JP4945688B2 - Chemically amplified resist composition and method for producing the same - Google Patents

Description

  The present invention relates to a method for producing chemically amplified positive and negative resist compositions used in semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. is there. More specifically, the present invention relates to a method for producing chemically amplified positive and negative resist compositions suitable for using far ultraviolet rays of 250 nm or less as an exposure light source.

  The chemically amplified positive resist composition is hardly soluble or insoluble in a developer immediately after film formation on a substrate, but generates an acid in an exposed portion by irradiation with radiation such as far ultraviolet light, and this acid is generated. It is a pattern forming material that improves the solubility of the active radiation irradiated portion in the developer by a reaction using a catalyst and forms a pattern on the substrate. In addition, the chemically amplified negative resist composition is readily soluble in a developer immediately after being formed on a substrate, but it generates an acid in an exposed portion by irradiation with radiation such as far ultraviolet light, and this acid is generated. This is a pattern forming material that reduces the solubility of the active radiation irradiated portion in the developer by a reaction using a catalyst and forms a pattern on the substrate.

In general, a chemically amplified resist composition using a KrF excimer laser, ArF excimer laser, F2 excimer laser, EUV (extreme ultraviolet light), EB (electron beam) or the like as a light source (radiation source) is described in, for example, Patent Document 1 As described above, it includes a resin component, an acid generator component that generates an acid upon exposure, and an organic solvent that can dissolve these components.
Such a chemically amplified resist composition is required to have a resist pattern having high resolution, high sensitivity, and a good shape.

In recent years, when a resist pattern with a high resolution of 0.11 microns or less is required, in addition to these characteristics, there is a defect (surface defect) of a resist pattern after development more than in the past. More improvement is needed.
This defect is a general defect detected when a developed resist pattern is observed from directly above with, for example, a surface defect observation apparatus (trade name “KLA”) manufactured by KLA Tencor. This defect is, for example, a scum after development, bubbles, dust, a bridge between resist patterns, and the like.

In order to improve such defects, improvement has been attempted mainly focusing on resist compositions such as a resin component, an acid generator component, and a solvent component of a resist composition (Patent Document 2).
In addition, the resist solution (resist composition in a solution state) is subjected to foreign matter aging characteristics of the resist solution in which fine particles are generated during storage (while the resist composition is being stored, the solid foreign matter contained in the resist composition). Is also a problem, and improvement is desired.
In order to improve the foreign matter aging characteristics, as in the above, improvement has been attempted centering on the resist composition (Patent Document 3).
However, the techniques described in Patent Documents 2 and 3 are not yet sufficient in their effects.

Furthermore, when the fine particles are generated, the defect may be caused, and it is strongly desired to improve the foreign matter aging characteristics for the purpose of improving the defect.
However, a method for sufficiently improving the defect and storage stability of the resist pattern after this phenomenon has not been known so far.

By the way, Patent Document 4 proposes a method for producing a resist composition in which the amount of fine particles in the resist composition circulating through the line is reduced by passing the resist composition through a filter.
As described in Patent Document 4, it is known to produce a resist composition and pass it through a filter in the production of a resist composition. The resist pattern defect and storage stability cannot be improved sufficiently.

  Patent Document 5 proposes a method for producing a resist composition that passes through a filter having a positive zeta potential. However, when the resist composition is processed by the method described in Patent Document 5, the composition may change. This change in composition is inconvenient because it causes changes in resist composition sensitivity and resist pattern size.

  In Patent Document 5, a method for producing a resist composition that passes through a filter having a negative zeta potential has been proposed. Recently, among resist pattern defects, in particular, after KrF excimer laser, that is, particularly KrF excimer laser, ArF. In the case of forming a fine resist pattern such as a resist pattern of 110 nm or less using an excimer laser, F2 excimer laser, EUV, EB or the like as a light source, the problem of defect resolution is becoming more severe. Not enough to respond.

  Patent Document 6 discloses that a filter having a film having a specific zeta potential is passed through in order to provide a resist composition capable of suppressing the occurrence of defects in a resist pattern after development.

  In other words, it has become a very important problem to suppress defects such as fine scum and microbridge after development, which has become more severe due to pattern miniaturization. However, none of the above-mentioned prior arts have sufficiently solved.

Further, Patent Document 7 improves preparation accuracy by mixing raw materials with a solution in the preparation of an i-line resist, and improves the dimensional accuracy of a resist pattern obtained from the composition.
Patent Document 8 discloses a method of using a novolak resin in which the amount of metal ions is reduced using an ion exchange resin in the preparation of a resist.
Patent Document 9 discloses a technique for reducing the amount of metal and improving film forming properties by filtering a resin solution.
Patent document 10 is disclosing performing the process which makes resin contact activated carbon in preparation of a resist.
Patent Document 11 discloses a method of filtering a resin solution in order to suppress the temporal change of the resist.

JP 2002-296679 A JP 2001-56556 A JP 2001-22072 A Japanese Patent Laid-Open No. 2002-62667 JP 2001-350266 A JP 2004-221975 A JP-A-10-232492 Japanese National Patent Publication No. 10-512970 Special table 2004-523806 gazette JP 2004-326092 A JP 2003-330202 A

  This invention is made | formed in view of the said situation, and makes it a subject to provide the technique from which the resist composition which can suppress the defect of the resist pattern after image development, especially generation | occurrence | production of a fine scum and a microbridge is obtained. . It is another object of the present invention to provide a technique for obtaining a resist composition having excellent foreign matter aging characteristics (storage stability).

The present invention has the following configuration, whereby the above object of the present invention is achieved.
<1> (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a resin whose solubility in an alkaline developer is changed by the action of an acid, (C) a basic compound, (D) a surfactant, (E) In the method for producing a chemically amplified resist composition containing a solvent, a step of preparing a solution of the component (A) and a solution of the component (B) , and filtering the solution of the component (A) with a filter. A process of filtering the component solution with a filter, and a step of mixing the solution of the component (A) and the solution of the component (B).
<2> The chemical amplification type according to <1>, wherein the material of the filter used for filtering the solution of the component (B) contains polyethylene, polypropylene, polytetrafluoroethylene, nylon, or polysulfone. A method for producing a resist composition.
<3> The method for producing a chemically amplified resist composition as described in <1> or <2> above, wherein the average pore size of the filter used for filtering the solution of the component (B) is 2.0 μm or less. .
<4> The method for producing a chemically amplified resist composition according to any one of <1> to <3>, wherein the resin (B) contains a hydroxystyrene repeating unit.
<5> The above-mentioned <1>, wherein the resin (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure, is decomposed by the action of an acid, and has increased solubility in an alkali developer. > The manufacturing method of the chemically amplified resist composition as described in any one of <3>.
<6> The chemically amplified resist composition as described in <5> above, wherein the resin (B) has a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI) Manufacturing method.
In general formula (pI),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
<7> The method for producing a chemically amplified resist composition as described in <5> or <6> above, wherein the resin (B) has a repeating unit having a lactone group.
<8> The chemical amplification type according to any one of <5> to <7>, wherein the resin (B) has a repeating unit having a structure represented by the following general formula (VIIa): A method for producing a resist composition.
In general formula (VIIa), R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group.
<9> The method according to any one of the above <1> to <8>, including a step of preparing all raw materials other than the component (E) as a solution and mixing each raw material as a solution. A method for producing a chemically amplified resist composition.
<10> The method for producing a chemically amplified resist composition as described in <9> above, comprising a step of filtering the solution of the components (C) and (D) with a filter.
<11> The method for producing a chemically amplified resist composition according to <10>, wherein the average pore size of the filter used for filtering the solution of the components (C) and (D) is 0.4 μm or less. .
<12> The chemically amplified resist according to any one of <1> to <11> above, wherein an average pore size of a filter used for filtering the solution of the component (A) is 0.4 μm or less. A method for producing the composition.
<13> A chemically amplified resist composition, wherein the chemically amplified resist composition according to any one of <1> to <12> is filtered with a filter having an average pore size of 0.05 μm or less. Production method.
<14> A chemically amplified resist composition produced by the production method according to any one of <1> to <13> .
Although this invention is invention of said <1>- <14> , below, it describes including other matters.
(1) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a resin whose solubility in an alkaline developer is changed by the action of an acid, (C) a basic compound, (D) a surfactant, (E) A method for producing a chemically amplified resist composition comprising a step of preparing and mixing a solution of component (A) in a method for producing a chemically amplified resist composition containing a solvent.

(2) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a resin whose solubility in an alkaline developer is changed by the action of an acid, (C) a basic compound, (D) a surfactant, (E) In the method for producing a chemically amplified resist composition containing a solvent, the above (1) is characterized by including a step of preparing and mixing a solution of the component (A) and a solution of the component (B). A method for producing the chemically amplified resist composition as described.

