JP5509660B2 - Method for producing radiation-sensitive resin composition - Google Patents

Description

  The present invention relates to a method for producing a radiation-sensitive resin composition that can be suitably used as a resist useful for fine processing.

  In the microfabrication field represented by the manufacture of integrated circuit elements, in order to obtain an integrated circuit with a higher degree of integration, lithography design rule miniaturization is rapidly progressing. For this reason, there is a strong demand to develop a lithography process that can stably perform fine processing.

  In order to meet such demands, various radiation-sensitive resin compositions for chemically amplified resists have been developed. With the growing demand for miniaturization in lithography processes, it is possible to avoid development defects and improve the manufacturing yield of semiconductor devices for foreign substances inevitably contained in radiation-sensitive resin compositions that have been negligible until now. There is a need for removal for such reasons.

  As related prior art, a filtration method for the purpose of removing foreign substances in the radiation-sensitive resin composition has been proposed (see, for example, Patent Documents 1 to 4).

JP 2002-311600 A JP 2002-31601 A JP 2004-53887 A JP 2004-195427 A

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to provide a radiation-sensitive resin composition that can remove foreign matters efficiently and contains very little foreign matter. It is in providing the manufacturing method of the radiation sensitive resin composition which can obtain the above.

  In order to achieve the above-mentioned problems, the present inventors diligently studied a method for removing foreign substances from a radiation-sensitive resin composition. As a result, a preliminary composition of a radiation-sensitive resin composition that is an object to be filtered is filtered effectively. In order to complete the present invention, it was found that a radiation-sensitive resin composition capable of greatly reducing the occurrence of development defects can be produced by controlling the amount of filtration per area and repeatedly filtering a plurality of times. It came.

  That is, according to this invention, the manufacturing method of the radiation sensitive resin composition shown below is provided.

[1] (A) Radiation sensitive acid generator comprising a diazomethane compound and a sulfonium salt, (B) an alkali insoluble or hardly soluble resin having an acid dissociable group, (C) a solvent, and (D) an acid diffusion controller. the preliminary composition of the radiation-sensitive resin composition containing, in a filter portion, a radiation-sensitive, including the step of repeating filtering 3-150 times retain the filtration rate per filter effective filtration area 30L / m ² or less For producing a conductive resin composition.

[ 2 ] The resin (B) is a repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), and a repeating unit represented by the following general formula (3). The method for producing a radiation-sensitive resin composition according to [1 ], wherein the resin has at least one repeating unit.

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² is a monovalent organic group (except for a group corresponding to “—OR ⁵ ” in the following general formula (2)). M represents an integer of 0 to 3, and n represents an integer of 1 to 3. However, when ^two or more R < ² > exists, several R < ² > may mutually be same or different.

In the general formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a monovalent organic group (excluding a group corresponding to “—OR ⁵ ”), and R ⁵ represents a monovalent group. In the formula, p represents an integer of 0 to 3, and q represents an integer of 1 to 3. However, if the R ⁴ there are a plurality, the plurality of R ⁴ may be different even mutually identical, if R ⁵ there is a plurality, the plurality of R ⁵ may be identical to each other May be different.

In the general formula (3), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents a monovalent acid dissociable group.

[ 3 ] The radiation sensitive material according to [ 2 ], wherein the resin (B) is a resin having a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2). For producing a conductive resin composition.

[ 4 ] The method for producing a radiation-sensitive resin composition according to any one of [1] to [ 3 ], wherein the filter portion is a filter device in which a plurality of polypropylene resin filters are connected in series.

  According to the method for producing a radiation-sensitive resin composition of the present invention, foreign matters can be efficiently removed, and a radiation-sensitive resin composition with very little foreign matter can be obtained. If the radiation sensitive resin composition manufactured by the manufacturing method of the radiation sensitive resin composition of this invention is used as a resist, generation | occurrence | production of a development defect can be suppressed and the manufacture yield of a semiconductor device can be improved.

It is a top view which shows typically the resist pattern formed in the Example.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like appropriately added to the embodiments described above fall within the scope of the present invention.

1. Method for producing radiation-sensitive resin composition:
The method for producing the radiation sensitive resin composition of the present invention comprises: (A) a radiation sensitive acid generator comprising a diazomethane compound and a sulfonium salt; (B) an alkali-insoluble or hardly soluble resin having an acid dissociable group; ) A solvent, and (D) an acid diffusion controller, a radiation-sensitive resin composition preliminary composition (hereinafter, also simply referred to as “radiation-sensitive resin composition preliminary composition” or “preliminary composition”). In the filter part, the filtration amount per filter effective filtration area is maintained at 30 L / m ² or less, and the process is repeatedly filtered 3 to 150 times (filtration process). The details will be described below.

[1] Filter part:
In the manufacturing method of the radiation sensitive resin composition of this invention, the preliminary composition of a radiation sensitive resin composition is filtered with a filter part. As the filter portion, it is preferable to use a filter device in which a plurality of filters are connected in series. Moreover, in this filter apparatus, it filters repeatedly 3 to 150 times , circulating the preliminary composition which is a to-be-filtered object. For this reason, it is preferable that a filter apparatus is equipped with the pump for supplying a preliminary composition to a filter other than a filter. In addition, a chemical pump etc. can be mentioned as a specific example of a pump.

  Specific examples of the filter constituting the filter device include a polypropylene resin filter, a polyamide resin filter, and a polyethylene resin filter. These filters may be used individually by 1 type, and may be used in combination of 2 or more types. When a plurality of filters made of different resins are connected in series, any of the filters may be connected so as to pass first.

[1-1] Polyamide resin filter:
The polyamide resin filter is a filter using a polyamide resin as a filter medium. The polyamide-based resin is a homopolymer or copolymer having an amide bond in the main chain, and specific examples thereof include polyamide 6 and polyamide 66. The filter pore size of the polyamide resin filter is preferably 0.02 to 0.05 μm, and more preferably 0.02 to 0.04 μm. If the filter pore size is too large, the foreign matters mixed in the preliminary composition may not be sufficiently removed. On the other hand, if the filter pore size is too small, the filtration rate tends to be too slow. Specific examples of the polyamide-based resin filter include “ABD1UND8E”, “ABD1UND7EJ”, “ABD1UND8EJ” (all manufactured by Pall Japan Co., Ltd.) and the like under the trade names below.

[1-2] Polyethylene resin filter:
The polyethylene resin filter is a filter using a polyethylene resin as a filter medium. The polyethylene resin is a homopolymer or copolymer having an ethylene unit in the main chain, and specific examples thereof include polyethylene and high density polyethylene. The filter pore size of the polyethylene resin filter is preferably 0.03 to 0.1 μm, and more preferably 0.03 to 0.05 μm. If the filter pore size is too large, the foreign matters mixed in the preliminary composition may not be sufficiently removed. On the other hand, if the filter pore size is too small, the filtration rate tends to be too slow. Specific examples of the polyethylene resin filter include “ABD1UG0037E”, “ABD1UG0038EJ”, and “ABD1UG0058EJ” (all manufactured by Pall Japan, Inc.) under the trade names.

