TW200839450A - Pattern formation method - Google Patents

Abstract

A method of forming pattern using a chemically amplified resist composition, includes: applying a lower layer film-forming material on a support to form a lower layer film; applying a silicon based hard mask-forming material on the lower layer film to form a hardmask; applying a chemically amplified negative-type resist composition on the hardmask to form a first resist film; exposing the first resist film selectively through a first mask pattern, followed by developing so as to form a first resist pattern; etching the hardmask using the first resist pattern as a mask to form a first pattern; applying a chemically amplified positive-type silicon based resist composition on the first pattern and the lower layer film to form a second resist film; exposing the second resist film selectively through a second mask pattern, followed by developing so as to form a second resist pattern; etching the lower layer film using the first pattern and the second resist pattern as a mask to form a second pattern.

Description

200839450 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a method of forming a pattern of a pattern formed by a double pattern using a chemically-enhanced photoresist composition. This application is based on the priority of 2006-267848, which was filed on September 29, 2006 in Japan, and its content is granted. [Prior Art] A technique in which a fine pattern is formed on a substrate, and the underlayer of the pattern is formed by etching as a mask (a technique for forming a pattern) is used in the semiconductor industry to produce 1C, and the like. Attention. The fine pattern is generally formed of an organic material, for example, using a photolithography method or a nanolithography method. For example, the lithography method is formed on a support such as a substrate, and a photoresist film formed of a photoresist composition containing a substrate component such as a resin is formed by a mask having a certain pattern (a mask pattern). The photoresist film is selectively exposed to radiation such as light or an electron beam, and then subjected to development processing, and the photoresist film is formed into a pattern of a photoresist pattern having a predetermined shape. The characteristic change of the exposed portion is that the photoresist composition dissolved in the developing liquid is called a positive type, and the characteristic of the exposed portion is changed to a photoresist composition which is insoluble in the developing liquid, which is called a negative type. Next, the above-mentioned photoresist pattern is used as a mask, and a semiconductor element or the like is manufactured by a processing step of etching the substrate. In recent years, with the advancement of the lithography technique, the pattern has been miniaturized. The method of miniaturization is generally carried out by the short wavelength of the exposure light source -5-200839450. Specifically, the ultraviolet rays represented by the g-line and the i-line are used in the past, but the KrF excimer laser and the ArF excimer laser mass-produced semiconductor element are currently used, for example, the lithography method using the ArF excimer laser can be 45 nm. The resolution of the hierarchy forms a pattern. In order to further improve the resolution, F 2 excimer lasers, electron lines, EUV (extreme ultraviolet rays) and X-rays, which use shorter wavelengths than the excimer laser, have also been reviewed. The photoresist composition is required to have such characteristics as the sensitivity of the exposure light source and the resolution of the pattern of the fine-grained image. A photoresist composition that has been used in accordance with this requirement, such as a chemically-enhanced photoresist composition containing a substrate component which changes to alkali solubility under the action of an acid, and an acid generator which generates an acid under exposure (for example, Patent Document 1). For example, a substrate of a chemically-strength type resist which is generally positive type contains a resin which increases alkali solubility under the action of an acid, and therefore, when a photoresist pattern is formed, an acid generated by an acid generator is exposed to cause exposure. The part becomes alkali soluble. The lithography engraving technique of the newly proposed one is a two-drawing method in which a pattern is formed two or more times (for example, refer to Non-Patent Documents 2 to 3). Using this dual patterning method, a pattern that is more subtle than the pattern formed by the one-step method can be formed. Patent Document 1: JP-A-2003-24 1 3 8 5 Non-Patent Document 1: SPIE Annual Report (Proceeding of SPIE), Vol. 5256, pp. 98-994 (2003) Non-Patent Document 2: SPIE Annual Report (proceeding) </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> 615, </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> In the previous double-drawing method, the pattern formed on the substrate is mixed with the pattern collapse and the shape with low verticality, and there is still a problem in the pattern forming high definition and high aspect ratio. φ In view of the above, an object of the present invention is to provide a pattern forming method capable of forming a pattern of high definition and high aspect ratio on a support. Means for Solving the Problems In order to achieve the above object, the present invention is a pattern forming method for forming a pattern using a chemically-enhanced photoresist composition, which comprises the step of forming an underlayer film on a support using an underlayer film forming material, And a step of forming a hard mask on the underlying film using a sand-based hard mask forming material, and applying a chemically-reinforced negative-type photoresist composition to the hard mask to form a first light-resist film a step of selectively exposing the first photoresist film through the first mask pattern, and then forming a first photoresist pattern, and using the first photoresist pattern as a mask a step of forming a first pattern by the hard mask, and a step of applying a chemically-reinforced positive-type lanthanide photoresist composition to the first pattern and the underlying film to form a second photoresist film, and The second mask pattern selectively exposes the second photoresist film, and then forms a second photoresist pattern, and the first pattern and the second photoresist pattern are used as masks to etch the underlying film. The step of forming the second pattern. 200839450 Effect of the Invention The present invention can form a pattern of high definition and high aspect ratio on a support. BEST MODE FOR CARRYING OUT THE INVENTION The materials used in the present invention will be described first. "Chemically reinforced positive lanthanide photoresist composition" The chemically reinforced positive lanthanide resist composition of the present invention is not particularly limited, and generally uses a component containing an acid to increase alkali solubility, and Under the exposure, it will produce the acid generator component. Further, it is preferable to form a pattern of the underlayer film to be resistant to general-purpose oxygen plasma etching. Among them, a resin component (A) (hereinafter referred to as (A) component) which increases alkali solubility under an acid action, and an acid generator component (B) which generates an acid under exposure (hereinafter referred to as (B) In the resist composition of the component), the resin component (A) contains a constituent unit (al) represented by the following general formula (al), and a constituent unit (a2) represented by the following general formula (a2) The photoresist composition of the resin (A 1 ). [1] H R1 I | (Si〇3/2*&quot;) - · · (a 1 ) ~Sl〇3/2&quot;) - - · (a 2) [In the formula (a2), R1 is the lower The acid-decomposable group represented by the general formula (I) is described. -8- 200839450 〔化2〕 ——(R2>“L——(R3卜2 r &quot; [In the formula (I), 'R2 to R3 are each independently a linking group; L 1 to 1 〇 is linear or Branched chain base, carbon number 2 to 20 or branched fluoroalkyl, substituted or unsubstituted aryl, substituted cyclic alkyl and substituted or unsubstituted alkylene a group in the group; Z is an acid dissociable group; g is ruthenium or 1; 11 is ruthenium or 1] &lt; The photoresist composition is alkali-insoluble before exposure, but the B) component is exposed to acid, When the acid acts on the component (a), the solubility is increased. Therefore, when the photoresist pattern is formed, selective exposure of the photoresist film obtained by using the photoresist group can be used to convert the exposed portion into a base. The change can retain the original test insolubility, so the photoresist pattern can be formed. <(A) component> [Resin (A1)] The constituent unit (al) can impart transparency to the resin (A1) and can increase the wavelength below 200 nm. The transparency of the light makes it possible to mention the sensitivity and resolution of the composition. In the resin (A1), the constituent unit (ai) is a constituent resin (all the constituent units are combined). The ratio of the measurement is preferably from 20 to 90 mol% from 30 to 80 mol%, particularly preferably from 40 to 60 mol%. When the ratio of the constituent a) is 20 mol% or more, the ratio can be increased to 200 nm. For the carbon number linear or no choice, it is possible to select (after adding a base to dissolve the image, especially the light resistance A1), and better unit (the following wave 200839450 long light transparency. 90 When the molar percentage is 5% or less, a good balance can be obtained with other constituent units such as the constituent unit (a2). The constituent unit (a2) has the acid-decomposable group R1 represented by the above general formula (I). R1 can be used by exposure (B) The acid produced by the component cuts the bond between Z in the above group and the atom bonded to Z, and is decomposed into Z and other moieties. In the formula (I), R2 to R3 are each independently a linking group. It is not particularly limited, and is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl group and an ethyl group. L is a linear or branched alkyl group, and is straight. a chain or branched fluoroalkyl group, an aryl group, a cyclic alkyl group or an alkylene group. The linear or branched alkyl group of L is preferably a carbon number of 1. 1 0, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group and an ethyl group. L is a linear or branched fluorine having 2 to 20 carbon atoms. The alkylene group is a group in which a part or the whole of a hydrogen atom having a carbon number of 2 to 20 in a straight bond or a branched chain is substituted by fluorine. The extended aryl group of L may be an unsubstituted extended aryl group, or may constitute The ring of the above-mentioned unsubstituted aryl group is substituted with an aryl group in which a part or the whole of a hydrogen atom bonded to a carbon atom is substituted by a substituent. The unsubstituted aryl group is, for example, removed by benzene, naphthalene or anthracene. The base of the hydrogen atom. The carbon number of the unsubstituted extended aryl group is preferably from 6 to 14. Substituents such as alkyl groups, alkoxy groups, aryl groups and the like are substituted for the exoaryl group. The carbon number of these substituents is preferably from 1 to 10%. The cyclic alkyl group of L may be an unsubstituted cyclic alkyl group, or the ring constituting the cyclic alkyl group of the former -10- 200839450 may be substituted with a substituent or a part of all hydrogen atoms bonded to a carbon atom. Substituting an alkyl group. The unsubstituted cyclic alkyl group is preferably a cyclic alkyl group having a carbon number of 4 to 12, for example, a group of two hydrogen atoms removed by a monocyclic alkane such as cyclopentane or cyclohexane; , polybutane, nortzene, methylzolidine, ethyldestenane, methylnorzene, ethylnorzene, isobornane, tricyclodecane, tetracyclododecane, etc. The alkane removes the base of two hydrogen atoms and the like. The substituent in the substituted cycloalkyl group is, for example, the substituent of the above substituted aryl group. The alkylene group of L is a group obtained by bonding two alkyl groups to an aromatic ring such as benzene, naphthalene or anthracene. The carbon number of the aromatic ring is preferably from 6 to 14. The above-mentioned alkylene group, for example, is the same as the above-mentioned alkyl group of R2 to R3, and the two alkylene groups may be the same or different. The unsubstituted alkylene group is a group represented by the following formula (AL-1). a substituted alkylene group such as a group in which an aromatic ring constituting the above-mentioned unsubstituted alkylene group is substituted with a substituent by a part or all of a hydrogen atom bonded to a carbon atom, and the above substituent is, for example, the same as the above-mentioned substitution A substituent for the aryl group. 〔化3〕

L is preferably a methyl group, an ethyl group, a cycloalkyl group, an alkylene group, more preferably an unsubstituted cyclic alkyl group, and particularly preferably a base for removing two hydrogen atoms from a nordane. Alkenyl). Z is an acid dissociable group. Further, the "acid dissociable group" of the present invention means that it will be exposed by exposure ( -11 -

200839450 B) The basis of the action of the acid produced by the component. A photoresist composition containing a resin having a constituent unit (a2) of the acid dissociable group and a component (B), which can be dissociated by an acid generated by (B) under exposure, thereby increasing the resin (A1). The acid-dissociable group of the alkali-soluble Z may be a group which is dissociated from the polymer main chain of the resin (A1) by the action of the component (B), and is not specifically prepared. For example, an acid dissociable dissolution inhibiting base which has been previously proposed as a substrate of a positive resist composition can be used. In addition, the "acid dissociable dissolution inhibiting group" is an acid-dissociable group in which the entire compound is alkali-insoluble in alkali dissolution before dissociation, and the dissociated core is changed to an alkali-soluble acid. The specific example of the acid-dissociable group is not particularly limited, and may be, for example, a group represented by the formula -COOR7, a group represented by the formula -OCOOR8, a group represented by OR9 or the like. In the above formula, each of R7 to R9 is an organic group which has an acid dissociation but a group represented by -OCOOR8 and a group represented by -OR9. The organic group means a group having at least a carbon atom and other atoms on the same. R7 is, for example, a chain 3 alkyl group; a cyclic fluorene group having a carbon atom of 3 on the ring; a 2-trialkylethyl group. The chain tertiary alkyl group is preferably a carbon number of 4 to 1 Torr, more preferably a 4 to a bond type 3 stage group, more specifically such as 'tert-butyl, tert-pentyl and the like. The "aliphatic cyclic group" of the present invention means that it does not have an aromatic monocyclic group or a polycyclic group. A fat containing 3 carbon atoms in the ring (A1 component. The other components of the acid Μ吏 before: can be expressed as a general formula - f: the action species is i ring family 8. The I-type ring -12 -

The base of the 200839450 is preferably a carbon number of 4 to 14 ‘ more preferably 5 to 1 〇. More specifically, the aforementioned lipid group is, for example, adamantyl, norptyl, isobornyl, 2-methyl(tri)yl, 2-ethyl-2-adamantyl, 2-methyl-2-isobornyl, 2-]gangyl , 2-propyl-2-isobornyl, 2-methyl-2-tetracyclodecenyl-2-dihydrodicyclopentadienyl-cyclohexyl, 1-methyl-bucyclopentyl-1 -cyclopentyl, 1-methyl-1-cyclohexyl, 1-ethyl-1-cyclohexyl 2-trialkylethyl, 2-trimethyldecylethyl, 2-alkylethyl, etc. . R8 is the same as the above R7. R9 is, for example, 'tetrahydro D-pyridyl group, 1-to-Golden oxymethyl group, 1-methyl group, three-yard phenyl group, and the like, and the above-mentioned three-yard alkyl group such as an alkyl group. The above Z is further preferably a group represented by the general formula -C0 0R7, wherein R7 is a chain of a tertiary alkyl group, and most preferably R7 is a tert_butyl tert-butoxycarbonyl group. g may be 〇 or 丨, preferably 0. h may be 〇 or 丨' preferably 0. The R1 of the present invention is particularly preferably the following general formula (1-1): jj [Chemical 4] Aromatic ring type _-2-Golden "yl-2-yl, 2-methyl, 1-ethyl and the like. Triethylsulfonium cyclohexyloxytrimethylhydrazine is more preferably a base thereof.

