JP2000098612A - Production of semiconductor device, photosensitive composition and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive composition having high transparency to light of short wavelength, high adhesion to a substrate, good resolution and dry etching resistance by incorporating a specified high molecular copolymer and a photo-acid generating agent. SOLUTION: The photosensitive composition contains at least a high molecular copolymer obtained by copolymerizing at least one of monomers of formulae I and II with at least one of monomers of formulae III-VII and a photo-acid generating agent. In the formulae I-VII, R is acryloyl or methacryloyl, R11 and R12 are each H or monovalent alkyl, R13 is OH, =O, COOH or COOR14 (R14 is a monovalent organic group), R31 is H or at least one group selected from OH, OR14 and =O, R32 is H or a monovalent organic group and R41 is vinyl, acryloyl or methacryloyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a semiconductor device, and more particularly, to a semiconductor device and a TFT.
The present invention relates to a photosensitive composition suitable for use in the production of electronic components such as (thin film transistors) and optical disks, and a pattern forming method using the same.

[0002]

2. Description of the Related Art Conventionally, in the manufacturing process of electronic parts such as semiconductor devices, a fine processing technique utilizing photolithography has been employed. That is, first, a resist solution is applied on a substrate or the like to form a resist film,
Next, after the obtained resist film is exposed to pattern light, a process such as alkali development is performed to form a resist pattern. Subsequently, the surface of the exposed substrate or the like is dry-etched using the resist pattern as an etching-resistant mask to form fine-width lines and openings, and finally, the resist is removed by ashing.

Accordingly, the resist used here is generally required to have high dry etching resistance. From such a viewpoint, resists containing an aromatic compound have been widely used so far, and specifically, a large number of resists using an alkali-soluble novolak resin or the like as a base resin have been developed.

[0004] On the other hand, with the high-density integration of LSIs and the like, the above-mentioned fine processing technology has recently reached the sub-half micron order, and it is expected that such fineness will become more remarkable in the future. For this reason, the wavelength of light sources in photolithography has been shortened,
ArF excimer laser light having a wavelength of 193 nm or a wavelength of 157 nm
formation of fine resist patterns by nm of the F ₂ laser beam have been tried.

However, in the case of a resist using a novolak resin as a base resin which has been generally used until now, there is a tendency that the benzene nucleus of the novolak resin absorbs a large amount of light with respect to the above-mentioned ArF excimer laser beam having a wavelength of 193 nm. Therefore, when trying to form a resist pattern, it is difficult to sufficiently reach light to the substrate side of the resist film during exposure, and as a result, it is difficult to form a pattern having a good pattern shape with high sensitivity and high precision. there were. As described above, a resist using a novolak resin as a base resin has high dry etching resistance and can be alkali-developed, but is insufficient in transparency to short-wavelength light, so that photolithography using ArF excimer laser light There is a strong demand for the development of a resist suitable for the above.

In view of these points, a resist containing an alicyclic compound instead of an aromatic compound has recently attracted attention. For example, Japanese Patent Application Laid-Open No. 4-39665 discloses a resist having a dry etching resistance and a short wavelength. As a resist excellent in transparency to light, a compound having an adamantane skeleton is copolymerized with an acrylic compound having a carboxylic acid group to impart alkali solubility to the copolymer, and the copolymer is used as a resist component Thus, an example in which a resist pattern is formed by alkali development is shown.

However, when a resist pattern containing an alicyclic compound is formed by alkali development in this manner, the portion having an alicyclic skeleton structure is generally highly hydrophobic, and alkali-dissolved with a carboxylic acid group or the like. Various problems arise because the characteristics are greatly different.

For example, during development, the dissolution / removal of a predetermined region of the resist film becomes non-uniform, resulting in a decrease in resolution. On the other hand, partial dissolution occurs in a region where the resist film is supposed to remain. This may cause surface roughness. Further, the alkaline solution may permeate the interface between the resist film and the substrate, and the resist pattern may be peeled off.

Regarding the problem due to the hydrophobicity of the alicyclic group, JP-A-9-221519 discloses one solution to introduce a methacrylic acid unit into the alicyclic group. However, according to this solution, the alicyclic site into which the methacrylic acid unit is introduced does not contribute to the dissolution contrast between the exposed part and the unexposed part.

On the other hand, Japanese Patent Application Laid-Open No. 10-161313 discloses a technique in which the alicyclic skeleton structure, which has been conventionally introduced as an etching resistant group, is eliminated with an acid in an exposed portion so as not to hinder alkali solubility. Are listed. However, there remains a problem in the adhesion between the unexposed portion and the substrate.

[0011]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned conventional problems and to provide a method of manufacturing a semiconductor device capable of ultrafine processing and a high transparency to short wavelength light. It is an object of the present invention to provide a photosensitive composition which has high adhesion to a substrate, and has good resolution and dry etching resistance, and a pattern forming method using the same.

[0012]

According to the present invention, at least one monomer selected from the monomers represented by the general formulas (1) and (2) is used together with a homopolymer or another vinyl monomer. Forming a film containing a polymer composition obtained by polymerization and a photosensitive composition comprising at least a photoacid generator on a film to be etched on a substrate; and forming a pattern on a predetermined region of the photosensitive composition-containing film. Step of performing exposure, a step of heat-treating the photosensitive composition-containing film after exposure, and developing the photosensitive composition-containing film after the heat treatment with an aqueous alkali solution, the photosensitive composition-containing film A semiconductor device comprising at least a step of forming a patterned photomask by selectively dissolving and removing, and a step of etching a film to be etched by a dry etching method using the photomask as a mask. It is a method of manufacture.

[0013]

Embedded image (Where R is an acryloyl or methacryloyl group,
R ₁₁ and R ₁₂ are a hydrogen atom or a monovalent alkyl group; R ₁₃ is an OH group, ＝ O group, COOH group, or COOR ₁₄
Group (R ₁₄ is a monovalent organic group)) The present invention also relates to at least one monomer selected from the monomers represented by the general formulas (1) and (2) and the general formula (3),
(4) A polymer copolymer obtained by copolymerizing at least one monomer selected from monomers represented by (5), (6) and (7), and at least a photoacid generator. A photosensitive composition characterized by comprising: a photosensitive composition; and a pattern forming method using the photosensitive composition.

[0014]

Embedded image (However, R ₃₁ is a hydrogen atom or an OH group, an OR ₁₄ group (R ₁₄ is a monovalent organic group), at least one group selected from the group consisting of an ＯO group, and R ₃₂ is a hydrogen atom or a monovalent group. An organic group, R ₄₁ represents a vinyl, acryloyl or methacryloyl group.)

