JP2004341482A - Resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist composition which can be used for not only UV rays such as i-line and g-line but visible rays, excimer laser light such as KrF, and radiations such as electron beams, X-rays and ion beams, and which has high sensitivity, high resolution and high heat resistance and solubility to a solvent. <P>SOLUTION: The resist composition contains one or more kinds of resist compounds satisfying all of the following conditions and an acid or base generating agent which directly or indirectly generates an acid or a base by irradiation of rays selected from visible rays, UV rays, excimer laser light, electron beams, X-rays and ion beams. The conditions are that: (a) the compound has at least one acid dissociating functional group in the molecule; (b) the compound has at least one functional group selected from a urea group, a urethane group, an amide group and an imide group in the molecule; (c) the molecular weight ranges from 500 to 5,000; (d) the compound has a branched structure; (e) the compound satisfies 3≤F≤5, where F represents the number of all atoms/(the number of all carbon atoms-the number of all oxygen atoms); and (f) the nitrogen element content ranges from 1 to 20 mass%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a radiation-sensitive resist composition containing a resist compound represented by a specific chemical structural formula and an acid or base generator, which is useful as an acid-amplifying non-polymeric resist material. The resist composition of the present invention is used as a radiation-sensitive material that responds to radiation such as ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc., in masks for manufacturing LSIs and VLSIs in the electronics field.

  Conventional resist materials are polymer materials that can form an amorphous thin film. For example, polymethyl methacrylate and a resist thin film prepared by applying a solution dissolved in a solvent dissolving the same on a substrate are irradiated with ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. A line pattern of the order is formed.

  However, since the polymer resist has a large molecular weight of about 10,000 to 100,000 and a broad molecular weight distribution, in lithography using the polymer resist, roughness is generated on the pattern surface in fine processing, and the pattern dimension is controlled. Becomes difficult, and the yield decreases. Therefore, there is a limit to miniaturization in lithography using a conventional polymer-based resist material. In order to produce a finer pattern, various methods for reducing the molecular weight of a resist material have been disclosed.

  Examples of non-polymeric resist materials include (1) positive and negative resists derived from fullerenes, (2) positive and negative resists derived from calixarenes, and (3) starburst compounds. A positive resist, (4) a positive resist derived from a dendrimer, (5) a positive resist derived from a dendrimer / calixarene, (6) a positive resist derived from a starburst compound having a high branching degree, And (7) a positive resist derived from a starburst compound having trimesic acid as a central skeleton and having an ester bond.

  Regarding (1), the etching resistance is good, but the applicability and sensitivity have not reached practical levels (see Patent Documents 1 to 5). Regarding (2), although the etching resistance is excellent, a satisfactory pattern cannot be obtained due to poor solubility in a developer (see Patent Documents 6 to 8). Regarding (3), images may be distorted during heat treatment after exposure due to low heat resistance (see Patent Documents 9 to 11). Regarding (4), since the manufacturing process is complicated and the heat resistance is low, the image may be distorted during the heat treatment after exposure, and it is not practical. . The method (5) is not practical because the production process is complicated and the raw materials are expensive. (See Patent Documents 12 and 13.) (6) is not practical because the production process is complicated and the raw materials are expensive. Regarding (7), since the heat resistance is low, the image may be distorted during the heat treatment after exposure, and the substrate adhesion is insufficient, so that it cannot be said that it is practical. . Further, a photoactive compound having a hydrophobic group selected from a hydrocarbon group and a heterocyclic group, a linking group, and a hydrophilic group protected by a protective group which can be removed by light irradiation is known (see Patent Reference 15), and a composition containing a resist compound satisfying specific chemical structural conditions described below are not disclosed.

JP-A-7-134413 JP-A-9-212962 JP-A-10-282649 JP-A-11-143074 JP-A-11-258796 JP-A-11-72916 JP-A-11-322656 JP-A-9-236919 JP 2000-305270 A JP-A-2002-99088 JP-A-2002-99089 JP-A-2002-49152 JP 2003-183227 A JP 2002-328466 A JP-A-2002-363123 Proceedings of SPIE vol. 3999 (2000) P1202 to 1206

  An object of the present invention is to provide a radiation-sensitive resist composition which can be used not only for ultraviolet rays such as i-rays and g-rays but also for radiations such as visible light, excimer laser light such as KrF, electron beam, X-ray and ion beam. To provide. Still another object of the present invention is to provide a non-polymeric radiation-sensitive resist composition having high sensitivity, high resolution, high heat resistance and solvent solubility in a simple manufacturing process.

The present inventors have conducted intensive studies and found that a composition containing a compound satisfying specific chemical structural conditions and an acid / base generator that directly or indirectly generates an acid or base upon irradiation with radiation is as described above. We found that it was useful for solving the problem.
That is, the present invention provides a resist compound that satisfies all the conditions of a) to f) and directly by irradiation with one or more resist compounds selected from visible light, ultraviolet light, excimer laser, electron beam, X-ray and ion beam. A resist composition comprising one or more acid or base generators that generate an acid or base indirectly or indirectly.
a) It has at least one acid dissociable functional group in the molecule.
b) The molecule has at least one functional group selected from a urea group, a urethane group, an amide group and an imide group.
c) The molecular weight is 500-5000.
d) It has a branched structure.
e) Formula 3 ≦ F ≦ 5 is satisfied (where F represents the total number of atoms / (the total number of carbon atoms−the total number of oxygen atoms)).
f) The nitrogen element content is 1 to 20% by mass.
Further, the present invention provides a resist substrate on which a resist film made of the resist composition is formed, and a pattern-formed substrate obtained by patterning the resist film.
Further, the present invention provides a step of applying the resist composition on a substrate to form a resist film, a step of heating the resist film, and applying a heat treatment to the resist film with visible light, ultraviolet light, excimer laser, electron beam, X-ray, Irradiating with any radiation selected from a line and an ion beam, and, if necessary, after heating, developing the exposed resist film using a developing solution. Provided is a method for forming a resist pattern.
Further, the present invention is characterized in that it includes a patterned wiring substrate obtained by etching after performing the resist pattern forming method, and further performing a step of etching after performing the resist pattern forming method. To provide a method for manufacturing a patterned wiring board.

  Since the non-polymeric radiation-sensitive resist composition according to the present invention has high sensitivity, a high-resolution resist pattern can be produced, and a highly integrated semiconductor element can be produced with high productivity. Become.

Hereinafter, the present invention will be described in detail.
The resist composition of the present invention contains at least one resist compound and at least one acid or base generator. The resist compound satisfies all of the following conditions a) to f) at the same time.

a) The molecule has at least one, preferably 1 to 12, more preferably 3 to 12 acid-dissociable functional groups in the molecule.
"Acid dissociable functional group" refers to a substituent that is cleaved in the presence of an acid to produce an acidic group such as a phenolic hydroxyl group or a carboxyl group, and is an alkoxy group, an alkylsulfanyl group, an acyloxy group, an alkoxycarbonyl group, Examples include an alkoxycarbonyloxy group and a phenoxycarbonyloxy group. It is preferable that the dissociative functional group has a property of causing a chain cleavage reaction in the presence of an acid in order to enable pattern formation with higher sensitivity and higher resolution. By having a dissociable functional group, even a small amount of acid generated by exposure can elicit a lot of reactions by using it as a catalyst, which has a great effect on increasing sensitivity and increasing development contrast. .

b) The molecule has at least one functional group selected from a urea group, a urethane group, an amide group and an imide group.
The resist compound preferably contains one or more functional groups of any one of the urea group, the amide group, the urethane group and the imide group, in particular, any one of the urea group, the amide group and the urethane group. Further, it may contain a functional group having another nitrogen component. Other functional groups include tertiary amine groups, quaternary ammonium groups, imino groups, azido groups, and functional groups containing heterocyclic amines such as pyridine, pyrrole, imidazole, indole, quinoline, pyrimidine, triazine, pyrrolidine, and morpholine. But not limited thereto. In addition, it is preferable not to include a basic functional group. By having the above functional group, it is possible to have heat resistance and substrate adhesion necessary for pattern production. Further, the process for producing a compound having a molecular weight of about 500 to 5,000 can be simplified.

c) The molecular weight is 500-5000.
The molecular weight is 500-5000, preferably 600-3000, more preferably 700-2000. When the content is in the above range, good film-forming properties can be imparted, and the resolution and alkali developing performance can be further improved.

d) It has a branched structure.
In the present invention, the “branched structure” refers to a chemical structure that satisfies at least one of the following conditions (1) to (4).
(1) It has a tertiary carbon atom or a tertiary nitrogen atom not included in the cyclic structure.
(2) It has a quaternary carbon atom.
(3) At least one aromatic or aliphatic ring having three or more substituents.
(4) It has a tertiary phosphorus atom.
By having the above-mentioned branched structure, a stable amorphous property can be imparted over a long period of time, and features such as excellent film forming properties, light transmittance, solvent solubility, and etching resistance required for pattern formation as a resist material. Having. Further, since the number of photosensitive groups can be increased, sensitivity can be increased.

e) Formula 3 ≦ F ≦ 5 is satisfied (where F represents the total number of atoms / (the total number of carbon atoms−the total number of oxygen atoms)).
If F is greater than 5, performance such as sensitivity, resolution, and etching resistance may be deteriorated.

f) The nitrogen element content is 1 to 20% by mass.