[1-3] Polypropylene resin filter:
The polypropylene resin filter is a filter using a polypropylene resin as a filter medium. The polypropylene resin is a homopolymer or copolymer having a propylene unit in the main chain, and specific examples thereof include polypropylene. The filter pore size of the polypropylene resin filter is preferably 0.02 to 0.1 μm, and more preferably 0.02 to 0.05 μm. If the filter pore size is too large, the foreign matters mixed in the preliminary composition may not be sufficiently removed. On the other hand, if the filter pore size is too small, the filtration rate tends to be too slow. Specific examples of the polypropylene-based resin filter include the following trade names “FOF70KS-P02R-8”, “FOF70KS-P05R-8”, “FOF70KW-P02R-8”, “FOF70KW-P05R-8”, “FOF70KS-P02R”. -7 "," FOF70KS-P05R-7 "," FOF70KW-P02R-7 "," FOF70KW-P05R-8 "," FOF70KS-P02R-7 "," FOF70KS-P02J-8 "," FOF70KS-P05J-8 " ”,“ FOF70KW-P02J-8 ”,“ FOF70KW-P05J-8 ”,“ FOF70KS-P02J-7 ”,“ FOF70KS-P05J-7 ”,“ FOF70KW-P02J-7 ”,“ FOF70KW-P05J-8 ”, "FOF70KS-P02J- ”,“ FOF50-P05T-2 ”,“ FOF50P02T-2 ”,“ FD05P05F-4 ”,“ FD05P02F-4 ”,“ FD05P10F-4 ”,“ FD10P05F-4 ”,“ FD10P02F-4 ”,“ FD10P10F-4 ” (Both manufactured by KITZ Micro Filter).

[2] Filtration step:
[2-1] Filtration amount of preliminary composition:
In the filtration step, the amount of filtration of the preliminary composition per filter effective filtration area (hereinafter also simply referred to as “the amount of filtration of the preliminary composition”) is maintained at 30 L / m ² or less, preferably 20 L / m ² or less. Filter the composition. Foreign matter can be efficiently removed by filtering the preliminary composition while maintaining the filtration amount at 30 L / m ² or less. And if the radiation sensitive resin composition manufactured by filtering in this way is used as a resist, the development defect which arises in the resist pattern formed can be reduced significantly.

The “filtration amount of the preliminary composition per filter effective filtration area (= the filtration amount of the preliminary composition)” in the present specification can be expressed by the following formula (1). The amount of filtration can be adjusted as appropriate by changing the number of filters constituting the filter portion used for filtration, for example.
“Filter amount of preliminary composition” = “Total preparation amount” / “Effective filtration area of filter” (1)

[2-2] Circulation filtration:
In the filtration step, the preliminary composition is filtered by repeatedly circulating 3 to 150 times in the filter portion (hereinafter, also simply referred to as “circulation filtration” or “repetitive filtration”). As described above, fine foreign matters contained in the preliminary composition can be effectively removed by filtering the preliminary composition while maintaining the filtration amount of the preliminary composition at 30 L / m ² or less. Furthermore, foreign matters can be removed more precisely by performing circulation filtration. And if the radiation sensitive resin composition manufactured by filtering in this way is used as a resist, the possibility that an electrical short circuit etc. will arise in the energization test of the device performed after an etching process falls remarkably.

In the circulation filtration times for filtering preliminary composition filter portion is 3-150 times. If the number of times of filtration is once or twice , the removal of foreign matters will be insufficient. For this reason, when the radiation sensitive resin composition obtained by filtering once or twice is used as a resist, it is not preferable because an electrical short circuit is likely to occur in a device energization test. In addition, if it filters 150 times, a foreign material can fully be removed, and even if the frequency | count of filtration is increased more, the removal effect of a foreign material will not improve dramatically.

There are no particular restrictions on other conditions of the circulation filtration. However, the rate at which the preliminary composition is filtered through the filter portion (filtration rate) is preferably 10 to 110 L / hr · m ² , more preferably 10 to 90 L / hr · m ² in terms of the linear filtration rate. . If the filtration linear velocity is less than 10 L / hr · m ² , when the solution viscosity of the preliminary composition is high, there is a possibility that filtration may be impossible due to insufficient pressure. On the other hand, if it exceeds 110 L / hr · m ² , there is a possibility that the foreign matter adsorbed or captured by the filter portion will be detached again from the filter portion.

  From the viewpoint of maintaining the quality of the preliminary composition, the temperature at which the preliminary composition is filtered through the filter portion (filtration temperature) is preferably 15 to 30 ° C, and more preferably 17 to 25 ° C. If the filtration temperature is less than 15 ° C., aggregates may be generated in the preliminary composition. On the other hand, if the filtration temperature is higher than 30 ° C., the preliminary composition may be altered.

[3] Preliminary composition of radiation-sensitive resin composition:
The preliminary composition of the radiation-sensitive resin composition, which is an object to be filtered through the filter portion, is usually a liquid material. This preliminary composition usually contains fine foreign substances together with the radiation-sensitive resin composition. The radiation sensitive resin composition includes (A) a radiation sensitive acid generator comprising a diazomethane compound and a sulfonium salt , (B) an alkali insoluble or hardly soluble resin having an acid dissociable group, (C) a solvent, And (D) an acid diffusion controller. Hereinafter, specific examples of each component contained in the radiation-sensitive resin composition will be described.

[3-1] (A) Radiation sensitive acid generator:
(A) The radiation-sensitive acid generator is an action of various radiations such as deep ultraviolet rays such as KrF excimer laser, ArF excimer laser, or F ₂ excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. Is a component that generates acid. (A) As a preferable example of a radiation sensitive acid generator, a diazomethane compound can be mentioned. Specific examples of the diazomethane compound include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane and the like can be mentioned. Among these, bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] Decane-7-sulfonyl) diazomethane can be preferably used. In addition, these diazomethane compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as another preferable example of (A) radiation sensitive acid generator, the sulfonium salt compound represented by following General formula (5) can be mentioned.

In said general formula (5), several R < ¹² > shows a hydrogen atom, a fluorine atom, a C1-C8 alkyl group, or an alkoxyl group mutually independently. Moreover, several d shows the integer of 0-5 mutually independently, and X < ^- > shows monovalent anion.

In the general formula (5), specific examples of the monovalent anion represented by X ⁻ include, for example, an anion represented by the formula “MX _i ⁻ ” (wherein M represents a boron atom, a phosphorus atom, An arsenic atom or an antimony atom, X represents a halogen atom, i represents a natural number of 4 to 6), a halogen anion, a sulfonate anion having 1 to 20 carbon atoms, or a carboxylate anion having 1 to 20 carbon atoms Etc. Among these, X ⁻ is preferably a sulfonate anion. The sulfonate anion and the carboxylate anion may be substituted with a halogen atom or an oxo group, respectively.