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the polymer according to the present invention, the monomers represented by the general formulas (1) and (2) are R ₁₁ ,
R ₁₂ is a hydrogen atom or a monovalent alkyl group. By having R ₁₁ and R ₁₂ , the high molecular weight polymer can be desorbed / decomposed more sensitively in the presence of an acid, and Becomes R ₁₁ and R ₁₂ are more preferably a methyl group, an ethyl group, or a propyl group or an isopropyl group than those having a hydrogen atom, since they are eliminated and decomposed with high sensitivity.

R ₁₃ is an OH group, ま た は O group or C
It is an OOH group or a COOR ₁₄ group (R ₁₄ is a monovalent organic group). By having this R ₁₃ , the hydrophobicity is reduced, and the adhesion between the photosensitive composition and the substrate and the alkali dissolution of the high polymer are dissolved. It has become possible to improve the performance. In order to enhance this function, a plurality of R ₁₃ may be introduced. In particular, the ＯO group is preferred because it hardly causes an unnecessary reaction with the introduced group of another side chain. R is an acryloyl group or a methacryloyl group, and those further substituted with a cyano group or a halogen atom are included in the scope of the present invention.

Further, the monomers represented by the general formulas (1) and (2) have the advantage of good transparency at 193 nm and also provide high dry etching resistance to the obtained resist pattern. It has an adamantane skeleton.

When a copolymer of the monomers represented by the general formulas (1) and (2) and another vinyl monomer is used,
The content of the monomer represented by the general formula (1) or (2) in the copolymer is preferably from 10 to 90 mol%. More preferably, it is 30 to 70 mol%. If it is less than 10 mol%, the function of maintaining the adhesion to the substrate and the high dry etching resistance in the unexposed area and the function of removing the alicyclic skeleton and increasing the alkali solubility of the polymer in the exposed area become insufficient. 90 mol%
This is because, when the value exceeds, it is difficult to control the alkali solubility of the high-molecular polymer, which tends to increase the cost.

Other vinyl monomers copolymerized with the monomers represented by the general formulas (1) and (2) include the following general formulas (3), (4), (5), (6) Or it is preferably at least one selected from (7).

[0020]

Embedded image (However, R ₃₁ is a hydrogen atom or an OH group, an OR ₁₄ group (R ₁₄ is a monovalent organic group), at least one group selected from the group consisting of an ＯO group, and R ₃₂ is a hydrogen atom or a monovalent group. The organic group and R ₄₁ represent a vinyl, acryloyl or methacryloyl group.) These monomers are copolymerized with the monomers listed in the general formula (1) to improve their alkali solubility, dry etching resistance and the like. In addition, it becomes possible to further enhance the function as the photosensitive composition. In particular, when the monomer represented by the general formula (7) is used, the dry etching resistance is improved, which is more preferable. Furthermore, each (1)
(6) is more preferable than (4) and (5) than (2) and (3) because the carbon content is higher than that of (2) and (3), so that the resistance to general etching gas such as CF4 is superior. In particular, when the monomer represented by the general formula (7) is contained, the content is desirably 5 to 50 mol%. If the amount is less than 5 mol%, the effect of the high dry etching resistance of the skeleton represented by the general formula (7) may not be sufficiently obtained. Conversely, if the amount exceeds 50 mol%, the transparency to light having a wavelength of 193 nm is reduced. This is because there is a possibility that it cannot be obtained sufficiently.

The above general formulas (3), (4),
Vinyl monomers other than those represented by (5), (6) and (7) may be used. In this case, the vinyl monomer desirably has an alicyclic structure. Examples of the alicyclic structure include a cyclic cyclo compound and a cyclic bicyclo compound represented by the general formula C _n H _2n (n is an integer of 3 or more), and a condensed ring thereof. Specifically, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring or those in which a bridging hydrocarbon is introduced to them, spiroheptane, a spiro ring such as spirooctane, a norbornyl ring, an adamantyl ring, a bornene ring, Menthyl ring, terpene ring such as menthane ring, tujang, sabinen, tsujong, karan, karen, pinan, norpinan, borane, fencan, tricyclene, cholesteric ring and other steroid skeleton, tanjusan, digitaloids,
Camnon ring, isocamphor ring, sesquiterpene ring,
Examples include a Sandton ring, a diterpene ring, a triterpene ring, and steroid saponins.

Even in the case of a condensed polycyclic structure instead of an alicyclic structure, the wavelength of the absorption band shifts, so that transparency at 193 nm can be ensured. Us
Progo. SPIE V
OL. 2195 (1994); 205; However, the object of the present invention is achieved even with a fused polycyclic structure.

Examples of those having a condensed polycyclic structure include indene, indane, benzobuldene, 1-indanone, 2-indanone, 1,3-indadione, ninhydrin, naphthalene, methylnaphthalene, ethylnaphthalene, dimethylnaphthalene, kadalene, Vinylnaphthalene, 1,2-dihydronaphthalene, 1,4-dihydronaphthalene, 1,2,3,4-tetrahydronaphthalenetetralin, 1,2,3,4,5,6,7,8-octahydronaphthalene, cis -Decalin, trans-decalin, fluoronaphthalene, chloronaphthalene, bromonaphthalene, iodonaphthalene, dichloronaphthalene,
(Chloromethyl) naphthalene, 1-naphthol, 2-naphthol, naphthalene diol, 1,2,3,4-tetrahydro-1-naphthol, 1,2,3,4-tetrahydro-2-naphthol, 5,6,7 , 8-Tetrahydro-1-naphthol, 5,6,7,8-tetrahydro-2
-Naphthol, decahydro-1-naphthol, decahydro-2-naphthol, chloronaphthol, nitronaphthol, aminonaphthol, methoxynaphthalene, ethoxynaphthalene, naphthyl ether, naphthyl acetate, naphthaldehyde, naphthalenedicarbaldehyde, hydroxynaphthaldehyde, dinaphthyl Ketone, 1 (2H)-
Naphthalenone, α-tetralone, β-tetralone, α-
Decalone, β-decalone, 1,2-naphthoquinone, 1,
4-naphthoquinone, 2,6-naphthoquinone, 2-methyl-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, isonaphthazarin, naphthoic acid, 1-naphthol-4-carboxylic acid, naphthalic acid, naphthalic anhydride Product, 1-naphthylacetic acid, thionaphthol, N, N-dimethylnaphthylamine, naphthonitrile, nitronaphthalene, pentalene, azulene, heptalene, fluorene,
9-phenylfluorene, nitrofluorene, 9-fluorenol, fluorenone, anthracene, methylanthracene, dimethylanthracene, 9,10-dihydroanthracene, anthrol, anthranol, hydroanthranol, dihydroxyanthracene, anthragalol, 1 (4H) -Anthracenone, anthrone,
Anthrarobin, chrysarobin, oxantrone, anthracenecarboxylic acid, anthramine, nitroanthracene, anthracenequinone, anthraquinone, methylanthraquinone, hydroxyanthraquinone, phenanthrene, phenanthrol, phenanthrene hydroquinone,
Phenanthraquinone, biphenylene, s-indacene,
as-indacene, phenalene, tetracene, chrysene, 5,6-chrysoquinone, pyrene, 1,6-pyrenequinone, triphenylene, benzo [α] anthracene, benzo [α] anthracene-7,12-quinone, benzantrone, aceanthrylene, Acephenanthrylene, acephenanthrene, 17H-cyclopenta [α] -phenanthrene, fluoranthene, pleiadene, pentacene, pentaphen, picene, pyrylene, dibenzo [a,
j] anthracene, benzo [α] pyrene, coronene, pyranthrene, pyranthrone and the like.

