JP2006060006A - Semiconductor device, method for manufacturing the same, and method for forming resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To use ArF (Argon Fluoride) excimer laser light as exposure light at the time of patterning, and to control the amount of thickening of a resist pattern uniformly even if conditions such as temperature and atmosphere change. An efficient manufacturing method of a high-performance semiconductor device having a fine wiring pattern exceeding the exposure limit of the light source of the exposure apparatus.
After forming a resist pattern on a processed surface, vacuum resist baking is performed on the resist pattern in a vacuum, and then a resist pattern thickening material containing at least a resin is applied to the surface of the resist pattern. A thickened resist pattern forming step of forming the thickened resist pattern by thickening the resist pattern, and a patterning step of patterning the processed surface by etching using the thickened resist pattern as a mask. A method for manufacturing a semiconductor device, comprising:
[Selection] Figure 1

Description

  The present invention is a resist pattern forming method capable of forming a fine pattern exceeding the exposure limit in a light source of an existing exposure apparatus by thickening a resist pattern formed when manufacturing a semiconductor device, and The present invention relates to a semiconductor device and a manufacturing method thereof.

At present, high integration of semiconductor integrated circuits has progressed, and LSI and VLSI have been put to practical use, and accordingly, the wiring pattern has a size of 0.2 μm or less, and the smallest one has a size of 0.1 μm or less. It has been miniaturized. In order to form a fine wiring pattern, the substrate to be processed is covered with a resist film, and after the resist film is selectively exposed, the resist pattern is formed by development, and the resist pattern is used as a mask. A lithography technique that obtains a desired pattern (for example, a wiring pattern) by performing dry etching on a substrate to be processed and then removing the resist pattern is very important. In this lithography technique, it is necessary to both shorten the wavelength of exposure light (light used for exposure) and develop a resist material having high resolution in accordance with the characteristics of the light.
However, in order to shorten the wavelength of the exposure light, it is necessary to improve the exposure apparatus, which requires enormous costs. On the other hand, it is not easy to develop a resist material corresponding to exposure light having a short wavelength.

  For this reason, a resist pattern thickening material (sometimes referred to as “resist swelling agent”) that makes it possible to thicken a resist pattern formed using an existing resist material and obtain a fine resist omission pattern. A technique for forming a finer pattern by using it has been proposed. For example, after forming a KrF resist pattern by exposing a KrF (krypton fluoride) resist film using KrF (krypton fluoride) excimer laser light (wavelength 248 nm) which is deep ultraviolet rays, a water-soluble resin composition is formed. A coating film is provided so as to cover the KrF resist pattern, and the coating film and the KrF resist pattern are allowed to interact at the contact interface, thereby increasing the thickness of the KrF resist pattern (hereinafter referred to as “swelling”). In some cases, the distance between the KrF resist patterns is shortened to form a fine resist removal pattern, and then a desired pattern (for example, a wiring pattern) is formed (Patent Literature). 1).

  From the viewpoint of forming a fine wiring pattern or the like, as exposure light, light having a shorter wavelength than KrF (krypton fluoride) excimer laser light (wavelength 248 nm), for example, ArF (argon fluoride) excimer laser light (wavelength 193 nm). ) Etc. are desired. On the other hand, in the case of pattern formation using an X-ray, electron beam or the like having a wavelength shorter than that of the ArF (argon fluoride) excimer laser light (wavelength 193 nm), the ArF It is desired to use (argon fluoride) excimer laser light (wavelength 193 nm).

In the case of a fine resist removal pattern formed by a resist pattern such as the ArF resist, it is sufficient if the resist pattern can be thickened (swelled) on the order of several tens of nanometers. Increasing the thickness may be undesirable, and in some cases, it may be sufficient if the edge roughness of the resist pattern can be improved. However, in the case of the conventional technique, there is a problem that it is difficult to control the amount of thickening (swelling) of the resist pattern, and it is difficult to perform fine patterning under delicate control.
Depending on the shape of the exposure pattern, for example, in a rectangular isolated pattern, the amount of thickening (swelling) in the long side direction of the pattern may be larger than the amount of thickening (swelling) in the short side direction, However, the amount of pattern thickening (swelling) varies greatly depending on the pattern density, and the pattern thickening (swelling) varies depending on the pattern position on the wafer. The cause was unknown.

Japanese Patent Laid-Open No. 10-73927

An object of the present invention is to solve the conventional problems and achieve the following objects. That is,
In the present invention, ArF (Argon Fluoride) excimer laser light can also be used as exposure light during patterning, and the thickness of the resist pattern can be kept constant and accurate even when conditions such as temperature and atmosphere change. A resist pattern forming method that can be controlled and can easily and efficiently form a fine resist omission pattern at a low cost exceeding the exposure limit of the light source of the exposure apparatus, and a fine pattern formed using the resist omission pattern An object of the present invention is to provide a high-performance semiconductor device having an appropriate wiring pattern and a method for manufacturing a semiconductor device capable of efficiently mass-producing the semiconductor device.

  As a result of intensive studies by the present inventors in order to solve the above-described problems, the present inventors have obtained the following knowledge. That is, in the process of thickening the resist pattern by applying a resist pattern thickening material (swelling material) to the resist pattern, an acid-dependent reaction that is thickened by residual acid in the resist pattern and The resist pattern does not use the residual acid, and there is an acid-free reaction that is thickened regardless of the presence of the residual acid. In the case of the acid-dependent reaction, the reaction depends on the residual acid. However, in the case of the acid-free reaction, since the reaction does not depend on the residual acid, the temperature and atmosphere (alkaline contamination) are greatly affected by other conditions such as temperature and atmosphere (alkali contamination, etc.). Etc.) and other conditions, it is easy to control, and the resist pattern is thickened (swelled). As small as about to 30 nm, a finding that is suitable for fine patterning. Therefore, fine patterning becomes possible by eliminating the acid-dependent reaction as an unstable element and utilizing the acid-free reaction.

The present invention is based on the above knowledge, and means for solving the above problems are as listed in the appendix to be described later.
In the method for producing a resist pattern of the present invention, a resist pattern thickening material containing at least a resin is applied to the surface of the resist pattern after the resist pattern is formed and vacuum baking is performed to bake the resist pattern in a vacuum. It is characterized by applying.
In the method for producing the resist pattern, after the resist pattern is formed, the resist pattern is baked in vacuum by the vacuum baking process. As a result, the residual acid in the resist pattern (particularly the residual acid near the surface of the resist pattern) is volatilized and removed from the resist pattern (particularly near the surface of the resist pattern). Thereafter, when the resist pattern thickening material is applied onto the resist pattern, the resist pattern thickening material in the vicinity of the interface with the resist pattern soaks into the resist pattern. Interacts with the material. Therefore, a surface layer (mixing layer) made of the resist pattern thickening material and the resist pattern is formed on the surface of the resist pattern as an inner layer. At this time, the acid has been removed from the resist pattern, and the resist pattern thickening material eliminates the unstable acid-dependent reaction with respect to the resist pattern, and reacts by the acid unnecessary reaction, The resist pattern is stably thickened (swelled) without greatly changing the amount of thickening (swelled) due to other conditions such as temperature and atmosphere (such as alkali contamination). As a result, the resist removal pattern formed by the thickened resist pattern has a finer structure that exceeds the exposure limit. The resist omission pattern is suitably used for manufacturing a semiconductor device.

In the method of manufacturing a semiconductor device of the present invention, after forming a resist pattern on a surface to be processed, vacuum resist baking is performed on the resist pattern in a vacuum, and then a resist pattern thickening material containing at least a resin is added. A thickened resist pattern forming step for forming the thickened resist pattern by thickening the resist pattern by applying to the surface of the resist pattern, and etching on the processed surface by using the thickened resist pattern as a mask And a patterning process for performing patterning.
In the manufacturing method of the semiconductor device, first, in the thickening resist pattern forming step, after forming a resist pattern on the surface to be processed which is a target for forming a pattern such as a wiring pattern, the resist pattern is vacuumed. A baking process for baking is performed. As a result, the residual acid in the resist pattern (particularly the residual acid near the surface of the resist pattern) is volatilized and removed from the resist pattern (particularly near the surface of the resist pattern). Next, a resist pattern thickening material containing at least a resin is applied to the surface of the resist pattern. Then, among the resist pattern thickening material, the material near the interface with the resist pattern soaks into the resist pattern and interacts (mixes) with the resist pattern material. Therefore, a surface layer (mixing layer) is formed on the surface of the resist pattern as an inner layer, and the resist pattern thickening material and the resist pattern interact with each other. At this time, the residual acid is removed from the resist pattern, and the resist pattern thickening material eliminates the unstable acid-dependent reaction with respect to the resist pattern, and reacts by the acid unnecessary reaction. The resist pattern is stably thickened (swelled) without greatly changing the amount of thickening (swelled) depending on other conditions such as temperature and atmosphere (alkali contamination, etc.). As a result, the thickened thickened resist pattern is uniformly thickened by the resist pattern thickening material. For this reason, the resist omission pattern formed by the thickened resist pattern has a finer structure beyond the exposure limit.
Next, in the patterning step, etching is performed using the thickened resist pattern formed in the thickened resist pattern forming step, so that the surface to be processed is patterned with high precision and dimensional accuracy. Therefore, a high-quality and high-performance semiconductor device having a pattern such as an extremely fine and high-definition and excellent dimensional accuracy such as a wiring pattern is efficiently manufactured.

  The semiconductor device of the present invention is manufactured by the method for manufacturing a semiconductor device of the present invention. For this reason, the semiconductor device has a fine and high-definition pattern having a high dimensional accuracy, such as a wiring pattern, and has high quality and high performance.

According to the present invention, conventional problems can be solved, and the above object can be achieved.
In addition, according to the present invention, ArF (argon fluoride) excimer laser light can also be used as exposure light during patterning, and the thickness of the resist pattern can be kept constant even when conditions such as temperature and atmosphere change. And a resist pattern forming method capable of easily and efficiently forming a fine resist omission pattern at a low cost exceeding the exposure limit in the light source of the exposure apparatus, and the resist omission pattern. A high-performance semiconductor device having a formed fine wiring pattern and a method for manufacturing a semiconductor device capable of efficiently mass-producing the semiconductor device can be provided.

(Semiconductor device and manufacturing method thereof, and resist pattern forming method)
The method for manufacturing a semiconductor device of the present invention includes a thickened resist pattern forming step and a patterning step, and further includes other steps appropriately selected as necessary.
The semiconductor device of the present invention is manufactured by the method for manufacturing a semiconductor device of the present invention. The details of the semiconductor device of the present invention will be clarified through the description of the manufacturing method of the semiconductor device of the present invention.
In addition, the method for producing a resist pattern of the present invention comprises forming a resist pattern, performing a vacuum baking process for baking the resist pattern in a vacuum, and then adding a resist pattern thickening material containing at least a resin to the resist pattern. It includes application to the surface, and further includes other treatments appropriately selected as necessary. Since the resist pattern forming method of the present invention is the same as the thickened resist pattern forming step in the semiconductor device manufacturing method of the present invention, the details will be clarified through the description of the thickened resist pattern forming step. To do.