  Specific examples of the sulfonium salt compound represented by the general formula (5) include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, and triphenyl. Sulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium p-trifluoromethylbenzenesulfonate, triphenylsulfonium perfluorobenzenesulfonate, tris (p-methoxyphenyl) sulfonium trifluoromethanesulfonate , Tris (p-methoxyphenyl) sulfonium nonafluoro-n-butanesulfur , Tris (p-methoxyphenyl) sulfonium perfluoro-n-octanesulfonate, tris (p-methoxyphenyl) sulfonium p-toluenesulfonate, tris (p-methoxyphenyl) sulfonium benzenesulfonate, tris (p-methoxyphenyl) sulfonium 10-camphorsulfonate, tris (p-methoxyphenyl) sulfonium p-trifluoromethylbenzenesulfonate, tris (p-methoxyphenyl) sulfonium perfluorobenzenesulfonate, tris (p-fluorophenyl) sulfonium trifluoromethanesulfonate, tris (p- Fluorophenyl) sulfonium p-toluenesulfonate, (p-hydroxyphenyl) diphenylsulfonium trifluoromethane Sulfonates, (p- hydroxyphenyl) diphenyl sulfonium p- toluenesulfonate, (p- fluorophenyl) diphenyl sulfonium trifluoromethanesulfonate, mention may be made of (p- fluorophenyl) sulfonium p- toluenesulfonate and the like.

  Further, other preferred examples of the radiation sensitive acid generator (A) include iodonium salt compounds represented by the following general formula (6).

In said general formula (6), several R < ¹³ > shows a hydrogen atom, a fluorine atom, or a C1-C8 linear or branched alkyl group mutually independently, and several e is mutual. Each independently represents an integer of 0 to 5, and X ⁻ represents a monovalent anion.

Specific examples of the monovalent anion represented by X ⁻ in the general formula (6) include those exemplified as specific examples of the monovalent anion represented by X ⁻ in the general formula (5). The same thing is illustrated. Among these, X ⁻ is preferably a sulfonate anion.

Among the compounds represented by the general formula (6), X ^- is as a specific example of a sulfonic acid anion, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro -n- butane sulfonate, diphenyliodonium perfluoro -n -Unsubstituted diphenyliodonium salt compounds such as octanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium p-trifluoromethylbenzenesulfonate, diphenyliodonium perfluorobenzenesulfonate;

  Bis (pt-butylphenyl) iodonium trifluoromethanesulfonate, bis (pt-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (pt-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (pt-butylphenyl) iodonium p-toluenesulfonate, bis (pt-butylphenyl) iodonium 10-camphorsulfonate, bis (pt-butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis ( pt-butylphenyl) iodonium perfluorobenzenesulfonate, bis (p-fluorophenyl) iodonium trifluoromethanesulfonate, bis (p-fluorophenyl) iodonium nonafluoro-n Butanesulfonate, bis (p-fluorophenyl) iodonium perfluoro-n-octanesulfonate, bis (p-fluorophenyl) iodonium 10-camphorsulfonate, (p-fluorophenyl) (phenyl) iodonium trifluoromethanesulfonate, (p-fluoro Substituted diphenyls such as (phenyl) (phenyl) iodonium nonafluoro-n-butanesulfonate, (p-fluorophenyl) (phenyl) iodonium perfluoro-n-octanesulfonate, (p-fluorophenyl) (phenyl) iodonium 10-camphorsulfonate Mention may be made of iodonium compounds.

  Among these, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium 10-camphorsulfonate, bis (p-fluorophenyl) iodonium trifluoromethanesulfonate, bis (p-fluorophenyl) iodonium nonafluoro -N-butanesulfonate, bis (p-fluorophenyl) iodonium 10-camphorsulfonate, (p-fluorophenyl) (phenyl) iodonium trifluoromethanesulfonate, (p-fluorophenyl) (phenyl) iodonium nonafluoro-n-butanesulfonate , (P-fluorophenyl) (phenyl) iodonium 10-camphorsulfonate and the like are preferable.

  (A) Still another preferred example of the radiation sensitive acid generator includes a sulfonimide compound. Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy)- 7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboximide;

  N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthyl Imido, N-[(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide;

  N- (n-octylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octylsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 Dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyl) Oxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide;

  N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octylsulfonyloxy) -7-oxa Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboximide and the like can be mentioned.

  Among these, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide, N- ( 10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-[(5-methyl-5-carboxymethylbicyclo [2.2. 1] heptan-2-yl) sulfonyloxy] succinimide is preferred. These sulfonimide compounds can be used singly or in combination of two or more.

One or more of the above-mentioned (A) radiation sensitive acid generators can be contained in the radiation sensitive resin composition. Among the above-mentioned (A) a radiation-sensitive acid generator also, diazomethane compounds, and have use of a substituted or unsubstituted sulfonium salt compound, it is good preferable to use a combination of two or more of these compounds. Since the diazomethane compound has a high radiation transmittance, and the pattern shape is deteriorated when the focus is deviated and the fluctuation of the pattern line width is small, the diazomethane compound has an effect of increasing the focal depth margin. By using a diazomethane compound exhibiting such an action in combination with a sulfonium salt compound having a high acid generation efficiency, a greater depth of focus margin can be achieved.

  In the case where a diazomethane compound and a substituted or unsubstituted sulfonium salt compound are used in combination, the mass ratio of the diazomethane compound to the sulfonium salt compound (diazomethane compound / sulfonium salt compound) is 99/1 to 5/95. Preferably, it is 95/5 to 40/60, more preferably 95/5 to 50/50. When the mass ratio of the diazomethane compound and the sulfonium salt compound is within the above range, a better focus depth margin improving effect can be obtained.

  (A) The content of the radiation-sensitive acid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (B) from the viewpoint of ensuring sensitivity and developability as a resist. More preferably, it is 1.0-15 mass parts. (A) It exists in the tendency for a sensitivity and developability to fall that content of a radiation sensitive acid generator is less than 0.1 mass part. On the other hand, if it exceeds 20 parts by mass, the transparency to radiation is lowered, and it tends to be difficult to form a rectangular resist pattern.

[3-2] (B) Resin:
(B) The resin is an alkali-insoluble or hardly soluble resin having an acid dissociable group. This resin becomes alkali-soluble when the acid dissociable group is dissociated. The term “alkali insoluble or hardly soluble” as used herein refers to an alkali development condition employed when a resist pattern is formed from a resist film formed using a radiation-sensitive resin composition containing (B) a resin. When a film using only the resin (B) is developed instead of the resist film, it means that 50% or more of the initial film thickness of the film remains after development. “Alkali-soluble” means a property that a film does not substantially remain when developed under the same conditions.

  (B) As the resin, for example, one or more types capable of dissociating a hydrogen atom of an acidic functional group in an alkali-soluble resin having one or more acidic functional groups such as a phenolic hydroxyl group or a carboxyl group in the presence of an acid Examples of such a resin substituted with an acid-dissociable group include alkali-insoluble or hardly-alkali-soluble resins.

  Specific examples of (B) resin include a repeating unit represented by the following general formula (1) (hereinafter also referred to as “repeating unit (1)”) and a repeating unit represented by the following general formula (2) ( Hereinafter, also referred to as “repeating unit (2)”) and at least one repeating unit represented by the following general formula (3) (hereinafter also referred to as “repeating unit (3)”). Resin (hereinafter, also referred to as “(B1) resin”).

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² is a monovalent organic group (except for a group corresponding to “—OR ⁵ ” in the following general formula (2)). M represents an integer of 0 to 3, and n represents an integer of 1 to 3. However, when ^two or more R < ² > exists, several R < ² > may mutually be same or different.