The polymer according to the present invention comprises at least one monomer represented by the general formula (1) or (2) and a monomer having an alicyclic skeleton or a condensed polycyclic skeleton. It is desirable to contain 50 mol% or more. Because 50mol
%, There is a possibility that sufficient dry etching resistance may not be obtained.

The polymer according to the present invention is obtained by subjecting a polymerizable compound having an alicyclic structure into which an acidic substituent is introduced and a polymerizable double bond in the molecule to radical polymerization or cationic polymerization.
It can be obtained by polymerizing by anionic polymerization or the like. In general, a polymerizable double bond having an alicyclic group in the polymer main chain can obtain a high molecular weight polymer by performing cationic polymerization or anionic polymerization. However, in the present invention, even if the molecular weight of the polymer is low, since there is no problem as long as the film can be formed, polymerization is performed using a simple method such as radical polymerization, and the polymer is used in a mixed state of the low molecular weight compound and the high molecular weight compound. May be.

At this time, acrylic acid, maleic anhydride and their ester-substituted products, vinylphenol,
Vinyl naphthol, hydroxyethyl methacrylate,
It may be copolymerized with SO ₂ or the like. Furthermore, the alkali-soluble group of these alkali-soluble compounds is copolymerized with a compound protected by an acid-decomposable group having the ability to inhibit dissolution in an alkali solution, thereby adjusting the alkali solubility of the polymer and the adhesion of the resist to the substrate. It is also possible to improve. However, in consideration of the transparency of the resist to short-wavelength light, it is preferable to copolymerize with a compound such as a benzene nucleus that does not have a molecular skeleton having a large light absorption in a short-wavelength region, specifically, a wavelength of 193 nm.
It is desired that the absorbance of the polymer with respect to the light of 4 μm / μm or less, more preferably 2 or less. However, when the photosensitive composition of the present invention is used as an upper layer resist on a substrate having an intermediate layer, the absorbance is 8 μm / μm.
It may be large to the extent.

The average molecular weight of the polymer according to the present invention is preferably set in the range of 1,000 to 500,000, more preferably 3,000 to 50,000. If the average molecular weight of the high molecular weight polymer is 1,0
If it is less than 00, it is disadvantageous in forming a resist film having sufficient mechanical strength. Conversely, if the average molecular weight of the polymer exceeds 500,000, a resist pattern having good resolution is formed. This is because it becomes difficult. These compounds are usually mixtures of the compounds of the invention with other copolymers of various molecular weight components.

The high molecular weight polymer according to the present invention is effective even at a relatively low molecular weight.
A large localization at an average molecular weight of 00 is also desirable because it suppresses non-uniform dissolution. Further, in this case, even if many monomers remain in the resin, the resin hardly deteriorates in dissolution characteristics and dry etching resistance.

As the photoacid generator used in the photosensitive composition of the present invention, for example, arylonium salts, naphthoquinonediazide compounds, diazonium salts, sulfonate compounds, sulfonium compounds, sulfamide compounds, iodonium compounds, sulfonyldiazomethane compounds and the like are used. be able to. Specific examples of these compounds include triphenylsulfonium triflate, diphenyliodonium triflate, 2,3,4,4'-tetrahydroxybenzophenone-4-naphthoquinonediazidosulfonate, 4-N-phenylamino-2 -Methoxyphenyldiazonium sulfate, 4-N-phenylamino-2-methoxyphenyldiazonium p-
Ethyl phenyl sulfate, 4-N-phenylamino-2-methoxyphenyldiazonium 2-naphthyl sulfate, 4-N-phenylamino-2-methoxyphenyldiazonium phenyl sulfate, 2,5-diethoxy-4-N-4 '-Methoxyphenylcarbonylphenyldiazonium 3-carboxy-4-hydroxyphenyl sulfate, 2-methoxy-4-N-phenylphenyldiazonium 3-carboxy-4-hydroxyphenyl sulfate, diphenylsulfonylmethane, diphenylsulfonyldiazomethane, diphenyldisulfone , Α-methylbenzoin tosylate, pyrogallol trimesylate, benzoin tosylate, MPI-103 manufactured by Midori Kagaku (CAS. NO. [87709-
41-9]), Midori Kagaku BDS-105 (CAS.
NO. [145612-66-4]), Midori Chemical N
DS-103 (CAS. NO. [110098-97-
0]), Midori Kagaku MDS-203 (CAS. NO.
[127855-15-5]), Midori Kagaku Pyrogall
ol tritosylate (CAS. NO. [20032-64-
8]), Midori Kagaku DTS-102 (CAS. NO.
[75482-18-7]), Midori Kagaku DTS-1
03 (CAS. NO. [71449-78-0]), MDS-103 manufactured by Midori Kagaku (CAS. NO. [1272]).
79-74-7]), MDS-105 (C
AS. NO. [116808-67-4]), MDS-205 manufactured by Midori Kagaku (CAS. NO. [81416-3]).
7-7]), Midori Kagaku BMS-105 (CAS.N
O. [149934-68-9]), TM manufactured by Midori Kagaku
S-105 (CAS. NO. [127820-38-
6]), Midori Kagaku NB-101 (CAS. NO.
[20444-09-1]), Midori Kagaku NB-20
1 (CAS. NO. [4450-68-4]), and Midori Kagaku's DNB-101 (CAS. NO. [114719]).
-51-6]), Midori Kagaku's DNB-102 (CA
S. NO. [131509-55-2]) and Midori Kagaku's DNB-103 (CAS. NO. [132828-8-3]).
5-2]), Midori Kagaku's DNB-104 (CAS.N
O. [132898-36-3]), Midori Chemical DN
B-105 (CAS. NO. [132828-37-
4]), Midori Kagaku DAM-101 (CAS. NO.
[1886-74-4]), DAM-10 manufactured by Midori Kagaku
2 (CAS. NO. [28343-24-0]) and DAM-103 manufactured by Midori Kagaku (CAS. NO. [14159]).
-45-6]), Midori Kagaku DAM-104 (CA
S. NO. [130290-80-1], CAS. N
O. [130290-82-3]), Midori Chemical DA
M-201 (CAS. NO. [28322-50-
1]), Midori Kagaku CMS-105, Midori Kagaku D
AM-301 (CAS No. [138529-81-
4]), Midori Kagaku SI-105 (CAS No.
[34694-40-7]), Midori Kagaku NDI-1
05 (CAS.No. [133710-62-
0]), EPI-105 manufactured by Midori Kagaku (CAS No.
[135133-12-9]) and the like. Further, the following compounds can also be used.