-Thickening resist pattern formation process-
In the thickening resist pattern forming step, after forming a resist pattern on the surface to be processed, vacuum resist baking is performed on the resist pattern in a vacuum, and then a resist pattern thickening material containing at least a resin is used. It is a step of forming a thickened resist pattern by thickening the resist pattern by applying to the surface of the resist pattern.
As described above, the thickened resist pattern forming step corresponds to the resist pattern forming method of the present invention.

--- Formation of resist pattern-
The material of the resist pattern (resist pattern to which a resist pattern thickening material is applied) is not particularly limited and can be appropriately selected from known resist materials according to the purpose. For example, g-line resist, i-line resist, KrF resist, ArF resist, F2 that can be patterned with g-line, i-line, KrF excimer laser, ArF excimer laser, F2 excimer laser, electron beam, etc. A resist, an electron beam resist, etc. are mentioned suitably. These may be chemically amplified or non-chemically amplified. Among these, a KrF resist, an ArF resist, a resist containing an acrylic resin, and the like are preferable. From the viewpoint of finer patterning, an improvement in throughput, and the like, an ArF resist whose extension of the resolution limit is urgently required. And at least one of resists comprising an acrylic resin is more preferable.

  Specific examples of the resist pattern material include novolak resist, PHS resist, acrylic resist, cycloolefin-maleic anhydride (COMA) resist, cycloolefin resist, and hybrid (alicyclic acrylic). -COMA copolymer) resist and the like. These may be modified with fluorine.

  The resist pattern can be formed on the surface to be processed (base material), and the surface to be processed (base material) is not particularly limited and can be appropriately selected according to the purpose. Specifically, a substrate such as a silicon wafer, an interlayer insulating film, a wiring material film, various oxide films, and the like are particularly preferable.

  The method for forming the resist pattern is not particularly limited and may be appropriately selected depending on the purpose. For example, after applying the above-described known resist material to form a coating film, the resist film is exposed to light. A method of forming a resist pattern having a desired shape by performing the method may be used. In addition, you may perform a baking process after the said exposure.

The light used for the exposure may be selected according to the type of the resist material, and examples thereof include g-line, i-line, KrF excimer laser, ArF excimer laser, F2 excimer laser, and electron beam.
The size, thickness and the like of the resist pattern are not particularly limited and can be appropriately selected according to the purpose.In particular, the thickness can be appropriately determined according to the surface to be processed, etching conditions, and the like. Generally, it is about 0.2 to 200 μm.

--Vacuum baking process--
There is no restriction | limiting in particular as temperature of the said vacuum baking process, According to the objective, it can select suitably, For example, 60-150 degreeC is preferable and 80-130 degreeC is more preferable.
When the temperature is lower than 60 ° C., the residual acid in the resist pattern has a small volatility effect, and the residual acid may not be sufficiently removed. The shape of the resist pattern may change.

There is no restriction | limiting in particular as a vacuum degree of the said vacuum baking process, According to the objective, it can select suitably, For example, 50 torr or less is preferable and 10 torr or less is more preferable.
When the degree of vacuum exceeds 50 torr, the residual acid in the resist pattern has a small volatility effect and the residual acid may not be sufficiently removed.

There is no restriction | limiting in particular as time of the said vacuum baking process, According to the objective, it can select suitably, For example, 10-300 seconds are preferable and 30-120 seconds are more preferable.
When the time is less than 10 seconds, the residual acid volatilization effect in the resist pattern is small, and the residual acid may not be sufficiently removed. In some cases, the process time cannot be shortened.

  In addition, the said vacuum baking process can be performed using the well-known apparatus selected suitably, for example, can be performed using a vacuum heating apparatus.

--Resist pattern thickening material--
The resist pattern thickening material contains at least a resin, and further includes a crosslinking agent, a surfactant, a water-soluble aromatic compound, and an aromatic compound, which are appropriately selected as necessary. It contains a resin, an organic solvent, a phase transfer catalyst, a polyhydric alcohol having at least two hydroxyl groups, and other components.

The resist pattern thickening material is water-soluble or alkali-soluble.
The water solubility is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the water solubility is such that 0.1 g or more of the resist pattern thickening material dissolves in 100 g of water at 25 ° C. preferable.
The alkalinity is not particularly limited and may be appropriately selected depending on the purpose. For example, the resist pattern is thick with respect to 100 g of a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 25 ° C. Water solubility in which 0.1 g or more of the chemical material is dissolved is preferable.
An embodiment of the resist pattern thickening material is an aqueous solution, but it may be an embodiment such as a colloid liquid or an emulsion liquid, but is preferably an aqueous solution.

---- Resin ---
The resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably water-soluble or alkali-soluble, and can cause a crosslinking reaction or does not cause a crosslinking reaction, but a water-soluble crosslinking agent. More preferably, it can be mixed with.
The resin preferably has two or more polar groups from the viewpoint of good water solubility or alkali solubility.
There is no restriction | limiting in particular as said polar group, According to the objective, it can select suitably, For example, a hydroxyl group, an amino group, a sulfonyl group, a carbonyl group, a carboxyl group, these derivative groups etc. are mentioned suitably. These may be contained alone in the resin, or may be contained in the resin in a combination of two or more.

In the case where the resin is a water-soluble resin, the water-soluble resin is preferably a water-soluble resin that dissolves 0.1 g or more in 100 g of water at 25 ° C.
Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, polyacrylic acid, polyvinyl pyrrolidone, polyethyleneimine, polyethylene oxide, styrene-maleic acid copolymer, polyvinylamine, polyallylamine, and an oxazoline group-containing water-soluble resin. Examples thereof include resins, water-soluble melamine resins, water-soluble urea resins, alkyd resins, and sulfonamide resins.

When the resin is an alkali-soluble resin, the alkali-soluble resin has an alkali-solubility that dissolves 0.1 g or more with respect to 100 g of an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 25 ° C. preferable.
Examples of the alkali-soluble resin include novolak resins, vinylphenol resins, polyacrylic acid, polymethacrylic acid, poly p-hydroxyphenyl acrylate, poly p-hydroxyphenyl methacrylate, and copolymers thereof.

  The said resin may be used individually by 1 type, and may use 2 or more types together. Among these, polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, and the like are preferable, and the polyvinyl acetal is more preferably contained in an amount of 5 to 40% by mass.

In the present invention, the resin may have a ring structure in at least a part thereof, and using such a resin imparts good etching resistance to the resist pattern thickening material. This is advantageous in that
In the present invention, the resin having at least a part of the cyclic structure may be used singly or in combination of two or more, or it may be used in combination with the resin.

  The resin having the cyclic structure in part is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a resin capable of causing a crosslinking reaction is preferable, and a polyvinyl aryl acetal resin, Preferred examples include polyvinyl aryl ether resins, polyvinyl aryl ester resins, and derivatives thereof. At least one selected from these is preferable, and an acetyl group is preferable in that it exhibits moderate water solubility or alkali solubility. Particularly preferred are those having

The polyvinyl aryl acetal resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-resorcin acetal.
There is no restriction | limiting in particular as said polyvinyl aryl ether resin, According to the objective, it can select suitably, For example, 4-hydroxybenzyl ether etc. are mentioned.
There is no restriction | limiting in particular as said polyvinyl aryl ester resin, According to the objective, it can select suitably, For example, benzoic acid ester etc. are mentioned.

  There is no restriction | limiting in particular as a manufacturing method of the said polyvinyl aryl acetal resin, According to the objective, it can select suitably, For example, the manufacturing method using a well-known polyvinyl acetal reaction etc. are mentioned suitably. The production method is, for example, a method in which an acetalization reaction is performed between polyvinyl alcohol and a stoichiometrically required amount of aldehyde under an acid catalyst. Specifically, USP 5,169, Preferable examples include the methods disclosed in U.S. Patent No. 897, No. 5,262,270, and Japanese Patent Laid-Open No. 5-78414.

  The method for producing the polyvinyl aryl ether resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a copolymerization reaction between the corresponding vinyl aryl ether monomer and vinyl acetate, in the presence of a basic catalyst. And etherification reaction between polyvinyl alcohol and an aromatic compound having a halogenated alkyl group (Williamson's ether synthesis reaction), and the like. Specific examples include JP-A-2001-40086, JP-A-2001-181383, The method etc. which were indicated by Unexamined-Japanese-Patent No. 6-116194 etc. are mentioned suitably.

  The method for producing the polyvinyl aryl ester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a copolymerization reaction between the corresponding vinyl aryl ester monomer and vinyl acetate, in the presence of a basic catalyst. And esterification reaction of polyvinyl alcohol and an aromatic carboxylic acid halide compound.

  The cyclic structure in the resin having the cyclic structure in part is not particularly limited and may be appropriately selected depending on the purpose. For example, a single ring (such as benzene), a polycycle (such as bisphenol), Any of condensed rings (such as naphthalene) may be used, and specific examples include aromatic compounds, alicyclic compounds, and heterocyclic compounds. The resin having a part of the cyclic structure may have one of these cyclic structures alone or two or more.

  Examples of the aromatic compounds include polyhydric phenol compounds, polyphenol compounds, aromatic carboxylic acid compounds, naphthalene polyhydric alcohol compounds, benzophenone compounds, flavonoid compounds, porphine, water-soluble phenoxy resins, aromatic-containing water-soluble dyes, and the like. Derivatives thereof, glycosides thereof, and the like. These may be used alone or in combination of two or more.

Examples of the polyhydric phenol compound include resorcin, resorcin [4] arene, pyrogallol, gallic acid, derivatives or glycosides thereof, and the like.
Examples of the polyphenol compound include catechin, anthocyanidin (pelargosine type (4′-hydroxy), cyanidin type (3 ′, 4′-dihydroxy), delphinidin type (3 ′, 4 ′, 5′-trihydroxy)), And flavan-3,4-diol, proanthocyanidins, and the like.
Examples of the aromatic carboxylic acid compound include salicylic acid, phthalic acid, dihydroxybenzoic acid, and tannin.
Examples of the naphthalene polyhydric alcohol compound include naphthalene diol, naphthalene triol, and the like.
Examples of the benzophenone compound include alizarin yellow A.
Examples of the flavonoid compound include flavone, isoflavone, flavanol, flavonone, flavonol, flavan-3-ol, aurone, chalcone, dihydrochalcone, quercetin, and the like.

Examples of the alicyclic compound include polycycloalkanes, cycloalkanes, condensed rings, derivatives thereof, glycosides thereof, and the like. These may be used individually by 1 type and may use 2 or more types together.
Examples of the polycycloalkanes include norbornane, adamantane, norpinane, and sterane.
Examples of the cycloalkanes include cyclopentane and cyclohexane.
Examples of the condensed ring include steroids.