In the general formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a monovalent organic group (excluding a group corresponding to “—OR ⁵ ”), and R ⁵ represents 1 Represents a divalent acid dissociable group, p represents an integer of 0 to 3, and q represents an integer of 1 to 3. However, if the R ⁴ there are a plurality, the plurality of R ⁴ may be different even mutually identical, if R ⁵ there is a plurality, the plurality of R ⁵ may be identical to each other May be different.

In the general formula (3), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents a monovalent acid dissociable group.

Specific examples of the monovalent organic group represented by R ² in the general formula (1) and R ⁴ in the general formula (2) are linear or branched having 1 to 12 carbon atoms. Alternatively, a cyclic alkyl group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent oxygen atom-containing organic group, a monovalent nitrogen atom-containing organic group, and the like can be given.

  Specific examples of the “alkyl group” include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, cyclopentyl. Group, cyclohexyl group and the like. Examples of the monovalent aromatic hydrocarbon group include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, 2,6-xylyl group, 3, Examples include 5-xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, benzyl group, phenethyl group, 1-naphthyl group, 2-naphthyl group and the like.

  Specific examples of the “monovalent oxygen atom-containing organic group” include a carboxyl group; a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- C1-C8 straight chain such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 3-hydroxycyclopentyl group, 4-hydroxycyclohexyl group, etc. A branched or cyclic hydroxyalkyl group;

  C1-C8 straight chain such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, cyclopentyloxy group, cyclohexyloxy group, etc. Linear, branched or cyclic alkoxyl groups; linear alkoxycarbonyloxy groups having 2 to 9 carbon atoms such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group and n-butoxycarbonyloxy group;

  (1-methoxyethoxy) methyl group, (1-ethoxyethoxy) methyl group, (1-n-propoxyethoxy) methyl group, (1-n-butoxyethoxy) methyl group, (1-cyclopentyloxyethoxy) methyl group, C1-C11 linear, branched or cyclic (1-alkoxyalkoxy) such as (1-cyclohexyloxyethoxy) methyl group, (1-methoxypropoxy) methyl group, (1-ethoxypropoxy) methyl group, etc. An alkyl group;

  Methoxycarbonyloxymethyl group, ethoxycarbonyloxymethyl group, n-propoxycarbonyloxymethyl group, i-propoxycarbonyloxymethyl group, n-butoxycarbonyloxymethyl group, cyclopentyloxycarbonyloxymethyl group, cyclohexyloxycarbonyloxymethyl group, etc. And a straight-chain, branched or cyclic alkoxycarbonyloxyalkyl group having 3 to 10 carbon atoms.

  Specific examples of the “monovalent nitrogen atom-containing organic group” include cyano group; cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 1-cyanopropyl group, 2-cyanopropyl group, 3-cyanopropyl group. 1-cyanobutyl group, 2-cyanobutyl group, 3-cyanobutyl group, 4-cyanobutyl group, 3-cyanocyclopentyl group, 4-cyanocyclohexyl group, etc., linear, branched, or cyclic groups having 2 to 9 carbon atoms A cyanoalkyl group etc. can be mentioned.

Specific examples of the monovalent acid dissociable group represented by R ⁵ in the general formula (2) include a substituted methyl group, a 1-substituted ethyl group, a 1-substituted propyl group, a 1-substituted butyl group, -Substituted pentyl group, 2-substituted butyl group, 2-substituted pentyl group, 2-substituted hexyl group, 1-branched alkyl group, triorganosilyl group, triorganogermyl group, alkoxycarbonyl group, acyl group, monovalent Examples include cyclic acid dissociable groups.

  Specific examples of the “substituted methyl group” include methoxymethyl group, n-propoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, Phenacyl group, bromophenacyl group, methoxyphenacyl group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl Group, methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycal Nirumechiru group, and a t- butoxycarbonyl methyl group.

  Specific examples of the “1-substituted ethyl group” include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1. -Diethoxyethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group 1-isopropoxycarbonylethyl group, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonyl Mention may be made of a methyl group and the like. Specific examples of the “1-branched alkyl group” include i-propyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group and the like. Can be mentioned.

  Specific examples of the “1-substituted propyl group” include 1-methoxypropyl group, 1-ethoxypropyl group, 1-n-propoxypropyl group and the like.

  Specific examples of the “1-substituted butyl group” include 1-methoxybutyl group, 1-ethoxybutyl group, 1-n-propoxybutyl group and the like.

  Specific examples of the “1-substituted pentyl group” include 1-methoxypentyl group, 1-ethoxypentyl group, 1-n-propoxypentyl group and the like.

  Specific examples of the “2-substituted butyl group” include 2-methoxy-2-butyl group, 2-ethoxy-2-butyl group, 2-n-propoxy-2-butyl group and the like.

  Specific examples of the “2-substituted pentyl group” include 2-methoxy-2-pentyl group, 2-ethoxy-2-pentyl group, 2-n-propoxy-2-pentyl group and the like.

  Specific examples of the “2-substituted hexyl group” include 2-methoxy-2-hexyl group, 2-ethoxy-2-hexyl group, 2-n-propoxy-2-hexyl group and the like.

  Specific examples of the “triorganosilyl group” include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propyl. Examples thereof include a silyl group, a t-butyldimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

  Specific examples of the “triorganogermyl group” include trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, isopropyldimethylgermyl group, methyldi-i-propylgermyl group, Tri-i-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group, etc. Can be mentioned.

  Specific examples of the “alkoxycarbonyl group” include methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, t-butoxycarbonyl group and the like. Specific examples of the “acyl group” include acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, Malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl Group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, i Nicotinoyl group, and the like can be mentioned.

  Specific examples of the “monovalent cyclic acid dissociable group” include cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, 4-methoxycyclohexyl group, tetrahydrofuranyl group, tetrahydropyranyl group, tetrahydrothiofuran group. Nyl group, tetrahydrothiopyranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-1,1-dioxide group, etc. it can.

  Among these monovalent acid dissociable groups, t-butyl group, benzyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-methoxypropyl group, 1-ethoxy group A propyl group, trimethylsilyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, tetrahydrofuranyl group, tetrahydropyranyl group, tetrahydrothiofuranyl group, tetrahydrothiopyranyl group and the like are preferable.

  Specific examples of the repeating unit (1) include 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-. Methylstyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 3, Mention may be made of repeating units formed by the polymerization of these monomers and the polymerization of unsaturated bonds of monomers such as 4-dihydroxystyrene and 2,4,6-trihydroxystyrene. In addition, repeating unit (1) may be contained individually by (B1) resin, and 2 or more types may be contained.

  Specific examples of the repeating unit (2) include 4-t-butoxystyrene, 4-t-butoxy-α-methylstyrene, 4- (methoxymethyl) styrene, 4- (methoxymethyl) -α-styrene, 4- (1-methoxyethyl) styrene, 4- (1-methoxyethyl) -α-styrene, 4- (1-methoxypropoxy) styrene, 4- (1-methoxypropoxy) -α-methylstyrene, 4- (1- Polymerization of monomers such as ethoxypropoxy) styrene, 4- (1-ethoxypropoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- (1-ethoxyethoxy) -α-methylstyrene Mention may be made of repeating units formed by cleavage of unsaturated bonds and polymerization of these monomers. In addition, repeating unit (2) may be contained individually by (B1) resin, and 2 or more types may be contained.