(3) A method for producing a chemically amplified resist composition as described in (1) above, comprising the steps of preparing all raw materials other than the component (E) as a solution and mixing each raw material as a solution. .
(4) The method for producing a chemically amplified resist composition as described in any one of (1) to (3) above, which comprises a step of filtering the solution of component (B) with a filter.

(5) The method for producing a chemically amplified resist composition as described in (4) above, wherein the average pore size of the filter is 2.0 μm or less.
(6) The method for producing a chemically amplified resist composition as described in any one of (1) to (5) above, which comprises a step of filtering the solution of component (A) with a filter.
(7) The method for producing a chemically amplified resist composition as described in (6) above, wherein the average pore size of the filter is 0.4 μm or less.

(8) The method for producing a chemically amplified resist composition as described in (3) to (7) above, which comprises a step of filtering the solution of the components (C) and (D) with a filter.
(9) The method for producing a chemically amplified resist composition as described in (8) above, wherein the average pore size of the filter is 0.4 μm or less.

(10) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a resin whose solubility in an alkaline developer is changed by the action of an acid, (C) a basic compound, (D) a surfactant, (E) The method for producing a chemically amplified resist composition according to any one of the above (1) to (9), wherein the chemically amplified resist composition containing a solvent is filtered with a filter having an average pore size of 0.05 μm or less.
(11) A chemically amplified resist composition produced by the production method according to any one of (1) to (10) above.

A feature of the method for producing a chemically amplified resist composition of the present invention is that a resist composition is produced by mixing raw materials in a solution state to suppress an increase in defects and particles over time. A solution containing a compound (component (A)) that generates an acid upon irradiation with radiation is prepared and used for the preparation of a resist composition.
When the raw material is added to the solvent as a powder as in the past, aggregates with the raw material particles as nuclei are generated, leading to an increase in defects and particles.
The raw materials that are likely to become the core of the aggregates are the component (A), and further a resin (component (B)) whose solubility in an alkaline developer is changed by the action of an acid, and a solution containing the component (A) and (B It is more preferable to prepare solutions containing the components, and to use these solutions for the preparation of the resist composition. Further, for each of all the raw materials, a solution (raw material solution) previously dissolved in a solvent is used. And mixing them is most preferable.
(E) component is used for the solvent used for preparation of the solution of raw materials, such as (A)-(D) component. When there are two or more types of component (E), one or more of them may be used, or all of them may be used. When more than one type of component (E) is used, the volume ratio is arbitrary. Can be determined by
The concentration of the raw material in the raw material solution may be not more than a concentration at which the raw material can be sufficiently dissolved, but is preferably 80% or less of the saturation solubility L of the raw material in the solvent at the resist preparation temperature.
L (%) = (mass of raw material at saturation dissolution / volume of solvent) × 100
When two or more raw materials are used for the same component (for example, two photoacid generators), a solution may be prepared for each raw material, or a mixed solution containing two or more raw materials may be prepared. Although it is good, it is preferable to prepare a solution for each raw material.

  Furthermore, it is preferable to use a method of mixing these raw material solutions after filtering them with a filter because fine particles that can become nuclei of aggregates in the solution can be further reduced.

  The filter used to filter the raw material solution is selected from those used in the resist field. Specifically, the filter material contains polyethylene, polypropylene, polytetrafluoroethylene, nylon or polysulfone. What to do is used. More specifically, Millipore's MicroGuard, MicroGuard Plus, MicroGuard Minichem-D, MicroGuard Minichem-D PR, Millipore Obsizer DEV / DEV-C, Millipore Obsmizer 16/14, Paul Examples include Ultiboa N66, Podyne, nylon falcon, and the like.

  When the solution of component (B) is filtered with a filter, the viscosity of the solution is high, and if the average pore size of the filter is too small, the filtration time becomes longer and the production efficiency may be lowered. On the other hand, when the average pore size of the filter is too large, fine particles that can be a core of aggregates present in the solution pass through the filter and cannot be removed. For this reason, it is preferable that the average pore diameter of the filter used for filtration of the component (B) solution is 0.1 μm or more and 2.0 μm or less.

  When the raw material solution other than the component (B) is filtered with a filter, the viscosity of the solution is not so high as in the case of the solution of the component (B), so the average pore size of the filter needs to be increased as in the case of the solution of the component (B) The average pore diameter is preferably 0.1 μm or more and 0.4 μm or less.

  Further, after mixing all the raw materials to obtain a uniform resist composition, it is preferable to further filter this resist composition through a filter, and in that case, the average pore size of the filter is preferably 0.05 μm or less. The filter used when filtering the resist composition may be the same material as described above.

  The solid content concentration in the final resist composition is generally 1.0 to 30.0% by mass, preferably 2.0 to 20.0% by mass.

Hereinafter, although each component is demonstrated in detail, it is not limited to these.
<Component (A): Compound that generates acid upon irradiation with actinic rays or radiation>
Examples of compounds that generate acid upon irradiation with actinic rays or radiation (also referred to as photoacid generators) include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, and photochromic agents. Or known light (400-200 nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h-line, i-line, KrF excimer laser beam), ArF excimer laser beam, electron beam, A compound that generates an acid by X-ray, molecular beam, or ion beam and a mixture thereof can be appropriately selected and used.

Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, o-nitrobenzyl sulfonates, SI Schlesinger, Photogr. Sci. Eng., 18,387 (1974). The diazonium salts described in TS Bal et al, Polymer, 21, 423 (1980), etc., the ammonium salts described in U.S. Pat.Nos. 4,069,055, 4,069,056, Re 27,992, JP 3-140140, etc. Necker et al, Macromolecules, 17, 2468 (1984), CS Wen et al,
Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, and the like, JV Crivello et al, Macromorecules, 10 (6), 1307 ), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,848, JP-A-2-296,514, etc. Iodonium salts described, JV Crivello et al, Polymer J. 17, 73 (1985), JV Crivello et al. J. Org. Chem., 43, 3055 (1978), WR Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Crivello et al, Polymer Bull., 14, 279 (1985), J.
V. Crivello et al, Macromorecules, 14 (5), 1141 (1981), JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent Nos. 370,693, 161,811 410,201, 339,049, 233,567, 297,443, 297,442, U.S. Patents 3,902,114, 4,933,377, 4,760,013, 4,734,444, 2,833,827, Yasukuni Patent 2,904,626, Sulfonium salts described in 3,604,580, 3,604,581, JP-A-7-28237, 8-27102, JVCrivello et al, Macromorecules, 10 (6), 1307 (1977), JV Crivello et al, J. Polymer Selenonium salts described in Sci., Polymer Chem. Ed., 17, 1047 (1979), and arsonium described in CS Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), etc. Onium salts such as salts, U.S. Pat.No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 55-32070, JP-A 60-2 39736, JP-A 61-169835 , JP 61-169837, JP 62-58241, JP 62-212401, Organohalogen compounds described in Kaisho 63-70243, JP-A 63-298339, etc., K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), TP Gill et al, Inorg Chem., 19, 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-16145, S Hayase et al, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al, J. Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu et al, J. Photochem., 36, 85, 39,
317 (1987), B. Amit et al, Tetrahedron Lett., (24) 2205 (1973), DHR Barton et al, J. Chem Soc., 3571 (1965), PM Collins et al, J. Chem. Soc. , PerkinI, 1695 (1975), M. Rudinstein et al, Tetrahedron Lett., (17), 1445 (1975), JW Walker et al, J. Am. Chem. Soc., 110, 7170 (1988), SC Busman et al, J. Imaging Technol., 11 (4), 191 (1985), HMHoulihan et al, Macormolecules, 21, 2001 (1988), PM Collinsetal, J. Chem. Soc., Chem. Commun., 532 ( 1972), S. Hayase et al, Macromolecules, 18, 1799 (1985), E. Reichman et al, J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan et al, Macromolcules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, U.S. Patents 3,901,710, 4,181,531, JP 60-198538, JP Photoacid generator having o-nitrobenzyl type protecting group described in Kaisho 53-133022, etc., M. TUNOOKA et al, Polymer Preprints Japan, 35 (8), G. Berner et al, J. Rad. Curing , 13 (4), WJ Mijs et a l, Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 044,115, Nos. 618,564, 0101,122, U.S. Pat.Nos. 4,371,605, 4,431,774, JP-A-64-18143, JP-A-2-245756, JP-A-3-140109, etc. Representative compounds that generate sulfonic acid by photolysis, disulfone compounds described in JP-A-61-166544 and JP-A-2-71270, JP-A-3-103854, JP-A-3-103856, and JP-A-4 And diazoketosulfone and diazodisulfone compounds described in JP-210960.