  Examples of the heterocyclic compound include nitrogen-containing cyclic compounds such as pyrrolidine, pyridine, imidazole, oxazole, morpholine, and pyrrolidone, oxygen-containing cyclic compounds such as polysaccharides including furan, pyran, pentose, and hexose. Etc. are preferable.

  Examples of the resin having the cyclic structure include hydroxyl group, cyano group, alkoxyl group, carboxyl group, amino group, amide group, alkoxycarbonyl group, hydroxyalkyl group, sulfonyl group, acid anhydride group, and lactone. It is preferable from the viewpoint of appropriate water solubility to have at least one functional group such as a group, a cyanate group, an isocyanate group, and a ketone group, and a sugar derivative, depending on the hydroxyl group, amino group, sulfonyl group, carboxyl group, and derivatives thereof. More preferably, it has at least one functional group selected from the group.

The molar content of the cyclic structure in the resin having a part of the cyclic structure is not particularly limited as long as the etching resistance is not affected, and can be appropriately selected according to the purpose, and has high etching resistance. If necessary, it is preferably 5 mol% or more, more preferably 10 mol% or more.
In addition, the molar content of the cyclic structure in the resin partially including the cyclic structure can be measured using, for example, NMR.

  The content of the resin (including the resin having the cyclic structure in part) in the resist pattern thickening material includes the resin not having the cyclic structure, a crosslinking agent described later, and a surface activity. It can be appropriately determined according to the type and content of the agent.

--- Crosslinking agent ---
There is no restriction | limiting in particular as said crosslinking agent, According to the objective, it can select suitably, For example, the water-soluble thing which bridge | crosslinks with a heat | fever or an acid is preferable, Among these, an amino type crosslinking agent is more preferable.
Suitable examples of the amino crosslinking agent include melamine derivatives, urea derivatives, uril derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the urea derivative include urea, alkoxymethylene urea, N-alkoxymethylene urea, ethylene urea, ethylene urea carboxylic acid, and derivatives thereof.
Examples of the melamine derivative include alkoxymethylmelamine and derivatives thereof.
Examples of the uril derivative include benzoguanamine, glycoluril, and derivatives thereof.
The content of the cross-linking agent in the resist pattern thickening material varies depending on the type and content of the resin and the like and cannot be defined unconditionally, but can be appropriately determined according to the purpose.

--- Surfactant ---
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, nonionic surfactants are preferable in that they do not contain metal ions.

  The nonionic surfactant is preferably selected from an alkoxylate surfactant, a fatty acid ester surfactant, an amide surfactant, an alcohol surfactant, and an ethylenediamine surfactant. Can be mentioned. Specific examples of these include polyoxyethylene-polyoxypropylene condensate compounds, polyoxyalkylene alkyl ether compounds, polyoxyethylene alkyl ether compounds, polyoxyethylene derivative compounds, sorbitan fatty acid ester compounds, glycerin fatty acid ester compounds, Primary alcohol ethoxylate compound, phenol ethoxylate compound, nonylphenol ethoxylate, octylphenol ethoxylate, lauryl alcohol ethoxylate, oleyl alcohol ethoxylate, fatty acid ester, amide, natural alcohol, ethylenediamine, Secondary alcohol ethoxylate type and the like.

  The cationic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkyl cationic surfactants, amide type quaternary cationic surfactants, and ester type quaternary cationic types. Surfactant etc. are mentioned.

  There is no restriction | limiting in particular as said amphoteric surfactant, According to the objective, it can select suitably, For example, an amine oxide type surfactant, a betaine type surfactant, etc. are mentioned.

  The content of the surfactant in the resist pattern thickening material differs depending on the type and content of the resin, the crosslinking agent, etc., and cannot be specified unconditionally, but is appropriately selected according to the purpose can do.

--- Water-soluble aromatic compound ---
The water-soluble aromatic compound is not particularly limited as long as it is an aromatic compound and exhibits water-solubility, and can be appropriately selected according to the purpose. However, 1 g or more is dissolved in 100 g of water at 25 ° C. Those exhibiting water solubility are preferable, those exhibiting water solubility of 3 g or more with respect to 100 g of water at 25 ° C. are more preferable, and those having water solubility of 5 g or more with respect to 100 g of water at 25 ° C. are particularly preferable.
When the resist pattern thickening material contains the water-soluble aromatic compound, the etching resistance of the resulting resist pattern can be remarkably improved by the cyclic structure contained in the water-soluble aromatic compound. Is preferable.

  Examples of the water-soluble aromatic compound include polyphenol compounds, aromatic carboxylic acid compounds, benzophenone compounds, flavonoid compounds, porphine, water-soluble phenoxy resins, aromatic-containing water-soluble dyes, derivatives thereof, glycosides thereof, Etc. These may be used alone or in combination of two or more.

  Examples of the polyphenol compound include catechin, anthocyanidin (pelargosine type (4′-hydroxy), cyanidin type (3 ′, 4′-dihydroxy), delphinidin type (3 ′, 4 ′, 5′-trihydroxy)), Examples include flavan-3,4-diol, proanthocyanidins, resorcin, resorcin [4] arene, pyrogallol, gallic acid, and the like.

  Examples of the aromatic carboxylic acid compound include salicylic acid, phthalic acid, dihydroxybenzoic acid, and tannin.

Examples of the benzophenone compound include alizarin yellow A and body.
Examples of the flavonoid compound include flavone, isoflavone, flavanol, flavonone, flavonol, flavan-3-ol, aurone, chalcone, dihydrochalcone, quercetin, and the like.

  These may be used individually by 1 type and may use 2 or more types together. Among these, the polyphenol compound is preferable, and catechin, resorcin, and the like are particularly preferable.

Among the water-soluble aromatic compounds, those having two or more polar groups are preferable, those having three or more are more preferable, and those having four or more are particularly preferable in terms of excellent water solubility.
There is no restriction | limiting in particular as said polar group, According to the objective, it can select suitably, For example, a hydroxyl group, a carboxyl group, a carbonyl group, a sulfonyl group etc. are mentioned.

  The content of the water-soluble aromatic compound in the resist pattern thickening material can be appropriately determined according to the type and content of the resin, the crosslinking agent, the surfactant, and the like.

--- Organic solvent ---
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohol-based organic solvents, chain ester-based organic solvents, cyclic ester-based organic solvents, ketone-based organic solvents, and chain ethers. And organic ether solvents and cyclic ether organic solvents.
When the resist pattern thickening material contains the organic solvent, the resist pattern thickening material improves the solubility of the resin, the polyhydric alcohol having at least two hydroxyl groups, the crosslinking agent, and the like. It is advantageous in that it can be made.

Examples of the alcohol organic solvent include methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, and the like.
Examples of the chain ester organic solvent include ethyl lactate and propylene glycol methyl ether acetate (PGMEA).
Examples of the cyclic ester organic solvent include lactone organic solvents such as γ-butyrolactone.
Examples of the ketone organic solvent include ketone organic solvents such as acetone, cyclohexanone, and heptanone.
Examples of the chain ether organic solvent include ethylene glycol dimethyl ether.
Examples of the cyclic ether organic solvent include tetrahydrofuran, dioxane, and the like.

  These organic solvents may be used individually by 1 type, and may use 2 or more types together. Among these, those having a boiling point of about 80 to 200 ° C. are preferable in that the thickness of the resist pattern can be finely increased.

  The content of the organic solvent in the resist pattern thickening material can be appropriately determined according to the type and content of the resin, the crosslinking agent, the surfactant, and the like.

---- Phase transfer catalyst ---
There is no restriction | limiting in particular as said phase transfer catalyst, According to the objective, it can select suitably, For example, organic substance etc. are mentioned, Among these, a basic thing is mentioned suitably.
When the phase transfer catalyst is contained in the resist pattern thickening material, it shows a good and uniform thickening effect regardless of the type of the resist pattern material, and the dependence on the resist pattern material is reduced. Is advantageous. Note that such an action of the phase transfer catalyst is, for example, whether or not the resist pattern to be thickened using the resist pattern thickening material contains or contains an acid generator. If not, it will not be harmed.

The phase transfer catalyst is preferably water-soluble, and the water-solubility is preferably 0.1 g or more dissolved in 100 g of water at 25 ° C.
Specific examples of the phase transfer catalyst include crown ethers, azacrown ethers, onium salt compounds, and the like.
The phase transfer catalyst may be used alone or in combination of two or more. Among these, an onium salt compound is preferable in view of high solubility in water.

  Examples of the crown ether or the azacrown ether include 18-crown-6 (18-crown-6), 15-crown-5 (15-crown-5), 1-aza-18-crown-6 (1 -Aza-18-crown-6), 4,13-diaza-18-crown-6 (4,13-Diaza-18-crown-6), 1,4,7-triazacyclononane (1,4,4) 7-Triazacyclonenone) and the like.

  The onium salt compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include quaternary ammonium salts, pyridinium salts, thiazolium salts, phosphonium salts, piperazinium salts, ephedrinium salts, and quininium salts. And cinchonium salts are preferred.

Examples of the quaternary ammonium salt include tetrabutylammonium hydrogen sulfate, tetramethylammonium acetate, and tetramethylammonium chloride, which are frequently used as organic synthesis reagents. Is mentioned.
Examples of the pyridinium salt include hexadecylpyridinium bromide.
Examples of the thiazolium salt include 3-benzyl-5- (2-hydroxyethyl) -4-methylthiazolium chloride (3-Benzyl-5- (2-hydroxyethyl) -4-methylthiazol chloride). Can be mentioned.
Examples of the phosphonium salt include tetrabutylphosphonium chloride.
Examples of the piperazinium salt include 1,1-dimethyl-4-phenylpiperazinium (1,1-dimethyl-4-phenylpiperazine iodide).
Examples of the ephedolinium salt include (-)-N, N-dimethylephedrineium bromide ((-)-N, N-dimethylephedrine bromide).
As said quininium salt, N-benzyl quininium chloride (N-Benzylquininium chloride) etc. are mentioned, for example.
Examples of the cinchonium salt include N-benzyl cinchonium chloride (N-Benzylcinchoinium chloride).

The content of the phase transfer catalyst in the resist pattern thickening material differs depending on the type and amount of the resin and the like, and cannot be specified unconditionally, but may be appropriately selected according to the type and content. For example, it is preferably 10,000 ppm or less, more preferably 10 to 10,000 ppm, still more preferably 10 to 5,000 ppm, and particularly preferably 10 to 3,000 ppm.
When the content of the phase transfer catalyst is 10,000 ppm or less, it is advantageous in that a resist pattern such as a line pattern can be thickened without depending on its size.
The content of the phase transfer catalyst can be measured, for example, by analyzing by liquid chromatography.

--- Polyhydric alcohol having at least two hydroxyl groups ---
The polyhydric alcohol having at least two hydroxyl groups is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include saccharides, saccharide derivatives, glycosides, and naphthalene polyhydric alcohol compounds. .
Etc. are preferable.