Wherein R' is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z' is a chain -13-200839450 3rd grade base. The constituent unit (a2) may be used alone or in combination of two or more. In the resin (A1), the ratio of the constituent unit (a2) to the total constituent unit of the constituent resin (A1) is preferably from 1 〇 to 8 〇 mol%, more preferably from 20 to 60 mol%, particularly preferably 30 to 50% by mole. When the ratio of the constituent unit (a2) is 1 〇 mol% or more, when used as a photoresist composition, the pattern can be obtained as an upper limit 値 or less, and a good balance can be obtained with other constituent units. Further, in the resin (A1) of the present invention, the ratio of the total constituent units (al) and (a2) to the total constituent units of the constituent resin (a1) is preferably 50 mol% or more, more preferably 7〇. More than % of Mo, it can be 1% Mo. The resin (A 1 ) may contain other constituent units other than the above constituent units (al ) and (a2 ) within the range which does not impair the effects of the present invention. The constituent units other than the constituent units (a 1 ) and (a2) are constituent units (a3) which are not included in the following formula (a3). R15 -f-Si〇3/2^—(a3) In the formula (a3), R15 is an alkyl group having 1 to 20 carbon atoms, or an aryl group. The alkyl group of R15 may be any of a linear chain, a branched chain or a cyclic group, preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 5 to 12 carbon atoms. Specifically, for example, a methyl group, an ethyl group, an η-propyl group, an isopropyl group, an η-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group or the like. -14- 200839450 The aryl group of R15 is, for example, a phenyl group, a naphthyl group or the like, which may have a substituent such as an alkyl group. The resin (A 1 ) can be produced by a known method for producing a hydrogen-containing sesquioxanes resin. For example, first, a hydrolyzed condensation of a trihalogenated decane such as trichlorosilane (HSiCl3) is carried out to synthesize a hydrogen-containing sulfonium sesquioxane resin (hereinafter referred to as a precursor resin) containing a constituent unit (a i ). The precursor resin thus obtained contains a constituent unit (a 1 ). Further, in the synthesis method, in general, in addition to the constituent unit (al), most of the constituents (Si(OH) 〇3/2), (HSi(OH) 〇2/2), (Si04/2) and the like are formed. unit. Further, the synthesized precursor resin generally contains a polymer having various network structures such as a ladder type, a random type, and a cage type. Next, a part of hydrogen atoms (e.g., hydrogen atoms constituting the unit (al)) contained in the precursor resin is substituted by R', and R1 is introduced into the precursor resin. Thereby, the partial constituent unit (al) can be made into the constituent unit (a2), and the resin (A1) constituting the unit (al) and the constituent unit (a2) can be contained. Further, when the precursor resin contains a constituent unit such as (Si(0H)03/2) or (HSi(0H)02/2), a constituent unit in which the hydrogen atom is replaced by R1 in the constituent unit may be formed. R1 may, for example, be a compound corresponding to R1 to be introduced in the presence of a catalyst (for example, = ring [2, 2, 1] "hept-5-ene-2-tert-butyl carboxylate, etc."), The precursor resin is introduced by reaction. At this time, the amount of the compound corresponding to the compound to be introduced, the reaction conditions, and the like are adjusted, and the ratio of the constituent units (a 1 ), (a2 ), and the like in the resin (A1) can be adjusted. -15- 200839450 Resin (A1) is preferably, the constituent unit (al): constituent unit ( ) = 90 : 10 to 10 : 90 (mole ratio), more preferably 80: 20 to 30 7 〇 'extra good 70: 3〇 to 3 5: 65, preferably 65: 35 to 40: mass average molecular weight (Mw) of the resin (A1) (from polystyrene conversion by gel permeation chromatography (hereinafter referred to as GPC), The following phase is not particularly limited, and is preferably 1,500 to 20,000, more preferably 6000 6 500. When the upper limit is less than 値, it has good solubility to an organic solvent, and when it is at least the lower limit, the shape of the formed photoresist pattern can be improved. Further, Mw/Mn is not particularly limited, and is preferably from ι·〇 to 6.0, and further from 1·0 to 2.5. The resin (A1) may be used alone or in combination of two or more. In the component (A), the excellent effect of forming a pattern of high precision and high aspect ratio on the support is obtained, and the ratio of the total mass of the resin (A1) or (A) is preferably 50% by mass or more. More preferably, the mass of 70 or more may be 100% by mass. The component (A) of the present invention contains the resin component (A2) other than the above resin (A1) (hereinafter referred to as (A2) component) within the range which does not impair the effects of the present invention. The (A2) component is not particularly limited, and can be used as a light source for a photoresist pattern, and is generally selected from most resins which are generally used as a basic resin for chemically reinforced photoresist compositions. <(B)Ingredient> (B) The composition is not particularly limited, and any of the above-mentioned a2 60 infiltration to the finest part can be used as the acid for the chemically-enhanced photoresist. The agent used. So far, such (B) components such as iodine, barium salts and the like are key acid generators, sulfonate acid generators, dialkyl or bisarylsulfonium diazomethanes, poly( Polysulfonium) diazomethane acid generator such as diazomethane, nitrobenzyl sulfonate acid generator, iminosulfonate acid generator, diphosic acid generator, etc. Things. The key salt acid generator is, for example, an acid generator represented by the following general formula (b-0). [6]

R51so3- • · · · (b — 0) [wherein R51 is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group; R52 is a hydrogen atom, a hydroxyl group, a halogen An atomic, linear or branched alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group; R53 is an aryl group which may have a substituent; U" is an integer from 1 to 3 In the general formula (b-Ο), R51 is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group. The above linear or branched alkyl group is preferably a carbon number. 1 to 10, more preferably a carbon number of 1 to 8, most preferably a carbon number of 1 to 4. The above cyclic alkyl group preferably has a carbon number of 4 to 12, more preferably a carbon number of 5 to 10, most preferably a carbon number. 6 to 10. The above fluorinated alkyl group preferably has a carbon number of 1 to 10, more preferably a carbon number of 1 to 8 -17 to 200839450, most preferably a carbon number of 1 to 4. Further, the fluorination ratio of the aforementioned fluorinated alkyl group (ratio of the number of substituted fluorine atoms to the number of all hydrogen atoms in the alkyl group) is preferably from 10 to 100%, more preferably from 50 to 100%, and particularly preferably all hydrogen atoms are substituted by fluorine atoms to enhance acid strength R51 is preferably a linear alkyl group or a fluorinated alkyl group. R52 is hydrogen. a hydroxyl group, a halogen atom, a linear or branched alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group. The halogen atom of R52 is, for example, a fluorine atom, a bromine atom or a chlorine atom. The atom, the iodine atom or the like is preferably a fluorine atom. The alkyl group of R52 is linear or branched, and its carbon number is preferably from 1 to 5, more preferably from 1 to 4, particularly preferably from 1 to 3. The halogenated alkyl group is a group in which a part or all of hydrogen atoms in the alkyl group are substituted by a halogen atom, and the alkyl group is, for example, the same as the "alkyl group" of the above R52. The halogen atom is replaced by the halogen atom as described above. The halogenated alkyl group is preferably such that 50 to 100% of the total number of hydrogen atoms is substituted by a halogen atom, and more preferably all of them are substituted. The alkoxy group of R52 is linear or branched, and its carbon number is preferably from 1 to 5, more preferably from 1 to 4, particularly preferably from 1 to 3. Among them, R52 is preferably a hydrogen atom. R53 is an aryl group which may have a substituent, and the structure of the basic ring (parent ring) other than the substituent is, for example, a naphthyl group, a phenyl group, a fluorenyl group or the like. The phenyl group is preferred from the viewpoints of the effects of the present invention and the absorption of an exposure light source such as an ArF excimer laser. The substituent is, for example, a hydroxyl group or a lower alkyl group (linear or branched, having a carbon number of -18 to 200839450 of 5 or less, particularly preferably a methyl group). “Low grade” in this specification and the scope of patent application refers to carbon numbers 1 to 5. The aryl group of R53 is more preferably a substance having no substituent. u" is an integer of 1 to 3, preferably 2 or 3, particularly preferably 3. The preferred product of the acid generator represented by the general formula (b-Ο) is as follows.

Further, other iron salt-based acid generators other than the above are compounds represented by the following general formula (b-1) or (b-2). -19- 200839450 〔化8】 R2—S+ R4MS〇3^ • · (fa-1)

(b_2) [wherein R1 to R3", R5" to R6" are each independently an aryl group or an alkyl group; and R4" is a linear, branched or cyclic alkyl group or a fluorinated alkyl group; Ri" to R3' At least one of 'in the aryl group, at least one of R5" to r6" is an aryl group. In the formula (b-1), 1^'' to R3" are each independently an aryl group or an alkyl group. At least one of Ri" to R3" is an aryl group. Preferably, in R3", two or more are aryl groups, and most preferably R1" to R3" are all aryl groups. The aryl group of R1'' to R3'' is not particularly limited, and for example, a carbon number of 6 to 20 The aryl group, and all or a part of the hydrogen atoms in the aforementioned aryl group may be substituted by an alkyl group, an alkoxy group, a halogen atom or the like, or may be unsubstituted. In terms of inexpensive synthesis, the aryl group is preferably a carbon number of 6 to 10 Specifically, for example, a phenyl group or a naphthyl group. The alkyl group of the above-mentioned hydrogen atom which may be substituted with an aryl group is preferably a fluorenyl group having a carbon number of i to 5, preferably a methyl group, an ethyl group, a propyl group, or an n-butyl group. And a tert-butyl group. The alkoxy group of the above-mentioned hydrogen atom which may be substituted with an aryl group is preferably an alkoxy group having a carbon number of i to 5, most preferably a methoxy group and an ethoxy group. The halogen atom is preferably a fluorine atom. The alkyl group of R1 to R3" is not particularly limited, and may be, for example, a linear, branched or cyclic alkyl group having a carbon number of 1 to i. In terms of excellent resolution, it is preferred to have a carbon number of 1 to 5. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an η-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a decyl group, a fluorenyl group and the like. In terms of excellent resolution and cheap synthesis, it is preferable to use methyl -20 - 200839450. Wherein R1 to R3" are each preferably a phenyl group or a naphthyl group. R4' is a linear, branched or cyclic alkyl group or a fluorinated alkyl group. The above linear alkyl group preferably has a carbon number of 丨 to 10, more Preferably, the carbon number is from 1 to 8, most preferably from 1 to 4. The cyclic fluorenyl group may be a cyclic group as defined by the above R1", preferably a carbon number of 4 to 15, more preferably a carbon number of 4 to 10, the best carbon number is 6 to 10. The fluorinated alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of lg 8 , most preferably a carbon number of 1 to 4. Further, the fluorination ratio of the fluorinated alkyl group (the ratio of the fluorine atom in the alkyl group) is preferably from 10 to 100%, more preferably from 50 to 100%, and particularly preferably the strength of the acid can be enhanced. A substance in which a hydrogen atom is replaced by a fluorine atom. R4'' is preferably a linear or cyclic alkyl group or a fluorinated alkyl group. In the formula (b-2), R5" to R6" are each independently an aryl group or an alkyl group. At least one of R5" to R6" is an aryl group. R5'' to R6" are preferably all aryl groups. The aryl group of R5'' to R6" is, for example, the aryl group of R1'' to R3". The alkyl group of R5'' to R6'' An alkyl group of R1'' to R3'' wherein R5" to R6'' are preferably all phenyl groups. R4" in the formula (b-2) is, for example, the same as the above (b-Ι) R4". Specific examples of the key salt acid generators represented by the formulae (b-1) and (b-2), for example, diphenyliodide trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert) -butylphenyl)iron iodide trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, three (4-methylphenyl)phosphonium trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutyrate sulfonate, dimethyl(4-pyridyl)-21 - 200839450 Trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate, triphenylmethanesulfonate of monophenyldimethylhydrazine, heptafluoropropane sulfonate or nonafluorobutyrate sulfonate, diphenyl Trimethyl sulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate, (4-methylphenyl)diphenylphosphonium trifluoromethanesulfonate, heptafluoropropane sulfonic acid Salt or nonafluorobutane sulfonate, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate, tris(4-tert- Butyl)phenylphosphonium trifluoromethane Acid salt, heptafluoropropane sulfonate or nonafluorobutane sulfonate, diphenyl(1-(4-methoxy)naphthyl)phosphonium trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane a sulfonate, a trifluoromethanesulfonate of bis(1-naphthyl)phenylhydrazine, heptafluoropropanesulfonate or nonafluorobutanesulfonate. Further, a key salt in which the anion portion of the iron salt is replaced by a methanesulfonate, a propane sulfonate, an η-butane sulfonate or an η-octane sulfonate can be used. In the above general formula (b-1) or (b-2), the anion moiety is a key salt acid generator (cationic moiety) substituted with an anion moiety represented by the following general formula (b-3) or (b_4). Same as (b-Ι) or (b-2)). 〔9

[wherein, X" is an alkyl group having 2 to 6 carbon atoms to be substituted with a fluorine atom; Y", Z" are each independently a carbon number of 1 at least one hydrogen atom substituted by a fluorine atom. Alkyl] -22- 200839450 X" is a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the alkyl group has a carbon number of 2 to 6, preferably a carbon number. 3 to 5, the best is carbon number 3. Y", Z" are each independently a straight-chain or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the carbon number of the alkyl group is from 1 to 10, preferably from carbon number 1 to 7. More preferably, the carbon number is 1 to 3. The carbon number of the alkyl group of X" or the carbon number of the alkyl group of Y" and Z" can give a good φ solubility to a photoresist solvent, and the smaller of the above carbon number ranges is preferable. Further, in the alkyl group of X" or the alkyl group of Y" or Z", when the number of hydrogen atoms substituted by a fluorine atom is large, the acid strength can be enhanced, and the high-energy light and electron line below 200 nm can be enhanced. The transparency is better. The fluorine atom ratio in the alkylene group or the alkyl group, that is, the fluorination rate is preferably from 70 to 100%, more preferably from 90 to 100%, most preferably the perfluoroalkylene group in which all hydrogen atoms are replaced by fluorine atoms. Base or perfluoroalkyl. Further, φ is preferably a key salt acid generator (hereinafter referred to as a component (b-5)) having an anion moiety represented by the following general formula (b-5). In recent years, as the photoresist pattern is gradually miniaturized, high resolution and high lithography etching characteristics are required. Among them, in order to increase the step limit at the time of pattern formation, it is required to increase the exposure limit (EL limit). The EL limit refers to the exposure amount that can form a resist pattern for a size within a certain range when the exposure amount is changed for exposure, that is, a range of exposure amount that can be faithful to the pattern of the photoresist pattern. It is better to have a larger EL limit. -23- 200839450 When the present invention uses a key salt acid generator having an anion moiety represented by the following general formula (b-5), the EL limit can be raised without deterioration of the photoresist pattern (Chemical 10 /S〇2- U,f —S〇2—v′_ (b-5) so2—w·· [In the formula (b-5), U′′, V′′, W” are each independently, at least one hydrogen atom is bonded to a fluorine atom. Substituting an alkyl group having a carbon number of 1 to 1 Torr. [In the formula (b-5), U", V", and W" are each independently a carbon number of 1 to 1 at least one hydrogen atom substituted by a fluorine atom. Alkyl. The above alkyl group is preferably linear or branched. The carbon number of the above alkyl group is preferably from 1 to 7, more preferably from 1 to 3. The carbon number of the alkyl group of U", V", and W" can give a good solubility to a photoresist solvent, and the like, and it is preferably a small number within the above carbon number range. Further, U", V", When the number of hydrogen atoms substituted by a fluorine atom in the alkyl group of W" is large, the acid strength can be enhanced, and the high-energy light of 200 nm or less and the transparency of the electron beam can be improved. The fluorine atom ratio in the above alkyl group, i.e., the fluorination rate, is preferably from 7 Torr to 100%, more preferably from 90 to 100%, most preferably 100%. That is, the alkyl group of U", V", W" is preferably a perfluoroalkyl group in which all hydrogen atoms are replaced by a fluorine atom. The cation portion of the component (b-5) is not particularly limited, and can be proposed as described so far. The cation portion of the acid generator. The cation portion of the component (b-5) is particularly preferably a cation portion of the sulfonate-based acid generator represented by the above general formula (b-Ι) -24-200839450 or (b-2). That is, the cation portion represented by the following general formula (b'-l) or formula (b'-2).