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image (Wherein C1 and C2 form a single bond or a double bond, R10 is a hydrogen atom, a fluorine atom, an alkyl group or an aryl group optionally substituted by a fluorine atom, R1,
R2 may be the same or different, and each represents a monovalent organic group, and R1 and R2 may combine with each other to form a ring structure. )

[0044]

Embedded image In the formula, Z represents an alkyl group.

[0045]

Embedded image

Regarding the above-described photoacid generator, conjugated polycyclic aromatic compounds such as arylonium salts having a naphthalene skeleton or dibenzothiophene skeleton, sulfonate compounds, sulfonyl compounds, and sulfamide compounds are transparent to short-wavelength light. This is advantageous in terms of heat resistance and heat resistance. Specifically, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, a biphenylene ring, an as-indacene ring, an s-indacene ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring in which a hydroxyl group is introduced, Anthracene ring, fluoranthene ring, acephenanthrylene ring, aceanthrylene ring, triphenylene ring, pyrene ring, chrysene ring, naphthacene ring, preyaden ring, picene ring, perylene ring, pentaphene ring, pentacene ring, tetraphenylene ring, hexaphene Ring, hexacene ring, rubicene ring, coronene ring,
Trinaphthylene ring, heptaphen ring, heptacene ring, pyranthrene ring, ovalene ring, dibenzophenanthrene ring, benz [a] anthracene ring, dibenzo [a, j]
Anthracene ring, indeno [1,2-a] indene ring,
Anthra [2,1-a] naphthacene ring, 1H-benzo [a] cyclopent [j] sulfonyl or sulfonate compound having anthracene ring; naphthalene ring,
Pentalene ring, indene ring, azulene ring, heptalene ring, biphenylene ring, as-indacene ring, s-indacene ring, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, anthracene ring, fluoranthene ring, acephenanthrylene ring, ASEAN Tolylene ring,
Triphenylene ring, pyrene ring, chrysene ring, naphthacene ring, pleiaden ring, picene ring, perylene ring, pentaphene ring, pentacene ring, tetraphenylene ring, hexaphene ring, hexacene ring, rubicene ring, coronene ring, trinaphthylene ring, heptafen ring, Heptacene ring, pyranthrene ring, ovalene ring, dibenzophenanthrene ring, benz [a] anthracene ring, dibenzo [a, j] anthracene ring, indeno [1,2-a] indene ring, anthra [2,1-a] naphthacene ring 4-quinonediazide compound having 1H-benzo [a] cyclopent [j] anthracene ring; naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, biphenylene ring, as
-An indacene ring, an s-indacene ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring,
Anthracene ring, fluoranthene ring, acephenanthrylene ring, aceanthrylene ring, triphenylene ring, pyrene ring, chrysene ring, naphthacene ring, preyaden ring, picene ring, perylene ring, pentaphene ring, pentacene ring,
Tetraphenylene ring, hexaphene ring, hexacene ring,
Rubicene ring, coronene ring, trinaphthylene ring, heptaphen ring, heptacene ring, pyranthrene ring, ovalene ring,
Dibenzophenanthrene ring, benz [a] anthracene ring, dibenzo [a, j] anthracene ring, indeno [1,2-a] indene ring, anthra [2,1-a] naphthacene ring, 1H-benzo [a] cyclopent [ j] Salts of anthracene with sulfonium or iodonium triflate having a side chain, and the like. In particular, a sulfonyl sulfamide or a sulfonate compound having a naphthalene ring or an anthracene ring; a 4-quinonediazide compound having a naphthalene ring or an anthracene ring in which a hydroxyl group is introduced; a sulfonium or iodonium triflate having a naphthalene ring or an anthracene ring in a side chain And the like.

Among such photoacid generators, in the present invention, triphenylsulfonium triflate, diphenyliodonium triflate, trinaphthylsulfonium triflate, dinaphthyliodonium triflate, dinaphthylsulfonylmethane, green Chemical NA
T-105 (CAS No. [137867-61-
9]), Midori Kagaku NAT-103 (CAS No.
[131582-00-8]), Midori Kagaku NAI-
105 (CAS. No. [85342-62-7]),
TAZ-106 manufactured by Midori Kagaku (CAS No. [694]
32-40-2]), Midori Kagaku NDS-105, Midori Kagaku PI-105 (CAS No. [41580]
-58-9]), s-alkylated dibenzothiophene triflate, s-fluoroalkylated dibenzothiophene triflate (manufactured by Daikin) and the like are preferably used. Among these, triphenylsulfonium triflate, trinaphthylsulfonium triflate,
Dinaphthyl iodonium triflate, dinaphthylsulfonylmethane, Midori Chemical's NAT-105 (CA
S. No. [137867-61-9]), Midori Kagaku NDI-105 (CAS No. [133710-6]
2-0]), Midori Kagaku NAI-105 (CAS.N
o. [85342-62-7]) and the like are particularly preferable.