The saccharide is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include pentose and hexose. Specific examples of the saccharide include arabinose, fructose, galactose, glucose, ribose, saccharose, maltose and the like.
There is no restriction | limiting in particular as a derivative | guide_body of the said sugar, According to the objective, it can select suitably, For example, an amino sugar, a sugar acid, a deoxy sugar, a sugar alcohol, a glycal, a nucleoside etc. are mentioned suitably.
There is no restriction | limiting in particular as said glycoside, It can select suitably according to the objective, For example, a phenol glycoside etc. are mentioned suitably. Preferable examples of the phenol glycoside include salicin, arbutin, 4-aminophenylgalactopyranoside, and the like.
Examples of the naphthalene polyhydric alcohol compound include naphthalene diol, naphthalene triol, and the like.

  These may be used individually by 1 type and may use 2 or more types together. Among these, those having an aromatic ring are preferable from the viewpoint of imparting etching resistance to the resist pattern thickening material, among which glycosides are preferable, and phenol glycosides are more preferable.

The content of the polyhydric alcohol having at least two hydroxyl groups in the resist pattern thickening material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the resist pattern thickening material 0.001-50 mass parts is preferable with respect to the whole quantity, and 0.1-10 mass parts is more preferable.
If the content of the polyhydric alcohol having at least two hydroxyl groups is less than 0.001 part by mass, the thickening amount of the resist pattern thickening material may depend on the resist pattern size. If it exceeds 10% by mass, a part of the resist pattern may be dissolved depending on the resist material.

---- Other resins ---
The other components are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected according to the purpose. Various known additives such as thermal acid generators, amines, amides, Quenchers such as ammonium chlorine are listed.

  The content of the other components in the resist pattern thickening material can be appropriately determined according to the type and content of the resin, the crosslinking agent, the surfactant, and the like.

--- Application of resist pattern thickening material ---
The method for applying the resist pattern thickening material is not particularly limited and can be appropriately selected from known application methods such as a roller coating method, a dip coating method, a spray coating method, and a bar coating method. , Kneader coating method, curtain coating method and the like, and spin coating method and the like are particularly preferable. In the case of the spin coating method, for example, the rotational speed is about 100 to 10000 rpm, preferably 800 to 5000 rpm, the time is about 1 to 10 minutes, and preferably 1 to 90 seconds.

  The coating thickness at the time of coating is usually about 100 to 10,000 mm (10 to 1,000 nm), preferably about 1,000 to 5,000 mm (100 to 500 nm).

  In addition, at the time of the application, the surfactant may not be contained in the resist pattern thickening material but may be separately applied before applying the resist pattern thickening material.

Pre-baking (heating and drying) the applied resist pattern thickening material during or after the application is performed at the interface between the resist pattern and the resist pattern thickening material. This is preferable in that mixing (impregnation) of the material into the resist pattern can be efficiently generated.
The pre-baking (heating / drying) conditions, methods, etc. are not particularly limited as long as the resist pattern is not softened, and can be appropriately selected according to the purpose. Or two or more times. In the case of two or more times, the temperature of the pre-bake in each time may be constant or may be different. When the temperature is constant, about 60 to 150 ° C is preferable, and 70 to 120 ° C is more preferable. The time is preferably about 30 to 300 seconds, more preferably 40 to 100 seconds.
The pre-baking is for removing the solvent, and is not directly related to the thickening of the resist pattern, and can be performed under the conditions recommended by the manufacturer of the resist to be used.

Further, after the pre-baking (heating / drying), the applied resist pattern thickening material is subjected to coating baking (mixing baking) at the interface between the resist pattern and the resist pattern thickening material. This is preferable in that the crosslinking reaction of the mixed (impregnated) portion can be efficiently advanced.
The conditions and method of the application baking (mixing baking) are not particularly limited and can be appropriately selected according to the purpose. However, a temperature condition usually higher than that of the pre-baking (heating / drying) is adopted. Is done. As conditions for the application baking (mixing baking), for example, the temperature is about 60 to 150 ° C, 90 to 130 ° C is preferable, the time is about 30 to 300 seconds, and 40 seconds to 100 seconds are preferable.
In addition, when the temperature of the application baking (mixing baking) is less than 60 ° C., the residual acid in the resist pattern has a small volatility effect and the residual acid may not be sufficiently removed. Exceeding the value may cause the shape of the resist pattern to change due to heat flow. Since the acid-free reaction is a kind of thermal reaction, usually, the higher the temperature, the greater the amount of thickening (swelling) of the resist pattern.

  Furthermore, it is preferable that after the coating baking (mixing baking), the applied resist pattern thickening material is developed. In this case, a portion of the applied resist pattern thickening material which is not interacting (mixing) with the resist pattern or a portion having weak interaction (mixing) (highly water-soluble portion) is dissolved and removed to increase the thickness. This is preferable in that the resist pattern can be developed (obtained).

  The development may be water development, development with a weak alkaline aqueous solution, or a combination thereof. However, water development is effective in that development processing can be performed efficiently at low cost. Development is preferred.

--- Thickening resist pattern--
The thickened resist pattern is preferably excellent in etching resistance, and the etching rate (nm / min) is preferably equal to or higher than that of the resist pattern. Specifically, the ratio between the etching rate (nm / min) of the surface layer (mixing layer) and the etching rate (nm / min) of the resist pattern (resist pattern / surface layer (mixing) when measured under the same conditions. The layer)) is preferably 1.1 or more, more preferably 1.2 or more, and particularly preferably 1.3 or more.
The etching rate (nm / min) is measured, for example, by performing a predetermined time etching process using a known etching apparatus, measuring the film thickness of the sample, and calculating the film thickness per unit time. be able to.
The surface layer (mixing layer) can be suitably formed using the resist pattern thickening material, and from the viewpoint of improving etching resistance, the ring such as a resin having the ring structure in part. It preferably includes a structure.

  Whether or not the surface layer (mixing layer) includes the ring structure can be confirmed, for example, by analyzing an IR absorption spectrum of the surface layer (mixing layer).

When the resist pattern thickening material is applied onto the resist pattern and allowed to interact (mixing) with the resist pattern, the resist pattern thickening material and the resist pattern interact on the surface of the resist pattern. Thus, a layer (mixing layer) is formed. As a result, the resist pattern is thickened as much as the mixing layer is formed, and a thickened resist pattern is formed.
At this time, if the resist pattern to which the resist pattern thickening material is applied has been previously vacuum-baked, the residual acid in the resist pattern is volatilized and removed, so that the interaction ( At the time of mixing, the resist pattern is thickened by the acid-free reaction in which the residual acid does not participate in the reaction. For this reason, the thickening of the resist pattern is performed uniformly or uniformly without being greatly affected by changes in conditions such as temperature. As a result, it is possible to always control the thickening of the resist pattern to a desired level.

  The diameter or width of the resist missing pattern formed by the resist pattern thus thickened is smaller than the diameter or width of the resist missing pattern formed by the resist pattern before thickening. As a result, exceeding the exposure limit of the light source of the exposure apparatus used at the time of patterning the resist pattern (smaller than the limit value of the opening or pattern interval size that can be patterned at the wavelength of the light used for the light source), and more A fine resist omission pattern is formed. That is, when the resist pattern obtained by using ArF excimer laser light at the time of patterning the resist pattern is thickened by using the resist pattern thickening material, the resist formed by the thickened resist pattern. The missing pattern is as fine and high-definition as if it was patterned using an electron beam.

Here, the thickening resist pattern forming step, that is, the resist pattern forming method of the present invention will be described below with reference to the drawings.
As shown in FIG. 1, after forming a resist pattern 3 on a work surface (base material) 5, the resist pattern thickening material 1 is applied (applied) to the surface of the resist pattern 3 after the vacuum baking treatment. And pre-baking (heating and drying) to form a coating film. Then, mixing (impregnation) of the resist pattern thickening material 1 to the resist pattern 3 occurs at the interface between the resist pattern 3 and the resist pattern thickening material 1, and as shown in FIG. 2, the inner layer resist pattern 10b (resist The mixing (impregnation) is performed at the interface between the pattern 3) and the resist pattern thickening material 1 to form a surface layer (mixing layer) 10a. At this time, since the residual acid is removed (at least the residual acid present on the surface is removed) in the resist pattern 3 by the vacuum baking, the reaction at the time of mixing (impregnation) Since this is an unnecessary reaction, the thickening of the resist pattern 3 is performed stably and uniformly without being greatly influenced (dependent on) by changes in conditions such as temperature.

  Thereafter, as shown in FIG. 3, a portion of the applied resist pattern thickening material 1 that has not been interacted (mixed) with the resist pattern 3 or interaction (mixing) by performing development processing. ) Are weakly dissolved (parts having high water solubility) are dissolved and removed, and a thickened resist pattern 10 having a uniform thickness is formed (developed). The development may be water development or development with an alkaline developer.

  The thickened resist pattern 10 has a surface layer (mixing layer) 10a formed by mixing the resist pattern thickening material 1 on the surface of the inner layer resist pattern 10b (resist pattern 3). Since the thickened resist pattern 10 is thicker than the resist pattern 3 by the thickness of the surface layer (mixing layer) 10a, the size of the resist removal pattern formed by the thickened resist pattern 10 (adjacent to the resist pattern 3). The distance between the thickened resist patterns 10 or the opening diameter of the hole pattern formed by the thickened resist pattern 10) is larger than the size of the resist missing pattern formed by the resist pattern 3 before thickening. Is also small. For this reason, the resist omission pattern can be finely formed exceeding the exposure limit of the light source in the exposure apparatus when forming the resist pattern 3. That is, for example, a fine resist removal pattern can be formed as if it was exposed using an electron beam, despite being exposed using ArF excimer laser light. The resist omission pattern formed by the thickened resist pattern 10 is finer and finer than the resist omission pattern formed by the resist pattern 3b.

  The surface layer (mixing layer) 10 a in the thickened resist pattern 10 is formed of the resist pattern thickening material 1. When the resist pattern thickening material 1 includes the annular structure, the resulting thickened resist pattern 10 is excellent in etching resistance even if the resist pattern 3 (inner layer resist pattern 10b) is a material inferior in etching resistance. .

As the resist removal pattern by the thickened resist pattern formed by the thickened resist pattern forming step, that is, the resist pattern forming method of the present invention, for example, a line & space pattern, a hole pattern (for contact holes, etc.) ), A trench (groove) pattern, and the like.
The thickened resist pattern can be used as, for example, a mask pattern, a reticle pattern, etc., and includes a metal plug, various wirings, a magnetic head, an LCD (liquid crystal display), a PDP (plasma display panel), a SAW filter (elastic surface). It can be suitably used for the manufacture of functional parts such as wave filters), optical parts used for connection of optical wiring, fine parts such as microactuators, and semiconductor devices, and particularly preferably used in the following patterning processes. Can do.