式（１）中、Ｘはそれぞれ独立に水素、又は下記式（I）〜（III）で表され、Ｘのうち少なくとも３つは式（I）〜（III）のいずれかであり、（Ｉ）または（II）であることが好ましい。
Ｅは、それぞれ独立に、メチレン基、エチレン基、プロピレン基、ブチレン基、ｓｅｃ−ブチレン等の炭素数１〜１２の二価の非環状炭化水素基；フェニレン基、トリレン基、キシリレン基、シクロヘキシレン基、シクロヘキシレンジメチレン基、イソホロニレン基等の二価の環状炭化水素基；またはメトキシエチレン基、エトキシメチレン基、エトキシエチレン基、メトキシプロピレン基、エトキシプロピレン基等の置換アルキレン基を表し、メチレン基、トリレン基、シクロヘキシレンジメチレン基、およびイソホロニレン基が好ましい。
ｓ、ｔ、ｕはそれぞれ独立に０〜３の整数を表す。また、ｓ＋ｔ＋ｕは０〜５であることが好ましく、更に好ましくは０〜２、特に好ましくはゼロである。 The resist compound is preferably represented by the following formula (1).

In the formula (1), X is each independently hydrogen or represented by the following formulas (I) to (III), and at least three of Xs are any of the formulas (I) to (III); ) Or (II).
E independently represents a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, and sec-butylene; a phenylene group, a tolylene group, a xylylene group, and a cyclohexylene A divalent cyclic hydrocarbon group such as a group, a cyclohexylene dimethylene group or an isophoronylene group; or a substituted alkylene group such as a methoxyethylene group, an ethoxymethylene group, an ethoxyethylene group, a methoxypropylene group, or an ethoxypropylene group; , A tolylene group, a cyclohexylene dimethylene group, and an isophoronylene group are preferred.
s, t, and u each independently represent an integer of 0 to 3. Further, s + t + u is preferably from 0 to 5, more preferably from 0 to 2, and particularly preferably 0.

において、Ｒ^１〜Ｒ^３は、それぞれ独立に水素原子；メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基等の炭素数１〜１２の直鎖状炭化水素基；フェニル基、トリル基、ビフェニル基、ナフチル基、シクロヘキシル基、置換シクロヘキシル基、シクロドデシル基、アダマンチル基、置換アダマンチル基等の炭素数３〜１２の環状炭化水素基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、フェノキシ基等のアルコキシ基；または、イソプロピル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、１，１−ジメチルプロピル基、１−メチルブチル基、１，１−ジメチルブチル基等の１−分岐アルキル基を表し、水素原子であることが好ましい。 Formulas (I) to (III) below:

In the formula, R ^{1 to} R ³ each independently represent a hydrogen atom; carbon such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, etc. A linear hydrocarbon group of formulas 1 to 12; a cyclic group having 3 to 12 carbon atoms such as a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a cyclohexyl group, a substituted cyclohexyl group, a cyclododecyl group, an adamantyl group and a substituted adamantyl group. Hydrocarbon groups; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, and phenoxy group; or isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group Represents a 1-branched alkyl group such as a 1,1-dimethylbutyl group, and is preferably a hydrogen atom.

Ar is each independently an aromatic hydrocarbon group having 6 to 12 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and particularly preferably a phenyl group.
Y is each independently a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, and sec-butylene; a phenylene group, a tolylene group, a xylylene group, and a cyclohexylene group A cycloalkylene dimethylene group, a divalent cyclic hydrocarbon group such as isophoronylene group, a methoxyethylene group, an ethoxymethylene group, an ethoxyethylene group, a methoxypropylene group, a substituted alkylene group such as an ethoxypropylene group; or a single bond; Preferred are a methylene group, a tolylene group, a cyclohexylene dimethylene group, an isophoronylene group and a single bond. The term “single bond” as used herein means that other structural units are directly connected to each other.
Z is each independently a single bond or a substituent selected from the group consisting of -O-, -S- and -NH-, and particularly preferably -O-, -NH- or a single bond. When Z is -O-, -S-, -NH-, or a single bond, control of the chemical structure is easy.
a1 to a3 are each independently an integer of 1 to 9, r1 to r3 are each independently an integer of 0 to 8, and a1 + r1 ≦ 9, a2 + r2 ≦ 9, and a3 + r3 ≦ 8. a1 to a3 are preferably 1, and r1 to r3 are preferably 0.
n is an integer of 1 to 5, preferably 1 or 2, and more preferably 1.

  A independently represents hydrogen or an acid dissociable functional group of the following formulas (IV) to (VIII), and at least one of A is any of formulas (IV) to (VIII). A is preferably (IV).

において、Ｒ^６およびＲ^８は、それぞれ独立に水素原子；メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基等の炭素数１〜１２の直鎖状炭化水素基；フェニル基、トリル基、ビフェニル基、ナフチル基、シクロヘキシル基、置換シクロヘキシル基、シクロドデシル基、アダマンチル基、置換アダマンチル基等の炭素数３〜１２の環状炭化水素基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、フェノキシ基等のアルコキシ基；または、イソプロピル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、１，１−ジメチルプロピル基、１−メチルブチル基、１，１−ジメチルブチル基等の一分岐アルキル基を表し、シクロヘキシル基、ｔｅｒｔ−ブチル基であることが好ましい。 Formulas (IV) to (VIII) below:

R ⁶ and R ⁸ are each independently a hydrogen atom; a carbon atom such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group. A linear hydrocarbon group of formulas 1 to 12; a cyclic group having 3 to 12 carbon atoms such as a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a cyclohexyl group, a substituted cyclohexyl group, a cyclododecyl group, an adamantyl group and a substituted adamantyl group. Hydrocarbon groups; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, and phenoxy group; or isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group Represents a one-branched alkyl group such as a 1,1-dimethylbutyl group, a cyclohexyl group, a tert-butyl group There it is preferable.

R ⁴ , R ⁵ and R ⁷ each independently represent a hydrogen atom, a substituted methyl group, a monosubstituted ethyl group, a monosubstituted n-propyl, a branched alkyl group, a silyl group, a germyl group, an acyl group, an alkoxycarbonyl group, Represents a substituted alkoxymethyl group or a cyclic substituent. At least one of R ^{4 to} R ⁸ is a characteristic group other than a hydrogen atom.

  Examples of the substituted methyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a phenacyl group, a bromophenacyl group, and a methoxyphenacyl group. A, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group, Ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, tert-butoxy Rubonirumechiru group, and the like can be mentioned.

  Examples of the monosubstituted ethyl group include a 1-methoxyethyl group, a 1-methylthioethyl group, a 1,1-dimethoxyethyl group, a 1-ethoxyethyl group, a 1-ethylthioethyl group, and a 1,1-diethoxyethyl group. , 1-cyclohexyloxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group , 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-isopropoxycarbonylethyl group, 1-n- Butoxycarbonylethyl group, 1-tert-butoxycarbonylethyl group and the like.

  Examples of the monosubstituted propyl group include a 1-methoxypropyl group and a 1-ethoxypropyl group.

  Examples of the one-branched alkyl group include an isopropyl group, a sec-butyl group, a tert-butyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, a 1,1-dimethylbutyl group, and the like.

  Examples of the silyl group include trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, and methyldi-tert-. Examples thereof include a butylsilyl group, a tri-tert-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

  Examples of the germyl group include a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an isopropyldimethylgermyl group, a methyldiisopropylgermyl group, a triisopropylgermyl group, and tert-butyl. Examples include a dimethylgermyl group, a methyldi-tert-butylgermyl group, a tri-tert-butylgermyl group, a phenyldimethylgermyl group, a methyldiphenylgermyl group, and a triphenylgermyl group.