  Specific examples of the repeating unit (3) include t-butyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, (Meth) acrylic acid 2-ethyladamantyl, (meth) acrylic acid 8-methyl-8-tricyclodecyl, (meth) acrylic acid 8-ethyl-8-tricyclodecyl, (meth) acrylic acid 3-methyl-3 -When the polymerizable unsaturated bond of monomers such as tetracyclododecenyl and 3-ethyl-3-tetracyclododecenyl (meth) acrylate is cleaved, these monomers are polymerized. Mention may be made of the repeating units formed. In addition, repeating unit (3) may be contained individually by (B1) resin, and 2 or more types may be contained.

  (B1) The resin may further contain a repeating unit other than the above repeating units (1) to (3) (hereinafter also referred to as “other repeating unit”). Specific examples of “other repeating units” include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, and the like. Vinyl aromatic compounds;

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate 1-methylpropyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl, 2-hydroxy-n-propyl (meth) acrylate, 3-hydroxy-n-propyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid 1-methyladamantyl, 1-ethyladamantyl (meth) acrylate, 2,5-dimethylhexane-2,5- (Meth) (meth) acrylic acid esters such as acrylate;

  Unsaturated carboxylic acids (anhydrides) such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, cinnamic acid; 2-carboxyethyl (meth) acrylate, (meth) acrylic acid 2 -Carboxyalkyl esters of unsaturated carboxylic acids such as carboxy-n-propyl and (meth) acrylic acid 3-carboxy-n-propyl; (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, etc. Unsaturated nitrile compounds;

  Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, and fumaramide; unsaturated imide compounds such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; N-vinyl Polymerization of other nitrogen-containing vinyl compounds such as -ε-caprolactam, N-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole and 4-vinylimidazole Mention may be made of repeating units formed by cleavage of unsaturated bonds and polymerization of these monomers. In addition, "other repeating unit" may be contained individually by (B1) resin, and 2 or more types may be contained.

  (B1) Preferred specific examples of the resin include 4-hydroxystyrene / 4-t-butoxystyrene copolymer, 4-hydroxystyrene / 4-ethoxyethoxystyrene copolymer, 4-hydroxystyrene / 4- t-butoxystyrene copolymer / 4-1-ethoxyethoxystyrene copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / 1-methylcyclopentyl acrylate copolymer, 4-hydroxystyrene / 4-t- Butoxystyrene / 1-ethylcyclopentyl acrylate copolymer, 4-hydroxystyrene / 4-tert-butoxystyrene / styrene copolymer, 4-hydroxystyrene / tert-butyl acrylate / styrene copolymer, 4-hydroxystyrene / 1-methylcyclopentyl acrylate / styrene copolymer, 4-hydride Kishisuchiren / acrylic acid 1-ethylcyclopentyl / styrene copolymer, may be mentioned 4-hydroxystyrene / 4-t-butoxystyrene / 2,5-dimethylhexane-2,5-diacrylate copolymer. Among these, 4-hydroxystyrene / 4-t-butoxystyrene copolymer, 4-hydroxystyrene / 4-ethoxyethoxystyrene copolymer, 4-hydroxystyrene / 4-t-butoxystyrene copolymer A / 4-1-ethoxyethoxystyrene copolymer is particularly preferable.

  (B) Introduction rate of acid-dissociable groups in resin ((B) ratio of number of acid-dissociable groups to total number of unprotected acidic functional groups and acid-dissociable groups in resin) Since it depends on the kind of the alkali-soluble resin into which the acid group or the acid dissociable group is introduced, it cannot be generally specified, but it is preferably 10 to 90%, and more preferably 15 to 90%. preferable.

  (B1) The proportion of the repeating unit (1) contained in the resin (the content of the repeating unit (1)) is preferably 60 to 80 mol%, and more preferably 60 to 75 mol%. When the content of the repeating unit (1) is less than 60 mol%, the adhesion of the resist pattern to the substrate tends to be lowered. On the other hand, when the content of the repeating unit (1) is more than 80 mol%, the contrast after development tends to be lowered.

  (B1) The ratio of the repeating unit (2) contained in the resin (the content of the repeating unit (2)) is preferably 10 to 40 mol%, and more preferably 10 to 35 mol%. When the content of the repeating unit (2) is less than 10 mol%, the resolution tends to decrease. On the other hand, when the content of the repeating unit (2) is more than 40 mol%, the adhesion of the resist pattern to the substrate tends to be lowered.

  (B1) The ratio of the repeating unit (3) contained in the resin (the content of the repeating unit (3)) is preferably 10 to 40 mol%, and more preferably 10 to 30 mol%. When the content of the repeating unit (3) is less than 10 mol%, the resolution tends to decrease. On the other hand, if the content of the repeating unit (3) is more than 40 mol%, the dry etching resistance may be insufficient.

  (B1) The ratio of “other repeating units” contained in the resin (content ratio of “other repeating units”) is usually 25 mol% or less, preferably 10 mol% or less. If the content of “other repeating units” exceeds 25 mol%, the resolution tends to decrease.

  (B) The weight average molecular weight (hereinafter also referred to as “Mw”) in terms of polystyrene measured by gel permeation chromatography (GPC) of the resin is preferably 1,000 to 150,000, and preferably 3,000 to More preferably, it is 100,000. The ratio (Mw / Mn) of (B) resin Mw and polystyrene-equivalent number average molecular weight (hereinafter also referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1 to 1. 10, preferably 1-5.

(B) Resin is, for example, a polymerizable unsaturated monomer corresponding to the repeating unit (1), if necessary, a polymerizable unsaturated monomer corresponding to the repeating unit (3), or “other repeating After (co) polymerizing with a polymerizable unsaturated monomer corresponding to “unit”, one or more monovalent acid-dissociable groups (R ⁵ ) are introduced into the phenolic hydroxyl group. The (B) resin may be, for example, a polymerizable unsaturated monomer corresponding to the repeating unit (1) and a polymerizable unsaturated monomer corresponding to the repeating unit (2), if necessary. It can also be produced by copolymerizing with a polymerizable unsaturated monomer corresponding to (3) or a polymerizable unsaturated monomer corresponding to “another repeating unit”. In addition, (B) resin can be used individually by 1 type or in combination of 2 or more types.

[3-3] (C) Solvent:
The radiation-sensitive resin composition is usually prepared by uniformly dissolving (A) a radiation-sensitive acid generator, (B) a resin, (D) an acid diffusion controller, and various components described later in (C) a solvent. After preparing the preliminary composition, it can be obtained by performing the filtration described above. (C) The amount of the solvent is such that the concentration of the total solid content in the preliminary composition is usually 0.1 to 50% by mass, preferably 1 to 40% by mass. By using the solvent (C) so as to have such a concentration, it can be filtered smoothly. The radiation-sensitive resin composition is also usually used in a solution state in which the total solid content concentration is within the above range. Therefore, if the total solid content concentration of the preliminary composition is adjusted to be the same as the total solid content concentration of the radiation-sensitive resin composition used as the resist agent, it is unnecessary to adjust the concentration after filtration. Become.