-Patterning process-
The patterning step is a step of patterning the surface to be processed by performing an etching process or the like using the thickened resist pattern as a mask.
There is no restriction | limiting in particular as the said etching method, Although it can select suitably according to the objective from well-known methods, For example, dry etching is mentioned suitably. The etching conditions are not particularly limited and can be appropriately selected depending on the purpose.
In the patterning step, the resist pattern remaining after the etching can be removed and removed as necessary. There is no restriction | limiting in particular as this peeling / removal method, According to the objective, it can select suitably, The process using an organic solvent, etc. are mentioned.

  Through the above patterning process, for example, various semiconductor devices including a flash memory, a DRAM, an FRAM, and the like can be efficiently manufactured.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
-Preparation of resist pattern thickening material-
A resist pattern thickening material was prepared. That is, as the “resin”, 100 parts by mass of a resin containing a polyvinyl acetal resin (KW-3, manufactured by Sekisui Chemical Co., Ltd.) and a polyvinyl alcohol resin (PVA2000, manufactured by Kanto Chemical Co., Ltd.) in a mass ratio of 7: 3; As a crosslinking agent, 35 parts by mass of tetramethoxymethylglycoluril (manufactured by Sanwa Chemical Co., Ltd., Nicarac), and as the surfactant, a polyoxyethylene-polyoxypropylene condensate surfactant (nonionic surfactant, KS-2010) manufactured by Kao Co., Ltd., 0.1 parts by mass, and a mixture of pure water (deionized water) and isopropyl alcohol as the main solvent component (mass ratio is pure water (deionized water): isopropyl alcohol = 98.6: 0.4) A composition containing 500 parts by mass was prepared and used as the resist pattern thickening material.

-Formation of resist pattern-
After forming the element region on the semiconductor substrate by a known method, a silicon oxide film and an interlayer insulating film were formed on the entire surface by a CVD (chemical vapor deposition) method. Then, a positive resist film made of ArF resist (positive resist: AX5190, manufactured by Sumitomo Chemical Co., Ltd.) is formed on the silicon oxide film, and then irradiated with ArF (argon fluoride) excimer laser light (exposure amount: 50 mJ / cm ² ) and development to form a hole pattern (hole diameter 250 nm, thickness 500 nm).

The vacuum baking process was performed on the formed hole pattern at 10 torr and 100 ° C. for 20 seconds. Then, the residual acid in the vicinity of the surface was removed.
Next, after applying the above-described resist pattern thickening material on the resist pattern by a spin coating method to a thickness of 300 nm first under the condition of 1000 rpm / 5 s and then under the condition of 3,500 rpm / 40 s, After performing the above-mentioned application baking under the condition of 110 ° C./60 s, the resist pattern thickening material is rinsed with pure water for 60 seconds to remove the non-interacting (mixing) portion, and the resist pattern thickening material is used. The thickened resist pattern was formed by developing the thickened resist pattern.

  In the resist pattern, the thickness increased by 20 nm compared to before the thickening, and the thickness of the unexposed part also increased by 20 nm, so the reaction of the thickening (swelling) It was found that the reaction was not the acid-dependent reaction described above but the acid-free reaction described above.

  When the coating baking temperature is 90 ° C., the thickness increases by 10 nm as compared to the thickness before the resist pattern is thickened. When the coating baking temperature is 130 ° C., the resist pattern It was confirmed that the thickness was increased by 30 nm as compared with before thickening.

Next, the following Comparative Example Experiment 1 and Example Experiment 1 were performed.
That is, a 200 nm diameter hole pattern and a 200 nm × 1000 nm line pattern were formed using a chemically amplified ArF resist (AR1240, manufactured by JSR). Each resist pattern had a thickness of 300 nm.
-Comparative Example Experiment 1-
As the resin, 100 parts by mass of polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd., KW-3) and 35 parts by mass of (N-methoxymethyl) methoxyethylene urea (manufactured by Sanwa Chemical Co., Ltd.) as the cross-linking agent After applying a resist pattern thickening material, which is a mixed solution containing 0.1 part by mass of a polyether type surfactant (PC-10, manufactured by Asahi Denka Co., Ltd.) as the surfactant, the mixing baking is performed. After 60 seconds, water development was performed to form the thickened resist pattern, and then the size change of the resist pattern was examined.

In the case of the hole pattern, when the temperature of the mixing bake was 100 ° C., the pattern size change amount was as small as about 2 nm, and the effect of reducing the edge roughness was not observed. When the temperature was 110 ° C., the pattern size change amount was about 60 nm, but the variation was large and about 5% of the holes were filled. Moreover, when it was 120 degreeC, it turned out that most patterns are filled and the amount of pattern size changes is 200 nm or more. From this, it was found that when the above-described vacuum baking process was not performed, the margin for the temperature change was narrow.
On the other hand, in the case of the line pattern, when the temperature of the mixing bake was 100 ° C., the pattern size change amount was as small as about 2 nm, and the effect of reducing the edge roughness was not observed. When the temperature was 110 ° C., the pattern size change amount was 50 nm in the long-side direction and 10 nm in the short-side direction, and the dependence on the pattern direction was large and the variation was large. Moreover, when it was 120 degreeC, it became 110 nm in the long side direction, and became 30 nm in the short side direction, and the variation was large.

Example Experiment 1
Next, after forming a resist pattern as in the comparative experiment, vacuum baking was performed at 110 ° C. for 60 seconds at about 1 torr. Thereafter, a resist pattern thickening material similar to that in Comparative Experiment 1 was applied, mixed baking and water development were performed, and changes in pattern size were examined.

In the case of the hole pattern, when the mixing baking temperature is 100 ° C., the pattern size change amount is 10 nm, and when the mixing bake temperature is 110 ° C., the pattern size change amount is 20 nm. The variation in the amount of change was small. Moreover, the effect which reduces edge roughness was seen. When the temperature was 120 ° C., the amount of change was 35 nm, and the variation was small as in the case of 110 ° C., and a good pattern shape was maintained.
On the other hand, in the case of a line pattern, when the temperature of the mixing bake is 100 ° C., the pattern size change amount is 12 nm in the long side direction, 10 nm in the short side direction, and the edge roughness is also reduced. It had been. When the temperature is 110 ° C., the pattern size change amount is 20 nm in the long side direction and 15 nm in the short side direction, and when 120 ° C., the pattern size change amount is 30 nm in the long side direction. And 27 nm, and the dependence on the pattern direction was small. Also, the edge roughness was reduced and a good pattern shape was obtained.

-Example experiment 2-
In Example Experiment 1, the change in the size of the resist pattern was examined in the same manner as in Example Experiment 1 except that the temperature of the vacuum baking process was changed.

In the case of the hole pattern, when the temperature of the vacuum baking process is 50 ° C., the pattern size change amount tends to decrease slightly as 2 nm, and when the temperature is 160 ° C. There was a tendency for pattern shape change (deformation) due to heat flow to be observed, such as opening of the resist pattern opening.
On the other hand, in the case of a line pattern, when the temperature of the vacuum baking process is 50 ° C., the pattern size change amount is about 2 nm in both the long side and the short side direction, and there is a tendency for the amount of thickening to decrease slightly. When the temperature was 160 ° C., pattern shape change (deformation) due to heat flow tended to be observed.

-Example Experiment 3-
In Example Experiment 1, the change in the size of the resist pattern was examined in the same manner as in Example Experiment 1 except that the time for vacuum baking was changed.

In the case of the hole pattern, when the time of the vacuum baking process is 5 seconds, if the temperature of the mixing baking is 100 ° C., the pattern size change amount is 2 nm, and the amount of thickening is slightly reduced. A trend was observed, and the change in pattern size was around 60 nm at 110 ° C., but there was a tendency for the variation to be slightly larger, and a tendency to fill about 4% of the holes was observed, and at 120 ° C. There was a tendency for most of the holes to fill up. From this result, it was found that the effect of the vacuum baking treatment tends to be insufficient when the time is 5 seconds.
On the other hand, in the case of a line pattern, when the time of the vacuum baking process is 5 seconds, if the mixing baking temperature is 100 ° C., the pattern size change amount is 2 nm, and the amount of thickening is slightly reduced. In addition, there is a tendency that the effect of reducing the edge roughness is not sufficiently obtained. At 110 ° C., the pattern size change amount is 50 nm in the long side direction and 20 nm in the short side direction. There is a tendency that the dependence on the direction becomes slightly large, and also a tendency that the variation becomes slightly large. At 120 ° C., the pattern size change amount is 120 nm in the long side direction and 50 nm in the short side direction. In addition, there was a tendency for the variation to increase. As a result, it has been found that the effect of the vacuum baking treatment tends to be insufficient when the time is 15 seconds.

  In the case of the hole pattern, when the time of the vacuum baking process is 600 seconds, both the hole pattern and the line pattern are almost the same as those in Example Experiment 1 (60 seconds). There was a tendency that the effect corresponding to the time of vacuum baking was not obtained.

-Example Experiment 4-
In Example Experiment 1, the change in the size of the resist pattern was examined in the same manner as in Example Experiment 1 except that the vacuum baking pressure was changed to 150 torr.

In the case of the hole pattern, if the temperature of the mixing bake is 100 ° C., the pattern size change amount tends to decrease slightly as 2 nm, and if it is 110 ° C., the pattern size change amount. However, at 120 ° C., most of the holes tend to be filled, and the pattern size change amount tends to be as large as 200 nm or more. As a result, it was found that the effect of the vacuum baking treatment tends to be insufficient when the pressure is 150 torr.
On the other hand, in the case of a line pattern, if the temperature of the mixing bake is 100 ° C., the pattern size change amount is 2 nm, and there is a tendency for the amount of thickening to decrease, and the effect of reducing edge roughness is sufficient. When the temperature is 110 ° C., the pattern size change amount is 60 nm in the long side direction and 15 nm in the short side direction. There was a tendency for the variation to be slightly larger. When the temperature was 120 ° C., the pattern size change amount was 100 nm in the long side direction and 50 nm in the short side direction, and there was a tendency for the variation to increase. As a result, it was found that the effect of the vacuum baking treatment tends to be insufficient when the pressure is 150 torr.

(Example 2)
As shown in FIG. 9, an interlayer insulating film 12 was formed on the silicon substrate 11, and as shown in FIG. 10, a titanium film 13 was formed on the interlayer insulating film 12 by sputtering. Next, as shown in FIG. 11, a resist pattern 14 was formed by a known photolithography technique, and this was used as a mask, and the titanium film 13 was patterned by reactive ion etching to form an opening 15a. Subsequently, the resist pattern 14 was removed by reactive ion etching, and an opening 15b was formed in the interlayer insulating film 12 using the titanium film 13 as a mask, as shown in FIG.

  Next, the titanium film 13 is removed by wet processing, and as shown in FIG. 13, a TiN film 16 is formed on the interlayer insulating film 12 by a sputtering method. Subsequently, a Cu film 17 is formed on the TiN film 16 by an electrolytic plating method. The film was formed. Next, as shown in FIG. 14, planarization is performed by leaving the barrier metal and Cu film (first metal film) only in the groove corresponding to the opening 15b (FIG. 12) by CMP, and the first layer wiring 17a is formed. Formed.