  Examples of the acyl group include acetyl, propionyl, butyryl, heptanoyl, hexanoyl, valeryl, pivaloyl, isovaleryl, lauryloyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl Group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azeolaoyl group, sebacoil group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, camphoryl group, benzoyl group , Phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydroatropoyl, atropoyl, cinnamoyl, furoyl, tenoyl, nicotinoyl, isonicoti Yl group, p- toluenesulfonyl group, and mesyl group.

  Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tert-butoxycarbonyl group.

  Examples of the monosubstituted alkoxymethyl group include 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctylmethoxymethyl group, 1-adamantylmethoxy Examples include a methyl group.

  Examples of the cyclic substituent include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, p-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiofuranyl Groups, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophen-1,1-dioxide group, adamantyl group, alkyladamantyl group and the like. it can.

Among the above acid dissociable functional groups, R ⁴ , R ⁵ and R ⁷ are tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl Groups, tert-butyl, trimethylsilyl, tetrahydropyranyl and 1-cyclohexylmethoxymethyl are preferred.

  As described above, in the formula (1), s + t + u is preferably 0 to 5, more preferably 0 to 2, and particularly preferably 0. That is, the resist compound used in the present invention is preferably a compound represented by the following formula (2), (3) or (4), and particularly preferably a compound represented by the formula (2). The compounds of the formulas (2) to (4) can provide high resolution and may reduce line etch roughness.

（式（２）〜（４）中、ＸおよびＥは前記と同様。）

(In the formulas (2) to (4), X and E are the same as described above.)

（式（IX）〜（XI）中、Ａは前記と同様であり、ｍは１〜２の整数である。） Further, X in the formula (1) is preferably a substituent represented by the following formulas (IX) to (XI).

(In the formulas (IX) to (XI), A is the same as described above, and m is an integer of 1 to 2.)

Further, at least one of A in the formulas (I) to (III) is preferably a substituent represented by the following formulas (XII) to (XV).

  The nitrogen content of the resist compound is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and particularly preferably 5 to 15% by mass. When the nitrogen element content is in the above range, sensitivity and resolution are excellent, and heat resistance and substrate adhesion required for pattern formation can be obtained.

  The resist compound is preferably produced from one or more polyisocyanates having three or more isocyanate groups. By using polyisocyanate, a resist compound having a branched structure can be manufactured by an easy process.

  The polyisocyanate having three or more isocyanate groups is not particularly limited, but tolylene diisocyanate, bis (isocyanatephenyl) methane, bis (isocyanatecyclohexyl) methane, phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanate methyl) Isocyanurates, burettes, allohanates, and urethanes derived from diisocyanates such as cyclohexane, metaxylene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, lysine diisocyanate, tetramethyl xylene diisocyanate, and trimethylhexamethylene diisocyanate; Oligomers of phenyl phenyl methane; and tris (isocyanate phenyl) methane, tris (isocyanate phenyl) thiophosphate, mesitylene triisocyanate, triisocyanate benzene, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8- It is preferably any one of triisocyanates such as diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate. The above compounds are widely used as a curing agent for urethane-based paints, and are preferable because they are relatively inexpensive and can reduce raw material costs. Among them, tolylene diisocyanate, bis (isocyanate phenyl) methane, isophorone diisocyanate, bis (isocyanate methyl) cyclohexane, isocyanurate derived from meta-xylene diisocyanate, and tris (isocyanate phenyl) methane, tris (isocyanate phenyl) thiophosphate are: It is particularly preferable because it has high heat resistance that can withstand a semiconductor process.

The method for producing the resist compound used in the present invention is not particularly limited. In particular, after reacting a polyisocyanate having three or more isocyanate groups with an aminophenol or a hydroxyalkylphenol, an acid dissociable functional group-introducing agent is added to a base. The production method in which a reaction is carried out under a catalyst is preferable because the entire process can be produced in the same reaction vessel, which is simpler and more practical.
The term "acid-dissociable functional group-introducing agent" used herein refers to an acid carboxylic acid derivative compound having an acid-dissociable functional group, an acid anhydride, an active carboxylic acid derivative compound such as dicarbonate, or an alkyl halide. Of these, acid anhydrides and dicarbonates are particularly preferred. The acid dissociable functional group is a substituted methyl group, a 1-substituted ethyl group, a 1-substituted-n-propyl group, a 1-branched alkyl group, a silyl group, a germyl group exemplified as R ⁴ , R ⁵ and R ^7. Group, acyl group, alkoxycarbonyl group, 1-substituted alkoxymethyl group, and cyclic substituent. The basic catalyst may be any alkaline compound, and examples thereof include mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, and tetramethylammonium hydroxide (TMAH). ), An alkaline compound such as choline, or a metal compound such as an alkylammonium salt or an alcoholate, and more preferably triethylamine.
Here, the aminophenols or hydroxyalkylphenols are not particularly limited as long as they have a functional group having higher reactivity with isocyanate than phenolic OH.

  Examples of the aminophenols include p-aminophenol, m-aminophenol, o-aminophenol, 4-aminocatechol, 3-aminocatechol, 2-aminoresorcinol, 4-aminoresorcinol, 5-aminoresorcinol, and 2-amino Hydroquinone, 4-aminopyrogallol, 5-aminopyrogallol, 2-aminomethylphenol, 3-aminomethylphenol, 4-aminomethylphenol, 4-aminomethylcatechol, 3-aminomethylcatechol, 2-aminomethyl Resorcinol, 4-aminomethylresorcinol, 5-aminomethylresorcinol, 2-aminomethylhydroquinone, 4-aminomethylpyrogallol, 5-aminomethylpyrogallol, 2-aminophloroglicinol, 2 And amino methyl phloroglucinol and the like. Particularly, p-aminophenol and m-aminophenol are preferable.

  Examples of the hydroxyalkylphenols include 4-hydroxymethylphenol, 3-hydroxymethylphenol, 2-hydroxymethylphenol, 4-hydroxymethylcatechol, 3-hydroxymethylcatechol, 2-hydroxymethylresorcinol, 4-hydroxymethylresorcinol, -Hydroxymethylresorcinol, 2-hydroxymethylhydroquinone, 4-hydroxymethylpyrogallol, 5-hydroxymethylpyrogallol and the like. Particularly, 4-hydroxymethylphenol and 5-hydroxymethylresorcinol are preferable.

The resist compound can be synthesized, for example, as follows. A polyisocyanate having three or more isocyanate groups and a compound having a phenolic hydroxyl group such as aminophenol and an amino group having a higher reactivity than the phenolic hydroxyl group are dimethylacetamide (hereinafter, referred to as “DMAc”) at equivalent weight, normal temperature and normal pressure. ) In an aprotic polar solvent. Thereby, the amino group selectively reacts with the isocyanate group. In this case, the reaction proceeds even without a catalyst, but the use of one or more of the base catalysts may increase the reaction rate.
Next, in order to introduce an acid-dissociable functional group such as a tert-butoxycarbonyl group in the same reaction vessel, di-tert-butyl dicarbonate is subjected to normal pressure at 60 to 70 ° C. in the presence of the base catalyst such as triethylamine. And react for 6-7 hours. The product is reprecipitated in distilled water, washed with distilled water and dried to obtain a resist compound.

  The resist compound may be a compound obtained by reacting hydroxybenzoic acid, dihydroxybenzoic acid, or trihydroxybenzoic acid with an acid dissociable functional group-introducing agent under a base catalyst, and a compound having three or more amino groups. It can also be obtained by condensation. This method is preferable because by-products can be suppressed.

  The compound having three or more amino groups is not particularly limited, but mesitylenetriamine, triaminobenzene, pararoseaniline, tris (aminophenylmethane), tris (aminophenyl) thiophosphate, lysine ester triamine, 1,6, Examples include 11-undecanetriamine, 1,8-diamino-4-aminomethyloctane, 1,3,6-hexamethylenetriamine, bicycloheptanetriamine, norbornanetriamine and the like. Among these compounds, mesitylenetriamine, triaminobenzene and pararoseaniline are particularly preferred.

  The resist compound can also be obtained by condensing a compound obtained by reacting an aminophenol or a hydroxyalkylphenol with an acid-dissociable functional group-introducing agent under a base catalyst, and a compound having three or more carboxyl groups. Can be This method is preferable because by-products can be suppressed.