(br -2) In the formula (b'-l), R1'' to R3'' are each independently an aryl group or an alkyl group, and at least one is an aryl group. In the formula (b'_2), R5" to R6'' are each independently an aryl group or an alkyl group, and at least one is an aryl group. In the formula (b'-l), R1" to R3", a formula (b) R5'' to R6" in , -2) are the same as R1" to R3" in the above formula (b-1), 115" to R6 in the formula (b-2), and the formula (b'-l) Or specific examples of the cationic moiety represented by (b'-2), for example, diphenyl iodide ion, bis(4-tert-butylphenyl) iodide ion, triphenylphosphonium ion, tris(4-methylbenzene)铳) 铳 ion, dimethyl (4-hydroxynaphthyl) phosphonium ion, monophenyl dimethyl hydrazine ion, diphenyl monomethyl hydrazine ion, (4-methylphenyl) diphenyl sulfonium ion, (4-methoxyphenyl)diphenylphosphonium ion, tris(4-tert-butyl)phenylphosphonium ion, diphenyl(1-(4-methoxy)naphthyl)phosphonium ion, diphenyl a mono-naphthyl anthracene ion, a bis(1-naphthyl)phenylphosphonium ion, etc. The (b-5) component is particularly preferably a key salt represented by the following general formula (b_5-l) ° -25 - 200839450 12

So2-cf3 ” C^~S〇2—CF; s〇2—cf3 (b-5 [in formula (b-5-l)] R61 to R63 are each independently a yard; a, seven, and 〇 are 0 to In the formula (b-5-i), R61 to r63 are each independently an alkyl group, and the alkyl group may be the same as the alkyl group which may substitute a hydrogen atom in the aryl group of R1" to r3". Preferably, the methyl group and/or tert-butyl group is preferably tert-butyl. a is an integer of 0 to 2, preferably 〇 or 1, particularly preferably 1. % b is an integer from 0 to 2, Preferably, it is 0 or 1, and particularly preferably 1. c is an integer of 〇 to 2, preferably 0 or 1, and particularly preferably 1. In the present specification, an oxime sulfonate-based acid generator means at least 1 The compound ψ of the group represented by the following general formula (1) has a property of generating an acid when irradiated with radiation. Most of the sulfonate-based acid generators use a chemically-reinforced photoresist composition. Therefore, it can be arbitrarily selected 0 -26- 200839450 [Chemical 1 3] -C=N-Ο-S〇2-R31 R32 ...· · (b-1) (In the formula (Bl), R31 and R32 are each independently Organic group) The organic group of R31 and R32 is a group containing a carbon atom and may contain a carbon atom. An external atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.), etc.). The organic group of R31 is preferably a linear, branched or cyclic alkyl group or an aryl group. The alkyl group or the aryl group may have a substituent. The above substituent is not particularly limited, and may be, for example, a cut-off atom, a linear, branched or cyclic group having 1 to 6 carbon atoms, wherein "having a substituent" It is meant that some or all of the hydrogen atoms of the alkyl or aryl group are replaced by a substituent. The alkyl group preferably has a carbon number of from 1 to 20, more preferably from 1 to 10 carbon atoms, still more preferably from 1 to 8 carbon atoms. Particularly preferred is a carbon number of 1 to 6, preferably a carbon number of 1 to 4. The alkyl group is preferably an alkyl group which is partially or completely halogenated (hereinafter referred to as a halogenated alkyl group), and a partially halogenated alkyl group. An alkyl group in which a part of a hydrogen atom is substituted by a halogen atom, an alkyl group which is completely halogenated, an alkyl group in which all hydrogen atoms are replaced by a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Particularly preferred is a fluorine atom. That is, the halogenated alkyl group is preferably a fluorinated alkyl group. The aryl group is preferably a carbon number of 4 to 20, more preferably a carbon number of 4 to 10, most preferably Preferably, the carbon number is from 6 to 10. The aryl group is preferably an aryl group which is partially or completely halogenated. The partially halogenated aryl group means an aryl group in which a part of hydrogen atoms are replaced by a halogen atom, and an aryl group which is completely halogenated. An aryl group in which all hydrogen atoms are replaced by a halogen atom. -27- 200839450 R31 is particularly preferably an alkyl group having 1 to 4 carbon atoms which does not have a substituent, or a fluorinated alkyl group having 1 to 4 carbon atoms. The organic group is preferably a linear, branched or cyclic alkyl group, an aryl group or a cyano group. The alkyl group and the aryl group of R32 may be the same as the alkyl group or the aryl group exemplified in the above R31. R32 is particularly preferred as cyanide. A group, an alkyl group having 1 to 8 carbon atoms which does not have a substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms. The oxime sulfonate acid generator is more preferably a compound represented by the following general formula (B-2) or (B-3). [Chemical Formula 1] R34—C=N—Ο-S02-&quot;: R35 R33 · · · · (B-2) [In the formula (B-2), R33 is a cyano group, an alkyl group having no substituent Or a halogenated compound; R34 is an aryl group; and R35 is a hospital group or a halogenated alkyl group having no substituent. [Chem. 15] R37-eC=N-Ο-S02-R38 R36 P, (B-3) [In the formula (B-3), R36 is a cyano group, an alkyl group having no substituent or a halogenated fluorenyl group. , R is a 2 or a trivalent aromatic hydrocarbon group; r38 is a fluorenyl group or a halogenated group having no substituent; p " is 2 or 3]. In the above general formula (B-2), R33 does not have The alkyl group of the substituent or the -28-200839450 alkyl halide is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, most preferably a carbon number of 1 to 6. R33 is preferably a halogenated alkyl group, more preferably The fluorinated alkyl group is preferably a fluorinated alkyl group of R33, wherein more than 50% of the hydrogen atoms of the alkyl group are fluorinated, more preferably 70% or more, and particularly preferably 90% or more. For example, a group in which one hydrogen atom is removed from a ring of an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group or a phenanthryl group, or The heterocyclic group in which a part of carbon atoms for the ring of the substituent is substituted by a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, etc., wherein a sulfhydryl group is preferred. The square group of R may have a number of carbon atoms of 1 to 10 Substituents such as halogenated hospital bases, hospitaloxy groups, and the like. The alkyl group or the halogenated alkyl group of the substituent is preferably a carbon number of 1 to 8, more preferably a carbon number of 丨 to 4. Further, the above-mentioned halogenated alkyl group is preferably a fluorinated alkyl group. Or a halogenated alkyl group preferably has a carbon number of 1 to 10', more preferably a carbon number of 1 to 8, most preferably 1 to 6. R35 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group, and most preferably a partially Fluorinated alkyl group. Preferably, the fluorinated alkyl group of R35 is such that more than 50% of the hydrogen atoms of the alkyl group are fluorinated, more preferably 70% or more, and particularly more than 90% are fluorinated to increase the acid produced. Preferably, the fluorinated alkyl group is 100% hydrogen atom completely substituted by fluorine. In the above general formula (B-3), the unsubstituted alkyl group or the halogenated alkyl group of R36 is the same as the above R33. An alkyl group having no substituent or a halogenated alkane-29- 200839450. A 2 or a trivalent aromatic hydrocarbon group of R37, for example, a group having 1 or 2 hydrogen atoms removed from the aryl group of the above R34. The alkyl group having a substituent or the halogenated alkyl group is, for example, an alkyl group having no substituent or a halogenated alkyl group as the above R3 5 . P ' is preferably 2. Specific examples of the sulfonate-based acid generator are, for example, a-(p-toluenesulfonyloxyimino)-benzyl cyanide, a-(p-chlorophenylsulfonyloxyimino)-benzyl Cyanide, a-(4-nitrophenylsulfonyloxyimino)-benzyl cyanide, a-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)-benzyl Cyanide, a-(benzylsulfonyloxyimino)-4-chlorobenzyl cyanide, a-(phenylsulfonyloxyimino)-2,4-dichlorobenzyl cyanide, A-(benzylsulfonyloxyimino)-2,6-dichlorohexyl cyanide, a-(phenylsulfonyloxyimino)-4-methoxybenzyl cyanide, a- (2-Chlorobenzenesulfonyloxyimino)-4-methoxybenzyl cyanide, a-(phenylsulfonyloxyimino)-thi-2-ylacetonitrile, a- (4- Dodecylbenzenesulfonyloxyimino)-benzyl cyanide, a-[(p-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile, a-[(10 Dialkylbenzenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile, a-(toluenesulfonyloxyimino)-4thienyl cyanide, a-(methylsulfonate Oxyimido)-1-cyclopentenylacetonitrile, a-(methylsulfonyloxy) Imino)-1-cyclohexenylacetonitrile, a-(methylsulfonyloxyimino)-1-cycloheptenylacetonitrile, a-(methylsulfonyloxyimino)-1 -cyclooctenylacetonitrile, a-(trifluoromethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, a-(trifluoromethylsulfonyloxyimino)-cyclohexylacetonitrile , a-(ethylsulfonyloxy-30-200839450-based imido)-ethylacetonitrile, a-(propylsulfonyloxyimino)-propylacetonitrile, a-(cyclohexylsulfonyloxy) Imino)-cyclopentylacetonitrile, a-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, a-(cyclohexylsulfonyloxyimino)-1 -cyclopentenylacetonitrile, a·(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, a-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, a-( η- Butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, a-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, a-(isopropylsulfonyloxy) Isoamino)-1-cyclohexenylacetonitrile, a-(η·butylsulfonyloxyimino)-1-cyclohexenylacetonitrile, a-(methylsulfonyloxyimino) )-phenylacetonitrile, a-(methylsulfonyloxy) Amino)methoxyphenylacetonitrile, a-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, a-(trifluoromethylsulfonyloxyimino)-P-methoxy Phenyl acetonitrile, a-(ethylsulfonyloxyimino)-P-methoxyphenylacetonitrile, a-(propylsulfonyloxyimino)methylphenylacetonitrile, a-( Methylsulfonyloxyimido)-P-bromophenylacetonitrile and the like are also disclosed in JP-A-9-2085 No. 54 (paragraphs [0012] to [0014] [Chem. 18] to [Chem. 19] The sulfonate-based acid generator disclosed in W Ο 2004/074242 A2 (Examplel to 40 on pages 65 to 85). The applicable items are as follows. -31 - 200839450 〔化16 ch3 ο

C—NΟ—S〇2—CF3 (CF2)e-H

ch3o-Q- C^N—O—S〇2—CF3 c2f5

Ch30-^^kc-n-

C-=N—o—S〇2—CF3 C3F7 N—〇—S02—CF3 (CF2)6—H C3F7 ch3o

O-S〇2-CF3

C^=N—0—S02—C4F9 icF尜-H

C—N—O—S〇2—CF3 (CF2)e-H

-0一S〇2一CFj (cf2)6- "^―〇—^ C-=N-0—SO2-CF3 C3F7 M—〇一〇2—C4F9

(CF2)6-H

-32- 200839450 In the above compound examples, the following four compounds are preferred. 17]

Ο—S〇2-C4H9 C4H9—〇2§—Ο

CN ^ CN H3C——C=N_0S02-{CH2}3CH3 H3C C—Μ—OS〇2-(ΟΗ2)3〇Η3

〆~C=N—Ο—S〇2—C4F9 |cF2)e - Η

C-=N—Ο—S02—C4F9 (Specific examples of bis- or bisarylsulfonyldiazomethanes in CF2U-H diazomethane acid generators, for example, bis(isopropylsulfonyl) II Azomethane, bis(P-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis ( 2,4-Dimethylphenylsulfonium)diazomethane.