  Next, after forming an interlayer insulating film 18 on the first layer wiring 17a as shown in FIG. 15, the first layer wiring 17a is formed as shown in FIG. Then, a Cu plug (second metal film) 19 and a TiN film 16a connected to an upper layer wiring to be formed later were formed.

By repeating the above steps, a multilayer wiring structure including a first layer wiring 17a, a second layer wiring 20, and a third layer wiring 21 was provided on the silicon substrate 11, as shown in FIG. A semiconductor device was manufactured. In FIG. 17, the illustration of the barrier metal layer formed in the lower layer of each wiring layer is omitted.
In Example 2, the resist pattern 14 is a thickened resist pattern formed using the resist pattern thickening material after the vacuum baking.

(Example 3)
-Flash memory and its manufacture-
Example 3 is an example of a semiconductor device of the present invention using the resist pattern thickening material and a method for manufacturing the same. In Example 3, the following resist films 26, 27, 29 and 32 were thickened by the same method as in Examples 1 and 2 using the resist pattern thickening material. is there.

  18 and 19 are top views (plan views) of a FLASH EPROM called a FLOTOX type or an ETOX type called a FLOTOX type or an ETOX type, and FIGS. 20 to 28 illustrate an example of a manufacturing method of the FLASH EPROM. In these drawings, the left figure is a memory cell portion (first element region), which is a gate width direction of a portion where a MOS transistor having a floating gate electrode is formed (FIGS. 18 and 19). FIG. 6 is a schematic view of the cross section (direction A cross section) in the X direction, the central view is the memory cell portion of the same portion as the left view, and the gate length direction (Y in FIGS. 18 and 19) perpendicular to the X direction. Direction) cross section (B direction cross section) is a schematic diagram, and the right figure is a portion of the peripheral circuit portion (second element region) where the MOS transistor is formed. FIG. 20 is a schematic view of a cross section (a cross section in the A direction in FIGS. 18 and 19).

First, as shown in FIG. 20, a field oxide film 23 made of a SiO ₂ film was selectively formed in an element isolation region on a p-type Si substrate 22. Thereafter, the first gate insulating film 24a in the MOS transistor in the memory cell portion (first element region) is formed by SiO ₂ film by thermal oxidation so that the thickness becomes 100 to 300 mm (10 to 30 nm). In the process, the second gate insulating film 24b in the MOS transistor in the peripheral circuit portion (second element region) was formed of a SiO ₂ film by thermal oxidation so as to have a thickness of 100 to 500 mm (10 to 50 nm). When the first gate insulating film 24a and the second gate insulating film 24b have the same thickness, an oxide film may be formed simultaneously in the same process.

Next, in order to form a MOS transistor having an n-type depletion type channel in the memory cell portion (left and center views in FIG. 20), the peripheral circuit portion (in FIG. 20) is formed for the purpose of controlling the threshold voltage. (Right figure) was masked with a resist film 26. Then, phosphorus (P) or arsenic (As) with a dose amount of 1 × 10 ¹¹ to 1 × 10 ¹⁴ cm ⁻² is introduced as an n-type impurity into a channel region immediately below the floating gate electrode by an ion implantation method, A first threshold control layer 25a was formed. Note that the dose amount and the conductivity type of the impurity at this time can be appropriately selected depending on whether the depletion type or the accumulation type is used.

Next, in order to form a MOS transistor having an n-type depletion type channel in the peripheral circuit portion (the right diagram in FIG. 21), a memory cell portion (the left diagram in FIG. The resist film 27 was masked. Then, phosphorus (P) or arsenic (As) having a dose amount of 1 × 10 ¹¹ to 1 × 10 ¹⁴ cm ⁻² is introduced as an n-type impurity into a channel region immediately below the gate electrode by an ion implantation method. Two threshold control layers 25b were formed.

  Next, as the floating gate electrode of the MOS transistor in the memory cell portion (left and center diagrams in FIG. 22) and the gate electrode of the MOS transistor in the peripheral circuit portion (right diagram in FIG. 22), the thickness is 500-2. A first polysilicon film (first conductor film) 28 having a thickness of 1,000,000 (50 to 200 nm) was formed on the entire surface.

  After that, as shown in FIG. 23, the first polysilicon film 28 is patterned by a resist film 29 formed as a mask, so that the floating gate electrode 28a in the MOS transistor of the memory cell portion (the left diagram and the central diagram in FIG. 23) is formed. Formed. At this time, as shown in FIG. 23, patterning is performed so that the final dimension width is in the X direction, and the region that becomes the S / D region layer is left covered with the resist film 29 without patterning in the Y direction. .

Next, as shown in the left diagram and the central diagram of FIG. 24, after removing the resist film 29, the capacitor insulating film 30a made of the SiO ₂ film has a thickness of about 30 mm so as to cover the floating gate electrode 28a. It formed by thermal oxidation so that it might become 200-500 mm (20-50 nm). At this time, the capacitor insulating film 30b made of the SiO ₂ film is also formed on the first polysilicon film 28 in the peripheral circuit portion (the right diagram in FIG. 24). Here, the capacitor insulating films 30a and 30b are formed of only the SiO ₂ film, but may be formed of a composite film in which two or _three SiO ₂ films and Si ₃ N ₄ films are laminated.

  Next, as shown in FIG. 24, the second polysilicon film (second conductor film) 31 serving as the control gate electrode is formed with a thickness of 500 to 2 so as to cover the floating gate electrode 28 a and the capacitor insulating film 30 a. , And a thickness of 50 to 200 nm.

  Next, as shown in FIG. 25, the memory cell portion (left and center views in FIG. 25) is masked with a resist film 32, and the second polysilicon film 31 in the peripheral circuit portion (right view in FIG. 25) is masked. Then, the capacitor insulating film 30b was sequentially removed by etching, and the first polysilicon film 28 was exposed.

  Next, as shown in FIG. 26, the second polysilicon film 31, the capacitor insulating film 30a of the memory cell portion (the left and middle views of FIG. 26), and the first polysilicon film 28a patterned only in the X direction. On the other hand, patterning in the Y direction is performed using the resist film 32 as a mask so as to have the final dimensions of the first gate portion 33a, and the control gate electrode 31a / capacitor insulating film 30c / floating gate having a width of about 1 μm in the Y direction. A stack of electrodes 28c is formed, and the final size of the second gate portion 33b is set with respect to the first polysilicon film 28 of the peripheral circuit portion (the right figure of FIG. 26) using the resist film 32 as a mask. Then, patterning was performed to form a gate electrode 28b having a width of about 1 μm.

Next, using the stack of the control cell electrode 31a / capacitor insulating film 30c / floating gate electrode 28c of the memory cell portion (left and center views of FIG. 27) as a mask, the dose of 1 × is applied to the Si substrate 22 in the element formation region. 10 ¹⁴ to 1 × 10 ¹⁶ cm ⁻² of phosphorus (P) or arsenic (As) is introduced by an ion implantation method to form n-type S / D region layers 35a and 35b, and the peripheral circuit portion (FIG. 27) (right figure)) using the gate electrode 28b as a mask, phosphorus (P) or arsenic (As) with a dose amount of 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm ^{−2 is applied} to the Si substrate 22 in the element formation region as an n-type impurity. S / D region layers 36a and 36b were formed by ion implantation.

  Next, the first gate portion 33a of the memory cell portion (left and center views of FIG. 28) and the second gate portion 33b of the peripheral circuit portion (right portion of FIG. 28) are formed on an interlayer insulating film 37 made of a PSG film. Was formed so as to have a thickness of about 5,000 mm (500 nm).

  Thereafter, contact holes 38a and 38b and contact holes 39a and 39b are formed in the interlayer insulating film 37 formed on the S / D region layers 35a and 35b and the S / D region layers 36a and 36b, and then the S / D electrode 40a. And 40b and S / D electrodes 41a and 41b were formed. The contact holes 38a and 38b and the contact holes 39a and 39b are formed by forming a hole pattern of a resist material, vacuum baking the hole pattern, and then increasing the thickness using the resist pattern thickening material. After forming a fine resist omission pattern (hole pattern), it was carried out in accordance with a conventional method.

  As described above, as shown in FIG. 28, a FLASH EPROM was manufactured as a semiconductor device.

  In this FLASH EPROM, the second gate insulating film 24b of the peripheral circuit portion (the right figure in FIGS. 20 to 28) is covered with the first polysilicon film 28 or the gate electrode 28b from the beginning to the end after the formation (FIG. 20). 20 to FIG. 28), the second gate insulating film 24b maintains the thickness when it is first formed. Therefore, the thickness of the second gate insulating film 24b can be easily controlled, and the conductivity type impurity concentration for controlling the threshold voltage can be easily adjusted.

  In the above-described embodiment, the first gate portion 33a is formed by first patterning with a predetermined width in the gate width direction (X direction in FIGS. 18 and 19) and then in the gate length direction (in FIGS. 18 and 19). Patterning is performed in the Y direction) to obtain a final predetermined width. Conversely, after patterning with a predetermined width in the gate length direction (Y direction in FIGS. 18 and 19), the gate width direction (in FIGS. 18 and 19) is obtained. The final predetermined width may be obtained by patterning in the X direction).

The manufacturing example of the FLASH EPROM shown in FIGS. 29 to 31 is the same as the above embodiment except that the steps shown in FIG. 28 in the above embodiment are changed as shown in FIGS. That is, as shown in FIG. 29, on the second polysilicon film 31 in the memory cell portion (left and center views in FIG. 29) and the first polysilicon film 28 in the peripheral circuit portion (right view in FIG. 29). Further, a refractory metal film (fourth conductor film) 42 made of a tungsten (W) film or a titanium (Ti) film is formed so as to have a thickness of about 2,000 mm (200 nm), and a polycide film is provided. Only differs from the above embodiment. The subsequent steps of FIG. 29, that is, the steps shown in FIGS. 30 to 31 were performed in the same manner as FIGS. The description of the same steps as in FIGS. 26 to 28 is omitted, and in FIGS. 29 to 31, the same components as those in FIGS. 26 to 28 are denoted by the same symbols.
As described above, as shown in FIG. 31, a FLASH EPROM was manufactured as a semiconductor device.

In this FLASH EPROM, since the refractory metal films (fourth conductor films) 42a and 42b are provided on the control gate electrode 31a and the gate electrode 28b, the electric resistance value can be further reduced.
Here, although the refractory metal films (fourth conductor film) 42a and 42b are used as the refractory metal film (fourth conductor film), a refractory metal silicide film such as a titanium silicide (TiSi) film is used. May be used.