  Examples of the compound having three or more carboxyl groups include benzenetetracarboxylic acid, cyclohexanetetracarboxylic acid, benzenetricarboxylic acid, and cyclohexanetricarboxylic acid. Particularly, benzenetricarboxylic acid such as trimesic acid and cyclohexanetricarboxylic acid such as each hydrogenated trimesic acid are exemplified. Acids are preferred.

  The resist composition of the present invention contains one or more resist compounds described above. When one type of resist compound is used, high sensitivity and high resolution may be obtained, and when two or more types are used, film-forming substrate adhesion may be improved.

The resist composition of the present invention may include a resist compound in which R ^{1 to} R ^{8 in the} formulas (I) to (VIII) are all hydrogen atoms. By including such a resist compound, high sensitivity, high resolution and etch roughness may be reduced.

  The composition of the present invention generates an acid or a base directly or indirectly by irradiating one or more of the resist compounds with visible light, ultraviolet light, excimer laser, electron beam, X-ray, or radiation such as an ion beam. It contains one or more acid or base generators (acid or base generators). When the resist compound has at least one structure of the formula (VII) as A in the formulas (I) to (III) and (IX) to (XI), a base generator is used instead of the acid generator be able to. When a base is present, the acid dissociable functional group is eliminated and converted to a phenolic hydroxyl group. The composition of the present invention may further include one or more solvents that dissolve the resist compound and the acid or base generator.

  The resist compound is an acid amplification type compound. When an acid coexists, the acid dissociable functional group is eliminated and converted to a phenolic hydroxyl group. The phenolic hydroxyl group allows the desorption to proceed effectively in combination with the autocatalytic effect and becomes an alkali-soluble substance, so that it can be used as a positive resist capable of being alkali-developable. The method for generating the acid is not particularly limited. For example, an acid is generated in a portion exposed to radiation such as ultraviolet rays and high energy by coexisting an acid generator.

  That is, in the present invention, a method for generating an acid is not limited as long as an acid is generated in the system. Finer processing is possible by using excimer lasers instead of ultraviolet rays such as g-rays and i-rays. Further finer processing is possible by using electron beams, X-rays and ion beams as high energy rays. is there.

  The acid generator is preferably at least one selected from the group consisting of compounds represented by the following formulas (5) to (12).

In the formula (5), R ²³ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group. X ^- is a sulfonate ion or a halide ion having an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.

  Compounds represented by the formula (5) include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, and diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate , Di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4- Hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium Trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfoniumtrifluoromethanesulfonate, tri (4-methoxyphenyl) sulfoniumtrifluoromethanesulfonate, tri (4-fluoro Phenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2 -Trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4 Trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl It is preferably at least one selected from the group consisting of -4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate and diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate.

In the formula (6), R ²⁴ may be the same or different and each is independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group. Represents a group or a halogen atom.

  Compounds represented by the formula (6) include bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butyl) Phenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) iodonium- 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis (4- t-butyl ether Nyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyl Iodonium p-toluenesulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzenesulfonate To diphenyliodonium Safluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium perfluoro- Group consisting of n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate Preferably, at least one type selected from the group consisting of:

In the formula (7), Q is an alkylene group, an arylene group or an alkoxylene group, and R ²⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.

  The compound represented by the formula (7) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (10 -Camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthyl Imide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2- Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4- Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicaroxyimide N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (per Fluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) naphthylimide , N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (Perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene- , It is preferably at least one kind selected from 3-dicarboximide, and N- (perfluoro--n- C1-12alkyl oxy) group consisting naphthylimide.

In formula (8), R ²⁶ may be the same or different and are each independently an optionally substituted straight-chain, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted A heteroaryl group or an optionally substituted aralkyl group.

  The compound represented by the formula (8) includes diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, It may be at least one selected from the group consisting of (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone, and di (4-trifluoromethylphenyl) disulfone. preferable.

In the formula (9), R ²⁷ may be the same or different and are each independently an optionally substituted straight-chain, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted A heteroaryl group or an optionally substituted aralkyl group.

  The compound represented by the formula (9) includes α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, and α- (trifluoromethylsulfonyloxyimino) -phenyl Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile and α It is preferably at least one selected from the group consisting of-(methylsulfonyloxyimino) -4-bromophenylacetonitrile.

In the formula (10), R ²⁸ may be the same or different, and each is independently a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.

In the formulas (11) and (12), R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopentyl group, a cyclohexyl group. A C1 -C3 alkoxyl group such as a cycloalkyl group, a methoxy group, an ethoxy group, and a propoxy group; or an aryl group such as a phenyl group, a toluyl group, and a naphthyl group, preferably an aryl group having a carbon number of 6 to 10. Group. L ²⁹ and L ³⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- group. Preferred are 1,2-quinonediazidosulfonyl groups such as 6-sulfonyl group. Particularly, a 1,2-naphthoquinonediazide-4-sulfonyl group and a 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ²⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (13), a carbonyl group, an ester group, an amide group or an ether group, and Y ²⁹ is It is a hydrogen atom, an alkyl group or an aryl group, and X ²⁹ and X ³⁰ are each independently a group represented by the following formula (14).

In the formula (14), Z ³² is each independently an alkyl group, a cycloalkyl group or an aryl group, R ³² is an alkyl group, a cycloalkyl group or an alkoxyl group, and r is an integer of 0 to 3. )

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, and bis (isobutylsulfonyl) ) Bissulfonyldiazomethanes such as diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3, 5-triazine, tris (2,3-dibromopropyl) Halogen-containing triazine derivatives, such as isocyanurate and the like.

  The base generator is preferably a compound that generates a base directly or indirectly by radiation such as ultraviolet rays and electron beams, and the compounds described in JP-A-10-083079 can be used.

  The acid or base generator may be used alone or in combination of two or more. In the composition of the present invention, the amount of the acid or base generator used is preferably from 0.1 to 30 parts by weight, more preferably from 0.5 to 20 parts by weight, and still more preferably from 1 to 30 parts by weight, per 100 parts by weight of the resist compound. 15 parts by weight. If the amount is less than 0.1 part by weight, the sensitivity and resolution tend to decrease, while if it exceeds 30 parts by weight, the cross-sectional shape of the resist pattern tends to decrease.

  Various additives such as an acid diffusion controller, a dissolution controller, a dissolution accelerator, a sensitizer, and a surfactant can be added to the resist composition of the present invention.

  In the present invention, an acid diffusion controller having an action of controlling an undesired chemical reaction in an unexposed region by controlling a diffusion phenomenon in a resist film of an acid generated from a photoacid generator by irradiation with radiation, You may mix. By using such an acid diffusion controlling agent, the storage stability of the resist composition is improved, the resolution is improved, and the laying time before electron beam irradiation and the fluctuation of the laying time after electron beam irradiation are increased. Therefore, a change in the line width of the resist pattern due to the above can be suppressed, and the process stability becomes extremely excellent. Examples of such an acid diffusion controller include electron beam radiolytic basic compounds such as a basic compound containing a nitrogen atom or a basic sulfonium compound and a basic iodonium compound. The acid diffusion controller can be used alone or in combination of two or more.

  The compounding amount of the acid diffusion controller in the present invention is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, and still more preferably 0.01 to 3 parts by weight, per 100 parts by weight of the resist compound. It is. When the compounding amount of the acid diffusion controller is less than 0.001 part by weight, the resolution, the pattern shape, the dimensional fidelity, and the like tend to deteriorate depending on the process conditions, and further, from electron beam irradiation to heating after radiation irradiation. When the storage time is longer, the pattern shape tends to deteriorate in the upper layer portion of the pattern. On the other hand, when the compounding amount of the acid diffusion controller exceeds 10 parts by weight, the sensitivity as a resist, the developability of an unexposed portion, and the like tend to decrease.

  The dissolution controlling agent is a component having an effect of controlling the solubility of the resist compound when the solubility of the resist compound in a developing solution such as an alkali is too high to appropriately reduce the dissolution rate during development. As such a dissolution controlling agent, a dissolution controlling agent that does not chemically change in the steps of baking, radiation irradiation, development and the like of the resist film is preferable.

  Examples of the dissolution controlling agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; sulfones such as methylphenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone; Can be mentioned. These dissolution controlling agents can be used alone or in combination of two or more. The amount of the dissolution controlling agent is appropriately adjusted depending on the type of the resist compound used, but is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of the resist compound.