  Further, a group that generates an acid by these lights, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, ME Woodhouse et al, J. Am. Chem. Soc., 104, 5586 (1982), SP Pappas et al, J. Imaging Sci., 30 (5), 218 (1986), S. Kondo et al, Makromol. Chem., Rapid Commun., 9, 625 (1988), Y. Yamada et al, Makromol Chem., 152, 153, 163 (1972), JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979), US Patent 3,849,137, Korean Patent 3914407, Special Kaisho 63-26653, JP 55-164824, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP The compounds described in 63-146029 and the like can be used. Furthermore, VNR Pillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971), DHR Barton et al, J. Chem. Soc., (C), 329 (1970), US Pat. No. 3,779,778, European Patent 126,712 and the like, compounds that generate an acid by light can also be used.

  The amount of component (A) added is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 7% by mass, based on the total solid content of the resist composition. is there.

  Preferred examples of the component (A) are shown below, but are not limited thereto.

<Component (B): a resin whose solubility in an alkali developer changes by the action of an acid>
Resin whose solubility in an alkali developer is changed by the action of an acid used in the present invention (hereinafter referred to as component (B)) is an alkali developer by an acid generated from a compound that generates an acid upon irradiation with actinic rays or radiation. It is a resin whose solubility in is changed.

The resist composition is a chemically amplified resist used for a light source (radiation source) having a wavelength of 250 nm or less such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet light), EB (electron beam), etc. As long as it is a composition and (B) component is suitable for each light source, it may be any.
For example, for the positive resist for KrF excimer laser, resins disclosed in Japanese Patent Application Laid-Open No. 2005-10217, Japanese Patent Application Laid-Open No. 11-84539, Japanese Patent No. 3116751, etc. can be used, and negative type for KrF excimer laser. Resins disclosed in Japanese Patent Application Laid-Open Nos. 2003-302670 and 2005-37414 can be used as the resist, and Japanese Patent Application Laid-Open Nos. Resins disclosed in JP 2005-41857 A, JP 2005-10217 A, and the like can be used.

  (B) Resin that is decomposed by an acid as component and has increased solubility in an alkaline developer can be decomposed with an acid on the main chain or side chain of the resin, or both of the main chain and side chain ( Hereinafter, it is also referred to as an “acid-decomposable group”). Among these, a resin having a group capable of decomposing with an acid in the side chain is more preferable.

A group preferable as a group that can be decomposed by an acid is a group in which a hydrogen atom of a —COOH group or —OH group is substituted with a group capable of leaving with an acid.
In the present invention, the acid-decomposable group is preferably an acetal group or a tertiary ester group.

  The base resin in the case where these acid-decomposable groups are bonded as side chains is an alkali-soluble resin having —OH or —COOH groups in the side chains. For example, the alkali-soluble resin mentioned later can be mentioned.

  The alkali dissolution rate of these alkali-soluble resins is preferably 170 kg / sec or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 330 A / second or more (Å is angstrom).

  From such a viewpoint, particularly preferable alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene). Hydroxystyrene structural units such as a part of poly (hydroxystyrene), O-alkylated or O-acylated product, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogenated novolak resin, etc. An alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid.

  Preferred examples of the repeating unit having an acid-decomposable group in the present invention include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, (meth) acrylic acid tertiary alkyl ester, and the like. Alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate are more preferred.

  The component (B) is a precursor of a group that can be decomposed into an acid in an alkali-soluble resin, as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It can be obtained by copolymerizing an alkali-soluble resin monomer having a group which can be reacted with the body or capable of decomposing with an acid, with various monomers.

When the resist composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light (EUV, etc.) having a wavelength of 50 nm or less, the resin of component (B) has a hydroxystyrene repeating unit. Is preferred. More preferably, hydroxystyrene / hydroxystyrene copolymer protected with an acid-decomposable group and hydroxystyrene / (meth) acrylic acid tertiary alkyl ester are preferred.
Although the specific example of (B) component is shown below, this invention is not limited to these.

  In the above specific example, tBu represents a t-butyl group.

The content of the group that can be decomposed by an acid is determined by the number of groups (B) that can be decomposed by an acid in the resin and the number of alkali-soluble groups that are not protected by a group capable of leaving by an acid (S). B + S).
The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

  When irradiating the positive resist composition of the present invention with ArF excimer laser light, the resin of component (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure, and is decomposed by the action of an acid. A resin that increases the solubility in an alkali developer is preferred.

  As a resin that has a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposes by the action of an acid, and increases its solubility in an alkaline developer (hereinafter also referred to as “alicyclic hydrocarbon-based acid-decomposable resin”) , At least selected from the group consisting of repeating units having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI) to general formula (pV) and repeating units represented by the following general formula (II-AB) A resin having one kind is preferred.

In general formulas (pI) to (pV),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms. However, at least one of R _{12 to} R ₁₄ , or any of R ₁₅ and R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general formula (II-AB),
R ₁₁ ′ and R ₁₂ ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

  The general formula (II-AB) is more preferably the following general formula (II-AB1) or general formula (II-AB2).

In general formulas (II-AB1) and (II-AB2),
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, —COOH, —COOR ₅ , a group that decomposes by the action of an acid, —C (═O) —XA ′. —R ₁₇ ′ represents an alkyl group or a cycloalkyl group. At least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring.
Here, R ₅ represents an alkyl group, a cycloalkyl group, or a group having a lactone structure.
X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.
A ′ represents a single bond or a divalent linking group.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or a group having a lactone structure.
R ₆ represents an alkyl group or a cycloalkyl group.
n represents 0 or 1.

In the general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. , N-butyl group, sec-butyl group, t-butyl group and the like.

The cycloalkyl group represented by R _{12 to} R ₂₅ or the cycloalkyl group formed by Z and the carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These cycloalkyl groups may have a substituent.

  Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and tricyclodecanyl group.

  These alkyl groups and cycloalkyl groups may further have a substituent. As further substituents for alkyl groups and cycloalkyl groups, alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (2 to 2 carbon atoms). 6). The above alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have a substituent. Examples of the substituent that the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

  The structures represented by the general formulas (pI) to (pV) in the resin can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.

  Specific examples include a structure in which a hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, or a thiol group is substituted with a structure represented by the general formulas (pI) to (pV), preferably a carboxylic acid Group, the hydrogen atom of a sulfonic acid group is the structure substituted by the structure represented by general formula (pI)-(PV).

  As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (pI) to (pV), a repeating unit represented by the following general formula (pA) is preferable.

In the general formula (pA), R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, or a combination of two or more groups. Represents. A single bond is preferable.
Rp1 represents any one of the general formulas (pI) to (pV).

  The repeating unit represented by the general formula (pA) is most preferably a repeating unit of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  Specific examples of the repeating unit represented by the general formula (pA) are shown below.

In the above structural formulas, Rx represents H, CH ₃ , CF ₃ or CH ₂ OH, and Rxa and Rxb each independently represents an alkyl group having 1 to 4 carbon atoms.

In the general formula (II-AB), examples of the halogen atom represented by R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

As the alkyl group for R ₁₁ ′ and R ₁₂ ′, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, linear group Or a branched butyl group, pentyl group, hexyl group, heptyl group, etc. are mentioned.

  The atomic group for forming the alicyclic structure of Z ′ is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in a resin, and among them, a bridged type alicyclic group. An atomic group for forming a bridged alicyclic structure forming a cyclic hydrocarbon repeating unit is preferred.

Examples of the skeleton of the alicyclic hydrocarbon formed include those similar to the cycloalkyl groups represented by R _{12 to} R _{25 in} the general formulas (pI) to (pVI).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2).

  In the alicyclic hydrocarbon-based acid-decomposable resin, the group decomposed by the action of an acid is a repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formula (pI) to the general formula (pV), It can be contained in at least one kind of repeating unit among the repeating unit represented by formula (II-AB) and the repeating unit of the copolymerization component described later.

Various substituents of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or the general formula (II-AB2) are atomic groups for forming an alicyclic structure in the general formula (II-AB). It can also be a substituent of the atomic group Z for forming a bridged alicyclic structure.

  Specific examples of the repeating unit represented by the general formula (II-AB1) or (II-AB2) include the following specific examples, but the present invention is not limited to these specific examples.

The alicyclic hydrocarbon-based acid-decomposable resin preferably has a repeating unit having a lactone group. As the lactone group, any group having a lactone structure can be used, but a group having a 5- to 7-membered ring lactone structure is preferred, and a bicyclo structure or spiro is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed to form a structure are preferred.
The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). . Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and a specific lactone structure is used. This improves line edge roughness and development defects.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. n2 represents an integer of 0 to 4. When n2 is an integer of 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to form a ring.

As the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-16), R _{13 in the} above general formula (II-AB1) or (II-AB2) may be used. A group having a group represented by general formula (LC1-1) to (LC1-16) at least one of 'to R ₁₆ ' (for example, R _{5 of} -COOR ₅ is represented by formula (LC1-1) to ( And a repeating unit represented by the following general formula (AI).

In general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group for Rb ₀ include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. The alkyl group for Rb ₀ may have a substituent. Preferable substituents that the alkyl group of Rb ₀ may have include, for example, a hydroxyl group and a halogen atom.

Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group.

Ab is an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. To express. Preferably, it is a linking group represented by a single bond or -Ab ₁ -CO _2- .
Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexyl residue, an adamantyl residue, or a norbornyl residue.

  V represents a group represented by any one of the general formulas (LC1-1) to (LC1-16).

The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
Specific examples of the repeating unit having a group having a lactone structure are given below, but the present invention is not limited thereto.

The alicyclic hydrocarbon-based acid-decomposable resin preferably has a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. This improves the substrate adhesion and developer compatibility.
The polar group is preferably a hydroxyl group or a cyano group.
Examples of the alicyclic hydrocarbon structure substituted with a polar group include structures represented by the following general formula (VIIa) or (VIIb).

In general formula (VIIa), R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom, more preferably _two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. It is.

  The group represented by the general formula (VIIa) is preferably a dihydroxy body or a monohydroxy body, and more preferably a dihydroxy body.

The repeating unit having a group represented by the general formula (VIIa) or (VIIb) includes at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2). Having the group represented by the above general formula (VIIa) or (VIIb) (for example, R _{5 in} —COOR ₅ represents a group represented by the general formula (VIIa) or (VIIb)), or the following general group Mention may be made of the repeating units of the formula (AIIa) or (AIIb).

In the general formulas (AIIa) and (AIIb), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c have the same meanings as in R ₂ c to R ₄ c in formula (VIIa).

  Specific examples of the repeating unit having an alicyclic hydrocarbon structure substituted with a polar group represented by the general formula (AIIa) or (AIIb) are shown below, but are not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin may have a repeating unit represented by the following general formula (VIII).

In General Formula (VIII), Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin preferably has a repeating unit having an alkali-soluble group, and more preferably has a repeating unit having a carboxyl group. By having this, the resolution in contact hole applications increases. The repeating unit having a carboxyl group includes a repeating unit in which a carboxyl group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a carboxyl group in the main chain of the resin through a linking group. Any of the bonded repeating units is preferable, and the linking group may have a monocyclic or polycyclic hydrocarbon structure. Most preferred are acrylic acid and methacrylic acid.

  The alicyclic hydrocarbon-based acid-decomposable resin may have a repeating unit having 1 to 3 groups represented by the following general formula (F1). This improves line edge roughness performance.

In general formula (F1), R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group, or an alkoxycarbonyl group).

The alkyl group of R _{50 to} R ₅₅ may be substituted with a halogen atom such as a fluorine atom, a cyano group, etc., preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group or a trifluoromethyl group. be able to.
R _{50 to} R ₅₅ are preferably all fluorine atoms.

  Examples of the organic group represented by Rx include an acid-decomposable protective group and an optionally substituted alkyl group, cycloalkyl group, acyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxycarbonylmethyl group, alkoxymethyl group. , 1-alkoxyethyl group is preferable.

  Preferred examples of the repeating unit having a group represented by the general formula (F1) include a repeating unit represented by the following general formula (F2).

In General Formula (F2), Rx represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rx may have include a hydroxyl group and a halogen atom.
Fa represents a single bond, a linear or branched alkylene group, and preferably a single bond.
Fb represents a monocyclic or polycyclic hydrocarbon group.
Fc represents a single bond or a linear or branched alkylene group, preferably a single bond or a methylene group.
F ₁ represents a group represented by the general formula (F1).
p ₁ is an integer of 1 to 3.

  The cyclic hydrocarbon group in Fb is preferably a cyclopentyl group, a cyclohexyl group, or a norbornyl group.

  Specific examples of the repeating unit having the structure of the general formula (F1) are shown below.

  In addition to the above repeating structural units, the alicyclic hydrocarbon-based acid-decomposable resin has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, resolving power and heat resistance. In order to adjust sensitivity and the like, various repeating structural units can be included.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, performance required for the alicyclic hydrocarbon-based acid-decomposable resin, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In alicyclic hydrocarbon-based acid-decomposable resins, the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution that is the general required performance of resists. In order to adjust heat resistance, sensitivity, etc., it is set appropriately.

Preferred embodiments of the alicyclic hydrocarbon-based acid-decomposable resin include the following.
(1) What contains the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by said general formula (pI)-(pV) (side chain type). Those having a repeating unit of (meth) acrylate preferably having a structure of (pI) to (pV).
(2) Those having a repeating unit represented by formula (II-AB) (main chain type). However, in (2), for example, the following can be further mentioned.
(3) Those having a repeating unit represented by the general formula (II-AB), a maleic anhydride derivative structure and a (meth) acrylate structure (hybrid type).

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having an acid-decomposable group is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, still more preferably 25 in all repeating structural units. -40 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (pI) to (pV) is 25 to 70 in all the repeating structural units. The mol% is preferable, more preferably 35 to 65 mol%, and still more preferably 40 to 60 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit represented by the general formula (II-AB) is preferably 10 to 60 mol%, more preferably 15 to 55 mol% in all repeating structural units. More preferably, it is 20-50 mol%.

  In addition, the content of the repeating structural unit based on the monomer of the further copolymer component in the resin can also be appropriately set according to the performance of the desired resist. 99 mol% with respect to the total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by (pV) and the repeating unit represented by the above general formula (II-AB) The following is preferable, More preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.

When the resist composition of the present invention is for ArF exposure, the resin preferably has no aromatic group from the viewpoint of transparency to ArF light.
The alicyclic hydrocarbon-based acid-decomposable resin used in the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units may be methacrylate, all of the repeating units may be acrylate, or a mixture of methacrylate / acrylate, but the acrylate repeating unit is preferably 50 mol% or less of the entire repeating unit.

  More preferably, the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulas (pI) to (pV) is 25 to 50%, the repeating unit having the lactone structure is 25 to 50%, and the polarity is A terpolymer copolymer having 5 to 30% of repeating units having an alicyclic hydrocarbon structure substituted with a group, or a repeating unit having a structure represented by a carboxyl group or general formula (F1) It is a quaternary copolymer having 20%.

The alicyclic hydrocarbon-based acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as that used in the resist composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50 to 100 ° C.

  When the composition of the present invention is used for the upper resist of the multilayer resist, the resin as the component (B) preferably has a silicon atom.

As the resin having a silicon atom and decomposing by the action of an acid to increase the solubility in an alkaline developer, a resin having a silicon atom in at least one of a main chain and a side chain can be used. Examples of the resin having a siloxane structure in the side chain of the resin include, for example, an olefin monomer having a silicon atom in the side chain, maleic anhydride and a (meth) acrylic acid monomer having an acid-decomposable group in the side chain. Mention may be made of copolymers.
As the resin having a silicon atom, a resin having a trialkylsilyl structure or a monocyclic or polycyclic siloxane structure is preferable, and a resin having a structure represented by the following general formulas (SS-1) to (SS-4) is used. More preferably, the resin which has a structure represented by general formula (SS-1)-(SS-4), and the resin which has a (meth) acrylic-ester type repeating unit, a vinyl type repeating unit, or an allyl type repeating unit which has a structure represented by general formula (SS-1)-(SS-4). preferable.

  In general formulas (SS-1) to (SS-4), Rs represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group.

  The resin having a silicon atom preferably has a repeating unit having two or more different types of silicon atoms, more preferably (Sa) a repeating unit having 1 to 4 silicon atoms and (Sb) 5 to 10 silicon atoms. A resin having both of the repeating units, and more preferably, at least one repeating unit having a structure represented by formulas (SS-1) to (SS-3) and formula (SS-4). It is resin which has a repeating unit which has the structure represented by these.

When the resist composition of the present invention is irradiated with F ₂ excimer laser light, the resin of component (B) has a structure in which fluorine atoms are substituted on the main chain and / or side chain of the polymer skeleton, and the acid A resin that decomposes by action and increases the solubility in an alkali developer (hereinafter also referred to as a fluorine group-containing resin) is preferable, and more preferably, a hydroxyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group or a fluorine atom at the 1-position Alternatively, it is a resin having a group in which a hydroxyl group substituted with a fluoroalkyl group is protected with an acid-decomposable group, and particularly preferably has a hexafluoro-2-propanol structure or a structure in which the hydroxyl group of hexafluoro-2-propanol is protected with an acid-decomposable group. Resin. By introducing fluorine atoms, it is possible to improve transparency to far ultraviolet light, particularly F ₂ (157 nm) light.

  (B) As a fluorine-group containing resin in acid-decomposable resin, resin which has at least 1 type of repeating unit shown by the following general formula (FA)-(FG) can be mentioned preferably, for example.