Further, a diazomethane acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei 11-035551, No. Hei. Further, poly(disulfonyl)diazomethane, such as 1,3-bis(phenylsulfonyldiazomethylsulfonyl)propane, 1,4-double (Japanese Patent Publication No. Hei 11-322707) Phenylsulfonium diazomethylsulfonyl)butane, 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane, 1,1 fluorene-bis(phenylsulfonyl diazo) Methylsulfonium) decane, 1,2_bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane, 1,3-bis(cyclohexylsulfonyldiazomethylsulfonyl)propane, 1 6·bis(cyclohexylsulfonium diazomethylsulfonyl)hexane, 1,10-bis(cyclohexylsulfonyldiazomethylsulfonyl)decane, and the like. -33- 200839450 (B) These acid generators may be used singly or in combination of two or more. The (B) component has excellent lithographic etching characteristics for the photoresist composition, and is preferably (b-5). Further, it is preferably an iron salt-based acid generator having a component (b-5) and an anion portion having a fluorinated alkylsulfonate ion. Among them, the component (b-5) and the key salt acid generator represented by the above general formula (b-Ι) are used. The content of the component (B) of the present invention is from 0.5 to 30 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the component (A). The pattern can be sufficiently formed in the above range. Further, it is preferable that a uniform solution and good storage stability are obtained. <Optional component> The chemically amplified positive lanthanide resist composition of the present invention preferably contains any of the components shown below. <Arbitrary component 1: T-butyrolactone> When any of the above-mentioned components is r-butyrolactone, the characteristics of the storage stability as a resist solution by particles can be improved under the characteristics of non-destructive lithography. The "advancement of the foreign matter with time characteristics" means that the storage stability can be improved when the chemically-enhanced positive-type lanthanum photoresist is stored in a solution. Specifically, it means that it is possible to suppress generation of fine particulate foreign matter in the above solution. Such time-dependent foreign matters are particularly likely to occur when using a fluorenated sesquiline-containing resin. When a foreign matter occurs over time, it is feared that the lithographic etching -34 - 200839450 deteriorates, and the formed photoresist pattern produces defects (surface defects). The term "瑕疵" refers to, for example, the use of a surface defect observation device (trade name "KLA") manufactured by KLA Dankel Co., Ltd., which is unsuitable for inspection from the top of the developed photoresist pattern. This inconvenience means, for example, scum after development, air bubbles, dust, bridge building (bridge formation between photoresist patterns), stains, precipitates, and the like. A method for improving the temporal properties of foreign materials has previously been used to adjust the composition of the substrate components. For example, the solubility of the substrate component in an organic solvent is increased, and the decomposition can suppress the precipitation of components after dissolution to generate foreign matter. However, when the composition of the ruthenium-containing resin is changed, the lithographic etching characteristics such as sensitivity and resolution are deteriorated, so that it is difficult to change the composition. In the present invention, when the positive-type lanthanum-based photoresist composition contains any component of butyrolactone, the temporal properties of the foreign matter can be improved without changing the composition of the ruthenium-containing resin and without impairing the lithographic characteristics. In the positive-working iridium resist composition of the present invention, the content of 7-butyrolactone to 100 parts by mass of the component (A) is preferably from 1 to 600 parts by mass, more preferably from 3 to 100 parts by mass. More preferably 5 to 3 parts by mass, particularly preferably 1 to 20 parts by mass. When the lower limit of the above range is 値 or more, the above-mentioned effects are excellent, and when the upper limit is 値 or less, the film formation property and coating property when the photoresist is formed by using the above-mentioned photoresist composition can be improved. <Option 2: Compound (C)> When the present invention contains any of the components of the compound (C) represented by the following general formula (c-1), it is possible to suppress the generation of ruthenium in the formation of a photoresist pattern. It can also enhance the shape of the photoresist pattern formed by -35- 200839450. "瑕疵" is as described above, but when a high-resolution photoresist pattern is formed, a fine image is formed by using an ArF excimer laser, that is, an ArF excimer laser, an F2 excimer laser, an EUV, an EB, or the like as a light source. For example, when forming a photoresist pattern of 130 nm or less, how to suppress the focus of the lanthanide system. The method of suppressing ruthenium is generally a method of adjusting the composition of the substrate component, and changing the composition of the ruthenium-containing resin is likely to cause deterioration of lithography characteristics such as sensitivity and resolution as described above. However, when the positive-working iridium resist composition of the present invention contains any component of the compound (C), the generation of ruthenium can be suppressed without changing the composition of the ruthenium-containing resin and without impairing the lithographic etching characteristics. 〔化1 8〕

[In the formula (c-Ι), R11 is an acid dissociable group, and R12 to R14 are each independently a hydrogen atom or a hydroxyl group]. In the formula (c-Ι), R11 is an acid dissociable group. The acid dissociable group of R11 may be a group which will be dissociated by the acid generated by the component (B), and is not particularly limited. For example, an acid dissociable dissolution inhibiting base of a basic resin for a chemically reinforced resist previously proposed can be used. Specific examples of the acid dissociable dissolution inhibiting group of R11 include, for example, a group of a (meth-36-200839450) acrylic acid or the like which forms a carboxyl group and a cyclic or chain tertiary alkyl ester; an alkoxyalkyl group or the like Type acid dissociative dissolution inhibitory group and the like. Further, "(meth)acrylic acid" means one or both of acrylic acid having a hydrogen atom bonded to the α-position and a mercaptoacrylic acid having a methyl group bonded to the α-position. The "(meth) acrylate ((m e t h ) a c r y 1 i c a c i d e s t e r )" means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded at the α-position. "(meth) acrylate" means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate of a methyl group bonded to the α-position. The ?3 alkyl ester" means that the hydrogen atom of the carboxyl group is substituted with a chain or a cyclic alkyl group to form an ester, and the oxygen atom at the end of the carbonyloxy group (-C(Ο)-0-) is bonded. The structure of the aforementioned chain or ring-shaped carbon atom of the third order. The tertiary alkyl ester cleaves the bond between the oxygen atom and the tertiary carbon atom due to the action of the acid. Further, the aforementioned chain or cyclic alkyl group may have a substituent. Hereinafter, a group which is a kind of acid dissociable property by forming a tertiary alkyl ester with a carboxyl group is referred to as a "third-order alkyl ester type acid dissociable dissolution inhibiting group". The tertiary alkyl ester type acid dissociable dissolution inhibiting group is, for example, a fatty group, a chain acid dissociable dissolution inhibiting group, and an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group. In the present specification, "aliphatic" means a substance which does not contain an aromatic group, a compound or the like with respect to aromaticity. The "aliphatic branched acid dissociable dissolution inhibiting group" may be a group formed of carbon and hydrogen (hydrocarbon group), and is not limited, but is preferably a hydrocarbon group. -37- 200839450 "Calcified hydrogen radical" can be either saturated or unsaturated, and is generally preferably saturated. The aliphatic branched acid dissociable dissolution inhibiting group is preferably a C 4 to 8 alkyl group, and specifically, for example, tert-butyl, tert-pentyl, tert-heptyl or the like. The "aliphatic cyclic group" of the "acid dissociable dissolution inhibiting group containing an aliphatic cyclic group" may be monocyclic or polycyclic, and the hydrogen atom may be substituted with or without a fluorinated hydroxyalkyl group. The "monocyclic aliphatic cyclic group" means a monocyclic group which does not have an aromatic group, and the "polycyclic aliphatic cyclic group" means a polycyclic group which does not have an aromatic group. The aliphatic cyclic group system includes a hydrocarbon group (alicyclic group) formed of carbon and hydrogen, and a part of carbon atoms of the ring constituting the alicyclic group are replaced by a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. Heterocyclic group and the like. The aliphatic cyclic group is preferably an alicyclic group. The aliphatic cyclic group may be saturated or unsaturated, but it may improve transparency for ArF excimer lasers, and excellent resolution, and depth of focus (DOF) are preferably saturated. The carbon number of the aliphatic cyclic group is preferably from 3 to 20, more preferably from 4 to 15, and particularly preferably from 5 to 15. In the specific example of the aliphatic cyclic group, the monocyclic group is, for example, a group in which one or more hydrogen atoms are removed from the cycloalkane. More specifically, for example, a group in which one or more hydrogen atoms are removed by cyclopentane or cyclohexane is preferably a group in which one or more hydrogen atoms are removed from cyclohexane. The polycyclic group is, for example, a dicycloalkane, a tricycloalkane or a tetracycloalkane, and the like, except for one or more hydrogen atoms. More specifically, a group of one or more hydrogen atoms is removed by a polycycloalkane such as adamantane, nordane, isobornane, tricyclodecane or tetracyclododecane. Such a polycyclic group can be suitably used, for example, in a resin for a positive resist composition used in the ArF excimer laser step. In terms of industrial availability, the monocyclic group is preferably a group in which one or more hydrogen atoms are removed from cyclopentane φ or cyclohexane, and particularly preferably one or more hydrogen atoms are removed from cyclohexane. base. Further, the polycyclic group is preferably one having one or more hydrogen atoms removed from adamantane, nordane or tetracyclododecane. The "acid dissociable dissolution inhibiting group containing an aliphatic cyclic group" may be a group having a carbon atom of a third order on the ring skeleton of the cyclic alkyl group, specifically, for example, 2-methyl-2-adamantyl group, 2-ethyl group a -2-adamantyl group or the like, or an aliphatic cyclic group having an adamantyl group or a group bonded to a branched alkyl group having a tertiary carbon atom. The φ "acetal type acid dissociable dissolution inhibiting group" generally bonds a hydrogen atom to a hydrogen atom at the end of the alkali-soluble group by a carboxyl group, a hydroxyl group or the like. Therefore, when an acid is generated under exposure, the acetal type acid dissociable dissolution inhibiting group can be cleaved by the action of the acid to bond with the oxygenator 's of the acetal type acid dissociable dissolution inhibiting group. The acetal type acid dissociable dissolution inhibiting group is a group represented by the following general formula (ρ 1 ). -39- 200839450 〔化1 9〕

• (1) wherein R 1 ' and R 2 ' are each independently a hydrogen atom or a lower alkyl group, η is an integer of 0 to 3, and hydrazine is a lower alkyl group or an aliphatic cyclic group. In the above formula, η is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 〇. R1' and R2' are a hydrogen atom or a lower alkyl group. The lower alkyl group of R1' and R2' is an alkyl group having 1 to 5 carbon atoms, and specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, an isobutyl group, a tert-butyl group, A lower linear or branched alkyl group such as a pentyl group, an isopentyl group or a neopentyl group. The lower alkyl group of R1' and R2' is preferably a methyl group or an ethyl group, and most preferably a methyl group. It is preferable that at least one of R1' and R2' of the present invention is a hydrogen atom. Namely, the acid dissociable dissolution inhibiting group (Pi) is preferably a group represented by the following general formula (pl-1). [Chemical 20] f —co-fc^^Y . . . (ρ1.υ [wherein R1', η, Υ are the same as above]. The lower alkyl group of hydrazine is, for example, the lower alkyl group of the above R1 '. The aliphatic ring group of hydrazine may be appropriately selected from the monocyclic or polycyclic aliphatic ring group of the prior art, such as the above-mentioned "Air aliphatic group". -40- 200839450 The acetal type acid dissociable dissolution inhibiting group is as defined in the following general formula (p 2 ). [Chemical 2 1]

Wherein R17 and R18 are each independently a linear or branched subgroup' or a hydrogen atom, and R19 is a linear, branched or cyclic alkyl group; and Rl7 and R19 are each independently linear or In the case of a branched alkyl group, the end of Rl7 and the end of R19 may be bonded to form a ring. The alkyl group of R17 and R18 preferably has 1 to 15 carbon atoms, and may be any of linear or branched, more preferably ethyl or methyl, and most preferably methyl. Particularly preferably, one of R17 and R18 is a hydrogen atom, and the other is a methyl group. R19 is a linear, branched or cyclic alkyl group, preferably having 1 to 15 carbon atoms, and may be any of a linear chain, a branched chain or a cyclic group. • When R19 is linear or branched, the carbon number is preferably from 1 to 5, more preferably ethyl and methyl, and most preferably ethyl. When R19 is a ring, the carbon number is preferably from 4 to 15, more preferably from 4 to 12' carbon atoms, most preferably from 5 to 1 carbon. Specifically, for example, one or more hydrogens are removed from a polycycloalkane such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracyclic chain which may be substituted with or substituted by a fluorine atom or a fluorinated alkyl group. The base of the atom. More specifically, such as 'monocyclic alkanes such as cyclopentane, cyclohexane, or more than one polycycloalkane such as adamantane, nordane, isobornyl, tricyclodecane or tetracyclododecane The base of the chlorine atom. Preferably, one or more hydrogenogen-41 - 200839450 subunits are removed from adamantane. Further, in the above formula, wherein R17 and R19 are each independently a linear or branched alkyl group (preferably, an alkylene group having 1 to 5 carbon atoms), the terminal of R19 may be bonded to the end of R17. In this case, R17 and R19 may be bonded to the oxygen atom of R19, and R17 may be bonded to the carbon atom of the oxygen atom to form a ring group. The aforementioned ring group is preferably a 4 to 7 membered ring, more preferably a 4 to 6 membered ring. Specific examples of the above cyclic group include, for example, a tetrahydropyranyl group, a tetrahydrofuranyl group and the like. In the present invention, the acid-dissociable group of R11 is preferably the above-mentioned tertiary alkyl ester type acid dissociable dissolution inhibiting group, more preferably a carbon number of 4 to 8 alkyl group, particularly preferably tert-butyl group. R12 to R14 are each independently a hydrogen atom or a hydroxyl group. In the present invention, at least one of R12 to R14 is preferably a hydroxyl group, and particularly preferably R12 is a hydroxyl group. More specifically, the compound (C) is a compound represented by the following formula (c-1-l) (c-1-l), and a compound represented by the following general formula (c-1-2) (ς_;ι_2) ), the following general formula (c-1-3), the compound (c-1-3), the following general formula (c-1-4), the compound (c-1-4), the following general formula; The compound (c-1-5) shown in (c-1-5). 〔化22〕

-42- 200839450

[wherein, R11 is the same as above]. The compound (C) can be obtained by substituting a hydrogen atom at the carboxy terminus of the compound (C ') represented by the following general formula (c '-1) with an acid dissociable group by a known method. For example, the above compounds (c-1-l) to (c-1-5) may each use choline (a compound of the formula (c'-l) wherein R12 is a hydroxyl group and R13 and R14 are a hydrogen atom) cholic acid ( a compound of the formula (c'-l) wherein R12 to R14 are a hydroxyl group), deoxycholic acid (a compound of the formula (c'-l) wherein R12 and R14 are a hydroxyl group, and R13 is a hydrogen atom), a cyanic acid (formula) a compound of the formula (c'-l) wherein R12 to R14 are a hydrogen atom), porcine deoxydecanoic acid (a compound of the formula (c'-l) wherein R12 and R13 are a hydroxyl group, and R14 is a hydrogen atom) (C, ) Manufacturing. -43 - 200839450 [Chem. 2 3]