  When the solubility of the resist compound in a developing solution such as an alkali is too low, the dissolution accelerator is a component having the function of increasing the solubility and appropriately increasing the dissolution rate of the resist compound during development. As such a dissolution accelerator, one that does not chemically change in steps such as baking of a resist film, electron beam irradiation, and development is preferable. Examples of the dissolution accelerator include low-molecular-weight phenolic compounds having about 2 to 6 benzene rings, and specific examples include bisphenols and tris (hydroxyphenyl) methane. it can. These dissolution promoters can be used alone or in combination of two or more. The compounding amount of the dissolution accelerator is appropriately adjusted depending on the type of the resist compound used, but is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of the resist compound.

  The sensitizer absorbs the energy of the irradiated radiation, transfers the energy to the photoacid generator, thereby increasing the amount of acid generated, and improves the apparent sensitivity of the resist. It is. Examples of such a sensitizer include, but are not particularly limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more. The compounding amount of the sensitizer is preferably at most 30 parts by weight, more preferably at most 10 parts by weight, per 100 parts by weight of the resist compound.

  The surfactant is a component having an effect of improving the coatability and striation of the resist composition of the present invention, the developability as a resist, and the like. As such a surfactant, any of anionic, cationic, nonionic and amphoteric surfactants can be used. Among these, preferred surfactants are nonionic surfactants. Nonionic surfactants have good affinity for the solvent used in the radiation-sensitive composition and are more effective. Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, and the like, and the following brand name, F-Top (manufactured by Jemco). , Megafac (Dainippon Ink and Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (from Asahi Glass), Pepol (Toho Chemical), KP (Shin-Etsu Chemical) And polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like, but there is no particular limitation.

  The amount of the surfactant is preferably 2 parts by weight or less as an active ingredient of the surfactant per 100 parts by weight of the resist compound. Further, by blending a dye or a pigment, the latent image in the exposed area can be visualized, and the effect of halation at the time of exposure can be reduced. Furthermore, by blending an adhesion aid, the adhesion to the substrate can be improved.

  When used, the resist composition of the present invention is dissolved in a solvent so that the solid content concentration is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass. After that, the solution is filtered, for example, with a filter having a pore size of about 0.2 μm to prepare a resist solution.

  Examples of the solvent used in the resist composition of the present invention include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like. Ethylene glycol monoalkyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (PGMEA) and other propylene glycol monoalkyl ether acetates; propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether and other propylene glycol Monoalkyl ethers; methyl lactate, ethyl lactate Lactic acid esters such as (EL); aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate; Other esters such as ethyl 3-ethoxypropionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; Cyclic ethers such as tetrahydrofuran and dioxane However, there is no particular limitation. These solvents can be used alone or in combination of two or more.

  The composition of the present invention is a resin which itself is insoluble or hardly soluble in an aqueous alkali solution, but becomes soluble in an aqueous alkali solution by the action of an acid, such as a phenolic resin and a resin having a phenolic hydroxyl group such as polyhydroxystyrene. And at least one kind of resin, polyalkyl methacrylate, or the like, in which a hydroxyl group is replaced with an acid dissociable functional group.

  In the present invention, the resist substrate is a resist substrate on which a resist film made of the composition is formed on a substrate, and the pattern-formed substrate is a pattern obtained by exposing and developing the resist film on the resist substrate. It is a substrate having a converted resist film. Further, the “pattern forming material” refers to a composition formed on a resist substrate and capable of forming a pattern by irradiation of light, an electron beam, radiation, or the like, and has the same meaning as a “resist film”. The “pattern wiring substrate” is a substrate having patterned wirings obtained by etching a pattern forming substrate.

  In order to form a resist pattern, first, a resist composition of the present invention is applied to a substrate such as a silicon wafer or a wafer coated with aluminum by a coating means such as spin coating, casting coating, and roll coating. A resist film is formed. If necessary, a surface treatment agent such as hexamethylene disilazane may be applied on the substrate in advance.

  Next, the resist film is exposed to a desired pattern with radiation such as ultraviolet rays and electron beams. Exposure conditions and the like are appropriately selected according to the composition of the radiation-sensitive composition and the like. In the present invention, in order to stably form a high-precision fine pattern in exposure, it is preferable to heat after irradiation with radiation. The heating conditions vary depending on the composition of the radiation-sensitive composition and the like, but are preferably 20 to 250C, more preferably 20 to 150C.

  Next, a predetermined resist pattern is formed by developing the exposed resist film with an alkali developing solution. Examples of the alkali developer include mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and alkalis such as choline. An alkaline aqueous solution in which one or more compounds are dissolved in a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used.

  Further, an appropriate amount of an alcohol such as methanol, ethanol, or isopropyl alcohol or the above-mentioned surfactant may be added to the alkali developer. Among them, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. In the case where such a developing solution composed of an alkaline aqueous solution is used, generally, after development, it is washed with water.

  After forming the resist pattern, etching is performed to obtain a patterned wiring board. The etching can be performed by a known method such as dry etching using a plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.

  After forming the resist pattern, plating can be performed. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

  Further, the resist pattern can be stripped with an organic solvent or an aqueous solution which is more alkaline than the aqueous alkaline solution used for development. Examples of the organic solvent include PGMEA, PGME, and EL. Examples of the strong alkaline aqueous solution include an aqueous solution of 1 to 20% by mass of sodium hydroxide and an aqueous solution of 1 to 20% by mass of potassium hydroxide. Examples of the peeling method include a dipping method and a spray method. Further, the wiring board on which the resist pattern is formed may be a multilayer wiring board, and may have a small diameter through hole.

  The wiring board obtained by the present invention can also be formed by a method of forming a resist pattern, depositing a metal in a vacuum, and then dissolving the resist pattern with a solution, that is, a lift-off method.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Synthesis example 1 of resist compound Synthesis of tBOC-TDIAP 50% by weight of butyl acetate solution of isocyanurate (TDI) of tolylene diisocyanate (Dai Nippon Ink Kogyo Co., Ltd., Burnock D-800, NCO equivalent: 592, nonvolatile matter: 51% by weight) 3.27 g (30 mmol) of p-aminophenol (AP) (Kanto Chemical Co., Ltd.) was added to 17.34 g of a solution obtained by adding 10 ml of DMAc (Kanto Kagaku Co., Ltd.) to a dropping funnel. The solution was slowly dropped into 10 ml of DMAc solution, and stirred at room temperature for 1 hour. Further, 8.0 g (36 mmol) of di-tert-butoxydicarbonate (a reagent manufactured by ACROS) and 4.0 g of triethylamine (a reagent manufactured by Kanto Chemical Co., Ltd.) were slowly added dropwise, followed by stirring at 60 ° C. for 7 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder (hereinafter, abbreviated as “tBOC-TDIAP composition”) was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4, and the main component was taken out. Finally, drying under reduced pressure was performed to obtain 21.1 g of a target product (hereinafter, abbreviated as “tBOC-TDIAP compound”). Structure FT-IR, confirmed by 400 MHz- ¹ H-NMR, nitrogen content in Table 1, the molecular weight, factor (F) are shown in Table 2.
IR: (cm ^-1 )
3355 (NH stretching vibration), 1709 (C = O, carbonyl)
¹ H-NMR: (400 MHz, CDCl ₃ , internal standard TMS)
_{δ (ppm) 7.0~8.1 (Ph- H} ), 3.5 (-C (C H 3) 3), 2.1~2.4 (Ph-C H 3), 9.0~ 9.1 (-N H -)

Synthesis Example 2 Synthesis of tBOC-TDIDHBA 3,5-dihydroxybenzyl alcohol (DHBA) (reagent made by ACROS ORGANICS) using a dropping funnel with a solution obtained by adding 20 ml of DMAc to 17.34 g of a 50% by weight solution of TDI in butyl acetate, 4 A solution of .20 g (30 mmol: 1.0 equivalent) in 30 ml of DMAc was slowly added dropwise, followed by stirring at room temperature for 1 hour. Further, 14.4 g (66 mmol) of di-tert-butyl dicarbonate and 7.2 g of triethylamine were slowly added dropwise, followed by stirring at 60 ° C. for 7 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder (hereinafter, abbreviated as “tBOC-TDIDHBA composition”) was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was performed to obtain 31.1 g of a target product (hereinafter, abbreviated as “tBOC-TDIDHBA compound”). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
3355 (NH stretching vibration), 1708 (C = O, carbonyl)
¹ H-NMR: (400 MHz, CDCl ₃ , internal standard TMS)
_{δ (ppm) 7.0~8.3 (Ph- H} ), 1.5 (-C (C H 3) 3), 2.1~2.4 (Ph-C H 3), 3.3 ( _{Ph-C H 2 -O -)} , 9.1~9.2 (-N H -)