The flash EPROM shown in FIGS. 32 to 34 is manufactured in the same manner as the above-described embodiment, except that the second gate portion 33c of the peripheral circuit portion (second element region) (the right diagram in FIG. 32) is also the memory cell portion (first portion). (1 element region) (first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) / second, similarly to the first gate portion 33a in the left and middle diagrams in FIG. 32) The structure is a polysilicon film 31b (second conductor film), and as shown in FIG. 33 or 34, the first polysilicon film 28b and the second polysilicon film 31b are short-circuited to form a gate electrode. Except for the differences, this embodiment is the same as the above embodiment.

Here, as shown in FIG. 33, the first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) / second polysilicon film 31b (second conductor film) is penetrated. The opening 52a is formed, for example, on a portion different from the second gate portion 33c shown in FIG. 32, for example, on the insulating film 54, and a third conductor film such as a W film or a Ti film is formed in the opening 52a. By embedding the melting point metal film 53a, the first polysilicon film 28b and the second polysilicon film 31b are short-circuited. Further, as shown in FIG. 34, an opening 52b penetrating the first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) is formed, and a lower layer is formed at the bottom of the opening 52b. After the first polysilicon film 28b is exposed, a third conductor film, for example, a refractory metal film 53b such as a W film or a Ti film is embedded in the opening 52b, whereby the first polysilicon film 28b and the first polysilicon film 28b are formed. 2 The polysilicon film 31b is short-circuited.

In this FLASH EPROM, since the second gate portion 33c of the peripheral circuit portion has the same structure as the first gate portion 33a of the memory cell portion, the peripheral circuit portion is simultaneously formed when the memory cell portion is formed. It can be formed, and the manufacturing process can be simplified and efficient.
Although the third conductor film 53a or 53b and the refractory metal film (fourth conductor film) 42 are separately formed here, they may be formed simultaneously as a common refractory metal film. Good.

Example 4
-Manufacture of magnetic heads-
Example 4 relates to the manufacture of a magnetic head as an application example of a resist pattern forming method using the resist pattern thickening material. In Example 4, the following resist patterns 102 and 126 were thickened by the same method as in Example 1 using the resist pattern thickening material after the vacuum baking. is there.

35 to 38 are process diagrams for explaining the manufacture of the magnetic head.
First, as shown in FIG. 35, a resist film is formed on the interlayer insulating layer 100 so as to have a thickness of 6 μm, exposed, and developed to have a resist having an opening pattern for forming a spiral thin film magnetic coil. A pattern 102 was formed.
Next, as shown in FIG. 36, Ti having a thickness of 0.01 μm on the interlayer insulating layer 100 on the resist pattern 102 and the portion where the resist pattern 102 is not formed, that is, on the exposed surface of the opening 104. A plating work surface 106 formed by laminating an adhesion film and a Cu adhesion film having a thickness of 0.05 μm was formed by vapor deposition.

Next, as shown in FIG. 37, the thickness of the portion of the interlayer insulating layer 100 where the resist pattern 102 is not formed, that is, the surface of the plating processing surface 106 formed on the exposed surface of the opening 104 is increased. A thin film conductor 108 made of a Cu plating film having a thickness of 3 μm was formed.
Next, as shown in FIG. 38, when the resist pattern 102 is dissolved and removed and lifted off from above the interlayer insulating layer 100, a thin film magnetic coil 110 having a spiral pattern of the thin film conductor 108 is formed.
A magnetic head was manufactured as described above.

  In the magnetic head obtained here, since the spiral pattern is finely formed by the resist pattern 102 thickened by using the resist pattern thickening material, the thin film magnetic coil 110 is fine and fine. Moreover, it is excellent in mass productivity.

39 to 44 are process diagrams for explaining the manufacture of another magnetic head.
As shown in FIG. 39, a gap layer 114 was formed on a nonmagnetic substrate 112 made of ceramic by a sputtering method. Although not shown, an insulating layer made of silicon oxide and a conductive work surface made of Ni—Fe permalloy are previously formed on the nonmagnetic substrate 112 by sputtering, and a lower portion made of Ni—Fe permalloy. A magnetic layer is formed. Then, a resin insulating film 116 was formed from a thermosetting resin in a predetermined region on the gap layer 114 excluding a portion that becomes a magnetic tip of the lower magnetic layer (not shown). Next, a resist material was applied onto the resin insulating film 116 to form a resist film 118.

  Next, as shown in FIG. 40, the resist film 118 was exposed and developed to form a spiral pattern. Then, as shown in FIG. 41, the resist film 118 having the spiral pattern was subjected to a thermosetting process at several hundred degrees C. for about one hour to form a first spiral pattern 120 having a protrusion shape. Further, a conductive work surface 122 made of Cu was formed on the surface.

  Next, as shown in FIG. 42, a resist material is applied onto the conductive work surface 122 by spin coating to form a resist film 124, and then the resist film 124 is patterned on the first spiral pattern 120. Thus, a resist pattern 126 was formed.

Next, as shown in FIG. 43, a Cu conductor layer 128 was formed by plating on the exposed surface of the conductive surface 122, that is, on the portion where the resist pattern 126 was not formed. Thereafter, as shown in FIG. 44, the resist pattern 126 was dissolved and removed to lift off from the conductive surface 122 to form a spiral thin film magnetic coil 130 made of the Cu conductor layer 128.
As described above, a magnetic head having the magnetic layer 132 on the resin insulating film 116 and the thin film magnetic coil 130 provided on the surface as shown in the plan view of FIG. 45 was manufactured.

  In the magnetic head obtained here, since the spiral pattern is finely formed by the resist pattern 126 thickened using the resist pattern thickening material, the thin film magnetic coil 130 is fine and fine. Moreover, it is excellent in mass productivity.

Here, it will be as follows if the preferable aspect of this invention is appended.
(Appendix 1) After forming a resist pattern on the surface to be processed, vacuum resist baking is performed on the resist pattern, and then a resist pattern thickening material containing at least a resin is applied to the surface of the resist pattern. A thickened resist pattern forming step of thickening the resist pattern to form a thickened resist pattern;
And a patterning step of patterning the surface to be processed by etching using the thickened resist pattern as a mask.
(Additional remark 2) The manufacturing method of the semiconductor device of Additional remark 1 whose temperature of a vacuum baking process is 60-150 degreeC.
(Additional remark 3) The manufacturing method of the semiconductor device in any one of Additional remark 1 to 2 whose time of a vacuum baking process is 10 to 300 seconds.
(Additional remark 4) The manufacturing method of the semiconductor device in any one of Additional remark 1 to 3 whose vacuum degree of a vacuum baking process is 50 torr or less.
(Additional remark 5) The manufacturing method of the semiconductor device in any one of additional remark 1 to 4 which performs the mixing baking process baked at 60-150 degreeC after application | coating of a resist pattern thickening material.
(Additional remark 6) The manufacturing method of the semiconductor device of Additional remark 5 whose time of a mixing bake process is 30 to 300 second.
(Additional remark 7) The manufacturing method of the semiconductor device in any one of additional remark 5 to 6 which develops a resist pattern thickening material after a mixing bake process.
(Additional remark 8) The manufacturing method of the semiconductor device of Additional remark 7 with which a development process is performed using a pure water.
(Supplementary note 9) The method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 8, wherein the resist pattern thickening material is water-soluble or alkali-soluble.
(Additional remark 10) The manufacturing method of the semiconductor device in any one of additional remark 1 to 9 in which resin has a cyclic structure in at least one part.
(Additional remark 11) The manufacturing method of the semiconductor device of Additional remark 10 whose cyclic structure is selected from an aromatic compound, an alicyclic compound, and a heterocyclic compound.
(Additional remark 12) The manufacturing method of the semiconductor device in any one of Additional remark 10 to 11 whose molar content rate in resin of cyclic structure is 5 mol% or more.
(Additional remark 13) The manufacturing method of the semiconductor device in any one of Additional remark 1 to 12 whose resin is water solubility thru | or alkali solubility.
(Supplementary note 14) The method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 13, wherein the resin is at least one selected from polyvinyl alcohol, polyvinyl acetal, and polyvinyl acetate.
(Additional remark 15) The manufacturing method of the semiconductor device in any one of Additional remark 1 to 14 in which resin contains 5-40 mass% of polyvinyl acetals.
(Additional remark 16) The manufacturing method of the semiconductor device in any one of additional remarks 1-15 in which resin has two or more polar groups.
(Supplementary note 17) The method for manufacturing a semiconductor device according to supplementary note 16, wherein the polar group is selected from a hydroxyl group, an amino group, a sulfonyl group, a carbonyl group, a carboxyl group, and a derivative group thereof.
(Supplementary note 18) The method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 17, wherein the resist pattern thickening material includes a crosslinking agent.
(Additional remark 19) The manufacturing method of the semiconductor device of Additional remark 18 whose crosslinking agent is at least 1 sort (s) selected from a melamine derivative, a urea derivative, and a uril derivative.
(Supplementary note 20) The method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 19, wherein the resist pattern thickening material includes a surfactant.
(Supplementary note 21) The semiconductor device according to supplementary note 20, wherein the surfactant is at least one selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. Production method.
(Supplementary Note 22) The surfactant is a polyoxyethylene-polyoxypropylene condensate compound, a polyoxyalkylene alkyl ether compound, a polyoxyethylene alkyl ether compound, a polyoxyethylene derivative compound, a sorbitan fatty acid ester compound, a glycerin fatty acid ester compound, Primary alcohol ethoxylate compound, phenol ethoxylate compound, alkoxylate surfactant, fatty acid ester surfactant, amide surfactant, alcohol surfactant, ethylenediamine surfactant, alkyl cation surfactant Addendum 20 to 21 selected from an agent, an amide type quaternary cationic surfactant, an ester type quaternary cationic surfactant, an amine oxide surfactant, and a betaine surfactant A method for manufacturing a semiconductor device.
(Supplementary note 23) The method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 22, wherein the resist pattern thickening material includes a cyclic structure compound.
(Supplementary note 24) The method for producing a semiconductor device according to supplementary note 23, wherein the cyclic structure compound is soluble in 1 g or more in either 100 g of water at 25 ° C. or 100 g of 2.38 mass% tetramethylammonium hydroxide. .
(Additional remark 25) The manufacturing method of the semiconductor device in any one of Additional remarks 23 to 24 in which a cyclic structure compound has two or more polar groups.
(Supplementary note 26) The method for manufacturing a semiconductor device according to supplementary note 25, wherein the polar group is selected from a hydroxyl group, an amino group, a sulfonyl group, a carbonyl group, a carboxyl group, and derivatives thereof.
(Additional remark 27) The manufacturing method of the semiconductor device in any one of additional marks 24 to 26 whose cyclic structure compound is at least 1 sort (s) selected from an aromatic compound, an alicyclic compound, and a heterocyclic compound.
(Supplementary note 28) The aromatic compound is selected from a polyphenol compound, an aromatic carboxylic acid compound, a naphthalene polyhydric alcohol compound, a benzophenone compound, a flavonoid compound, a derivative thereof and a glycoside thereof,
The alicyclic compound is selected from polycycloalkanes, cycloalkanes, steroids, derivatives thereof and glycosides thereof,
28. The method of manufacturing a semiconductor device according to appendix 27, wherein the heterocyclic compound is selected from pyrrolidine, pyridine, imidazole, oxazole, morpholine, pyrrolidone, furan, pyran, saccharide, and derivatives thereof.
(Supplementary note 29) The method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 28, wherein the resist pattern thickening material includes an organic solvent.
(Supplementary Note 30) In Supplementary Note 29, the organic solvent is at least one selected from alcohol solvents, chain ester solvents, cyclic ester solvents, ketone solvents, chain ether solvents, and cyclic ether solvents. The manufacturing method of the semiconductor device of description.
(Additional remark 31) The manufacturing method of the semiconductor device in any one of Additional remark 1 to 30 in which a resist pattern thickening material contains a phase transfer catalyst.
(Supplementary note 32) The method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 31, wherein the resist pattern thickening material includes a polyhydric alcohol having at least two hydroxyl groups.
(Supplementary note 33) The method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 32, wherein the resist pattern is formed of at least one of an ArF resist and a resist including an acrylic resin.
(Supplementary note 34) The supplementary note 33, wherein the ArF resist is at least one selected from an acrylic resist having a cycloaliphatic functional group in the side chain, a cycloolefin-maleic anhydride resist, and a cycloolefin resist. Semiconductor device manufacturing method.
(Additional remark 35) The manufacturing method of the semiconductor device in any one of additional marks 1-34 whose surface to be processed is a semiconductor substrate surface.
(Supplementary Note 36) The semiconductor device according to any one of Supplementary notes 1 to 35, wherein the resist removal pattern formed by the thickened resist pattern is at least one selected from a line & space pattern, a hole pattern, and a trench pattern. Manufacturing method.
(Appendix 37) A semiconductor device manufactured by the method for manufacturing a semiconductor device according to any one of Appendixes 1 to 36.
(Appendix 38) A resist pattern thickening material containing at least a resin is applied to the surface of the resist pattern after the resist pattern is formed and then vacuum baking is performed to bake the resist pattern in a vacuum. Forming a resist pattern.