The photoacid generator is diffused by baking after exposure to cause a elimination / decomposition reaction of the polymer. The photoacid generators can be used alone or as a mixture. The amount of the photoacid generator is 0.01 to 10% by weight, preferably 0.3 to 5% by weight, based on the resin. If it is less than 0.01% by weight, the sensitivity is lowered and the developability is also deteriorated. Meanwhile, 1
If the content is more than 0% by weight, the transparency may be reduced, and the control of diffusion may be difficult, and it may be difficult to obtain a desired pattern. Further, in order to control the diffusion by the photoacid generator and reduce the roughness of the resist pattern, a nitrogen-containing basic compound such as triethylamine and 1-naphthylamine, salts thereof or other Lewis base additives may be added. .

The photosensitive composition of the present invention can form a resist pattern by acid decomposition even when used alone. However, a compound having an acid-decomposable group having an ability to inhibit dissolution in an alkaline solution introduced for higher sensitivity. May be added as a dissolution inhibitor. The dissolution inhibitor used in the present invention has a sufficient dissolution inhibiting ability in an alkaline solution, and the product after decomposition with an acid is-(C = O) OH, -S (= O) _{2 in an} alkaline solution. OH or -OH
The compound which has an acid-decomposable group which can produce | generate is illustrated. Such compounds include, for example, bisphenol A, bisphenol F, tri (hydroxyphenyl) methane, phenolphthalein, cresolphthalein, thymolphthalein, catechol, pyrogallol, naphthol, bisnaphthol A, bisnaphthol F, and benzoic acid derivatives such as benzoic acid derivatives. It can be obtained by introducing an acid-decomposable group into low molecular weight aliphatic alcohols such as molecular aromatic compounds, cholates, steroids, terpenoid derivatives, and saccharides.

Specifically, the phenolic compound is converted to t-butoxycarbonyl ether, tetrahydropyranyl ether, 3-bromotetrahydropyranyl ether, 1-
Methoxycyclohexyl ether, 4-methoxytetrahydropyranyl ether, 1,4-dioxan-2-yl ether, tetrahydrofuranyl ether, 2,3
3a, 4,5,6,7,7a-octahydro-7,8,
8-trimethyl-4,7-methanobenzofuran-2-yl ether, t-butyl ether, trimethylsilyl ether, triethylsilyl ether, triisopropylsilyl ether, dimethylisopropylsilyl ether, diethylisopropylsilyl ether, dimethylsexylsilyl ether, t- Compounds modified with butyldimethylsilyl ether and the like, Meldrum's acid derivatives and the like can be mentioned. Among these, a compound in which the hydroxyl group of a phenolic compound is protected with a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group, a trimethylsilyl group, a t-butyldimethylsilyl group, a tetrahydropyranyl group, or the like; meldrum acid in naphthalaldehyde Compounds obtained by addition; compounds obtained by adding Meldrum's acid to a carbonyl compound having an alicyclic structure are preferred.

Further, the dissolution inhibitor used in the photosensitive composition of the present invention includes isopropyl ester, tetrahydropyranyl ester, tetrahydrofuranyl ester, methoxyethoxymethyl ester, 2-methoxycarboxylic acid ester of polycarboxylic acid.
Trimethylsilylethoxymethyl ester, t-butyl ester, trimethylsilyl ester, triethylsilyl ester, t-butyldimethylsilyl ester, isopropyldimethylsilyl ester, di-t-butylmethylsilyl ester, oxazole, 2-alkyl-1,
3-oxazoline, 4-alkyl-5-oxo-1,3
-Oxazoline, 5-alkyl-4-oxo-1,3-
Dioxolan or the like may be used. Further, the following compounds can also be used.

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

Among such dissolution inhibitors, ditert
-Butyl 2-((1-adamantyl) carbonylmethyl) malonate and the like are particularly preferred. In the photosensitive composition of the present invention, the amount of the dissolution inhibitor is preferably set in the range of 3 to 60% by weight, more preferably 10 to 40% by weight, based on the weight of the polymer. If the amount of the dissolution inhibitor is less than 3% by weight, it becomes difficult to form a resist pattern having good resolution.
If the amount exceeds 10% by weight, the mechanical strength and the like of the resist film may be impaired when the resist film is formed, and the dissolution rate when dissolving and removing the resist film in the exposed portion with an alkaline solution tends to be greatly reduced. Because.

Examples of the solvent for the photosensitive composition of the present invention include ketone solvents such as cyclohexanone, acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolve solvents such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate; Ester solvents such as ethyl acetate, butyl acetate, isoamyl acetate and γ-butyrolactone; glycol solvents such as propylene glycol monomethyl ether acetate; nitrogen-containing solvents such as dimethyl sulfoxide, hexamethylphosphoric triamide dimethylformamide and N-methylpyrrolidone It is possible to use a solvent or a mixed solvent to which dimethyl sulfoxide, dimethylformaldehyde, N-methylpyrrolidinone, etc. are added to improve the solubility. That. Also, propionic acid derivatives such as methyl methyl propionate, lactic acid esters such as ethyl lactate, PGMEA (propylene glycol monoethyl acetate), and the like have low toxicity and can be preferably used.
In the present invention, such solvents can be used alone or in combination of two or more. Further, isopropyl alcohol, ethyl alcohol, methyl alcohol, butyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl An aliphatic alcohol such as alcohol or isobutyl alcohol, or an aromatic solvent such as toluene or xylene may be contained.

Next, a method for manufacturing a semiconductor device using the photosensitive composition of the present invention and a method for forming a pattern will be described. First, after a solution of the photosensitive composition dissolved in the organic solvent as described above is applied on a predetermined substrate by a spin coating method, a dipping method, or the like, 150 ° C. or lower, preferably 70 to
After drying at 120 ° C., a resist film is formed. In addition, as a substrate here, for example, a silicon wafer, a silicon wafer having various insulating films, electrodes, wirings, etc. formed on a surface thereof,
III for blank mask, GaAs, AlGaAs, etc.
Group V compound semiconductor wafer, chromium or chromium oxide deposition mask, aluminum deposition substrate, BPSG coated substrate, PS
G coated substrate, BSG coated substrate, SOG coated substrate,
A carbon film sputtered substrate or the like can be used.