  Specific examples of the solvent (C) include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate. ;

  Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n -Propylene glycol dialkyl ethers such as propyl ether and propylene glycol di-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol such as Roh alkyl ether acetates;

  Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate; formate esters such as n-amyl formate and i-amyl formate; ethyl acetate, n-propyl acetate, i-acetate Acetic esters such as propyl, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; i-propyl propionate, propionate Propionic acid esters such as n-butyl acid, i-butyl propionate, 3-methyl-3-methoxybutyl propionate; ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-3- Methyl methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxy Other esters such as ethyl lopionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate ;

  Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N-methylformamide, N, N-dimethylformamide Amides such as N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-butyrolacun. These (C) solvents can be used singly or in combination of two or more.

[3-4] (D) Acid diffusion controller:
The (D) acid diffusion controller contained in the radiation-sensitive resin composition controls the diffusion phenomenon in the resist film of the acid generated from the (A) radiation-sensitive acid generator by exposure, and is preferably in the non-exposed region. It is a component that has the action of suppressing chemical reactions.

  (D) Preferable examples of the acid diffusion controller include nitrogen-containing organic compounds and photosensitive basic compounds. Specific examples of the nitrogen-containing organic compound include a compound represented by the following general formula (7) (hereinafter also referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (i)”). (Also referred to as “nitrogen-containing compound (ii)”), polyamino compounds and polymers having three or more nitrogen atoms (hereinafter collectively referred to as “nitrogen-containing compound (iii)”), amide group-containing compounds, urea compounds And nitrogen-containing heterocyclic compounds. The (D) acid diffusion controller may be a single compound or a mixture containing two or more compounds.

In the general formula (7), R ¹⁴ is independently of each other a hydrogen atom, a substituted or unsubstituted linear, branched, or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or non-substituted group. A substituted aralkyl group is shown.

  Preferred examples of the nitrogen-containing compound (i) include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; -Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Of di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octyl Amine, tri-n-nonylamine, tri-n-decylamine, cyclohexyl Tri (cyclo) alkylamines such as dimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline, etc. And aromatic amines.

  Preferable examples of the nitrogen-containing compound (ii) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino. Diphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-amino Phenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methyl ester Benzene], bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, N, N, N ′ , N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and the like.

  Preferable examples of the nitrogen-containing compound (iii) include polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, and the like.

  Preferable examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt -Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)- (-)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxy Piperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl Perazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′- Diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl-1 , 7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl-1,9-diaminononane, N, N′-di- t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N -Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole Nt-butoxycarbonyl group-containing amino compounds such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, Examples thereof include N-methylpyrrolidone, N-acetyl-1-adamantylamine, and isocyanuric acid tris (2-hydroxyethyl).

  Preferred examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl. Examples include thiourea.

  Preferable examples of the nitrogen-containing heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2. -Imidazoles such as methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenyl Pyridines such as pyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ′: 6 ′, 2 ″ -terpyridine; piperazine, 1- (2-hydroxy In addition to piperazines such as ethyl) piperazine, pyra , Pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3 -(N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like can be mentioned.

  (D) A photosensitive basic compound that is one of the preferred examples of the acid diffusion controller is a component that is efficiently decomposed into the corresponding neutral fragment in the exposed area, but remains in the unexposed area without being decomposed. is there. Since such a photosensitive basic compound can effectively use an acid generated in an exposed portion (exposed region) as compared with a non-photosensitive basic compound, the sensitivity as a resist can be improved. .

  Preferable examples of the photosensitive basic compound include compounds represented by the following general formula (8-1) or the following general formula (8-2).

In the general formula (8-1), R ^{15 to} R ¹⁷ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted fat. A cyclic hydrocarbon group is shown. In the general formula (8-2), R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted group. An alicyclic hydrocarbon group is shown. Furthermore, in the general formulas (8-1) and (8-2), Z ⁻ represents independently of each other “OH ⁻ ”, “R ²⁰ O ⁻ ”, or “R ²⁰ COO ⁻ ” (where “ R ²⁰ 'represents an anion represented as shown) a monovalent organic group.

“Substituted or unsubstituted alkyl group having 1 to 10 carbon atoms” represented by R ^{15 to} R ¹⁷ in the general formula (8-1) and R ¹⁸ and R ¹⁹ in the general formula (8-2). Specific examples of "" include a methyl group, an ethyl group, an n-butyl group, a t-butyl group, a trifluoromethyl group, a methoxy group, a t-butoxy group, and a t-butoxycarbonylmethyloxy group. R ^{15 to} R ¹⁷ in the general formula (8-1) and R ¹⁸ and R ¹⁹ in the general formula (8-2) may be independently a hydrogen atom or a t-butyl group. preferable.

Formula (8-1) and (8-2) in the Z ^- of the exemplary, represented by ^{"R 20"} in the anion represented by ^{"R 20} O ^{- -"} and ^"R 20 COO" Examples of the “monovalent organic group” include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and the like.

In the general formula (8-1) and the general formula (8-2), the anion represented by Z ⁻ is selected from OH ⁻ , CH ₃ COO ⁻ , and an anion group represented by the following formula (9). It is preferable that it is any one anion.

Preferred examples of the photosensitive basic compound, wherein a general formula (8-1) triphenylsulfonium compounds represented by the anion ^{- is,} OH (Z) _-, CH 3 COO ^-, and the following The compound which is either selected from the anion group represented by Formula (10) can be mentioned.

  (D) The content of the acid diffusion controller is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass, and more preferably 0.005 to 100 parts by mass of (B) resin. 5 parts by mass is particularly preferable. (D) When the content of the acid diffusion controller is more than 15 parts by mass, the sensitivity as a resist and the developability of the exposed part may be deteriorated. On the other hand, if the content is less than 0.001 part by mass, the pattern shape and dimensional fidelity as a resist may be lowered depending on the process conditions.

[3-5] Additive:
Various additives, such as surfactant and a sensitizer, can be mix | blended with a radiation sensitive resin composition as needed. A surfactant is a component that exhibits an effect of improving coating properties, striation, developability as a resist, and the like. Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenol ether, polyoxyethylene-n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene Examples include glycol distearate. Commercially available surfactants are the following trade names: “F-top EF301”, “same EF303”, “same EF352” (above, manufactured by Tochem Products); “Megafax F171”, “same F173” “Florard FC430”, “Same FC431” (above, Sumitomo 3M), “Asahi Guard AG710”, “Surflon S-382”, “SC101”, “ “SC102”, “SC103”, “SC104”, “SC105”, “SC106” (manufactured by Asahi Glass Co., Ltd.); “KP341” (manufactured by Shin-Etsu Chemical Co., Ltd.), “Polyflow N2.75”, “ N2.95 ”(manufactured by Kyoeisha Chemical Co., Ltd.). The blending amount of the surfactant is preferably 2 parts by mass or less with respect to 100 parts by mass of the (B) resin.