Synthesis Example 3 Synthesis of tBOC-BICAP 2039 g of bisisocyanatocyclohexane (a reagent manufactured by Kanto Chemical Co., Ltd.) was heated to 50 ° C. while stirring, and as a catalyst, a tetramethylammonium / ethyl 2-ethylhexanoate cellosolve solution (DABCO / TMR) ) (Manufactured by Nippon Emulsifier Co., Ltd.) was added dropwise over 20 minutes. Thereafter, the reaction was followed by gel permeation chromatography (hereinafter abbreviated as GPC) while stirring at 70 ° C., and when the isocyanuration rate reached 40%, phosphoric acid (Kanto Chemical ( 0.35 g) was added. After filtering the reaction solution cooled to 50 ° C. to remove the salt of the catalyst and the reaction terminator, thin film distillation was performed using a thin film distillation apparatus, and the composition was confirmed by GPC. 739 g of bisisocyanatocyclohexane isocyanurate (BIC) of 2% was obtained. Thereafter, a 71.8% by weight butyl acetate solution was obtained.

A solution obtained by adding 5 ml of DMAc to 6.50 g of a 71.8% by weight solution of BIC in butyl acetate (NCO equivalent: 324, nonvolatile content: 71.8% by weight) was used to add 2.18 g of AP (20 mmol: 1.0 mmol) using a dropping funnel. (Equivalent) was slowly added dropwise to a solution of 5 ml of DMAc and stirred at room temperature for 1 hour. Further, 5.47 g (25 mmol) of di-tert-butyl dicarbonate and 2.83 g of triethylamine were slowly dropped, and the mixture was stirred at 60 ° C. for 7 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder (hereinafter, abbreviated as “tBOC-BICAP composition”) was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was performed to obtain 7.26 g of a target product (hereinafter, abbreviated as “tBOC-BICAP compound”). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
3344 cm ^-1 (NH stretching vibration), 1754, 1687 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
_{δ (ppm) 7.0~7.4ppm (Ph- H} ), 1.5ppm (-C (C H 3) 3), 1.2~2.4ppm (Ch- H), 3.3~3. _{6ppm (-C H 2 -),} 6.6,8.4ppm (-N H -) ( wherein, Ch denotes a cyclohexylene group.)

Synthesis Example 4 Synthesis of tBOC-IPDIAP A solution in which 5 ml of DMAc was added to 7.16 g of a 70% by weight butyl acetate solution of an isocyanurate form of isophorone diisocyanate (IPDI) (manufactured by Degussa, NCO equivalent: 358, nonvolatile matter: 70% by weight). Was slowly added dropwise to a solution of 2.19 g (20 mmol: 1.0 equivalent) of AP in 5 ml of DMAc using a dropping funnel, followed by stirring at room temperature for 1 hour. Further, 5.46 g (25 mmol) of di-tert-butyl dicarbonate and 2.83 g of triethylamine were slowly added dropwise, followed by stirring at 60 ° C. for 7 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder (hereinafter, abbreviated as “tBOC-IPDIAP composition”) was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was performed to obtain 7.77 g of a target product (hereinafter, abbreviated as “tBOC-IPDIAP compound”). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
3344 cm ^-1 (NH stretching vibration), 1756, 1685 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
_{δ (ppm) 6.9~7.4ppm (Ph- H} ), 0.9~1.4ppm (-C H 3), 1.5ppm (-C (C H 3) 3), 1.0~1 _{.6,3.7ppm (Ch- H), 3.6ppm (} -C H 2 -), 8.4~8.5ppm (-N H -)

Synthesis Example 5 Synthesis of tBOC-BICAP5 5.02 g of the tBOC-BICAP composition was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/8. Finally, drying under reduced pressure was carried out to obtain 1.02 g of a target product whose BIC is an isocyanurate pentamer (hereinafter, abbreviated as “tBOC-BICAP5 compound”). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
3344 cm ^-1 (NH stretching vibration), 1754, 1687 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
_{δ (ppm) 7.0~7.4ppm (Ph- H} ), 1.5ppm (-C (C H 3) 3), 1.2~2.4ppm (Ch- H), 3.3~3. _{6ppm (-C H 2 -),} 6.6,8.4ppm (-N H -) ( wherein, Ch denotes a cyclohexylene group.)

Synthesis Example 6 Synthesis of tBOC-BICAP7 15.32 g of the tBOC-BICAP composition was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 1/4. Finally, drying under reduced pressure was performed to obtain 0.90 g of a target product (hereinafter, abbreviated as “tBOC-BICAP7 compound”) in which BIC is an isocyanurate heptamer. The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
3344 cm ^-1 (NH stretching vibration), 1754, 1687 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
_{δ (ppm) 7.0~7.4ppm (Ph- H} ), 1.5ppm (-C (C H 3) 3), 1.2~2.4ppm (Ch- H), 3.3~3. _{6ppm (-C H 2 -),} 6.6,8.4ppm (-N H -) ( wherein, Ch denotes a cyclohexylene group.)

Synthesis Example 7 Synthesis of Ac-TDIAA Acetoxybenzoic acid (Ac-AA) (a reagent manufactured by Kanto Chemical Co., Ltd.) 1 was prepared by adding a solution obtained by adding 5 ml of DMAc to 5.78 g of a 50% by weight solution of TDI in butyl acetate and using a dropping funnel. A solution of 0.80 g (10 mmol: 1.0 equivalent) in 5 ml of DMAc was slowly added dropwise, followed by stirring at room temperature for 1 hour. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder (hereinafter, abbreviated as “Ac-TDIAA composition”) was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was carried out to obtain 2.54 g of a target product (hereinafter, abbreviated as "Ac-TDIAA compound"). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
3305 cm ^-1 (NH stretching vibration), 1708, 1645 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
_{δ (ppm) 6.8~8.0ppm (Ph- H} ), 2.1~2.4 (Ph-C H 3), 2.3 (C H 3 -), 10.3ppm (-N H - )

Comparative Synthesis Example 1 Synthesis of tBOC-H-TMADHBA 10.9 g (50 mmol) of di-tert-butyl dicarbonate, 3.5 g (50 mmol) of DHBA, 6.9 g (50 mmol) of potassium carbonate (a reagent manufactured by Kanto Chemical Co., Ltd.) ) And 125 ml of acetone (Kanto Chemical Co., Ltd. reagent). Thereafter, the mixture was stirred at room temperature for 30 hours. The solid substance was filtered from the reaction solution, acetone was removed under reduced pressure by a rotary evaporator, and the obtained colorless liquid was dissolved in 50 ml of tert-butyl methyl ether, and three times with 50 g of 1 M sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.). The extract was washed with 50 ml of water three times, dried over sodium sulfate, filtered, and tert-butyl methyl ether was removed by a rotary evaporator under reduced pressure to obtain a white powder (hereinafter abbreviated as “tBOC-DHBA”). was gotten. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was carried out to obtain 3,5-di-tert-butoxycarbonyloxybenzyl alcohol in a yield of 60% (hereinafter abbreviated as "tBOC-DHBA compound"). The structure was confirmed by FT-IR and 400 MHz-1H-NMR.
IR: (cm ^-1 )
3546 cm ^-1 (NH stretching vibration), 1758, 1731 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
_{δ (ppm) 7.0~7.2 (Ph- H} ), 1.5 (-C (C H 3) 3), 5.1 (Ph-C H 2 -O -), 5.4 (- O H )

A solution obtained by adding 4 ml of methylene chloride to 1.46 g (4.2 mmol) of the tBOC-DHBA compound, 0.31 g (1.4 mmol) of H-TMA, and 1.02 g (10.1 mmol) of triethylamine was added to tetrafluoroboric acid 2- The solution was added to a solution obtained by adding 1.39 g (5.0 mmol) of bromo-1-ethylpyridinium (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) to 6 ml of methylene chloride. Stirred at 40 ° C. for 1 hour. The reaction solution was dissolved in 50 ml of tert-butyl methyl ether, washed three times with 50 ml of water, dried using sodium sulfate, filtered, and tert-butyl methyl ether was removed under reduced pressure using a rotary evaporator to obtain a white powder ( Hereinafter, "tBOC-H-TMADHBA composition" is obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was performed to obtain 1.60 g of a target product (hereinafter, abbreviated as “tBOC-H-TMADHBA compound”). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
2979 cm ^-1 (NH stretching vibration), 1756, 1730 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm) 7.0~7.1 (Ph- H ), 1.3~1.5 (-C (C H 3) 3) + (- C 6 H 3 -), 5.0~5. _{1 (Ph-C H 2 -O-} )