After film formation, the resist film is exposed by irradiating it with actinic radiation through a predetermined mask pattern or by directly scanning the resist film surface with actinic radiation. As described above, the photosensitive composition of the present invention has excellent transparency with respect to light in a wide wavelength range including short-wavelength light. Water source lamp light i
Using the line, h-line, g-line, a xenon lamp light, deep UV light or synchrotron orbital Raj instantiation of excimer laser light or the like of the KrF or ArF or F ₂ (SOR), electron beam (EB), gamma rays, an ion beam It is possible. After exposure, baking is performed at 200 ° C. or lower, preferably 70 to 160 ° C., in order to diffuse the acid released from the photoacid generator and cause a desorption / decomposition reaction.

Next, the resist film is developed by an immersion method, a spray method, or the like, and the exposed or unexposed portion of the resist film is selectively dissolved and removed in an alkaline solution to form a desired pattern. At this time, as a specific example of the alkaline solution,
Examples thereof include an aqueous solution of an organic alkali such as an aqueous solution of tetramethylammonium hydroxide and choline, an aqueous solution of an inorganic alkali such as potassium hydroxide and sodium hydroxide, and a solution obtained by adding an alcohol or a surfactant to these. Here, the concentration of the alkaline solution is preferably 15 wt% or less, more preferably 5 wt% or less, from the viewpoint of making the difference in dissolution rate between the exposed part and the unexposed part sufficient.

The resist pattern formed by using the alkaline developing resist of the present invention has an extremely good resolution. For example, a quarter-micron pattern is formed on an exposed substrate by dry etching using this resist pattern as an etching mask. The following ultra-fine patterns can be faithfully transferred. It should be noted that other steps other than the above-described steps may be added without any problem, for example, a flattening layer forming step as a base of the resist film, a pretreatment step for improving adhesion between the resist film and the base, After the development of the resist film, a rinsing step of removing the developing solution with water or the like and a step of re-irradiating ultraviolet rays before dry etching can be appropriately performed.

[0065]

The present invention will be described in more detail with reference to Synthesis Examples and Examples. (Synthesis Example 1) 6.0 g of 2- (3-carboxy-1-adamantyl) -2-propyl acrylate was mixed with 20 g of tetrahydrofuran (THF). Subsequently, 0.20 g of azoisobutylnitrile (AIBN) was added, and the mixture was heated at 60 ° C. with stirring for 35 hours, the reaction solution was dropped into n-hexane, and the precipitate was filtered and dried to obtain the following chemical formula. A copolymer having the indicated weight average molecular weight (in terms of styrene) of about 5,000 was obtained.

[0066]

Embedded image

(Synthesis Example 2) 2- (3,7-dimethyl-4)
-Adamantanone-1-yl) -2-propyl acrylate and 3- (3-hydroxy-1-adamantyl)-
20 g of tetrahydrofuran (THF) in total of 6.0 g of 3-pentyl acrylate at 50 mol% each.
Was mixed. Subsequently, azoisobutylnitrile (AIB
N) was added thereto, and the mixture was heated at 60 ° C. with stirring for 35 hours. The reaction solution was added dropwise to n-hexane, and the precipitate was filtered and dried to obtain a weight average molecular weight (styrene) represented by the following chemical formula. About 5,500 copolymers were obtained.

[0068]

Embedded image

Synthesis Example 3 1- (3-hydroxy-1-)
(Adamantyl) -1-propyl acrylate, t-butyl acrylate, and methacrylic acid each in an amount of 65 mol.
%, 25 mol%, and 10 mol%, a total of 6.0 g, were mixed with 20 g of tetrahydrofuran (THF). Subsequently, 0.36 g of azoisobutylnitrile (AIBN) was added, and the mixture was heated at 60 ° C. with stirring for 35 hours, and the reaction solution was n-
The solution was dropped into hexane, and the precipitate was filtered and dried to obtain a weight average molecular weight (styrene equivalent) of about 8,
000 copolymers were obtained.

[0070]

Embedded image

Synthesis Example 4 3- (3-hydroxy-1-)
Adamantyl) -3-pentyl acrylate and 4,
6,6-Trimethyl-2-oxepanone-4-yl acrylate was mixed with 20 g of tetrahydrofuran (THF) in a total of 6.0 g, 80 mol% and 20 mol%, respectively. Subsequently, 0.20 g of azoisobutylnitrile (AIBN) was added, and the mixture was heated at 60 ° C. with stirring for 35 hours, the reaction solution was dropped into n-hexane, and the precipitate was filtered and dried to obtain the following chemical formula. A copolymer having the following weight average molecular weight (styrene equivalent) of about 7,000 was obtained.

[0072]

Embedded image

(Synthesis Example 5) 2- (3-hydroxy-1-)
Adamantyl) -2-propyl acrylate, 5-acryloyloxy-2-adamantanone, and methacrylic acid at 60 mol%, 30 mol%, and 10 mol, respectively.
%, A total of 6.0 g, and 20 g of tetrahydrofuran (THF)
Was mixed. Subsequently, azoisobutylnitrile (AIB
N) was added thereto, and the mixture was heated at 60 ° C. with stirring for 35 hours. The reaction solution was added dropwise to n-hexane, and the precipitate was filtered and dried to obtain a weight average molecular weight (styrene equivalent) represented by the following chemical formula. ) About 7,000 copolymers were obtained.

[0074]

Embedded image

Synthesis Example 6 2- (3-hydroxy-1-)
(Adamantyl) -2-propyl acrylate, 2-vinylnaphthalene, 70 mol of methacrylic acid each
%, 20 mol%, and 10 mol%, a total of 6.0 g, were mixed with 20 g of tetrahydrofuran (THF). Subsequently, 0.18 g of azoisobutylnitrile (AIBN) was added, and the mixture was heated at 60 ° C. with stirring for 35 hours, and the reaction solution was n-
By dripping into hexane, and filtering and drying the precipitate, the weight average molecular weight (styrene conversion) of about 7,
000 copolymers were obtained.

[0076]

Embedded image

Synthesis Example 7 2- (3-hydroxy-1-)
(Adamantyl) -2-propyl acrylate and maleic anhydride were mixed at 50 mol% and 50 mol%, respectively, in a total of 6.0 g, in 20 g of tetrahydrofuran (THF). Subsequently, 0.18 g of azoisobutylnitrile (AIBN) was added, and the mixture was heated for 24 hours while stirring at 75 ° C., and the reaction solution was poured into methanol. After the copolymer was once coagulated, it was dissolved again in THF. The solution was dropped into n-hexane, and the precipitate was filtered and dried to obtain a copolymer having a weight average molecular weight (styrene equivalent) of about 4,000 represented by the following chemical formula.