The resist pattern forming method of the present invention includes, for example, a mask pattern, a reticle pattern, a magnetic head, an LCD (liquid crystal display), a PDP (plasma display panel), a SAW filter (surface acoustic wave filter), and other functional parts, The present invention can be suitably applied to the manufacture of optical components used for connection, fine components such as microactuators, and semiconductor devices, and can be preferably used in the method of manufacturing a semiconductor device of the present invention described later.
The semiconductor device manufacturing method of the present invention can be suitably used for manufacturing various semiconductor devices including flash memory, DRAM, FRAM, and the like.
The semiconductor device of the present invention can be suitably used as a flash memory, DRAM, FRAM, or the like.

FIG. 1 is an explanatory diagram of a mechanism for thickening a resist pattern using a resist pattern thickening material, and shows a state in which the resist pattern thickening material is applied to the surface of the resist pattern. FIG. 2 is an explanatory diagram of a mechanism for thickening a resist pattern using a resist pattern thickening material, and shows a state in which the resist pattern thickening material has permeated the resist pattern surface. FIG. 3 is an explanatory diagram of a mechanism for thickening a resist pattern using a resist pattern thickening material, and shows a state in which the resist pattern surface is thickened by the resist pattern thickening material. FIG. 4 is a schematic view for explaining an example of a resist pattern forming method of the present invention, and shows a state in which a resist film is formed. FIG. 5 is a schematic view for explaining an example of a resist pattern forming method of the present invention, and shows a state in which a resist pattern is formed by patterning a resist film. FIG. 6 is a schematic view for explaining an example of a resist pattern forming method of the present invention, and shows a state in which a resist pattern thickening material is applied to the resist pattern surface. FIG. 7 is a schematic diagram for explaining an example of a resist pattern forming method of the present invention, and shows a state in which a resist pattern thickening material is mixed and soaked into the resist pattern surface. FIG. 8 is a schematic view for explaining an example of the resist pattern forming method of the present invention, and shows a state in which the thickened resist pattern is developed. FIG. 9 is a schematic view for explaining an example of the method for manufacturing a semiconductor device of the present invention, and shows a state in which an interlayer insulating film is formed on a silicon substrate. FIG. 10 is a schematic view for explaining an example of the method for manufacturing a semiconductor device of the present invention, and shows a state in which a titanium film is formed on the interlayer insulating film shown in FIG. FIG. 11 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, and shows a state in which a resist film is formed on a titanium film and a hole pattern is formed on the titanium layer. FIG. 12 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, and shows a state in which a hole pattern is also formed in an interlayer insulating film. FIG. 13 is a schematic diagram for explaining an example of a method for manufacturing a semiconductor device according to the present invention, and shows a state in which a Cu film is formed on an interlayer insulating film in which a hole pattern is formed. FIG. 14 is a schematic diagram for explaining an example of a method for manufacturing a semiconductor device according to the present invention, and shows a state in which Cu deposited on an interlayer insulating film other than on the hole pattern is removed. FIG. 15 is a schematic diagram for explaining an example of a method for manufacturing a semiconductor device according to the present invention, and shows a state in which an interlayer insulating film is formed on a Cu plug and an interlayer insulating film formed in a hole pattern. FIG. 16 is a schematic diagram for explaining an example of a method for manufacturing a semiconductor device of the present invention, and shows a state in which a hole pattern is formed in an interlayer insulating film as a surface layer and a Cu plug is formed. FIG. 17 is a schematic view for explaining an example of a method for manufacturing a semiconductor device according to the present invention, and shows a state in which a wiring having a three-layer structure is formed. FIG. 18 is a plan view showing a first example of a FLASH EPROM manufactured by the method for manufacturing a semiconductor device of the present invention. FIG. 19 is a plan view showing a first example of a FLASH EPROM manufactured by the method for manufacturing a semiconductor device of the present invention. FIG. 20 is a schematic explanatory view of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention. FIG. 21 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 22 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 23 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 24 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 25 is a schematic explanatory view of a first example of the manufacture of FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 26 is a schematic explanatory view of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 27 is a schematic explanatory view of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 28 is a schematic explanatory view of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 29 is a schematic explanatory diagram of a second example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention. FIG. 30 is a schematic explanatory diagram of a second example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 31 is a schematic explanatory diagram of a second example of the manufacture of FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 32 is a schematic explanatory diagram of a third example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention. FIG. 33 is a schematic explanatory view of a third example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 34 is a schematic explanatory view of a third example of the manufacture of FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 35 is a schematic cross-sectional explanatory diagram of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head. FIG. 36 is a schematic cross-sectional explanatory view of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 37 is a schematic cross-sectional explanatory diagram of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 38 is a schematic cross-sectional explanatory diagram of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 39 is a schematic cross-sectional explanatory view of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 40 is a schematic cross-sectional explanatory diagram of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 41 is a schematic cross-sectional explanatory view of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 42 is a schematic cross-sectional explanatory diagram of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 43 is a schematic cross-sectional explanatory view of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 44 is a schematic cross-sectional explanatory diagram of an example in which a resist pattern thickened using a resist pattern thickening material is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 45 is a plan view showing an example of a magnetic head manufactured through the steps of FIGS.

Explanation of symbols

1 Resist pattern thickening material 3 Resist pattern 5 Surface to be processed (base material)
10 resist pattern (present invention)
10a Surface layer 10b Inner layer resist pattern 11 Silicon substrate 12 Interlayer insulating film 13 Titanium film 14 Resist pattern 15a Opening 15b Opening 16 TiN film 16a TiN film 17 Cu film 17a Wiring 18 Interlayer insulating film 19 Cu plug 20 Wiring 21 Wiring 22 Si substrate (Semiconductor substrate)
23 field oxide film 24a first gate insulating film 24b second gate insulating film 25a first threshold control layer 25b second threshold control layer 26 resist film 27 resist film 28 first polysilicon layer (first conductor film)
28a Floating gate electrode 28b Gate electrode (first polysilicon film)
28c Floating gate electrode 29 Resist film 30a Capacitor insulating film 30b Capacitor insulating film 30c Capacitor insulating film 30d SiO ₂ film 31 Second polysilicon layer (second conductor film)
31a Control gate electrode 31b Second polysilicon film 32 Resist film 33a First gate part 33b Second gate part 33c Second gate part 35a S / D (source / drain) region layer 35b S / D (source / drain) region layer 36a S / D (source / drain) region layer 36a S / D (source / drain) region layer 37 Interlayer insulating film 38a Contact hole 38b Contact hole 39a Contact hole 39b Contact hole 40a S / D (source / drain) electrode 40b S / D (source / drain) electrode 41a S / D (source / drain) electrode 41b S / D (source / drain) electrode 42 refractory metal film (fourth conductor film)
42a refractory metal film (fourth conductor film)
42b refractory metal film (fourth conductor film)
44a First gate portion 44b Second gate portion 45a S / D (source / drain) region layer 45b S / D (source / drain) region layer 46a S / D (source / drain) region layer 46b S / D (source / drain) region layer Drain) region layer 47 Interlayer insulating film 48a Contact hole 48b Contact hole 49a Contact hole 49b Contact hole 50a S / D (source / drain) electrode 50b S / D (source / drain) electrode 51a S / D (source / drain) electrode 51b S / D (Source / Drain) Electrode 52a Opening 52b Opening 53a Refractory Metal Film (Third Conductor Film)
53b refractory metal film (third conductor film)
54 Insulating film 100 Interlayer insulating layer 102 Resist pattern 104 Opening 106 Surface to be plated 108 Thin film conductor (Cu plating film)
DESCRIPTION OF SYMBOLS 110 Thin film magnetic coil 112 Nonmagnetic board | substrate 114 Gap layer 116 Resin insulating layer 118 Resist film 118a Resist pattern 120 1st spiral pattern 122 Conductive processed surface 124 Resist film 126 Resist pattern 128 Cu conductor film 130 Thin film magnetic coil 132 Magnetic layer

Claims (5)

After forming a resist pattern on the surface to be processed, the resist pattern is baked in a vacuum, and then a resist pattern thickening material containing at least a resin is applied to the surface of the resist pattern. A thickened resist pattern forming step of forming a thickened resist pattern by thickening the resist pattern;
And a patterning step of patterning the surface to be processed by etching using the thickened resist pattern as a mask.   The method of manufacturing a semiconductor device according to claim 1, wherein the temperature of the vacuum baking process is 60 to 150 ° C.   The method for manufacturing a semiconductor device according to claim 1, wherein the time of the vacuum baking process is 10 to 300 seconds.   A semiconductor device manufactured by the method for manufacturing a semiconductor device according to claim 1. After the resist pattern is formed, the resist pattern is subjected to a vacuum baking process in which the resist pattern is baked in a vacuum, and then a resist pattern thickening material containing at least a resin is applied to the surface of the resist pattern. Forming method.

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