Comparative Synthesis Example 2 Synthesis of tBOC-TMADHBA A solution obtained by adding 4 ml of methylene chloride to 1.46 g (4.2 mmol) of tBOC-DHBA, 0.31 g (1.4 mmol) of TMA, and 1.02 g (10.1 mmol) of triethylamine was used. Was added to a solution of 1.39 g (5.0 mmol) of 2-bromo-1-ethylpyridinium tetrafluoroborate and 6 ml of methylene chloride. Stirred at 40 ° C. for 1 hour. The reaction solution was dissolved in 50 ml of tert-butyl methyl ether, washed three times with 50 ml of water, dried using sodium sulfate, filtered, and tert-butyl methyl ether was removed under reduced pressure using a rotary evaporator to obtain a white powder ( Hereinafter, abbreviated as “tBOC-TMADHBA composition”) was obtained. Table 1 shows the nitrogen content and the weight average molecular weight. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was performed to obtain 1.60 of a target product (hereinafter, abbreviated as “tBOC-TMADHBA compound”). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
2985 cm ^-1 (NH stretching vibration), 1756, 1729 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
_{δ (ppm) 7.1~8.7 (Ph- H} ), 1.4 (-C (C H 3) 3), 5.3~5.4 (Ph-C H 2 -O-)

Comparative Synthesis Example 3 Synthesis of BCOTPB In a 20% by weight solution of 3.00 g (8.5 mmol) of 1,3,5-tris (4-hydroxyphenyl) benzene (manufactured by Aldrich) in butyl acetate, di-tert-butyl dicarbo was added. 6.00 g (28 mmol) of nate and 3.01 g of triethylamine were slowly added dropwise, followed by stirring at 60 ° C. for 7 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder (hereinafter, abbreviated as “BCOTPB” composition) was obtained. The white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was performed to obtain 5.00 g of a target product (hereinafter, abbreviated as “BCOTPB” compound). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
1752 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, CDCl ₃ , internal standard TMS)
δ (ppm) 7.0~7.5ppm (Ph- H ), 1.4ppm (-C (C H 3) 3)

Comparative Synthesis Example 4 Synthesis of tBOC-PIAP To a solution obtained by adding 6.53 g (60 mmol) of AP to 10 ml of DMAc, a solution obtained by adding 10 ml of DMAc to 7.15 g (60 mmol) of phenyl isocyanate (PI) (manufactured by Kanto Chemical Co., Ltd.) was added dropwise. The mixture was slowly added dropwise using a funnel and stirred at room temperature for 1 hour. Further, 14.4 g (66 mmol) of di-tert-butyl dicarbonate and 7.2 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) were slowly added dropwise, followed by stirring at 60 ° C. for 7 hours. The reaction solution was added to a large amount of water, and reprecipitation was repeated. As a result, a powder (hereinafter, abbreviated as “tBOC-PIAP” composition) was obtained. The white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was performed to obtain 11.00 g of a target product (hereinafter, abbreviated as “tBOC-PIAP” compound). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
3355 (NH stretching vibration), 1709 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
_{δ (ppm) 7.0~8.1 (Ph-} H), 3.5 (-C (CH 3) 3), 2.1~2.4 (Ph-CH 3)

Comparative Synthesis Example 5 Synthesis of Ac-TAPPA A solution obtained by adding 5 ml of methylene chloride to 3.75 g (30 mmol) of triaminopyridine (TAP) (manufactured by Aldrich) was treated with 6-hydroxy-2-pyridinecarboxylic acid using a dropping funnel. (PA) 12.5 g (90 mmol) of a reagent (manufactured by Aldrich), 30.0 g (108 mmol) of 2-bromo-1-ethylpyridinium tetrafluoroborate, and 15.0 g of triethylamine were slowly dropped into a solution of 5 ml of methylene chloride at 40 ° C. For 4 hours. The reaction solution was dissolved in 50 ml of tert-butyl methyl ether, washed three times with 50 ml of water, dried using sodium sulfate, filtered, and tert-butyl methyl ether was removed under reduced pressure using a rotary evaporator. 0.02 g were obtained. 16.41 g (75 mmol) of di-tert-butyl dicarbonate and 8.21 g of triethylamine were slowly added dropwise to 2.02 g of the obtained white powder, followed by stirring at 60 ° C. for 7 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder (hereinafter, abbreviated as “Ac-TAPPA composition”) was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, drying under reduced pressure was performed to obtain 1.10 g of a target product (hereinafter, abbreviated as “Ac-TAPPA compound”). The structure was confirmed by FT-IR and 400 MHz-1H-NMR. Table 1 shows the nitrogen content, and Table 2 shows the molecular weight and factor (F).
IR: (cm ^-1 )
3349 cm ^-1 (NH stretching vibration), 1645 cm ^-1 (C = O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
_{δ (ppm) 7.2~8.0ppm (Ph- H} ), 2.3ppm (-C H 3), 9.3ppm (-O H), 10.3ppm (-N H -)

Each measuring method is shown below.
(1) Nitrogen content: determined by CHN elemental analysis.
(2) Molecular weight: A pure substance identified by IR and ¹ H-NMR was determined by calculation.
(3) Factor (F): calculated by calculation.

Film forming test examples 1 to 7 and comparative examples 1 to 5
The resist compounds (0.5 g) synthesized in Synthetic Examples 1 to 7 and Comparative Synthetic Examples 1 to 5, the acid generators shown in Table 3 (compounding amounts shown in Table 3), and the solvents shown in Table 3 (4 0.5 g) was made into a homogeneous solution, and then filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.2 μm to prepare a resist solution. The obtained resist solution was spin-coated on the substrates shown in Table 4 to form a resist film. Table 4 shows the film formability of each of the obtained resist films. The film forming property was evaluated by the following method.
Evaluation of Film Formability A resist film of 10 × 10 mm square was divided into 100 sections, and the sections not covered with the resist film and the sections crystallized were counted and evaluated according to the following criteria.
Zero: + (good)
One or more places:-(bad)

溶媒
ＰＧＭＥ：プロピレングリコールメチルエーテル
ＥＬ：乳酸エチル
ＰＧＭＥＡ：プロピレングリコールモノエチルアセテート
酸発生剤
ＤＮＱ：１，２−ナフトキノン−２−ジアジド−５−スルホン酸ナトリウム
ＷＰＩ００７：ジフェニルヨードニウムトリフルオロスルホネート
ＷＰＡＧ５９６：ジフェニルキサントン−２−イルスルホニウムヘキサフルオロホスフェート

Solvent PGME: Propylene glycol methyl ether EL: Ethyl lactate PGMEA: Propylene glycol monoethyl acetate acid generator DNQ: Sodium 1,2-naphthoquinone-2-diazide-5-sulfonate WPI007: Diphenyliodonium trifluorosulfonate WPAG596: Diphenylxanthone- 2-ylsulfonium hexafluorophosphate

Examples 8 to 14 of forming resist pattern and Comparative Examples 6 to 8
The resist compounds (0.5 g) synthesized in Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1, 2, and 5; the acid generators shown in Table 3 (compounding amounts shown in Table 3); and the solvents shown in Table 3 ( 4.5 g) was made into a homogeneous solution, and then filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.2 μm to prepare a resist solution. The obtained resist solution was spin-coated on a clean silicon wafer, and baked (PB) before exposure in an oven under the conditions shown in Table 5 to form a resist film having a thickness of 0.2 μm. The resist film was exposed to an i-ray having a wavelength of 365 nm under the conditions shown in Table 5. Thereafter, the film was exposed and baked in an oven under the conditions shown in Table 6, and was developed at 23 ° C. by a standing method under the conditions shown in Table 6. Thereafter, the substrate was washed with water for 30 seconds and dried to form a positive resist pattern. Each of the obtained resist patterns was evaluated by the following method.

(1) 5 μmL & S
The resist pattern after development was observed with an optical microscope to confirm the formation of a 5 μm line and space, and evaluated according to the following criteria.
Confirmation: +
Not confirmed:-
A scanning electron micrograph of the resist pattern obtained in Example 9 is shown in FIG. The dark portions indicate the remaining resist in the unexposed portions, and the light portions indicate portions where the resist is removed in the exposed portions.