In the general formula,
R _{100 to} R ₁₀₃ each represents a hydrogen atom, a fluorine atom, an alkyl group or an aryl group.
R ₁₀₄ and R ₁₀₆ are each a hydrogen atom, a fluorine atom or an alkyl group, and at least one of R ₁₀₄ and R ₁₀₆ is a fluorine atom or a fluoroalkyl group. R ₁₀₄ and R ₁₀₆ are preferably both trifluoromethyl groups.
R ₁₀₅ is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group, or a group that decomposes under the action of an acid.
A ₁ is a single bond, a divalent linking group such as an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, —OCO—, —COO—, or —CON (R ₂₄ ) —, and a plurality of these. A linking group containing R ₂₄ is a hydrogen atom or an alkyl group.
R ₁₀₇ and R ₁₀₈ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group that decomposes under the action of an acid.
R ₁₀₉ is a hydrogen atom, an alkyl group, a cycloalkyl group, or a group that decomposes under the action of an acid.
a represents 0 or 1.
b is 0, 1 or 2;
R ₁₀₀ and R ₁₀₁ in the general formulas (FA) and (FC) may form a ring via an alkylene group (having 1 to 5 carbon atoms) which may be substituted with fluorine.
The repeating unit represented by the general formulas (FA) to (FG) has at least one, preferably three or more fluorine atoms per one repeating unit.

  In the general formulas (FA) to (FG), the alkyl group is, for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, Preferred examples include sec-butyl group, hexyl group, 2-ethylhexyl group, and octyl group.

  The cycloalkyl group may be monocyclic or polycyclic. Preferred examples of the monocyclic type include those having 3 to 8 carbon atoms, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group, An androstanyl group etc. can be mentioned preferably. However, the carbon atom in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

  Examples of the fluoroalkyl group include those having 1 to 12 carbon atoms, specifically, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. A perfluorooctylethyl group, a perfluorododecyl group and the like can be preferably exemplified.

  As the aryl group, for example, an aryl group having 6 to 15 carbon atoms, specifically, phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, Preferable examples include 9,10-dimethoxyanthryl group.

  Examples of the alkoxy group include an alkoxy group having 1 to 8 carbon atoms, and specifically include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group, and an octoxy group. Preferred examples include groups.

  As the acyl group, for example, an acyl group having 1 to 10 carbon atoms, specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, an octanoyl group, a benzoyl group and the like can be preferably exemplified. it can.

  Examples of the alkoxycarbonyl group include i-propoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, 1-methyl-1-cyclohexyloxycarbonyl group and the like, preferably secondary, more preferably tertiary alkoxycarbonyl. Groups.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.

  The alkenylene group is preferably an alkenylene group having 2 to 6 carbon atoms such as an ethenylene group, a propenylene group, or a butenylene group.

  Preferred examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group.

  The arylene group is preferably an arylene group having 6 to 15 carbon atoms such as a phenylene group, a tolylene group and a naphthylene group.

  These groups may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, and a carboxy group. Those having active hydrogen, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl) Groups, benzoyl groups, etc.), acyloxy groups (acetoxy groups, propanoyloxy groups, benzoyloxy groups, etc.), alkoxycarbonyl groups (methoxycarbonyl groups, ethoxycarbonyl groups, propoxycarbonyl groups, etc.), cyano groups, nitro groups, etc. It is done.

  Here, examples of the alkyl group, cycloalkyl group, and aryl group include those described above, but the alkyl group may be further substituted with a fluorine atom or a cycloalkyl group.

Fluorine-containing are contained in the resin of the present invention, examples of the group in a disassembled alkali solubility by the action of an acid, for example, _{-O-C (R 36) (} R 37) (R 38), - O-C (R 36 ) (R ₃₇ ) (OR ₃₉ ), —O—COO—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —O—C (R ₀₁ ) (R ₀₂ ) COO—C (R ₃₆ ) (R _{37) (R 38), -} COO-C (R 36) (R 37) (R 38), - COO-C (R 36) (R 37) (OR 39) , and the like.

R _{36 to} R ₃₉ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, and R ₀₁ and R ₀₂ are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group (vinyl group, allyl group). , Butenyl group, cyclohexenyl group, etc.), aralkyl group (benzyl group, phenethyl group, naphthylmethyl group, etc.) or aryl group.

  Preferable specific examples include t-butyl group, t-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4-methylcyclohexyl). ) Ether group or ester group of tertiary alkyl group such as 2-propyl group, acetal group or acetal ester group such as 1-alkoxy-1-ethoxy group, tetrahydropyranyl group, t-alkyl carbonate group, t-alkyl A carbonylmethoxy group etc. are mentioned preferably.

  Specific examples of the repeating structural units represented by the general formulas (FA) to (FG) are shown below, but the present invention is not limited thereto.

  The total content of the repeating units represented by formulas (FA) to (FG) is generally 10 to 80 mol%, preferably 30 to 70 mol%, more preferably based on all repeating units constituting the resin. Is used in the range of 35 to 65 mol%.

  In addition to the above repeating structural units, the fluorine group-containing resin may be copolymerized with other polymerizable monomers for the purpose of further improving the performance of the resist of the present invention.

  Examples of copolymerizable monomers that can be used include those shown below. For example, an addition polymerizable unsaturated bond selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters other than the above. A compound having one.

Such a fluorine group-containing resin contains other repeating units as a copolymerization component in addition to the repeating unit having fluorine atoms, from the viewpoints of improving dry etching resistance, adjusting alkali solubility, and improving substrate adhesion. Is preferred. Preferred as other repeating units are:
1) A repeating unit having an alicyclic hydrocarbon structure represented by the general formulas (pI) to (pVI) and (II-AB). Specifically, the repeating units 1 to 23 and the repeating units [II-1] to [II-32]. Of the above specific examples 1 to 23, Rx is preferably CF ₃ .
2) A repeating unit having a lactone structure represented by the general formulas (Lc) and (V-1) to (V-5). Specifically, the repeating units exemplified above, particularly the repeating units having the groups represented by the general formulas (Lc) and (V-1) to (V-4) exemplified above.
3) The following general formula (XV) (XVI) (XVII) derived from a maleic anhydride, vinyl ether or a vinyl compound having a cyano group, specifically, the repetitions listed in (C-1) to (C-15) Units are listed. These other repeating units may or may not contain a fluorine atom.

Where
R ₄₁ represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. The alkyl group of R ₄₁ may be substituted with an aryl group.
R ₄₂ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
A ₅ represents a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₂₂ —, —CO—O—R ₂₃ —, —CO—N (R ₂₄ ). -R ₂₅ - represents a.
R ₂₂ , R ₂₃ and R ₂₅ may be the same or different, and may be a single bond, or may have an ether group, ester group, amide group, urethane group or ureido group, a divalent alkylene group, alkenylene. Represents a group, a cycloalkylene group or an arylene group.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.
Here, examples of each substituent include those similar to the substituents of the general formulas (FA) to (FG).

  Moreover, although the specific example of the repeating structural unit represented by general formula (XV)-(XVII) is shown, this invention is not limited to this.

  The total amount of the repeating units represented by the general formulas (XV) to (XVII) and other repeating units is generally 0 to 70 mol%, preferably 10 to 60 mol%, based on all repeating units constituting the resin. More preferably, it is used in the range of 20 to 50 mol%.

The fluorine group-containing resin may contain an acid-decomposable group in any repeating unit.
As for content of the repeating unit which has an acid-decomposable group, 10-70 mol% is preferable with respect to all the repeating units, More preferably, it is 20-60 mol%, More preferably, it is 30-60 mol%.

  The fluorine group-containing resin can be synthesized by radical polymerization in substantially the same manner as the alicyclic hydrocarbon-based acid-decomposable resin.

  The weight average molecular weight of the resin of component (B) is preferably 2,000 to 200,000 as a polystyrene conversion value by GPC method. By making the weight average molecular weight 2,000 or more, heat resistance and dry etching resistance can be improved, and by making the weight average molecular weight 200,000 or less, developability can be improved. And since a viscosity becomes low, film forming property can be improved. The molecular weight is more preferably 5,000 to 50,000, and still more preferably 7,000 to 30,000. By adjusting the molecular weight, it is possible to achieve both heat resistance, resolution, development defects, and the like of the composition. The dispersity (Mw / Mn) of the component (B) resin is preferably 1.0 to 3.0, more preferably 1.2 to 2.5, and even more preferably 1.2 to 1.6. It is. The line edge roughness performance can be improved by adjusting the degree of dispersion to an appropriate range.

  In the resist composition of the present invention, the blending amount of the resin of the component (B) in the entire composition is preferably 40 to 99.99% by mass, more preferably 50 to 99% by mass, and still more preferably in the total solid content. Is 80-96 mass%.

<(C) component: basic compound>
Examples of the component (C) include nitrogen-containing basic compounds such as organic amines, basic ammonium salts, basic sulfonium salts and the like, as long as they do not deteriorate sublimation or resist performance.
Among these nitrogen-containing basic compounds, organic amines are preferable in terms of excellent image performance.