[In the formula (c, -l), R12 to Ri4 are each the same as R12 to R14 in the above formula (c-i)]. (C) The components may be used alone or in combination of two or more. In the above invention, the compound (c-1 stomach 1) and/or the compound (c-1-2) are used as the oxime, and particularly preferably (^ -1 · 1 ). In the chemically amplified positive lanthanide resist composition of the present invention, the content of the compound (C) to the component (A) is preferably from 20 parts by mass, more preferably from 1 to 15 parts by mass, more preferably from 1 to 15 parts by mass. It is preferably from 3 to 10 parts by mass. The above-mentioned effects are excellent when the lower limit of the above range is 値 or more, and a good sensitivity is obtained when the upper limit is 値 or less. <Optional Component 3: Nitrogen-containing Organic Compound (D)> The present invention preferably further contains any of the aforementioned components containing a nitrogen-containing organic compound (D) (hereinafter referred to as (D) component). Thus, the post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer, etc., has various proposals for the (D) component. Therefore, it is known to use -44 - 200839450, such as an aliphatic amine such as a secondary aliphatic amine or a tertiary aliphatic amine, an aromatic amine or the like. The "aliphatic" as described above with respect to aromatics means a substance which does not contain an aromatic base compound or the like. The "aliphatic amine" means an amine having one or more aliphatic groups, and the carbon number of the above aliphatic group is preferably from 1 to 12. An amine (for example, an alkylamine or an alkylolamine) in which at least one hydrogen atom of ammonia NH3 is substituted by a linear or branched alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group: An aliphatic cyclic amine having an aliphatic cyclic group or the like. The "aliphatic cyclic group" is a monocyclic or polycyclic group which does not have an aromaticity. Specific examples of the alkylamine and the alkylolamine are, for example, a monoalkylamine such as η-hexylamine, η-heptylamine, η-octylamine, η-decylamine or η-decylamine; diethylamine a dialkylamine such as di-η-propylamine, di-η-heptylamine, di-η-octylamine or dicyclohexylamine; trimethylamine, triethylamine, tri-n-propyl Amine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, a trialkylamine such as tris-n-decylamine or tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-η-octanolamine, three - an alkyl alcohol amine such as η-octanolamine. The aliphatic cyclic amine is, for example, an aliphatic heterocyclic compound containing a hetero atom of a nitrogen atom. The above heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine). Specific examples of the aliphatic monocyclic amine are, for example, piperidine, piperazine and the like. The aliphatic polycyclic amine is preferably a carbon number of 6 to 10, specifically, for example, -45 to 200839450, :U5-diazabicyclo[4.3.0]-5-nonene, 1,8-diaza Heterobicyclo[5.4.0]-7-Eleven-burning, Hexamethylenetetramine, iota, 4-diazabicyclo[2·2·2]octane, and the like. The "aromatic amine" means a compound in which at least one hydrogen atom of the ammonia oxime 3 is substituted with a group having a β aromaticity (hereinafter referred to as an aromatic group). The 〇φ aromatic hydrocarbon group such as an aromatic group such as an aromatic carbonized hydrogen group or an aromatic heterocyclic group preferably has a carbon number of 4 to 20, more preferably 5 to 15, most preferably a carbon number of 6 to 10. Specific examples of the aromatic hydrocarbon group include a group in which one hydrogen atom is removed by an aromatic ring such as benzene, naphthalene or anthracene (for example, a phenyl group, a naphthyl group, an anthracenyl group, etc.); and a linear or branched chain having a carbon number of 1 to 5; a group in which a part of hydrogen atoms in an alkyl group is substituted by an aromatic ring (for example, a benzyl group, a phenylethyl group (C6H5-CH2-CH2), a naphthylmethyl group (C1()H7-CH2-), a naphthylethyl group (C 〇H7-CH2-CH2-), etc. The aromatic ring of these groups may have a substituent such as an alkyl group having 1 to 5 carbon atoms, etc. # aromatic heterocyclic group having carbon atoms and An aromatic ring group having a ring skeleton composed of a hetero atom other than a carbon atom (a nitrogen atom, an oxygen atom, a sulfur atom or the like), for example, a group having one hydrogen atom removed from an aromatic hetero ring such as coumarin. The anthracene ring group may have a substituent such as 'alkyl group having 1 to 5 carbon atoms, etc.. The excellent effect of forming a pattern of high definition and high aspect ratio on the support of the present invention, aromatic group It is preferably an aromatic heterocyclic group, and particularly preferably a group in which one hydrogen atom is removed from a coumarin having a substituent. The aromatic amine is further a 2- to amine and/or 3 Preferably, the amine is preferably a grade 3 - 46 - 200839450 amine. The above-mentioned grade 2 amine and/or grade 3 amine may have at least one aromatic group, and the other may have a linear chain of 1 to 5 or a chain or The cyclic aliphatic hydrocarbon group or a group in which a part of hydrogen atoms of the aliphatic hydrocarbon group is substituted with a hetero atom such as a nitrogen atom, etc. The aromatic amine is particularly preferably a compound represented by the following general formula (d-1). 〔化24〕

[wherein, R41 to R42 are each independently an alkyl group having 1 to 10 carbon atoms, R43 is an alkyl group having 1 to 5 carbon atoms, and η is an integer of 0 to 2]. The component (D) may be used singly or in combination of two or more. In the chemically amplified positive lanthanide resist composition of the present invention, the content of the component (D) component (100 parts by weight) is preferably from 0.01 to 1 part by mass, more preferably from 0.01 to 5 parts by mass. . • "Option 4: 铳 compound (Ε)> ' The present invention further contains an optional compound (E) (hereinafter referred to as (E) component) represented by the following general formula (e-Ι) It is better. As a result, the fluctuation of p Η during the storage of the photoresist composition in the form of a solution can be suppressed to improve the storage stability. In particular, when the positive-type lanthanum-based photoresist composition contains the above-mentioned (D) component, it tends to cause ρΗ fluctuation during storage in a solution form, and therefore it is preferable to use a ruthenium (Ε) component. -47- 200839450 [Chemical 2 5] Γ R22—S+ OH&quot; 丄23 · · · » (e -1) [In the formula (el), R21 to R23 are each independently an alkyl group which may have a substituent, or may have The aryl group of the substituent]. The alkyl group of R21 to R23 is not particularly limited, and may be, for example, a linear, branched or cyclic group having a carbon number of 丨 to 1 〇. Specific examples thereof include methyl group, ethyl group, η-propyl group, isopropyl group, η-butyl group, isobutyl group, η-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, fluorenyl group, fluorenyl group and the like. The aforementioned alkyl group may have a substituent. That is, some or all of the hydrogen atoms of the alkyl group may be substituted with a substituent. The alkyl group may have a substituent such as a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 20 carbon atoms; and the like. The above substituent is particularly preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an η-butyl group or a tert-butyl group. The aryl group of R21 to R23 is not particularly limited and may, for example, be a carbon number of 6 to 20 to an aryl group, specifically, for example, a phenyl group or a naphthyl group. The aforementioned aryl group may have a substituent. That is, some or all of the hydrogen atoms of the aryl group may be substituted with a substituent. The above aryl group may have a substituent such as a substituent which the aforementioned alkyl group may have. The (E) component is preferably, for example, a triphenyl compound represented by the following general formula (e-2), a tricyclohexyl compound represented by the following general formula (e-3), or the like. More preferably, it is a triphenyl compound represented by the general formula (e-2), and particularly preferably a compound wherein R2()1 to R215 are all hydrogen atoms. -48- 200839450 [Chem. 26]

2) Substituent, halogen [In the formula (e-2), R2G1 to R215 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms]. [27]

A 3) -49- 200839450 [In the formula (e-3), R221 to r25 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms]. (E) The components may be used singly or in combination of two or more. In the chemically-reinforced positive-type lanthanum resist composition of the present invention, the content of the component (E) to 100 parts by weight of the component (A) is preferably from 〇1 to 5 parts by mass, more preferably 〇.〇5 to 4 parts by weight, particularly preferably 0.1 to 3 parts by mass. <Optional Component 5: Compound (F)> The present invention may further contain an organic carboxylic acid, a phosphorus oxyacid, and a derivative thereof for the purpose of preventing sensitivity change, enhancing formation of a photoresist pattern, and setting stability over time. Any of the above-mentioned optional components of at least one compound (F) (hereinafter referred to as (F) component) is selected. The organic carboxylic acid is, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like, and particularly preferably malonic acid. The oxyacid of phosphorus and a derivative thereof are, for example, an ester in which a hydrogen atom of the above oxyacid is substituted with a hydrocarbon group. The aforementioned hydrocarbon group is, for example, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, or the like. A derivative of phosphoric acid such as a phosphate such as di-η-butyl phosphate or diphenyl phosphate. Derivatives of phosphonic acid, such as phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate, phosphonic acid dibenzyl ester and the like. Derivatives of phosphinic acid, such as phosphinates such as phenylphosphinic acid. (F) The ingredients may be used alone or in combination of two or more. The component (F) is generally used in an amount of from -50 to 200839450 0.01 to 5.0 parts by mass per 100 parts by mass of the component (A). <Other optional components> In the present invention, any of the above-mentioned optional components of a mixed additive may be appropriately added, for example, an additional resin for improving the properties of the photoresist film, a surfactant for improving coating properties, and a dissolution inhibitor. , plasticizers, stabilizers, colorants, antihalation agents, dyes, etc. The chemically-reinforced positive-type lanthanum-based photoresist composition used in the present invention can be obtained by dissolving a material in an organic solvent (hereinafter referred to as (S) component). The component (S) may be any one or two or more selected from the known ones for the solvent of the chemically reinforced resist. For example, 'acetone, methyl ethyl ketone, cyclohexanone, methyl-η-amyl ketone, methyl isoamyl ketone, 2-heptanone and other ketones; ethylene glycol, diethylene glycol, propylene glycol, two a polyvalent alcohol such as propylene glycol; a compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate; the aforementioned polyvalent alcohol or the aforementioned a polyvalent alcohol derivative of a compound having an ester bond, such as a monomethyl ether such as monomethyl ether, monoethyl ether, monopropyl ether or monobutyl ether, or a compound having an ether bond such as a monophenyl ether [ Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME)]: a cyclic ether such as dioxane; methyl lactate, ethyl lactate (EL), and acetic acid Ester, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate, etc.; anisole, ethyl benzyl ether, cresol Methyl ether, diphenyl ether, dibenzyl-51 - 200839450 ether, phenylethyl ether, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, A , Xylene, methyl, isopropyl benzene, Levin and aromatic organic solvents. These organic solvents may be used singly or in combination of two or more. Among them, preferred are propylene glycol-methyl ether acetate (PGMEA), propylene glycol-methyl ether (PGME), and EL. Φ is preferably a mixed solvent of PGMEA and a polar solvent. The addition ratio (mass ratio) can be appropriately determined by considering the compatibility of PGMEA and the polar solvent, and is preferably in the range of 1:9 to 9:1, more preferably 2:8 to 8:2. More specifically, the mass of PGMEA: EL when the polar solvent EL is added is preferably from 1:9 to 9:1, more preferably from 2:8 to 8:2. Further, when the polar solvent PGME is added, the mass of PGMEA ··PGME is preferably 1 ·· 9 to 9 :1, more preferably 2 : 8 to 8 : 2 , and most preferably 5 : 5 to 8 : 2 . • The amount of (S) component used is not particularly limited. It can be applied to the concentration of the substrate, plate, etc., and the solid concentration of the photoresist composition is generally 2 to 20% by mass, depending on the thickness of the coating film. Preferably, it is 5 to 15 mass graves. 〇 "Hard mask" The hard mask used in the present invention may be a material for forming a photoresist base film by using a lanthanide hard mask forming material, and is not particularly limited. . Among them, a composition containing a siloxane-based polymer is preferable, and a (B Η ) decane-based poly-52-200839450 compound and an (AH) oxalyl-based compound having a mass average molecular weight of 3,000 or less are more preferable. The composition (hereinafter referred to as a composition for forming a hard mask). The hard mask of this type will be described in detail below. <(AH) oxirane compound>

The (AH) siloxane compound has a mass average molecular weight of 3,000 or less. When the mass average molecular weight is within this range, the phenomenon of the photoresist pattern formed on the hard mask can be reduced, and the shape of the pattern can be improved. v.· * The above (AH) fluorene-based compound preferably has a fluorene structure, a cyclic structure, or a general structure (ah-1), (ah-2), and (ah-3) Any of the structures in the box construction.

[wherein, Rlh, R3h, R4h, R5h, and R6h are each independently a hydrogen atom -53-200839450, a transradical, a thiol or a decyloxy group, and each of R2h is independently a linear, branched or cyclic hydrocarbon group. In (ah-1), Rlh and R3h and/or R/h and R5h may be from -* to -〇- 'm is from 1 to 8' and η is from 2 to 8]. The "alkyl group" and "alkoxy group" of Rlh, R3h, R4h, R5h, and R6h are preferably those having 1 to 3 carbon atoms. Such alkyl groups are, for example, methyl, ethyl, propyl, isopropyl and the like. These hospitaloxy groups are, for example, 'methoxy, ethoxy, propoxy and the like. φ The compound of the above general formula (ah-1) or (ah-2) is preferably a hydroxyl group of 25 mol% or more in total of Rih, R3h, R4h and R5h. Further, in the compound of the general formula (ah-3), it is more preferably 25 mol% or more of R6h. Further, the hydrocarbon group of R2h is preferably a linear, branched or cyclic aliphatic hydrocarbon having 1 to 18 carbon atoms or an aromatic hydrocarbon group. The above linear or branched hydrocarbon group such as methyl, ethyl, propyl, isopropyl, t-butyl, pentyl, neopentyl, hexyl, octyl, decyl, fluorenyl , undecyl, dodecyl and the like alkyl; vinyl, allyl, propenyl, etc. alkenyl; cyclopentyl, cyclohexyl, nortzyl, adamantyl, etc. cyclic _ alkyl Wait. The above aromatic hydrocarbon group such as phenyl, naphthyl, methylphenyl, ethylphenyl, tolyl, chlorophenyl, bromophenyl, fluorophenyl, etc.; benzyl, phenethyl, An aralkyl group such as naphthylmethyl, diphenylmethyl, triphenylmethyl or 1-methyl-1-phenylethyl. These hydrocarbon groups may have a substituent such as a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or the like. Wherein R2h is preferably a decyl group or a group represented by the following formula (ah-4). -54- 200839450 〔化 29〕

h — 4) [where 'P is 〇 or 〗, q is 〇 to 5〕). 5 is particularly preferably a group represented by the formula (ah-4) which has excellent compatibility with a component (BH) and an organic solvent which will be described later. The azide-based compound represented by the formulae (aH) and (ah-2) preferably has a molar content of at least R 2h, more preferably 25 mol% or more, and a group represented by the formula (ah-4). Further, the azide-based compound represented by the formula (ahd) is preferably 12.5 mol% or more of R2h, more preferably 25 mol% or more, and a group represented by the formula (ah-4). When the above enthalpy is above, the compatibility of the (ah) oxime compound with respect to an organic solvent can be improved. Further, in the compound of the formula (ah-Ι), Rlh and R3h and/or R/h and R5h may together be -〇-. At this time, a box type structure is formed. When it is a box type structure, m is preferably 2 to 4, and it can form a T8 structure of a slightly cubic shape, a T 1 0 structure of a slightly pentagonal column shape, and a T 1 2 structure of a slightly hexagonal column shape. Specific examples of the azoxy-based compound represented by the above general formulas (ah·1) and (ah-3) are preferably 'the following structural formulas (ah -1 -1 ) , ( ah -1 - 2 ) and ( Ah-3-1). • 55- 20〇鈥450 200839450 The above hydroxyl groups of (ali-1-1), (ah-1-2) and (ah-3-1) are replaced by alkoxy groups such as methoxy and ethoxy. The mass average molecular weight of the ί (AH) fluorene-based compound is 3,000, preferably 2,800. Further, the lower limit 値 is preferably 300, and more preferably the lower limit 値 is 300 00 to suppress evaporation of the siloxane compound, and the film forming property of the composition for the hard mask. <(BH)Hexane-Based Polymer> (BH) The siloxane-based polymer has a unit of the general formula (bh-Ι). [Chem. 3 1] ^ 2 5 % Limited to 500 〇 This can be suggested R7h