(2) Substrate Adhesion A 10 × 10 mm square resist film was divided into 100 sections, the sections where the resist film was peeled were counted, and evaluated according to the following criteria.
Zero: + (good)
One or more places:-(bad)

(3) Etching resistance An aluminum (alloy of Si and Cu) thin film (about 200 nm) was deposited on a silicon wafer using a SH-550 type high-rate sputtering device manufactured by Japan Vacuum Engineering.
Etching solution: 0.1N sodium hydroxide aqueous solution Etching time: 3 min
After etching under the above conditions, the resist was washed with pure water and the remaining resist was dissolved with acetone. The etching pattern at that time was observed with an optical microscope, and the shape of the pattern was visually determined.
Good: +
Bad:-
Table 7 shows the evaluation results.

現像液
ＴＭＡＨ：テトラメチルアンモニウムヒドロキシド２．３８ｗｔ％水溶液
ＴＭＡＨ／ＩＰＡ：テトラメチルアンモニウムヒドロキシド２．３８ｗｔ％水溶液／イソプロピルアルコールの混合液

Developer TMAH: 2.38 wt% aqueous solution of tetramethylammonium hydroxide TMAH / IPA: Mixed solution of 2.38 wt% aqueous solution of tetramethylammonium hydroxide / isopropyl alcohol

  In Examples 8 to 13, 5 μmL & S patterns having good pattern shapes were obtained. On the other hand, in Comparative Examples 6 to 8, a 5 μmL & S pattern having a good pattern shape was not obtained.

Example 15 of electron beam irradiation test
The resist solution was prepared by filtering with a Teflon (registered trademark) membrane filter having a pore size of 0.2 μm in the composition of Examples 1-2 and 2-2. The obtained resist solution was spin-coated on a clean silicon wafer, and baked in an oven under the conditions shown in Table 5 before exposure to form a resist film having a thickness of 0.2 μm. The resist film was exposed to an electron beam using an electron beam exposure apparatus (JBX-5FE type manufactured by JEOL Ltd.) under the conditions of a current amount of 200 pA and an exposure amount of 10 μC / cm ² . Then, after baking after exposure in an oven under the conditions shown in Table 6, development was carried out at 23 ° C. by a static method under the conditions shown in Table 6. Thereafter, the substrate was washed with water for 30 seconds and dried to form a positive resist pattern and obtain a drawn pattern.

FIG. 1 is a scanning electron micrograph showing a line pattern of the resist pattern obtained in Example 9.

Claims (18)

Directly or indirectly by irradiating one or more resist compounds satisfying all the conditions of a) to f) with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, X-ray and ion beam. A resist composition comprising at least one acid or base generator that generates an acid or base.
a) It has at least one acid dissociable functional group in the molecule.
b) The molecule has at least one functional group selected from a urea group, a urethane group, an amide group and an imide group.
c) The molecular weight is 500-5000.
d) It has a branched structure.
e) Formula 3 ≦ F ≦ 5 is satisfied (where F represents the total number of atoms / (the total number of carbon atoms−the total number of oxygen atoms)).
f) The nitrogen element content is 1 to 20% by mass. The resist composition according to claim 1, wherein the branched structure of the resist compound has a chemical structure satisfying at least one of the following conditions (1) to (4).
(1) It has a tertiary carbon atom or a tertiary nitrogen atom not included in the cyclic structure.
(2) It has a quaternary carbon atom.
(3) At least one aromatic or aliphatic ring having three or more substituents.
(4) It has a tertiary phosphorus atom. The resist compound has at least one acid-dissociable functional group in each branched molecular chain, and is selected from a urea bond, a urethane bond, an amide bond, and an imide bond in each branched molecular chain. 3. The resist composition according to claim 1, having at least one kind of bonded structure. The resist composition according to any one of claims 1 to 3, wherein the resist compound is represented by the following formula (1).

(In equation (1),
X is each independently hydrogen, or the following formulas (I) to (III):

(In the formulas (I) to (III),
R ^{1 to} R ³ are each independently a hydrogen atom or a substituent selected from the group consisting of a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group, an alkoxy group, and a 1-branched alkyl group. And;
A is each independently hydrogen or the following formulas (IV) to (VIII):

(In the formulas (IV) to (VIII), R ⁶ and R ⁸ each independently represent a hydrogen atom, or a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group, an alkoxy group, and a 1-branch. A substituent selected from the group consisting of an alkyl group, wherein R ⁴ , R ⁵ , and R ⁷ are each independently a hydrogen atom, or a substituted methyl group, a 1-substituted ethyl group, a 1-substituted-n-propyl, A substituent selected from the group consisting of a branched alkyl group, a silyl group, a germyl group, an acyl group, an alkoxycarbonyl group, a 1-substituted alkoxymethyl group, and a cyclic substituent, wherein at least one of R ^{4 to} R ⁸ is A characteristic group other than a hydrogen atom), wherein at least one of A is any of formulas (IV) to (VIII);
Ar independently represents an aromatic hydrocarbon group having 6 to 12 carbon atoms;
Y each independently represents a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group, a substituted alkylene group, or a single bond;
Z independently represents a single bond or a substituent selected from the group consisting of -O-, -S- and -NH-;
a1 to a3 are each independently an integer of 1 to 9;
r1 to r3 are each independently an integer of 0 to 8;
a1 + r1 ≦ 9, a2 + r2 ≦ 9, a3 + r3 ≦ 8;
n is an integer of 1 to 5)
Wherein at least three of Xs are any of formulas (I) to (III);
E independently represents a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group, or a substituted alkylene group;
s, t, and u each independently represent an integer of 0 to 3. ) The resist composition according to any one of claims 1 to 4, wherein the resist compound has a molecular weight of 600 to 3000 and a nitrogen element content of 2 to 15% by mass. The resist composition according to any one of claims 1 to 5, wherein the resist compound is represented by the following formulas (2) to (4).

(In the formulas (2) to (4), X and E are the same as described above.) The resist composition according to any one of claims 4 to 6, wherein X in the formulas (1) to (4) is represented by the following formulas (IX) to (XI).

(In the formulas (IX) to (XI), A is the same as described above, and m is an integer of 1 to 2.) 8. The method according to claim 4, wherein at least one of A in the formulas (I) to (III) and (IX) to (XI) is represented by the following formulas (XII) to (XV). The resist composition according to the above.

The resist composition according to any one of claims 1 to 8, wherein the resist compound is produced from one or more polyisocyanate compounds having three or more isocyanate groups. The polyisocyanate compound is tolylene diisocyanate, bis (isocyanatephenyl) methane, bis (isocyanatecyclohexyl) methane, phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, metaxylene diisocyanate, norbornane diisocyanate Isocyanurate, buret, allohanate or urethane derived from at least one diisocyanate compound selected from the group consisting of, trizine diisocyanate, naphthalenediisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, and trimethylhexamethylene diisocyanate; Oligomers of socyanate phenylmethane; or tris (isocyanatephenyl) methane, tris (isocyanatephenyl) thiophosphate, mesitylene triisocyanate, triisocyanate benzene, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8 10. The resist according to claim 9, wherein the resist is at least one triisocyanate selected from the group consisting of diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate. Compound. The resist composition according to claim 1, comprising two or more kinds of the resist compounds. The resist composition according to any of claims 4-11, wherein R ⁴ to R ⁸ in Formula (IV) ~ (VIII) comprises a resist compound are all hydrogen atoms. The resist composition according to any one of claims 1 to 12, further comprising a resin which is insoluble or hardly soluble in an aqueous alkali solution, but becomes soluble in an aqueous alkali solution by the action of an acid. A resist substrate comprising a resist film comprising the resist composition according to claim 1 formed on a substrate. A pattern-formed substrate obtained by patterning the resist film according to claim 14. A step of forming a resist film by applying the resist composition according to any one of claims 1 to 13 on a substrate, a step of heating the resist film, a step of heating the resist film by visible light, ultraviolet light, an excimer laser, Irradiating with any radiation selected from an electron beam, an X-ray and an ion beam, and, if necessary, performing a heat treatment and then developing the exposed resist film using a developing solution. A method for forming a resist pattern. A pattern wiring substrate obtained by etching after performing the pattern forming method according to claim 16. 17. A method for manufacturing a patterned wiring board, comprising a step of further etching after performing the pattern forming method according to claim 16.

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