  For example, JP-A-63-149640, JP-A-5-249662, JP-A-5-127369, JP-A-5-289322, JP-A-5-249683, JP-A-5-289340, JP-A-5-232706 JP-A-5-257282, JP-A-62-242605, JP-A-6-242606, JP-A-6-266100, JP-A-6-266110, JP-A-6-317902, JP-A-7-120929, JP-A-7-65558, JP-A-7-319163, JP-A-7-508840, JP-A-7-333844, JP-A-7-219217, JP-A-7-92678, JP-A-7-28247, Special Kaihei 8-22120, JP-A-8110638, JP-A8-123030, JP-A-9-274312, JP-A-9-66871, JP-A-9-292708, JP-A-9-325496, Special table Basic compounds described in JP-A-7-508840, US Pat. No. 5,552,543, US Pat. No. 5,629,134, US Pat.

  Preferable structures include structures represented by the following formulas (A) to (E).

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl having 1 to 20 carbons, a cycloalkyl group having 3 to 20 carbons or an aryl group having 6 to 20 carbons, R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. A 20 hydroxyalkyl group or a C 3-20 hydroxycycloalkyl group is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.

  Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, and may have a substituent. More preferable compounds include compounds having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, a hydroxyl group and / or Or the aniline derivative which has an ether bond etc. can be mentioned.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undec-7-ene. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of aniline compounds include 2,6-diisopropylaniline and N, N-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  These basic compounds are used alone or in combination of two or more. The usage-amount of a basic compound is 0.001-10 mass% normally based on solid content of a resist composition, Preferably it is 0.01-5 mass%. In order to obtain a sufficient addition effect, 0.001% by mass or more is preferable, and 10% by mass or less is preferable in terms of sensitivity and developability of the non-exposed area.

<(D) component: surfactant>
Examples of the component (D) include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan aliphatic esters, polyoxyethylene sorbitan aliphatic esters, and the like. Nonionic surfactants can be mentioned. These surfactants may be added alone or in some combination.

  As the surfactant, one of fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant, surfactant containing both fluorine atom and silicon atom), or two or more kinds thereof It is preferable to contain.

  Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Surfactant can be mentioned, The following commercially available surfactant can also be used as it is.

  Examples of commercially available surfactants include F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189 and R08 (large) Nippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. A surfactant or a silicon-based surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. It may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. It can be.

  The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the resist composition (excluding the solvent).

<(E) component: solvent>
As the component (E), ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide , Dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferred, and these solvents may be used alone or in combination. Mixed to use.

  Among these, preferable solvents include 2-heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate , Methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, and tetrahydrofuran.

<F component: a dissolution inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkaline developer>
As a dissolution inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkali developer, it does not decrease the transmittance of 220 nm or less, and is described in Proceeding of SPIE, 2724, 355 (1996). An alicyclic or aliphatic compound containing an acid-decomposable group is preferred, such as a cholic acid derivative containing an acid-decomposable group. Examples of the acid-decomposable group and alicyclic structure are the same as those described above for the alicyclic hydrocarbon-based acid-decomposable resin.

  When the resist composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

  The molecular weight of the dissolution inhibiting compound is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

  The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the solid content of the resist composition.

  Specific examples of the dissolution inhibiting compound are shown below, but are not limited thereto.

<(G) component: resin soluble in alkali developer>
The alkali dissolution rate of a resin soluble in an alkali developer (alkali-soluble resin) is preferably 20 kg / second or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 200 Å / second or more (Å is angstrom).

  Examples of the alkali-soluble resin include novolak resin, hydrogenated novolak resin, acetone-pyrogalol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen or alkyl-substituted polyhydroxy. Styrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, partially O-alkylated product of hydroxyl group of polyhydroxystyrene (for example, 5-30 mol% O -Methylated product, O- (1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t-butoxycarbonyl) methylated product, etc.) or O-acylated product (E.g. 5-30 mol% o-acetylation , O- (t-butoxy) carbonylated compounds, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and derivatives thereof Polyvinyl alcohol derivatives can be mentioned, but are not limited thereto.

  Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrenes, partially O-alkylated polyhydroxystyrenes, Alternatively, O-acylated product, styrene-hydroxystyrene copolymer, and α-methylstyrene-hydroxystyrene copolymer.

  The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

  Moreover, the weight average molecular weight of alkali-soluble resin is 2000 or more, Preferably it is 5000-200000, More preferably, it is 5000-100000.

  Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

  Two or more alkali-soluble resins may be used in combination.

  The usage-amount of alkali-soluble resin is 40-97 mass% with respect to solid content of the whole composition of a resist composition, Preferably it is 60-90 mass%.

<(H) component: an acid crosslinking agent that crosslinks with the alkali-soluble resin by the action of an acid>
In the case of a negative resist composition, it contains a crosslinking agent.

For example, in the case of a negative type resist such as a negative resist for KrF excimer laser, the dissolution rate in the developer is decreased by causing a cross-linking reaction between the cross-linking agent and the resin by the catalytic reaction of the acid generated in the exposed area. Since a resist pattern is formed, a crosslinking agent may be necessary.
Examples of the crosslinking agent include amino resins such as glycoluril resins disclosed in JP-A-1-293339 and JP-A-2-15270, and glycoluril resins disclosed in JP-A-5-34922. Cross-linking agent, cross-linking agent composed of N- (alkoxymethyl) glycoluril compound disclosed in JP-A-6-301200, N- (alkoxyalkyl) glycoluril compound disclosed in JP-A-2003-302670 N- (alkoxyalkyl) melamine compounds and the like can be used.

Any crosslinking agent can be used as long as it is a compound that crosslinks a resin soluble in an alkaline developer by the action of an acid, but the following (1) to (3) are preferred.
(1) Hydroxymethyl, alkoxymethyl, and acyloxymethyl forms of phenol derivatives.
(2) A compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group.
(3) A compound having an epoxy group.

  The alkoxymethyl group preferably has 6 or less carbon atoms, and the acyloxymethyl group preferably has 6 or less carbon atoms.

  Of these crosslinking agents, particularly preferred are listed below.

In the formula, L ^{1 to} L ⁸ may be the same or different and each represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.
The crosslinking agent is generally used in an amount of 3 to 70% by mass, preferably 5 to 50% by mass, in the solid content of the resist composition.

<Other additives>
If necessary, the resist composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a compound that promotes solubility in a developer, and the like.
All of these additives are also preferably produced in a solution state to produce a resist composition.

  The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable.

  A preferable addition amount of these dissolution promoting compounds is 2 to 50% by mass, and more preferably 5 to 30% by mass with respect to the resin of the component (B) and the resin of the component (G). 50 mass% or less is preferable at the point of development residue suppression and the pattern deformation prevention at the time of image development.

  Such phenolic compounds having a molecular weight of 1000 or less can be obtained by referring to methods described in, for example, JP-A-4-1222938, JP-A-2-28531, U.S. Pat. No. 4,916,210, European Patent 219294, and the like. Can be easily synthesized.

  Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

<Pattern Forming Method Using Resist Composition>
The resist composition is applied onto the substrate to form a thin film. The thickness of this coating film is preferably 0.05 to 1.5 μm. In the present invention, a commercially available inorganic or organic antireflection film can be used if necessary.
As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, and silicon nitride, and an organic film type made of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. Examples of the organic antireflection film include a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin, a light absorber, and a maleic anhydride copolymer described in US Pat. No. 5,294,680. A reaction product of a diamine type light absorbent, a resin binder described in JP-A-6-186863 and a methylolmelamine-based thermal crosslinking agent, a carboxylic acid group described in JP-A-6-118656, an epoxy group and a light-absorbing group in the same molecule And an acrylic resin type antireflection film having a methylol melamine and a benzophenone light absorber described in JP-A-8-87115, and a polyvinyl alcohol resin described in JP-A-8-179509 to which a low molecular light absorber is added. Further, as the organic antireflection film, DUV series and ARC series manufactured by Brewer Science, AC series and AR series manufactured by Shipley, etc. can be used.

Appropriate use of the resist solution on a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements (on a substrate provided with the antireflection film if necessary), spinner, coater, etc. A good resist pattern can be obtained by applying through a predetermined coating method, exposing through a predetermined mask, baking and developing. Here, the exposure light is preferably light having a wavelength of 150 nm to 250 nm. Specific examples include a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, and an electron beam.

Examples of the alkaline developer used in development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used. Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these. In addition, Examples 1-4, 8-11, and 15-18 are reference examples.

[Synthesis of Resin (B-2) Used for Positive Resist for KrF Excimer Laser]
35.25 g (0.2 mol) of p-tert-butoxystyrene monomer dehydrated and purified by distillation according to a conventional method and 5.21 g (0.05 mol) of t-Bu styrene monomer were dissolved in 100 ml of tetrahydrofuran. Under a nitrogen stream and stirring, 0.033 g of azobisisobutyronitrile (AIBN) was added three times every 2.5 hours at 80 ° C., and finally stirring was further continued for 5 hours to carry out the polymerization reaction. . The reaction solution was added to 1200 ml of hexane to precipitate a white resin. The obtained resin was dried and then dissolved in 150 ml of tetrahydrofuran. This was hydrolyzed by adding 4N hydrochloric acid and heating to reflux for 6 hours, and then reprecipitated in 5 L of ultrapure water. The resin was filtered off, washed with water and dried. Furthermore, it melt | dissolved in tetrahydrofuran 200 ml, and it dripped and reprecipitated, stirring vigorously in 5 L of ultrapure water. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / t-butylstyrene) copolymer alkali-soluble resin (B-1). The weight average molecular weight of the obtained resin was 12,000.