Wherein R7h is a light absorbing group, R8h is a hydrogen atom, a hydroxyl group, an alkyl group of 6, an alkoxy group, and r is ruthenium or 1). The above light absorbing group refers to a group having a wavelength of 15 〇 nm to 300 00 nm. The light absorbing group is a group of a benzene ring, an anthracene ring, a naphthalene ring or the like. The light absorbing portion may be bonded to the main group by a stretching alkyl group having a carbon number of 1 to 2 Å interrupted by "-0 (CO)-

On the Si atom. Further, the photoreceptor of the benzene ring, the anthracene ring, the naphthalene ring or the like may be substituted by a substituent having an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a hydroxyl group, and a benzene ring is preferably used in the light absorbing group. Further, in addition to the above-mentioned absorbing group, it has a group of a light absorbing portion containing a Si-Si bond. In addition, these light absorption -57- carbon number 1 has a light absorption: -0 -, one of the skeleton. These usable parts can be used in 200839450 on the main skeleton of the @Oxygen Institute polymer. The above light absorbing group is an aryl group such as a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a tolyl group, a chlorophenyl group, a bromophenyl group or a fluorophenyl group; a benzyl group, a phenethyl group, a naphthyl group; An aralkyl group such as a diphenylmethyl group, a diphenylmethyl group or a 1-methyl-1-phenylethyl group. Among them, phenyl is preferred. When it is a phenyl group, it has a good light absorptivity, and it is particularly preferable as an oxygen-based plasma for improving the uranium resistance. Further, the (BH) fluorene-based polymer preferably has at least one constituent unit represented by the general formula (bh-2). 〔化 3 2〕

• (bh — 2) where R9h is a hydrogen atom, an alkyl group, or a monovalent organic group having at least one functional group selected from the group consisting of a carbonyl group, an ester, a lactone, a guanamine, an ether, and a nitrile ; RWh. 楱 hydrogen atom, hydroxy group, alkyl group having 1 to 6 carbon atoms, alkoxy group; s is ruthenium or 1; the aforementioned functional group has 1 to 6 carbon atoms, and the above-mentioned monovalent organic group has 1 to 6 carbon atoms; 6]. The lower limit 质量 of the mass average molecular weight of the (BH) fluorene-based copolymer is preferably 80 00, more preferably 1,000,000. When the mass average molecular weight of the (BH) component is 800 or more, the film formation property of the hard mask can be improved. Further, the upper limit 质量 of the mass average molecular weight of the (BH) component is preferably 50,000, more preferably 30,000. When the mass average molecular weight of the component (BH) is 50,000 or less, the coatability of the composition for forming a hard mask can be improved. -58- 200839450 <Method for Producing (BH) Oxane-Based Polymer> (BH) A siloxane-based copolymer can be obtained by hydrolyzing and copolymerizing each monomer containing each constituent unit with the (AH) component. . The ratio of the (AH) component to the (BH) component in the hard mask forming composition is preferably a mass ratio of 1:9 to 7:3, more preferably 3:7 to 6:4, and most preferably 5:5. . When the ratio of the (AH) component to the (BH) component is in the above range, the phenomenon of the photoresist φ pattern formed on the hard mask formed of the above composition can be reduced. Further, when the content of the (AH) component and the (BH) component is in the above range, a pattern having a good shape can be formed even if an acid generator is added, so that a hard mask can be formed. ^ <(CH) Solvent> The composition for forming a hard mask may contain (C Η ) a solvent (hereinafter also referred to as a (CH) component). Specifically, for example, methanol, ethanol, propanol, butanol, etc.; valence alcohol; ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylol propyl alcohol, hexane triol, etc.; Ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene dipropyl ether, diethylene glycol monobutyl a monoether of an alcohol such as ether, propylene glycol monocarboxylic acid (•PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; monoethyl acetate of the above monoether, methyl acetate, ethyl acetate, and acetic acid Esters such as esters and ethyl lactate (EL); ketones such as acetone, methyl ethyl ketone, cycloalkyl ketone, and methyl isoamyl ketone; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene Alcohol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol di-59- 200839450 methyl ether (PGDM), propylene glycol diethyl ether, propylene glycol dibutyl ether dimethyl ether, diethylene glycol methyl ether, diethylene glycol An alcohol ether or the like in which an ether group is etherified by an alkyl group. Among them, propylene glycol monomethyl ether acetate (PGMEA) and EL are preferred. These organic solvents may be used singly or in combination of two or more kinds, and the mixed solvent of the mixed P GME A and the polar solvent may be appropriately determined, and preferably the ratio of PGMEA to the polar solvent is preferably 1:9 to 9: 1, more preferably 2: 8 to more specifically, PGMEA when adding polar solvent EL: preferably 1:9 to 9:1, more preferably 2:8 to 8: 2 PGMEA when polar solvent PGME : PGME quality is better than 9:1, more preferably 2:8 to 8:2, especially preferably 3:7 to 7 The total amount of the solvent (ΑΗ) component and (ΒΗ) component is preferably 1 to When the amount is 100 times, more preferably 2 to 20 times, the coating property of the composition for forming a hard mask can be improved. <(DH) Crosslinking Agent> The hard mask forming composition may contain a (DH) crosslinking agent (which is a (DH) component). When a (DH) crosslinking agent is added, film formability can be improved. The crosslinking agent used can be a general use. Specifically, for example, an epoxy compound such as a bisphenol type epoxy resin, a bisphenol F type ring bisphenol S type epoxy resin, a phenol novolac type epoxy resin, or a varnish type epoxy resin. It is also possible to use hydroxy PGME of di- or di- ethane and other alcohols. good. Its solubility is 8:2 ° EL quality. Also add έ to a mass of 1.9:3 °. Below this range, it is also referred to as a hard mask oxygen resin, cresol novolac vinyl benzene-60-200839450, divinyl fluorene, tripropylene acetal, glyoxal, polyvalent alcohol acrylate or methacrylate . In addition, a compound having at least two amine groups of melamine, urea, benzoguanamine, and glycoluril substituted with a methylol group, a lower alkoxymethyl group or a lower methoxymethyl group has two or more reactive groups. Compounds and the like. The lower alkoxymethyl group and the lower methoxymethyl group preferably have a carbon number of 2 to 6. a compound in which at least two amine groups of melamine are substituted with a methylol group or an alkoxymethyl group, for example, one to six methoxy groups of hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine Methylated compounds and mixtures thereof; hexaethoxymethyl melamine, hexamethoxymethyl melamine, hexamethylol melamine, one to five hydroxymethyl groups, methyloxymethylated compounds and Mixture, etc. Compounds in which at least two amine groups of urea are replaced by a methylol group or a lower alkoxymethyl group, such as tetramethylolurea, tetramethoxymethylurea, tetraethoxymethylurea, tetramethylolurea One to four hydroxymethyl groups are methoxymethylated compounds or mixtures thereof and the like. a compound in which at least two amine groups of a benzo dieamine amine are substituted with a methylol group, a lower alkoxymethyl group or a lower methoxymethyl group, such as tetramethylol guanine, tetramethoxymethylguanine a compound in which one to four methylol groups of an amine, tetramethylol guanine are methoxymethylated, and mixtures thereof; tetraethoxymethylguanine, tetradecyl guanine, four A compound in which one to four methylol groups of hydroxymethylguanine are methylated by a methoxy group, a mixture thereof, and the like. a compound in which at least two amine groups of glycoluril are substituted with a methylol group, a lower alkoxymethyl group or a lower methoxymethyl group, such as tetramethylol glycoluril, tetramethoxy-61 - 200839450 glycoluril, four a compound of methoxymethyl glycoluril, tetramethylol glycoluril to 4 hydroxymethyl groups by methoxymethyl group or a mixture thereof; 1 to 4 methylol groups of tetramethylol glycoluril A compound that is methylated by oxime or a mixture thereof. These crosslinking agents may be used singly or in combination of two or more. The amount of the crosslinking agent to be added to the total amount of the (AH) component and the decaneoxy polymer is preferably from 0.1 to 50 parts by mass, more preferably from 5% by mass. 40 parts by mass. <(EH) acid generator> The hard mask forming composition may contain an (EH) acid generator (hereinafter also referred to as (EH) component). The acid generator used may be a salt of a salt, a diazomethane derivative, an ethylenediazine derivative, a biguanide derivative, a ruthenium-oxonium derivative, a dioxane derivative or a nitrobenzylsulfonate. A known acid generator such as a sulfonate derivative or a sulfonate derivative of an N-hydroxyquinone imine compound. #键盐如, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, Tetramethylammonium sulfonate, tetraphenylammonium trifluoromethanesulfonate, p-tert-butoxyphenyl phenyl iodine gun, p-tert-butoxybenzene diphenyl Iodine: iron, p-toluenesulfonic acid (p_tert·butoxyphenyl)phenyliron iodide, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) Phenylhydrazine, tris(p-tert-butoxyphenyl)phenylphosphonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)phosphonium trifluoromethanesulfonate, p-toluenesulfonic acid Phenylhydrazine, p-tert-butoxyphenyl)diphenyl-62- 200839450 锍, p-tert-butoxyphenyl)phenyl hydrazine, p-toluenesulfonic acid, Tris(p-tert-butoxyphenyl)phosphonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, P -trimethylsulfonium tosylate, cyclohexylmethyl trifluoromethanesulfonate (2-carbonylcyclohexyl) hydrazine, P-toluene Cyclohexylmethyl(2-carbonylcyclohexyl)phosphonium, dimethylphenylphosphonium trifluoromethanesulfonate, dimethylphenylphosphonium p-toluenesulfonate, dicyclohexylphenylphosphonium trifluoromethanesulfonate, p -dicyclohexylphenylphosphonium tosylate, trinaphthyltrifluoromethanesulfonate, cyclohexylmethyl (2-carbonylcyclohexyl)phosphonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (2-nortzyl) )methyl(2-carbonylcyclohexyl)anthracene, ethyl bis[methyl(2-carbonylcyclopentyl)phosphonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothiophene Trifluoride and the like. Diazomethane derivatives such as bis(phenylsulfonyl)diazomethane, bis(P-toluenesulfonyl)diazomethane, bis(xylylenesulfonyl)diazomethane, bis(cyclohexylsulfonium) Diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(η-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, double (sec- Butylsulfonium)diazomethane, bis(η-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazo Methane, bis(η-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert--pentyl) Sulfo]diazomethane, 1-cyclohexylsulfonium-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonium-1 - (tert·-pentylsulfonyl)dim Nitrogen Institute, 1-1 ert-pentylsulfonium-1-(tert-butylsulfonate) diazo-methyl hospital. Ethylene derivatives such as bis-indole-(P-toluenesulfonyl)-a-dimethylethyl-63- 200839450 diterpene, bis-indole-(P-toluenesulfonyl)-a-diphenyl Diterpenoid, bis-indole-(P-toluenesulfonyl)-a-dicyclohexylethylenedifluoride, bis-indole-(p-toluenesulfonyl)-2,3-pentanedione oxime, double-0 -(P-toluenesulfonate)-2-methyl-3,4-pentanedione ethanedioxime, bis-indole-(η-butanesulfonyl)-a-dimethylglyoxime, bis-indole -( η-butanesulfonyl)-a-diphenylglyoxime, bis-indole-(η-butanesulfonyl)-a-dicyclohexylethylenedifluoride, bis--0-(n·butane Sulfonium)-2,3-pentanedione ethanedioxime, bis-indolyl-(η-butanesulfonyl)-2-methyl-3,4-pentanediol ethanediazine, bis-indole-(methane Sulfonamide)-a-dimethylglyoxime, bis--0-(trifluoromethanesulfonate)-a-dimethylglyoxime, double_0-(1,1,1-trifluoromethanesulfonate )-a-dimethylglyoxime, double-0-(tert-butanesulfonyl)-a-dimethylglyoxime, bis-indole-(perfluorooctanesulfonyl)-a-dimethyl Ethylene, di-O-(cyclohexanesulfonyl)-a-dimethylglyoxime, bis--0-(phenylsulfonyl)-a-dimethylglyoxime, double-0-( P-fluorobenzenesulfonate)-a-dimethyl B Bismuth, double-0-(p-tert-butylbenzenesulfonyl)-a-dimethylglyoxime, double-0-(toluenesulfonyl)-a-dimethylglyoxime, double-0- (莰 醯)-a-dimethylglyoxime and the like bismuth bismuth derivatives such as bisnaphthylsulfonium methane, bistrifluoromethylsulfonium methane, bismethylsulfonium methane, diethyl sulfonium sulfonate Methane, bispropylsulfonium methane, diisopropylsulfonyl methane, bis-P-toluenesulfonium methane, bisbenzenesulfonyl methane, and the like. An oxonium derivative such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane or the like. A diterpene derivative such as a diphenyl di maple derivative or a dioxenyl derivative such as a dicyclohexyl difluorene derivative. -64- 200839450 Nitrobenzyl sulfonate derivatives such as p-toluenesulfonic acid 2,6-dinitrobenzyl ester, p-toluenesulfonic acid 2,4-dinitrobenzyl ester, etc. Acid ester derivatives and the like. Sulfonate derivatives such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tri (p a sulfonate derivative such as toluenesulfonyloxy)benzene or the like. Sulfonic acid ester derivatives of N-hydroxy quinone imine compounds, such as N-hydroxysuccinimide, imine methane sulfonate, N-hydroxysuccinimide, imidium trifluoromethanesulfonate, N-hydroxyamber Amine ethanesulfonate, N-hydroxysuccinimide imine 1-propane sulfonate, N-hydroxysuccinimide 2-propane sulfonate, N-hydroxysuccinimide imine 1-pentane sulfonate Acid ester, N-hydroxysuccinimide imine 1-octane sulfonate, N-hydroxysuccinimide imine p-toluenesulfonate, N-hydroxysuccinimide imine P-methoxybenzenesulfonic acid Ester, N-hydroxyamber, imine, 2-chloroethanesulfonate, N-hydroxysuccinimide, sulfonate, N-hydroxysuccinimide, 2,4,6-trimethylbenzenesulfonate Acid ester, N-hydroxysuccinimide imine 1-naphthalene sulfonate, N-hydroxysuccinimide imine 2-naphthalene sulfonate, N-hydroxy-2-phenyl phenyl azeline imine methane sulfonate , N-hydroxymaleimide methane sulfonate, N-hydroxymaleimide ethane sulfonate, N-hydroxy-2-phenyl maleimide methane sulfonate, N-hydroxy pentyl Dimethyleneimine methane sulfonate, N-hydroxypentamethylene imide benzene sulfonate, N-hydroxy quinone Amine methane sulfonate, N-hydroxy quinone benzene sulfonate, N-hydroxy quinone imine trifluoromethane sulfonate, N-hydroxy quinone imine p-toluene sulfonate, N-hydroxynaphthalene Yttrium imide methane sulfonate, N-hydroxynaphthyl imide benzene sulfonate, N-hydroxy-S-norzene-2,3-dihydroxy quinone imide methane sulfonate, N-hydroxy-5- Deazol-2,3-dicarboxy-65- 200839450 quinoneimine trifluoromethane sulfonate, N-hydroxy-5-norzene 2,3-dicarboxy quinone imine P-tosylate Wait. These acid generators may be used singly or in combination of two or more. The amount of the acid component to be added to the total of the (AH) component and the (BH) component is preferably from 0.1 part by mass to 50 parts by mass', more preferably from 5 parts by mass to 40 parts by mass. The hard mask forming composition of the present invention is obtained by mixing the above (AH) component to the (EH) component. Further, the resulting photoresist base film composition is preferably filtered by a filter. <Method for Forming Hard Mask> When the hard mask is formed by using the above-described preferable composition for forming a hard mask, it can be applied to a film to be processed by using a spin coater, a slit nozzle coater or the like (may be formed in a case where it is formed) On the base film on the film to be processed, it is dried and then heated. One-stage heating or multi-stage heating can be used for heating. When the multi-stage heating method is used, for example, it may be heated at 100 ° C to 120 ° C for 60 seconds to 120 seconds, and then heated at 200 ° C to 25 ° C for 60 seconds to 120 seconds. The thickness of the hard mask thus formed is preferably from 20 nm to 150 nm. Then, a photoresist film is formed on the hard mask by using a composition for a photoresist film having a thickness of, for example, from 10 nm to 200 nm. "Support" The support is not particularly limited, and previously known things can be used. For example, a substrate for an electronic component, a material having a certain wiring pattern formed thereon, or the like. More -66 - 200839450 For example, a metal substrate such as a circuit, copper, chromium, iron, or aluminum, or a glass substrate. The wiring pattern materials are, for example, copper, aluminum, nickel, gold, and the like. The underlayer film used in the "base film" may be a known one, or may be any one of an inorganic or organic film, preferably a dry-corrodible organic film, for example, a general multilayer photoresist method or the like may be used. Organic film. Among them, a material which can form an organic film which can be etched by oxygen plasma etching or the like is preferable. The material for forming the organic film may be a material for forming an organic film such as an organic antireflection film (organic BARC). For example, the ARC series manufactured by Pluvar, the AR series manufactured by Lom Ann, and the SWK series manufactured by Tokyo Yinghua Industrial Co., Ltd. In particular, when etching is performed by oxygen plasma etching as described above, the organic film is etched by easy plasma etching using oxygen, and has high resistance to a halogen gas, specifically, a fluorinated carbon gas such as CF4 gas or CHF3 gas. The material composition is better. These materials are easily etched by oxygen plasma etching or the like, and have high resistance to a fluorinated carbon-based gas, and are therefore suitable for use in the present invention. In other words, when a substrate is etched, a halogen gas such as a fluorinated carbon-based gas is used. Therefore, when an organic film is formed from such a material, the processing using oxygen plasma etching can be improved when the organic film pattern is formed, and the fluorine can be used. Etching resistance such as a step of etching a substrate by a halogen gas such as a carbon-based gas. These resin components may be used singly or in combination of two or more. -67- 200839450 The organic film-forming material may optionally contain a mixture of additives, such as an additive resin for improving the performance of the organic film. Surfactants for coating properties, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, and the like. The material for forming an organic film can be obtained by dissolving a material such as the above resin component in an organic solvent. The organic solvent to be used may be the (S) component of the above chemically-enhanced positive-type lanthanide resist composition. <<Chemically Enhanced Negative Photoresist Composition>> The chemically amplified negative resist composition can be used as previously known, and is not particularly limited. For example, an alkali-soluble resin is added, an acid generator and a cross-linking agent which generate an acid upon exposure, and an acid generated by exposure can be used in forming a photoresist pattern, and an alkali-soluble resin and a crosslinking agent are acted by the action of the aforementioned acid. Crosslinking occurs between them, and the exposed portion is changed to an alkali-insoluble matter. Further, in the alkali-soluble resin, a resin having at least one selected unit selected from the group consisting of a-(hydroxyalkyl)acrylic acid or a lower alkyl ester of a-(hydroxyalkyl)acrylic acid, a resin having a fluorinated alcohol, and the like It is better to reduce the formation of a good photoresist pattern by expansion. Further, a-(base-based) propyl acid refers to an acrylic acid bonded to a hydrogen atom at a carbon atom of the a-position thiol group, and a hydroxyalkyl group bonded to a carbon atom at the a-position (preferably One or both of the a-hydroxyalkylacrylic acids having a hydroxyalkyl group having 1 to 5 carbon atoms. The crosslinking agent to be used is, for example, an amine-based crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group, and it is preferred to reduce the formation of a good photoresist with a light resistance of -68 to 200839450. It is preferably from 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin. Next, the pattern forming method of the present invention will be explained. <<Forming Method of Forming Pattern>> The pattern forming method of the present invention comprises the steps of forming an underlayer film on a support using an underlayer film forming material, and forming a hard mask on the underlying film using a lanthanide hard mask forming material. a step of applying a chemically-reinforced negative photoresist composition to the hard mask to form a first photoresist film and selectively exposing the first photoresist film via the first mask pattern a step of re-forming the first photoresist pattern, and a step of etching the hard mask to form the first pattern by using the first photoresist pattern as a mask (referred to as the manufacturing step (1)), And a step of applying a chemically-reinforced positive-type lanthanide photoresist composition to the first pattern to form a second photoresist film, and selectively selecting the second photoresist film via the second mask pattern The step of exposing, re-forming the second photoresist pattern, and the step of forming the second pattern by the uranium engraved film by using the second photoresist pattern as the mask (the drawing step (1) is referred to as drawing Step (2)). The following will be illustrated by the drawings. <Drawing Step (1)> Fig. 1 is a schematic view showing a step of the drawing step (1) in a preferred embodiment of the pattern forming method of the present invention. In the present embodiment, first, as shown in FIG. 1A, after the underlayer film 2 is formed on the support 1 by using the underlayer film forming material, the ruthenium-based hard-69-200839450 pattern forming material is formed on the underlying film 2. The hard mask 3 is coated with a chemically-reinforced negative photoresist composition on the hard mask 3 to form a first photoresist film 4. The steps of forming the underlayer film 2, the hard mask 3, and the first photoresist film * are respectively applied to the previously known methods. For example, the method of applying the underlayer film forming material to the support 1 is not particularly limited. The substrate film forming material may be appropriately selected, for example, by a spray method, a roll coating method, a rotary coating method or the like. • The thickness of the underlying film 2 can be appropriately selected in consideration of the aspect ratio of the purpose and the time required for dry etching the underlying film 2, preferably 55 〇nrn or more and 500 nm or less, more preferably 200 nm or more. 50 nm or less, particularly preferably 200 nm or more and 300 nm or less. When the thickness of the underlayer film 2 is in this range, a high aspect ratio photoresist pattern can be formed. The aspect ratio refers to the ratio 値(y/x) of the pattern height y formed on the support for the pattern width X of the resist pattern. The pattern width of the photoresist pattern is the same as the width of the pattern after the underlying film. Φ The width of the pattern refers to the width of the ridge (line) when the pattern of the photoresist is the line pattern and the line pattern of the vertical line. When the photoresist pattern is a hole pattern, the pattern width refers to the inner diameter of the hole (hole) formed. The photoresist pattern is the diameter of the cylindrical dot pattern. Further, the width of the pattern is the width of the pattern (the side of the support). Further, for example, the method of applying the above-described enamel hard mask forming material to the underlying film 2 is not particularly limited. The above method of forming a hard mask using the preferred hard mask forming composition. -70- 200839450 The thickness of the hard mask 3 is preferably 20 nm or more and 150 nm or less, more preferably 30 nm or more and 50 nm or less. The ruthenium content of the lanthanum hard mask forming material can be formed into a high aspect ratio pattern, preferably 20% or more, more preferably 30% or more. Further, for example, a chemically-reinforced negative-type photoresist composition is applied onto the hard mask 3 by a spin coater or the like, and then a coating film formed by heat treatment (preheating) is applied, so that the first photoresist film 4 can be formed. membrane. The thickness of the first photoresist film 4 can be appropriately selected in consideration of the aspect ratio of the purpose and the time required for the dry uranium hard mask 3, and is preferably 50 nm or more and 200 nm or less, more preferably 1 〇〇. When nm is 200 nm or less and the thickness is 200 nm or less, a photoresist pattern can be formed with high resolution, and when it is 5 Onm or more, sufficient resistance to dry uranium can be obtained. Next, as shown in FIG. 1B, the first photoresist film 4 is selectively exposed through the first mask pattern 5, and then the post exposure bake (PEB) is applied to the photoresist film 4, and thereafter The photoresist film 4 is developed to form a first photoresist pattern 4'. Selective exposure and visualization are suitable for previously known methods. The first mask pattern 5 used at this time can be appropriately selected in consideration of the desired pattern. In the figure, the space width d and the distance 2d are taken as an example, but are not limited thereto. The selective exposure conditions are not particularly limited, and the exposure range, exposure time, exposure intensity, and the like can be appropriately selected in accordance with the light source and method for exposure. The exposure light source is not particularly limited, and an ArF excimer laser, a KrF excimer laser, an F2 excimer laser, an EUV (very ultraviolet ray), a VUV (vacuum ultraviolet ray), an EB (electron line), an X-ray, a soft X can be used. Line, etc. -71 - 200839450 Ray. The alkali developing solution for development is not particularly limited. For example, 0. 〇 5 mass% or more and 1 〇 mass% or less can be used, and 四 5 mass% or more and 3% by mass or less of a tetramethylammonium hydroxide aqueous solution is preferable. The chemically-enhanced negative-type photoresist composition used is an alkali-soluble resin. When a resin, an acid generator, and a cross-linking agent are used, selective exposure causes acid to be generated in the exposed portion, and the acid acts under the action of the acid. Crosslinking occurs between the alkali-soluble resin and the crosslinking agent φ, and the exposed portion is changed to alkali-insoluble. Therefore, when wet development is carried out using an alkali developing solution, the unexposed portion can be dissolved in the developing liquid to form the first photoresist pattern 4'. The first photoresist pattern 4' is shown in Fig. 1C, and the line and space resist pattern (hereinafter referred to as L/S pattern) with a line width d/2 and a space width of 3d/2 and a distance of 2d. . The heat treatment conditions are not particularly limited. For example, it may be heated at a temperature of 70 ° C or more and 130 ° C or less for 40 seconds to 180 seconds, preferably 60 seconds to 90 seconds. • Next, the first photoresist pattern 4 ′ is used as a mask, and the hard mask 3 is etched to form a first pattern. That is, the first photoresist pattern 4' is overlaid on the hard mask 3. The previously known method is applied to uranium engraving. For example, plasma and/or reactive ions are irradiated. The etching conditions can be appropriately selected depending on the type of gas used. The plasma and/or reactive ion gas used for the engraving may be a gas used in the general dry uranium field, and is not particularly limited. For example, oxygen, halogen, sulfur dioxide, etc., but it is preferable to use a halogen-containing plasma such as CF4 or CHF3 and/or a reactive ion. -72-