[0078]

Embedded image

Synthesis Example 8 2- (3,3-dimethyl-3)
-Hydroxy-1-adamantyl) -2-propyl methacrylate and tetrahydropyranyl methacrylate were mixed in a total of 6.0 g of 70 mol% and 30 mol%, respectively, in 20 g of tetrahydrofuran (THF). Subsequently, 0.18 g of azoisobutylnitrile (AIBN) was added, and the mixture was heated at 60 ° C. with stirring for 35 hours, and the reaction solution was n-
By dropping into hexane, and filtering and drying the precipitate, a weight average molecular weight (styrene conversion) of about 6, represented by the following chemical formula:
000 copolymers were obtained.

[0080]

Embedded image

Synthesis Example 9 2- (3-tetrahydropyranyloxycarbonyl-1-adamantyl) -2-propyl acrylate, 1-methacryloyloxy-3-
Each of hydroxyadamantane was 60 mol%, 40 mol%
mol%, a total of 6.0 g in tetrahydrofuran (THF)
20 g. Subsequently, 0.18 g of azoisobutylnitrile (AIBN) was added, and the mixture was heated at 60 ° C. with stirring for 35 hours, the reaction solution was added dropwise to n-hexane, and the precipitate was filtered and dried to obtain the following chemical formula. A copolymer having the indicated weight average molecular weight (in terms of styrene) of about 6,000 was obtained.

[0082]

Embedded image

(Synthesis Example 10) Carboxytricyclododecyl acrylate and ethoxyethoxycarbonyltricyclododecyl metachlorate were each 70 mol%,
30 mol%, a total of 6.0 g, in tetrahydrofuran (TH
F) 20 g. Subsequently, 0.18 g of azoisobutylnitrile (AIBN) was added, and the mixture was heated at 60 ° C. with stirring for 35 hours, and the reaction solution was added dropwise to n-hexane.
The precipitate was filtered and dried to obtain a copolymer having a weight average molecular weight (in terms of styrene) of about 15,000 represented by the following chemical formula.

[0084]

Embedded image

(Synthesis Example 11) 2-adamantyl-2-propyl methacrylate and mevalonic lactone methacrylate were mixed at 50 mol% and 50 mol%, respectively, in a total of 6.0 g, in 20 g of tetrahydrofuran (THF). Subsequently, 0.18 g of azoisobutylnitrile (AIBN) was added, and the mixture was heated at 60 ° C. with stirring for 35 hours, the reaction solution was added dropwise to n-hexane, and the precipitate was filtered and dried to obtain the following chemical formula. A copolymer having the indicated weight average molecular weight (styrene equivalent) of about 11,000 was obtained.

[0086]

Embedded image

Example 1 To the polymer obtained in Synthesis Example 1, triphenylsulfonium triflate was added
wt.% was added to make the composition into a 10 wt.% ethyl lactate solution. The solution was filtered through a 0.2 μm membrane filter on a hexamethyldisilazane-treated Si wafer, and then applied by spin coating.
Pre-bake for 0 second to a thickness of 0.2 μm.
Exposure was performed with an F excimer laser (NA = 0.55). After the exposure, the wafer was baked at 110 ° C. for 60 seconds, and then developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds.
With a DOSE amount of mJ / cm2, L / S of 0.25 μm could be resolved. When observed with an optical microscope, no pattern peeling or the like was observed from the substrate, and the adhesion to the substrate was good.
In addition, there was no residual scum called resist which was easily formed during development.

(Examples 2 to 9 and Comparative Example)
9 and the polymers obtained in Synthesis Examples 10 and 11 were each added with triphenylsulfonium triflate in one of the polymers.
Each composition was dissolved in an appropriate solvent by adding wt%, and pattern formation was attempted in the same steps as in Example 1. The results are shown in Table 1 below.

[0089]

[Table 1]

As described above, the photosensitive composition of the present invention was superior to Comparative Example 1 in sensitivity and developability. The resist of Comparative Example 2 had poor adhesion to the substrate, and a fine pattern could not be formed unless a step of drawing a base film was performed. In addition, scum remained during pattern formation after development as in Comparative Example 1, and the photosensitive composition of the present invention was also excellent in this respect.

Semiconductor Device Manufacturing Example 1 A method for manufacturing a semiconductor device using the photosensitive composition of the present invention and a pattern forming method will now be described with reference to the drawings.

FIG. 1 is a sectional view showing an example of a process for manufacturing a semiconductor chip using the photosensitive composition of the present invention. First,
As shown in FIG. 1A, a silicon oxide film having a thickness of about 0.8 μm is
A resist film 3 containing the photosensitive composition of Example 1 was formed thereon to a thickness of about 0.3 μm by the VD method.

The resist film 3 was patterned by the above-described method to form a hole pattern having a diameter of 0.3 μm, and the obtained resist pattern 3A was heated at 130 ° C. for 30 minutes in a nitrogen atmosphere. Using the resist pattern 3A as an etching mask, the silicon oxide film 2 to be etched was selectively etched by RIE using CF ₄ gas to transfer the pattern as shown in FIG. 1B.

Finally, the resist pattern 3A was carbonized and removed in O2 plasma to obtain a silicon oxide film 2 having fine openings 6 as shown in FIG. The diameter of the opening 6 formed in the silicon oxide film 2 was 0.32 μm, and the variation in the film thickness was suppressed to 2% or less.

Semiconductor Device Manufacturing Example 2 As shown in FIG.
An 8 μm silicon oxide film 2 was formed by a CVD method. In the semiconductor substrate 1, for example, a MOSFET, a diode, and other elements (not shown) are formed.
Then, a lower layer wiring 10 made of Al-Si-Cu and having a thickness of about 0.3 μm and an interlayer insulating film 7 made of SiO _{2 having} a thickness of 0.5 μm are formed thereon.
The upper wiring layer 11 of Cu having a thickness of about 0.3 μm was formed. At this time, a step of about 0.2 μm was formed in the upper wiring layer. Further, a resist film 3 containing a photosensitive composition is formed to a thickness of 0.3 μm on the upper wiring 11 in the same manner as in the semiconductor device manufacturing example 1.
Was formed on the substrate.

This resist film is patterned in the same manner as in Semiconductor Manufacturing Example 1 to form a resist pattern, and the upper wiring layer 11 is etched and removed by RIE using a chlorine-based gas such as CCl 4 as an etching mask. As a result, an upper wiring 11A was obtained as shown in FIG.