  Resin (B-1) (20 g) and propylene glycol monomethyl ether acetate (320 g) were dissolved in a flask, distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 24 g of ethyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added and stirred at room temperature for 1 hour. Thereto was added 0.28 g of triethylamine to quench the reaction. Ethyl acetate was added to the reaction mixture, and the mixture was further washed with water. Then, ethyl acetate, water and azeotropic PGMEA were distilled off by distillation under reduced pressure to obtain Resin (B-2).

[Synthesis of Resin (B-3) Used for Negative Resist for KrF Excimer Laser]
100 g of pt-butoxystyrene, 19.7 g of styrene, 8.1 g of azobisisobutyronitrile and 2.5 g of t-dodecyl mercaptan are dissolved in 180 g of propylene glycol monomethyl ether, and the polymerization reaction is carried out at 80 ° C. for 9 hours. went. The polymerization solution was purified by reprecipitation with methanol to obtain 100 g of a pt-butoxystyrene / styrene copolymer (Mw; 7200, Mw / Mn; 1.80). This copolymer and 50 g of 10% by mass sulfuric acid solution were dissolved in 300 g of propylene glycol monomethyl ether and subjected to a hydrolysis reaction at 90 ° C. for 6 hours. And the resin (B-3) which is a p-hydroxy styrene / styrene = 75/25 mol% copolymer was obtained by reprecipitation refine | purifying the reaction liquid until it became neutral with a lot of water. The weight average molecular weight of the obtained resin was 5200.

[Synthesis of Resin (B-4) Used for Positive Resist for ArF Excimer Laser]
2-Methyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 40/20/40 (molar ratio) and dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5, and the solid content concentration was 20 mass. 100 mL of a% solution was prepared. To this solution, 2 mol% of a polymerization initiator V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added and added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours in a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and a resin (B-4) which was a white powder crystallized and precipitated in 3 L of a mixed solvent of distilled water / ISO propyl alcohol = 1/1 (mass ratio) was obtained. . ^The polymer composition ratio determined from ¹³ CNMR was 41/21/38. The weight average molecular weight of the obtained resin was 10700.

[Explanation of abbreviations]
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether PAG-1: Triphenylsulfonium nonaflate AMINE-1: 2,6-diisopropylaniline ADD-1: N, N, N, N-tetra (methoxymethyl) glycol Uril W-1: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.)

[Example 1]
Resin (B-4) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and PAG-1 is mixed with PGMEA and PGME (mass ratio of 60). / 40) to prepare a solution having a solid content concentration of 20% by mass. Resin (B-4) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), PGME (28 g) And the resulting mixture was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

[Example 2]
Resin (B-4) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and PAG-1 is mixed with PGMEA and PGME (mass ratio of 60). / 40) to prepare a solution having a solid content concentration of 20% by mass, and AMINE-1 to a solvent mixture of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass. Then, W-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass. Resin (B-4) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), W-1 solution (0.1 g), PGMEA (42 g), PGME (28 g) was mixed, and the obtained mixed solution was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 3
Resin (B-4) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass. Resin (B-4) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), PGME (28 g) And the resulting mixture was filtered through a 0.05 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 4
Resin (B-4) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and AMINE-1 is a mixed solvent of PGMEA and PGME (mass ratio 60/40). A solution having a solid content concentration of 10% by mass was prepared, and W-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass. Resin (B-4) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), W-1 solution (0.1 g), PGMEA (42 g), PGME (28 g) was mixed, and the obtained mixed solution was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 5
Resin (B-4) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). Resin (B-4) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), PGME (28 g) And the resulting mixture was filtered through a 0.05 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 6
Resin (B-4) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). AMINE-1 is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass, and W-1 is a mixed solvent of PGMEA and PGME (mass ratio 60/40). And a solution having a solid content concentration of 10% by mass was prepared. Resin (B-4) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), W-1 solution (0.1 g), PGMEA (42 g), PGME (28 g) was mixed, and the obtained mixed solution was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 7
Resin (B-4) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). AMINE-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution with a solid content concentration of 10% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). W-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution with a solid content concentration of 10% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). Resin (B-4) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), W-1 solution (0.1 g), PGMEA (42 g), PGME (28 g) was mixed, and the obtained mixed solution was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 8
Resin (B-2) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and PAG-1 is mixed with PGMEA and PGME (mass ratio of 60). / 40) to prepare a solution having a solid content concentration of 20% by mass. Resin (B-2) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), PGME (28 g) And the resulting mixture was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 9
Resin (B-2) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and PAG-1 is mixed with PGMEA and PGME (mass ratio of 60). / 40) to prepare a solution having a solid content concentration of 20% by mass, and AMINE-1 to a solvent mixture of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass. Then, W-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass. Resin (B-2) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), W-1 solution (0.1 g), PGMEA (42 g), PGME (28 g) was mixed, and the obtained mixed solution was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 10
Resin (B-2) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass. Resin (B-2) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), PGME (28 g) And the resulting mixture was filtered through a 0.05 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 11
Resin (B-2) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and AMINE-1 is a mixed solvent of PGMEA and PGME (mass ratio 60/40). A solution having a solid content concentration of 10% by mass was prepared, and W-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass. Resin (B-2) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), W-1 solution (0.1 g), PGMEA (42 g), PGME (28 g) was mixed, and the obtained mixed solution was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 12
Resin (B-2) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). Resin (B-2) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), PGME (28 g) And the resulting mixture was filtered through a 0.05 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 13
Resin (B-2) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). AMINE-1 is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass, and W-1 is a mixed solvent of PGMEA and PGME (mass ratio 60/40). And a solution having a solid content concentration of 10% by mass was prepared. Resin (B-2) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), W-1 solution (0.1 g), PGMEA (42 g), PGME (28 g) was mixed, and the obtained mixed solution was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 14
Resin (B-2) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). AMINE-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution with a solid content concentration of 10% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). W-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution with a solid content concentration of 10% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). Resin (B-2) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), W-1 solution (0.1 g), PGMEA (42 g), PGME (28 g) was mixed, and the obtained mixed solution was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

Example 15
Resin (B-3) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and PAG-1 is mixed with PGMEA and PGME (mass ratio of 60). / 40) to prepare a solution having a solid content concentration of 20% by mass. Resin (B-3) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 (0.12 g), ADD-1 (0.3 g), W-1 (0.01 g), PGMEA (42 g) and PGME (28 g) are mixed, and the resulting mixture is filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a negative resist composition. did.

Example 16
Resin (B-3) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and PAG-1 is mixed with PGMEA and PGME (mass ratio of 60). / 40) to prepare a solution having a solid content concentration of 20% by mass, and AMINE-1 to a solvent mixture of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass. Then, ADD-1 is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass, and W-1 is mixed with PGMEA and PGME (mass ratio of 60/40). 40) to prepare a solution having a solid concentration of 10% by mass. Resin (B-3) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), ADD-1 solution (1.5 g), W-1 solution (0.1 g), PGMEA (42 g), and PGMEA (28 g) were mixed, and the resulting mixture was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to obtain a negative. A mold resist composition was prepared.

Example 17
The resin (B-3) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass. Resin (B-3) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 (0.12 g), ADD-1 (0.3 g), W-1 (0.01 g), PGMEA (42 g) and PGME (28 g) were mixed, and the resulting mixed solution was filtered through a 0.05 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a negative resist composition. did.

Example 18
The resin (B-3) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and AMINE-1 is a mixed solvent of PGMEA and PGME (mass ratio 60/40). To prepare a solution with a solid content concentration of 10% by mass, and ADD-1 is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution with a solid content concentration of 10% by mass. -1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass. Resin (B-3) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), ADD-1 solution (1.5 g), W-1 solution (0.1 g), PGMEA (42 g), and PGMEA (28 g) were mixed, and the resulting mixture was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to obtain a negative. A mold resist composition was prepared.

Example 19
The resin (B-3) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). Resin (B-3) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 (0.12 g), ADD-1 (0.3 g), W-1 (0.01 g), PGMEA (42 g) and PGME (28 g) were mixed, and the resulting mixed solution was filtered through a 0.05 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a negative resist composition. did.