200839450 There are no special restrictions on uranium engraving methods. For example, chemical etching such as dry etching, sputtering etching or ion etching, and chemical methods such as RIE (Reactive Ion Etching) can be used. The most common dry etching method is a parallel flat type RIE. The layer forming the photoresist pattern is placed in an etch gas of the RIE device. Secondly, a high-frequency voltage is applied to the holder of the electrode S-resistive laminate in the sheath, so that there are positive and negative ions and electron-charged particles in the gas_ion, and the seed is adsorbed to the bottom. There is a chemical reaction that causes the reaction product to be detached from the surface and etched. After the etching of the hard mask 3 is completed, the pattern 4' of the pattern of FIG. 1E can be used, and the pattern 3 of the hard mask on the underlying film 2 is used, or the first photoresist pattern 4' remains as shown in FIG. 1D. Figure 4' and the pattern 3' of the hard mask are used as the first pattern. <Picture Step (2)> Next, a preferred embodiment of the second embodiment of the pattern forming method of the present invention is formed after the above-described patterning step (1). In Fig. 2, after the removal, the pattern 3' of the hard mask is used as the first pattern, and the pattern of the photoresist pattern 4' is used as the first pattern. Further, the method of removing the first photoresist pattern may be a method in which physical physical etching such as flow etching or etch etching is used to first ionize the light which must be placed in parallel. Because the neutral active species is on the same layer, gas is produced to the outside to remove: the first photoresist is removed as the first pattern and the first photoresist pattern is used. Fig. 2 is a graph showing a step of drawing a photoresist pattern 4'', but the first step is formed to form a second pattern, and the stripping pattern is obtained by a method such as a stripping solution. The second resist film 6 can be formed by applying the chemically-reinforced positive-type lanthanum-based photoresist composition to the first pattern and the underlying film 2 formed as shown in Fig. 2A. The second photoresist film 6 and the first photoresist film 4 can be formed by a previously known method. The thickness of the second photoresist film 6 can be appropriately selected in view of the aspect ratio of the purpose and the time required for the dry-base film 2, and is preferably 100 nm or more and 200 nm or less. When the thickness is 200 nm or less, the photoresist pattern can be formed with high resolution, and when it is 1 〇 〇 nm or more, sufficient resistance to dry uranium can be obtained. Further, the ruthenium content of the chemically-reinforced positive iridium-based photoresist composition is preferably 1% by mass or more, more preferably 20% or more, in terms of a pattern having a good high aspect ratio. Next, as shown in Fig. 2B, the second photoresist film 6 is selectively exposed through the second mask pattern 7, and then developed to form a second photoresist pattern 6'. When selective exposure and development can be formed with the first photoresist pattern 4', the previously known method is applied. The second mask pattern 7 used at this time can be appropriately selected in consideration of the pattern of the first mask pattern 5 as described above. In the figure, when the second photoresist pattern 6' is formed to form the first photoresist pattern 4', the second mask pattern 7 and the first mask pattern 5 are objects having a spatial width d and a pitch 2d. That is, when the second photoresist pattern 6' is formed specifically, the first mask pattern 5 is used as the second mask pattern 7, and the mask pattern is set to be different from the first photoresist film 4. The position of the selective exposure is performed, so that the second photoresist film 6 can be selectively exposed. -74- 200839450 When the chemically-enhanced positive-type lanthanide resist composition used is the above-mentioned substance, the exposed portion can generate an acid under selective exposure, and the resin of the exposed portion can be changed to alkali solubility by the action of the acid. . Therefore, when wet development is performed using an alkali developing solution, the exposed portion is completely dissolved in the developing liquid to form the second photoresist pattern 6, . The second photoresist pattern 6' is shown in Fig. 2C, and the L/S pattern with a line width d/2, a spatial width, and a width of 3d/2 is 2d, and is adjacent to the spatial width d/2. Figure 3' of the hard mask used in the first pattern. 0, as shown in FIG. 2D, using the first pattern 3 and the second photoresist pattern 6' as a mask, etching the underlying film 2 to form the first pattern 3 and the second photoresist pattern 6' The pattern 2 is engraved on the underlying film 2, and the pattern 2 of the obtained underlayer film 2 is the second pattern. The method of etching the underlying film 2 can be the same as the method of etching the hard mask 3, using a previously known method. The plasma and/or reactive ion gas for etching is not particularly limited, and examples thereof include oxygen, halogen, sulfur dioxide, and the like. In order to improve the resolution and versatility of the resulting pattern, it is preferred to use an oxygen-containing plasma and/or a reactive ion. Φ The foregoing second pattern is an L/S pattern of line width d/2, space width d/2, and spacing d. For example, when d is 1 80 nm, the present invention can form a high-definition pattern having a line width and a spatial width of 9 Onm. The resulting second line width and spatial width will vary depending on the conditions of each step. The pattern thus formed on the substrate can be obtained with a high aspect ratio, and is excellent in that the shape is collapsed, the shape and the verticality are high. Previously, the previous pattern obtained by single-layer photoresist pattern could not achieve such high definition and high aspect ratio. In addition, the previously proposed double-drawing method is mixed with objects with poor pattern accuracy, pattern collapse, and low vertical shape, so high-definition objects cannot be obtained. [Embodiment] Embodiments Hereinafter, the present invention will be described in more detail by way of specific examples, without being limited to the examples. <Modulation of hard mask forming material> According to International Publication No. 2006/06532 No. 1, synthesis of a naphthenic copolymer represented by the following chemical formula (1): PGMEA 120 g and phenyltrichloromethane 5.29 g under gas (0, a mixture of 3.77 g (0.050 mol) of trichloromethane, 0.15 mmol of methyltrichloropurine) and 5.54 g of 2-carbomethoxyethyl chloride () were placed in the reactor. 200 g of liquid and 10 g (0.55 5 m) of water were added to the above three for more than one hour. 20 After stirring the reaction for 1 hour, it was concentrated to about 10% by weight using a mechanical grease solution at 40 Torr. About 40 g of ethanol was added, and the solution was again stripped to 20 wt%. After removing the flask, the force [, diluting the solution to l〇wt%, and using 0.20 metric PTFE, the mass of the following chemical formula (1) synthesized by the method (Mw) 24000, dispersion (Mw/Mn) 3.17 100 parts by mass of the oxime, the acid generation of the following chemical formula (2), and 3 parts by mass of cetyltrimethylammonium chloride are dissolved in PGMEA/EL at a mass ratio of 2% by mass. = 6/4 (in the solvent, a hard mask is formed to form the material. However, the synthetic method of the present invention. That is, nitrogen • 025 mol) alkane 22.43 g (0.025 mol of PGMEA dissolved chlorodecane solution to the evaporator will be In the mechanical fat solution, I was filtered into a PGMEA filter. The average molecular oxygen oxyalkylene copolymer was mixed with 7 parts by mass of solid content. -76- 200839450 [Chem. 3 3]