  Specific examples of the sensitizer include rose bengal. The blending amount of the sensitizer is preferably 50 parts by mass or less with respect to 100 parts by mass of the (B) resin. Further, by adding a dye and / or pigment to the radiation-sensitive resin composition, it is possible to visualize the latent image in the exposed area and to reduce the influence of halation during exposure. Specific examples of the dye include anthracene carboxylic acid, anthracene-9-carboxylic acid methoxycarbonylmethyl, anthracene-9-carboxylic acid t-butoxycarbonylmethyl, 9-methoxycarbonylmethylanthracene, 9-t-butoxycarbonylmethylanthracene, etc. Anthracene derivatives; carbazole derivatives such as N- (methoxycarbonylmethyl) carbazole, N- (t-butoxycarbonylmethyl) carbazole, 9-carbazoylacetic acid; benzophenone-2-carboxylic acid t-butoxycarbonylmethyl, benzophenone-4- Examples thereof include benzophenone derivatives such as t-butoxycarbonylmethyl carboxylate. In addition, these dyes can be used individually by 1 type or in combination of 2 or more types. Furthermore, the adhesiveness of a board | substrate and a resist film can be improved more by mix | blending an adhesion aid with a radiation sensitive resin composition.

  In addition, as components other than the above-mentioned various additives, an antihalation agent such as 4-hydroxy-4'-methylchalcone, a shape improver, a storage stabilizer, an antifoaming agent, and the like can be blended.

2. Resist pattern formation method:
An example of the resist pattern formation method using the radiation sensitive resin composition manufactured by the manufacturing method of the radiation sensitive resin composition of this invention is demonstrated. In order to form a resist pattern, first, a substrate such as a silicon wafer, a wafer coated with aluminum, or the like, by applying an ordinary liquid radiation-sensitive resin composition by an appropriate application means such as spin coating, cast coating or roll coating. A resist film is formed by coating on the top. Next, after heat treatment (hereinafter also referred to as “PB”) at a temperature of about 70 to 160 ° C. as necessary, selective exposure is performed through a predetermined mask pattern.

The type of radiation used for exposure is appropriately selected according to the type of (A) the radiation sensitive acid generator. Specifically, deep ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and F ₂ excimer laser (wavelength 157 nm); X-rays such as synchrotron radiation; charged particle beams such as electron beams It can be used by appropriately selecting from the above. Of these, far ultraviolet rays such as KrF excimer laser (wavelength 248 nm) are preferable. The exposure conditions such as the exposure amount are appropriately set according to the blending composition of the radiation-sensitive resin composition, the type of additive, and the like.

  In order to stably form a high-precision fine pattern, it is preferable to perform heat treatment (hereinafter also referred to as “PEB”) for 30 seconds or more at a temperature of about 70 to 160 ° C. after exposure. If the temperature of the PEB is less than 70 ° C., the variation in sensitivity may spread depending on the type of substrate.

  After exposure (or after PEB, if necessary), an alkaline developer is used, usually at 10-50 ° C. for 10-200 seconds, preferably at 15-30 ° C. for 15-100 seconds, more preferably 20-25. By developing at 15 ° C. for 15 to 90 seconds, a predetermined resist pattern can be formed. As an alkaline developer, for example, an alkaline compound such as a tetraalkylammonium hydroxide is usually dissolved in a concentration of 1 to 10% by mass, preferably 1 to 5% by mass, and more preferably 1 to 3% by mass. An alkaline aqueous solution is used. In addition, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant can be appropriately added to the alkaline aqueous solution. In forming the resist pattern, it is also preferable to provide a protective film on the resist film in order to prevent the influence of basic impurities contained in the environmental atmosphere.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. The weight average molecular weight (Mw) and number average molecular weight (Mn), Tosoh Corp. GPC column (trade name "G2000H _XL" two, trade name "G3000H _XL" one, trade name "G4000H _XL" one ), Flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: polystyrene conversion value measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of 40 ° C. It is.

(Synthesis Example 1: Synthesis of Resin (B-1))
A solution obtained by dissolving 24 g of poly (p-hydroxystyrene) having an Mw of 12,000 in 100 g of dioxane was bubbled with nitrogen gas for 30 minutes. Thereafter, a reaction solution obtained by adding 5 g of ethyl vinyl ether and 1 g of p-toluenesulfonic acid pyridinium salt as a catalyst to this solution was reacted at room temperature for 12 hours. The reaction solution was then added dropwise to a 1% aqueous ammonia solution. The resulting precipitate was filtered off and then dried overnight at 50 ° C. under reduced pressure to obtain Resin (B-1). Mw of the obtained resin (B-1) was 15,000 and Mw / Mn was 1.7. As a result of ¹³ C-NMR analysis, the obtained resin (B-1) was substituted with 1-ethoxyethyl group in 35 mol% of the hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene). It was a copolymer having a structure.

(Synthesis Example 2: Synthesis of Resin (B-2))
101 g of p-acetoxystyrene, 50 g of pt-butoxystyrene, 6 g of AIBN, and 1 g of t-dodecyl mercaptan were dissolved in 160 g of propylene glycol monomethyl ether, and then polymerization was performed for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. I let you. A precipitate formed by dropping the reaction solution into 2000 g of n-hexane was dried at 50 ° C. under reduced pressure for 3 hours. After 190 g of the dried precipitate was dissolved in 150 g of propylene glycol monomethyl ether, 300 g of methanol, 80 g of triethylamine and 15 g of water were added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the hydrolysis reaction, the solid obtained by distilling off the solvent and triethylamine under reduced pressure was redissolved in acetone so that the solid content concentration was 20%, and then dropped into 2000 g of water. The produced precipitate (white powder) was filtered off, and then dried at 50 ° C. under reduced pressure overnight to obtain a resin (B-2). Mw of the obtained resin (B-2) was 16,000 and Mw / Mn was 1.7. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene and pt-butoxystyrene was 72:28.

(Synthesis Example 3: Synthesis of Resin (B-3))
25 g of a copolymer of 4-hydroxystyrene and 4-t-butoxystyrene (4-hydroxystyrene: 4-t-butoxystyrene (molar ratio) = 90: 10, trade name “VPT1503S” manufactured by Nippon Soda Co., Ltd.) A solution obtained by dissolving in 100 g of n-butyl was bubbled with nitrogen gas for 30 minutes. Thereafter, a reaction solution obtained by adding 3.3 g of ethyl vinyl ether and 1 g of pyridinium 4-toluenesulfonate as a catalyst to this solution was reacted at room temperature for 12 hours. The reaction solution was then added dropwise to a 1% aqueous ammonia solution. The resulting precipitate was filtered off and dried overnight at 50 ° C. under reduced pressure to obtain Resin (B-3). Mw of the obtained resin (B-2) was 13,000, and Mw / Mn was 1.01. Moreover, as a result of ¹³ C-NMR analysis, the obtained resin (B-3) was a 4-hydroxystyrene unit: a unit in which a hydrogen atom of a phenolic hydroxyl group was substituted with an ethoxyethyl group: a 4-t-butoxystyrene unit. = 67:23:10 (molar ratio) copolymer.

(Synthesis Example 4: Synthesis of Resin (B-4))
The polymerization reaction was performed using 100 g of p-acetoxystyrene, 25 g of t-butyl acrylate, 18 g of styrene, 6 g of azobisisobutyronitrile, 1 g of t-dodecyl mercaptan, and 260 g of propylene glycol monomethyl ether, and dried. Resin (B-4) is obtained in the same manner as in Synthesis Example 2 except that the hydrolysis is performed using 135 g of precipitate, 150 g of propylene glycol monomethyl ether, 300 g of methanol, 80 g of triethylamine, and 15 g of water. It was. Mw of the obtained resin (B-4) was 11,500, and Mw / Mn was 1.6. As a result of ¹³ C-NMR analysis, the obtained resin (B-4) was a copolymer of p-hydroxystyrene unit: t-butyl acrylate unit: styrene unit = 61: 19: 20 (molar ratio). Met.