Finally, the resist pattern 3A was carbonized and removed in O ₂ plasma to obtain a two-layer wiring as shown in FIG. 2 (c). Semiconductor Device Manufacturing Example 3 FIG. 3 is a process sectional view showing an example in which the present invention is applied to formation of an Au wiring.

First, as shown in FIG. 3A, a 0.8 μm thick silicon oxide film 2 was formed on a semiconductor substrate 1 by a CVD method. In the semiconductor substrate 1, for example, MO
SFETs, diodes, and other elements (not shown) are formed. Then, on this silicon oxide film 2, titanium-containing tungsten (Ti-
W) A film 12 and a gold (Au) film 13 having a thickness of about 0.1 μm were sequentially formed by a sputtering method. Further, a resist film containing the same photosensitive composition as in Semiconductor Production Example 1 was formed to a thickness of about 0.3 μm.
It was formed on the Au film with a thickness of m.

This resist film 3 is patterned by the same method as in the semiconductor device manufacturing example 1 to form a resist pattern 3A as shown in FIG.
A groove was provided. Ti-W film 1 exposed at the bottom of the obtained groove
Using the Au film 2 and the Au film 13 as electrodes, an Au plating film 14 having a thickness of 1 μm was formed in the groove by electrolytic plating.

Subsequently, the Au plating film 14 was projected on the Au film 13 by carbonizing and removing the resist pattern 3A in O2 plasma as shown in FIG. 3 (c). Finally, Au exposed by ion milling
After removing the film 13, the exposed Ti—W film 13 was removed using a fluorine-based gas, thereby forming an Au wiring 20 as shown in FIG. 3D.

[0101]

As described in detail above, the photosensitive composition according to the present invention has low absorption to a short wavelength light source such as an ArF excimer laser and an electron beam, and has high resolution and dry etching resistance. Have. The photosensitive composition according to the present invention has, in addition to these features, excellent adhesiveness to a substrate. According to the method for manufacturing a semiconductor device of the present invention using such a photosensitive composition, ultrafine processing on the order of less than sub-quarter micron is possible. Further, according to the pattern forming method of the present invention, an ultrafine pattern on the order of less than sub-quarter micron can be formed with a good rectangular cross section.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a manufacturing process of a semiconductor device using the present invention.

FIG. 2 is a cross-sectional view showing another example of a manufacturing process of a semiconductor device using the present invention.

FIG. 3 is a cross-sectional view illustrating another example of a manufacturing process of a semiconductor device using the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate 2 ... Silicon oxide film 3 ... Resist film 3A ... Resist pattern 6 ... Opening 7 ... Interlayer insulating film 10 ... Lower wiring 11 ... Upper wiring Layer 11A ... Upper layer wiring 12 ... Ti-W film 13 ... Au film 14 ... Au plating film 20 ... Au wiring

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor, Naomi Shinda 1st, Komukai Toshiba-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Prefecture Inside of Toshiba R & D Center Co., Ltd. No. 1 Toshiba Town F-term in Toshiba R & D Center (reference) 2H025 AA00 AA02 AA03 AA09 AA14 AB16 AB17 AC06 AC08 AD03 BE00 BE10 BG00 FA01 FA03 FA12 FA17 FA41 2H096 AA25 AA27 BA20 DA01 EA05 EA06 FA01 GA01 RA03 JA03 RA12 SA79 SA80 SA83 SA84 SA86 SA87 TA07 TA08 UA01 UA03 UA04 UA05 VA01 WA01

Claims (8)

[Claims] 1. A polymer obtained by homopolymerizing at least one monomer selected from the monomers represented by the general formulas (1) and (2) or copolymerizing it with another vinyl monomer. When,
Forming a film containing a photosensitive composition comprising at least a photoacid generator on a film to be etched on a substrate, performing pattern exposure on a predetermined region of the photosensitive composition-containing film, Heat-treating the photosensitive composition-containing film, and developing the photosensitive composition-containing film after the heat treatment with an aqueous alkali solution, and selectively dissolving and removing the photosensitive composition-containing film to be patterned. A method of manufacturing a semiconductor device, comprising: a step of forming a photomask; and a step of etching a film to be etched by a dry etching method using the photomask as a mask. Embedded image (Where R is an acryloyl or methacryloyl group,
R ₁₁ and R ₁₂ are a hydrogen atom or a monovalent alkyl group, R ₁₃ is an OH group, an OR ₁₄ group (R ₁₄ is a monovalent organic group), COOR ₁₄
Group, ＝ O group, and at least one group selected from the group consisting of COOH groups) 2. The method according to claim 1, wherein R _{13 of the} high molecular polymer is an ＯO group. 3. At least one of R ₁₁ and R ₁₂ of the polymer is at least one group selected from the group consisting of C ₂ H ₅ , C ₃ H ₇ and C ₄ H ₉ groups. 2. The method for manufacturing a semiconductor device according to claim 1, wherein: 4. The polymer of the formula (1) or (2)
2. The method for manufacturing a semiconductor device according to claim 1, comprising 10 to 90 mol% of a monomer represented by the formula: 5. The polymer of the general formula (1) or (2)
2. The method for manufacturing a semiconductor device according to claim 1, comprising at least one monomer represented by the formula (1) and containing at least 50 mol% of a monomer having an alicyclic skeleton or a condensed polycyclic skeleton. 6. A compound represented by the general formula (3), wherein at least one monomer selected from the monomers represented by the general formulas (1) and (2)
(4) A polymer copolymer obtained by copolymerizing at least one monomer selected from monomers represented by (5), (6) and (7), and at least a photoacid generator. A photosensitive composition comprising: a photosensitive composition; Embedded image (However, R ₃₁ is a hydrogen atom or an OH group, an OR ₁₄ group (R ₁₄ is a monovalent organic group), at least one group selected from the group consisting of an ＯO group, and R ₃₂ is a hydrogen atom or a monovalent group. An organic group, R ₄₁ represents a vinyl, acryloyl or methacryloyl group.) 7. The polymer according to claim 6, wherein the high molecular weight polymer contains 5 to 50 mol% of the monomer represented by the general formula (7).
The photosensitive composition as described in the above. 8. A step of forming a film containing the photosensitive composition according to claim 4 on a substrate, a step of subjecting a predetermined region of the photosensitive composition-containing film to pattern exposure, and a step of: A step of heating the photosensitive composition-containing film, and a step of developing the photosensitive composition-containing film after the heat treatment to selectively dissolve and remove the photosensitive composition-containing film. Pattern forming method.