(Preparation of Chemically Enhanced Negative Photoresist Composition) 100 parts by mass of a resin represented by the following chemical formula (Al)-1 having a mass average molecular weight of 4,400 and a degree of dispersion of 1.7, and 2.0 parts by mass of triphenylsulfonium trifluoromethanesulfonate 5.0 parts by mass of tetramethoxymethylated glycoluril MX270 (manufactured by Sanwa Chemical Co., Ltd.) and 0.4 parts by mass of triisopropanolamine, dissolved in a mixed solvent of PGMEA/PGME = 6/4 (mass ratio) 1 5 5 The negative photoresist composition was prepared in 0 parts by mass. -77- 200839450 〔化 34〕

<Modulating chemically-enhanced positive lanthanide photoresist composition> (Preparation of yttrium-containing sesquial resin) Toluenesulfonic acid monohydrate (TSAM) solution obtained by sulfonating toluene with concentrated H2S04 and S03 gases 〇g was placed in a 500 mL flask equipped with a condenser, a thermometer, a magnetic stir bar, and a nitrogen foamer. A solution of trichloromethane (10 g, 0.075 mol) dissolved in 50 g of toluene was slowly stirred under vigorous stirring, and the mixture was dropped into the flask to obtain a mixture. After the resulting mixture was washed at least three times with deionized water, the organic phase was extracted. The solvent of the obtained organic phase was removed by a rotary evaporator under reduced pressure to obtain a hydrogen-containing sulfonium sesquioxane resin (HSQ) solution having a solid content of 5 to 25% by mass. (Introduction of acid-decomposable group) Mixing about 2 moles of [2,2,1]hept-5-ene-2_t-butylcarboxylate and toluic anhydride (50:50) to prepare an olefin solution . 220 ppm of 1,3 -divinyl-1,1,3,3-tetramethyldioxane complex (platinum, concentrated) was added to the obtained olefin solution, and the olefin solution was placed in a condenser. Nitrogen cleaning was carried out in a flask of a thermometer, a magnetic stir bar and a nitrogen foamer. After nitrogen purge, the above prepared HSQ solution was slowly added to the olefin solution -78 - 200839450, and the system was refluxed for 8 hours while slowly stirring. The intra-system reaction (hydrogen alkylation reaction) was monitored by 1H-NMR, and the reaction was terminated when the olefin peak completely disappeared, and the following formula (the acid-decomposable group represented by Ο-1) was introduced into the HSQ sand oxo-based copolymer. The mass average molecular weight of the polystyrene conversion standard determined by the gel permeation chromatography (GPC) is 6300', and the degree of dispersion is 2.1. In the oxane copolymer, the acid decomposition property shown by the following formula is introduced into the HSQ and the HSQ. The composition ratio of the constituent units of the base is 5 7 : 43 (Morby). [Chemical 3 5]

The obtained resin solution was subjected to solvent substitution using a mixed solvent of PGMEA/PGME = 8/2 (mass ratio) to obtain a PGMEA/PGME solution having a solid content concentration of 5% by mass of the above-described alkoxysilane copolymer. PGMEA/PGME solution (containing 1 part by mass of a pyrithione-based copolymer in terms of solid content) of the above-mentioned siloxane-based copolymer, (B) component and compound of the type and addition amount shown in Table 1 below (〇, (D) component, (E) component and (F) component' and the amount of r-butyrolactone shown in Table 1 below, dissolved and modulating the photoresist composition. -79- 200839450 [Table 1] ( A) Ingredient oxirane copolymer [1] (8) Ingredient (B) -1 [6.0] (B) -2 [2.0] Compound (C) (C) -1 (7.0) (D) Ingredients (D) ) -1 [0.2] (8) Ingredient (8)-1 C1.5] (F) Ingredient (F) 4 [0.84] r-butyrolactone [20] In Table 1, the number in [] is the amount of addition (parts by mass) Each of the codes is the following: (B) -1 : a compound represented by the following formula (B) -1 (B) -2 : a compound represented by the following formula (B) - (C) - 1 : A compound represented by the following formula (C)-1: (D) -1 : a compound represented by the following formula (D)-1. (E) -1 : a compound represented by the following formula (E)-1. (F) -1 : Malonic acid -80- 200839450 [Chem. 3 6]

/SOgCF3 -c"s%cf3 S〇tCF3

<Formation Pattern> A pattern is formed in the following order with the steps shown in Figs. 1 and 2. The underlayer film forming material was applied to an 8-inch ruthenium circuit board by BLC 73 0 (trade name: manufactured by Tokyo Ohka Kogyo Co., Ltd.), and heat-treated at 25 ° C for 9 sec seconds to form a bottom layer having a film thickness of 25 Onm. membrane. The hard mask forming material was applied onto the underlayer film, and heat-treated at 250 - 81 _ 200839450 ° C for 90 seconds to form a hard mask having a film thickness of 45 nm. Next, the negative resist composition was applied onto the hard mask by a spin coater, and preheated (PAB) at 80 ° C for 60 seconds to form a first photoresist film having a thickness of 160 nm. ^ Next, using the ArF excimer laser exposure machine NSR-S302 (Nikon Corporation, Si, ΝΑ = 0.6, s = 〇.75), the first photoresist film was selectively exposed through the mask. • Next, post-exposure heating (PEB) was carried out under conditions of 10 ° C for 60 seconds, and a 2.38 mass % tetramethylammonium hydroxide aqueous solution was used, and the image was imaged at 23 t for 30 seconds. Thereafter, it was rinsed with pure water for 3 seconds to form a first photoresist pattern. Next, the first photoresist pattern is used as a mask, and an etching apparatus "TCE-781 1" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is used, and the output power is 3 at a tabletop temperature of 25/20 ° C. The hard mask was etched by introducing an etching gas of CF4/CHF3/He (seem) = 60/20/160 for 26 Φ seconds under conditions of 00 W and a pressure of 30,000 mTorr. As a result, the first photoresist pattern is duplicated onto the hard mask to form a first pattern. The cross-sectional shape of the L/S pattern was observed by SEM (scanning electron microscope), and it was confirmed that the line width was 90 nm and the space width was 270 nm. Thereafter, 40 Λ: immersed in a stripping solution of tetramethyl hinged hydroxide ( TMAH ) / dimethyl hydrazine (DMSO ) / water = 1 0/5 0 / 40 (mass ratio) for 6 minutes, peeling off the photoresist film . The chemically-enhanced positive-type lanthanum-based photoresist composition was applied onto the first pattern by a spin coater, and preheated (PAB) at 85 ° C for 60 seconds to form a film thickness of 130 nm. Second photoresist film. -82- 200839450 Next, the mask is placed at 90 nm from the position where the first photoresist film is exposed, and the ArF excimer laser exposure machine NSR-S 302 is used through the mask (Nikon Corporation, ΝΑ = 0·6, σ = 0.75), the second photoresist film is selectively exposed. Next, post-exposure heating (PEB) was carried out at 95 ° C for 60 seconds, and a 2.38 mass % tetramethylammonium hydroxide aqueous solution was used, and the image was imaged at 23 ° C for 30 seconds. Thereafter, rinsing treatment was carried out for 30 seconds with pure water to form a second photoresist pattern. The cross-sectional shape of the L/S pattern at this time was observed using an SEM (scanning electron microscope), and it was confirmed that the line widths were each, the hard mask was 9 3 urn and the second photoresist film was 90 nm, and the spatial width was 88 nm. Next, the first pattern and the second photoresist pattern are used as the mask, and an etching apparatus "GP-12" (trade name: manufactured by Tokyo Ohka Kogyo Co., Ltd.) is used, and the desktop temperature is 25/20 ° C. The uranium engraving gas of 02/N2 (sccm) = 60/40 was introduced for 4 minutes under the conditions of an output power of 1 600 W / a bias voltage of 100 W and a pressure of 3 mTorr, and the underlying film was etched to form a second pattern. The cross-sectional shape of the L/S pattern was observed by SEM (scanning electron microscope), and it was confirmed that the line widths were 90 nm in the portion covered by the hard mask and 89 nm in the portion covered by the second photoresist film. The spatial width is also 92 nm. Further, the aspect ratio after the formation of the second pattern is about 3.2, so that it is confirmed that a high aspect ratio pattern can be obtained. Industrial Applicability The present invention can provide a pattern forming method capable of forming a high-definition and a wide aspect ratio pattern on a support, which is extremely effective in the industry. - 83 - 200839450 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing a step of the drawing step (1) in a preferred embodiment of the pattern forming method of the present invention. 2 is a schematic diagram of a schematic step of the pattern forming step (2) in a preferred embodiment of the pattern forming method of the present invention. Φ [Description of main component symbols] 1 : Support 2 : Underlying film 2 ' : Pattern of the underlying film 3 : Hard mask 3 '· Hard graphic pattern 4 : First photoresist film 4 ' : First light Resistance diagram type % 5 : First mask pattern β 6 : Second photoresist film 6 ': Second photoresist pattern 7: Second mask pattern -84-

Claims (1)

200839450 X. Patent Application No. 1 · A method for forming a type of 匮1 type, which is a pattern forming method for forming a pattern using a chemically amplified photoresist composition, characterized in that it comprises using an underlayer film forming material for a support a step of forming an underlayer film, and a step of forming a hard mask on the underlying film using a sand-based hard mask forming material and applying a chemically-reinforced negative-type photoresist composition to the hard mask a step of the first photoresist film, and a step of selectively exposing the first φ-th photoresist film via the first mask pattern, and then performing the step of forming the first photoresist pattern and the first photoresist The pattern is a mask, the step of etching the hard mask to form the first pattern, and applying the chemically-reinforced positive-type lanthanum photoresist composition to the first pattern and the underlying film to form a second photoresist film a step of selectively exposing the second photoresist film via the second mask pattern, and then forming a second photoresist pattern, and using the first pattern and the second photoresist pattern The pattern is a mask, and the underlying film is etched to form a second pattern. step. 2. The method for forming a pattern according to the first paragraph of the patent application, wherein: the chemically-reinforced positive-type lanthanide photoresist composition is a resin component (A) containing an acid solution which increases solubility, and exposure The photoresist composition of the acid-producing agent (B) which produces an acid, and the resin component (A) is a composition unit (a1) having the following general formula (al) and the following general Resin (A1) constituting unit (a2) represented by formula (a2), -85- 200839450 [Chemical 1] (a 1) f -f-Si〇3/2-) [In the formula (a2), R i is an acid-decomposable group represented by the following formula (] [)] (Chem. 2) - (r2) " l(R3)h—^ (1) [In the formula (I), R2 to R3 are each independently a linking group; L is a linear or branched alkyl group having a carbon number of 1 to 1 Å, and a carbon number of 2 a linear or branched fluoroalkyl group of 20, a substituted or unsubstituted extended aryl group, a substituted or unsubstituted cyclic alkyl group, and a substituted or unsubstituted alkylene group selected from the group consisting of Z is an acid dissociable group; g is 〇 or ih is 0 or 1] 3. The method for forming a pattern according to claim 1 or 2, wherein the first pattern is as described above The second mask pattern is used, and the first mask pattern is disposed at a position different from the first photoresist film for selective exposure, and the second photoresist film is selectively exposed.