(Synthesis Example 5: Synthesis of Resin (B-5))
154 g of p-acetoxystyrene, 7 g of styrene, 53 g of pt-butoxystyrene, 9 g of azobisisobutyronitrile, 7 g of t-dodecyl mercaptan, and 260 g of propylene glycol monomethyl ether, and drying Resin (B-5) was prepared in the same manner as in Synthesis Example 2 except that 215 g of the resulting precipitate, 260 g of propylene glycol monomethyl ether, 300 g of methanol, 80 g of triethylamine, and 15 g of water were used for the hydrolysis reaction. Obtained. Mw of the obtained resin (B-5) was 16,000 and Mw / Mn was 1.7. Moreover, as a result of the ¹³ C-NMR analysis, the obtained resin (B-5) was found to have a p-hydroxystyrene unit: styrene unit: pt-butoxystyrene unit = 72: 5: 23 (molar ratio) It was a coalescence.

Example 1
Resin (B-1) 50 parts, Resin (B-2) 50 parts, Radiation sensitive acid generator (A-1) 7 parts, Radiation sensitive acid generator (A-2) 1 part, Solvent (C- 1) 190 parts, 430 parts of solvent (C-2), and 0.7 part of acid diffusion controller (D-1) were mixed to prepare a preliminary composition. Two polypropylene resin filters (trade name “FOF50-P02T-2”, manufactured by KITZ Micro Filter, filter diameter: 0.02 μm, polypropylene, effective filtration area: 0.38 m ² ) were prepared from the prepared preliminary composition. Using the connected filter apparatus, it filtered repeatedly 100 times with the filtration amount of 20 L / m < ² >, and the radiation sensitive resin composition was obtained. During filtration, a chemical pump (model “DP-10F”, manufactured by Yamada) was used as a circulation pump, the filtration temperature was set to 23 ° C., and the filtration rate (linear velocity) was set to 65 L / m ² hr. Moreover, the preparation amount (15.2 L) of the preliminary composition was set so that the filtration amount of the preliminary composition of the radiation sensitive resin composition per filter effective filtration area was 20 L / m ² .

(Example 2-6, Comparative Example 1 to 5)
Except that the preliminary composition was prepared according to the formulation shown in Table 1, and that the preliminary composition shown in Table 1 was charged, filtered, and filtered at the number of times of filtration, the same as in Example 1 above. A radiation sensitive resin composition was obtained by the operation. In addition, each component used by each Example and the comparative example is as showing below.

<(A) Radiation sensitive acid generator>
A-1: Bis (1,4-dioxaspiro [4.5] decan-7-sulfonyl) diazomethane A-2: Triphenylsulfonium trifluoromethanesulfonate A-3: Tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate

<(C) Solvent>
C-1: Ethyl lactate C-2: Propylene glycol monomethyl ether acetate

<(D) Acid diffusion controller>
D-1: Trioctylamine D-2: Triphenylsulfonium salicylate

(Evaluation: Measurement of the number of scum defects)
The radiation-sensitive resin compositions (solutions) obtained in Examples and Comparative Examples were spin-coated on a predetermined substrate so that the film thickness after pre-baking (PB) was 0.70 μm, and then 90 ° C. for 90 seconds. Pre-baking (PB) was performed. Next, after exposing with the exposure amount of 30 mJ / cm < ² > using an exposure apparatus, the post-exposure baking (PEB) was performed for 90 second at 100 degreeC. Next, using a coater / developer, the film was developed by an immersion method at 23 ° C. for 60 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution. After washing with pure water, it was dried to obtain a wafer on which a resist pattern having an unexposed portion 10 and an exposed portion 20 was formed as shown in FIG. Using a defect inspection apparatus, the number of scum defects generated in the wafer surface was measured. The measurement results of the number of scum defects are shown in Table 1. The “scum defect” means a defect that is hardly soluble in an alkali developer and exists in an exposed area after development. This “scum defect” causes a decrease in device yield. Details of the substrate and apparatus used are shown below.

<Board>
Substrate (thickness: 550 Å, firing condition: 205 ° C. × 60 seconds) on which an organic underlayer film (trade name “DUV42”, manufactured by Brewer Science Co., Ltd.) is formed on a silicon wafer having a diameter of 200 mm

<Exposure device>
KrF excimer laser scanner (trade name “NSR S203B”, manufactured by Nikon Corporation, optical conditions: NA = 0.68, 2 / 3-Annu. Σ = 0.75)

<Coater / Developer>
Product name "KLA2351", manufactured by KLA-Tencor

<Defect measuring device>
Product name "KLA2351", manufactured by KLA-Tencor

From the results shown in Table 1 and Table 2, while using a radiation sensitive resin composition obtained by repeatedly filtering the preliminary composition with a filtration device while maintaining the filtration amount of the preliminary composition at 30 L / m ² or less. When the resist pattern is formed, the occurrence of scum defects is clearly reduced.

  If the radiation sensitive resin composition manufactured by the manufacturing method of the radiation sensitive resin composition of this invention is used, generation | occurrence | production of a scum defect will be very few and a high quality resist pattern can be manufactured.

10: unexposed area, 20: exposed area

Claims (4)

(A) a radiation sensitive acid generator comprising a diazomethane compound and a sulfonium salt, (B) an alkali-insoluble or hardly soluble resin having an acid dissociable group, (C) a solvent, and (D) an acid diffusion controller. A radiation-sensitive resin composition comprising a step of repeatedly filtering a preliminary composition of a radiation-sensitive resin composition to be filtered 3 to 150 times while maintaining a filtration amount per filter effective filtration area at 30 L / m ² or less at a filter portion Manufacturing method. The resin (B)
A repeating unit represented by the following general formula (1):
A repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3):
The method for producing a radiation-sensitive resin composition according to claim 1, wherein

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group (however, a group corresponding to “—OR ⁵ ” in the following general formula (2) is excluded) M represents an integer of 0 to 3, and n represents an integer of 1 to ^3. However, when a plurality of R ² are present, the plurality of R ² may be the same or different from each other. Also good)

(In the general formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a monovalent organic group (excluding a group corresponding to “—OR ⁵ ”), and R ⁵ represents 1 indicates the valence of the acid-dissociable group, p is an integer of 0 to 3, q is an integer of 1-3. However, if R ⁴ there are a plurality, the plurality of R ⁴ a in mutually identical and or different, if R ⁵ there is a plurality, the plurality of R ⁵ may be the same or different from each other)
(In the general formula (3), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents a monovalent acid-dissociable group) The radiation-sensitive resin composition according to claim 2 , wherein the resin (B) is a resin having a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2). Manufacturing method. The method for producing a radiation-sensitive resin composition according to any one of claims 1 to 3 , wherein the filter portion is a filter device in which a plurality of polypropylene resin filters are connected in series.

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