Example 20
The resin (B-3) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). AMINE-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass, and ADD-1 was mixed with PGMEA and PGME (mass ratio 60/40). A solution having a solid content concentration of 10% by mass was prepared, and W-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 10% by mass. Resin (B-3) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), ADD-1 solution (1.5 g), W-1 solution (0.1 g), PGMEA (42 g), and PGMEA (28 g) were mixed, and the resulting mixture was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to obtain a negative. A mold resist composition was prepared.

Example 21
The resin (B-3) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). PAG-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). AMINE-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution with a solid content concentration of 10% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). ADD-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 10% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). W-1 was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution with a solid content concentration of 10% by mass, and a 0.1 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) ). Resin (B-3) solution (30 g), PAG-1 solution (1.5 g), AMINE-1 solution (1.2 g), ADD-1 solution (1.5 g), W-1 solution (0.1 g), PGMEA (42 g), and PGMEA (28 g) were mixed, and the resulting mixture was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to obtain a negative. A mold resist composition was prepared.

[Comparative Example 1]
Resin (B-4) (6 g), PAG-1 (0.3 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (56 g), and PGME (38 g) were mixed. The obtained mixed solution was filtered with a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

[Comparative Example 2]
Resin (B-4) was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass. A solution (30 g) of resin (B-4), PAG-1 (0.3 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), and PGME (28 g) are mixed. Then, the obtained mixed solution was filtered with a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

[Comparative Example 3]
Resin (B-4) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). A solution (30 g) of resin (B-4), PAG-1 (0.3 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), and PGME (28 g) are mixed. Then, the obtained mixed solution was filtered with a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

[Comparative Example 4]
Resin (B-2) (6 g), PAG-1 (0.3 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (56 g), and PGME (38 g) are mixed, The obtained mixed solution was filtered with a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

[Comparative Example 5]
Resin (B-2) was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass. A solution (30 g) of resin (B-2), PAG-1 (0.3 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), and PGME (28 g) are mixed. Then, the obtained mixed solution was filtered with a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

[Comparative Example 6]
Resin (B-2) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). A solution (30 g) of resin (B-2), PAG-1 (0.3 g), AMINE-1 (0.12 g), W-1 (0.01 g), PGMEA (42 g), and PGME (28 g) are mixed. Then, the obtained mixed solution was filtered with a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a positive resist composition.

[Comparative Example 7]
Resin (B-3) (6 g), PAG-1 (0.3 g), AMINE-1 (0.12 g), ADD-1 (0.3 g), W-1 (0.01 g), PGMEA (56 g) , PGME (38 g) was mixed, and the obtained mixed solution was filtered through a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a negative resist composition.

[Comparative Example 8]
Resin (B-3) was dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass. Resin (B-3) solution (30 g), PAG-1 (0.3 g), AMINE-1 (0.12 g), ADD-1 (0.3 g), W-1 (0.01 g), PGMEA ( 42 g) and PGME (28 g) were mixed, and the obtained mixed solution was filtered with a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a negative resist composition.

[Comparative Example 9]
The resin (B-3) is dissolved in a mixed solvent of PGMEA and PGME (mass ratio 60/40) to prepare a solution having a solid content concentration of 20% by mass, and a 1.0 μm PE filter (47 mm UPE Membrane Disks, micro (Manufactured by Squirrel). Resin (B-3) solution (30 g), PAG-1 (0.3 g), AMINE-1 (0.12 g), ADD-1 (0.3 g), W-1 (0.01 g), PGMEA ( 42 g) and PGME (28 g) were mixed, and the obtained mixed solution was filtered with a 0.02 μm PE filter (47 mm UPE Membrane Disks, manufactured by Microlith) to prepare a negative resist composition.

[Resist pattern formation of Examples 1-7 and Comparative Examples 1-3]
ARC29A manufactured by Brewer Science Co., Ltd. was uniformly applied to a silicon wafer with a spin coater at 78 nm, and heat-dried at 205 ° C. for 60 seconds to form an antireflection film. Thereafter, each positive resist composition immediately after preparation was applied by a spin coater and dried (PB) at 120 ° C. for 60 seconds to form a 150 nm resist film.
An ArF excimer laser stepper (PAS5500 / 1100 manufactured by ASML Co., Ltd.) was passed through the resist film through a 6% halftone mask of 110 nm line and space.
NA = 0.75 (2/3 annular illumination)), and immediately after exposure, it was heated (PEB) on a hot plate at 120 ° C. for 60 seconds. Further, the resist film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a 110 nm line and space resist pattern.

[Resist pattern formation of Examples 8 to 14 and Comparative Examples 4 to 6]
ARC29A manufactured by Brewer Science Co., Ltd. was uniformly applied to a silicon wafer with a spin coater at 78 nm, and heat-dried at 205 ° C. for 60 seconds to form an antireflection film. Thereafter, each positive resist composition immediately after preparation was applied by a spin coater and dried (PB) at 120 ° C. for 60 seconds to form a 150 nm resist film.
This resist film was exposed with a KrF excimer laser (Canon FPA-3000EX5 with a wavelength of 248 nm, NA = 0.63, σ = 0.65) through a 6% halftone mask of 200 nm line / 120 nm space, and immediately after exposure. Heated (PEB) on a hot plate at 100 ° C. for 60 seconds. Further, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a resist pattern with 210 nm line / 110 nm space.

[Resist pattern formation of Examples 15 to 21 and Comparative Examples 7 to 9]
ARC29A manufactured by Brewer Science Co., Ltd. was uniformly applied to a silicon wafer with a spin coater at 78 nm, and heat-dried at 205 ° C. for 60 seconds to form an antireflection film. Thereafter, each positive resist composition immediately after preparation was applied with a spin coater and dried (PB) at 110 ° C. for 60 seconds to form a 150 nm resist film.
This resist film is exposed with a KrF excimer laser (Canon FPA-3000EX5 with a wavelength of 248 nm, NA = 0.63, σ = 0.65) through a 6% halftone mask of 120 nm line / 200 nm space, and immediately after the exposure. Heated (PEB) on a hot plate at 110 ° C. for 60 seconds. Further, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a resist pattern with 210 nm line / 110 nm space.

[Development defect evaluation]
The number of development defects was measured for the above pattern with a KLA2112 machine (manufactured by KLA Tencor) (Threshold = 12, Pixel size = 0.39). The evaluation results are shown in Tables 1 to 3 below by the number of defects for each wafer.

  In Tables 1-3, A means the photoacid generator that is the component (A), and B means the resin that is the component (B).

  It can be seen that the resist composition produced by the method of the present invention has few development defects on the pattern.

Claims (14)

(A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a resin whose solubility in an alkaline developer is changed by the action of an acid, (C) a basic compound, (D) a surfactant, (E) In the method for producing a chemically amplified resist composition containing a solvent, a step of preparing a solution of component (A) and a solution of component (B) , filtering the solution of component (A) with a filter, A method for producing a chemically amplified resist composition, comprising a step of filtering the solution with a filter, and a step of mixing the solution of component (A) and the solution of component (B).   2. The chemically amplified resist composition according to claim 1, wherein the filter material used for filtering the component (B) solution contains polyethylene, polypropylene, polytetrafluoroethylene, nylon, or polysulfone. Production method.   The method for producing a chemically amplified resist composition according to claim 1 or 2, wherein the average pore size of the filter used for filtering the solution of the component (B) is 2.0 µm or less.   The method for producing a chemically amplified resist composition according to any one of claims 1 to 3, wherein the resin (B) contains a hydroxystyrene repeating unit.   The resin (B) is a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposed by the action of an acid, and increased in solubility in an alkali developer. The manufacturing method of the chemically amplified resist composition as described in any one of Claims. 6. The method for producing a chemically amplified resist composition according to claim 5, wherein the resin (B) has a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI): .

In general formula (pI),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.   The method for producing a chemically amplified resist composition according to claim 5 or 6, wherein the resin (B) has a repeating unit having a lactone group. The method for producing a chemically amplified resist composition according to any one of claims 5 to 7, wherein the resin (B) has a repeating unit having a structure represented by the following general formula (VIIa). .

In general formula (VIIa), R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group.   The chemical amplification resist composition according to claim 1, comprising a step of preparing all raw materials other than the component (E) as a solution and mixing each raw material as a solution. Manufacturing method.   The method for producing a chemically amplified resist composition according to claim 9, comprising a step of filtering the solution of the components (C) and (D) with a filter.   The method for producing a chemically amplified resist composition according to claim 10, wherein the average pore size of the filter used for filtering the solution of the components (C) and (D) is 0.4 μm or less. The method for producing a chemically amplified resist composition according to any one of claims 1 to 11, wherein an average pore size of a filter used for filtering the solution of the component (A) is 0.4 µm or less. A method for producing a chemically amplified resist composition, comprising filtering the chemically amplified resist composition according to any one of claims 1 to 12 through a filter having an average pore size of 0.05 µm or less. Chemically amplified resist composition produced by the production method according to any one of claims 1 to 13.