape, resolution, roughness performance, and pattern cross-sectional shape, particularly when forming a pattern of ultrafine (for example, a line width of 50 nm or less). A composition, a resist film using the same, a pattern forming method, and a method of producing an electronic component.

詳細且參照特定的實施態樣對本發明進行了說明，但業者應明確，可於不偏離本發明的精神及範圍的情況下加以各種變更或修正。 本申請案是基於2015年9月30日提出申請的日本專利申請案（日本專利特願2015-194446）、及2016年2月18日提出申請的日本專利申請案（日本專利特願2016-029197），將其內容以參照的方式併入至本文中。The present invention has been described in detail with reference to the specific embodiments thereof. It is to be understood that various changes and modifications may be made without departing from the spirit and scope of the invention. The present application is based on a Japanese patent application filed on September 30, 2015 (Japanese Patent Application No. 2015-194446), and a Japanese patent application filed on February 18, 2016 (Japanese Patent Application No. 2016-029197) ), the contents of which are incorporated herein by reference.

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Claims (18)

一種感光化射線或感放射線性組成物，含有：（A）具有兩個以上的下述通式（1）所表示的結構且不具有酸交聯性基的化合物、以及藉由光化射線或放射線而產生酸的化合物，式中，X表示氧原子或硫原子，R表示氫原子或一價有機基；*表示結合鍵。A photosensitive ray or a radiation sensitive composition comprising: (A) a compound having two or more structures represented by the following formula (1) and having no acid crosslinkable group, and by actinic rays or a compound that emits radiation to produce an acid, In the formula, X represents an oxygen atom or a sulfur atom, R represents a hydrogen atom or a monovalent organic group; * represents a bond. 如申請專利範圍第1項所述的感光化射線或感放射線性組成物，其中所述通式（1）中的多個R中的至少一個為氫原子。The sensitized ray or radiation sensitive composition according to claim 1, wherein at least one of the plurality of R in the formula (1) is a hydrogen atom. 如申請專利範圍第1項所述的感光化射線或感放射線性組成物，其中所述化合物（A）具有下述通式（2）所表示的結構作為所述通式（1）所表示的結構，式中，X及R分別與所述通式（1）中的X及R為相同含意；A表示-NR'-或氧原子；R'表示氫原子或一價有機基；*表示結合鍵。The sensitized ray or the radiation sensitive composition according to the first aspect of the invention, wherein the compound (A) has a structure represented by the following formula (2) as represented by the formula (1) structure, In the formula, X and R each have the same meaning as X and R in the above formula (1); A represents -NR'- or an oxygen atom; R' represents a hydrogen atom or a monovalent organic group; * represents a bond. 如申請專利範圍第1項所述的感光化射線或感放射線性組成物，其中所述化合物（A）的分子量為450以上。The sensitized ray or radiation sensitive composition according to claim 1, wherein the compound (A) has a molecular weight of 450 or more. 如申請專利範圍第1項所述的感光化射線或感放射線性組成物，其中所述化合物（A）具有芳香族基。The actinic ray or radiation sensitive composition according to claim 1, wherein the compound (A) has an aromatic group. 如申請專利範圍第1項所述的感光化射線或感放射線性組成物，其中所述化合物（A）的共軛酸的pKa為1以下。The sensitizing ray or the radiation sensitive composition according to claim 1, wherein the conjugate acid of the compound (A) has a pKa of 1 or less. 如申請專利範圍第1項所述的感光化射線或感放射線性組成物，其中所述化合物（A）不具有極性基經藉由酸的作用發生分解而脫離的脫離基保護的結構。The actinic ray or radiation sensitive composition according to claim 1, wherein the compound (A) does not have a structure in which a polar group is deprotected by decomposition by an action of an acid. 如申請專利範圍第1項所述的感光化射線或感放射線性組成物，其中所述化合物（A）具有3個以上的所述通式（1）所表示的結構。The sensitized ray or the radiation sensitive composition according to claim 1, wherein the compound (A) has three or more structures represented by the above formula (1). 如申請專利範圍第8項所述的感光化射線或感放射線性組成物，其中所述化合物（A）為下述通式（a）所表示的化合物，L表示三價連結基，Y1 、Y2 及Y3 分別獨立地表示具有所述通式（1）所表示的結構的一價有機基。The sensitized ray or radiation sensitive composition according to claim 8, wherein the compound (A) is a compound represented by the following formula (a), L represents a trivalent linking group, and Y 1 , Y 2 and Y 3 each independently represent a monovalent organic group having a structure represented by the above formula (1). 如申請專利範圍第1項所述的感光化射線或感放射線性組成物，其中所述化合物（A）為聚合物。The actinic ray or radiation sensitive composition according to claim 1, wherein the compound (A) is a polymer. 如申請專利範圍第1項至第10項中任一項所述的感光化射線或感放射線性組成物，更含有樹脂（B），相對於所述樹脂（B）的含量，所述化合物（A）的含量為1質量%～30質量%。The photosensitive ray or the radiation sensitive composition according to any one of the items 1 to 10, further comprising a resin (B), the compound (the content of the resin (B) The content of A) is from 1% by mass to 30% by mass. 如申請專利範圍第1項至第10項中任一項所述的感光化射線或感放射線性組成物，更含有樹脂（B），所述樹脂（B）具有芳香族基。The sensitized ray or the radiation sensitive composition according to any one of the items 1 to 10, further comprising a resin (B) having an aromatic group. 如申請專利範圍第1項至第10項中任一項所述的感光化射線或感放射線性組成物，更含有交聯劑（C）。The sensitized ray or the radiation sensitive composition according to any one of the items 1 to 10, further comprising a crosslinking agent (C). 如申請專利範圍第1項至第10項中任一項所述的感光化射線或感放射線性組成物，更含有疏水性樹脂（D）。The sensitized ray or the radiation sensitive composition according to any one of the items 1 to 10, further comprising a hydrophobic resin (D). 一種抗蝕劑膜，其是藉由如申請專利範圍第1項至第10項中任一項所述的感光化射線或感放射線性組成物而形成。A resist film formed by the sensitized ray or the radiation sensitive composition according to any one of claims 1 to 10. 一種圖案形成方法，包括：對如申請專利範圍第15項所述的抗蝕劑膜照射光化射線或放射線；以及對經所述光化射線或放射線照射的膜進行顯影。A pattern forming method comprising: irradiating a resist film according to claim 15 to irradiate actinic rays or radiation; and developing a film irradiated with the actinic rays or radiation. 如申請專利範圍第16項所述的圖案形成方法，其中藉由含有有機溶劑的顯影液對經所述光化射線或放射線照射的膜進行顯影，形成負型圖案。The pattern forming method according to claim 16, wherein the film irradiated with the actinic ray or the radiation is developed by a developing solution containing an organic solvent to form a negative pattern. 一種電子元件的製造方法，包括如申請專利範圍第16項所述的圖案形成方法。A method of manufacturing an electronic component, comprising the pattern forming method according to claim 16 of the patent application.
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