JPH02294649A - Chemical ray sensitive polymer composition - Google Patents

Abstract

PURPOSE:To obviate the generation of a film roughening without lowering a residual film rate by consisting the above compsn. of a specific polymer, a compd. contg. a quaternarized salt, an arom. azide compd. and/or arom. sulfonazide compd., and N-allyl glycine compd. CONSTITUTION:This compsn. consists of the polymer essentially consisting of the structural unit expressed by formula I, the compd. contg. the unsatd. bond which can be dimerized or polymerized by chemical rays and an amino group or the quaternarized salt thereof, the arom. azide compd. and/or arom. sulfonazide compd. and the N-allyl glycine compd. In the formula I, R1 denotes a tervalent or quadrivalent org. group having at least>=2 carbon atoms; R2 denotes a bivalent org. group having at least>=2 carbon atoms; R3 denotes hydrogen or the paired ion of an alkaline metal; n denotes 1 or 2. The film thinning and film roughening at the time of a (g) ray stepper exposing are lessened in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an actinic radiation-sensitive polymer silk composition, and more specifically, to obtaining a high residual film rate during exposure using a G-ray stepper. The present invention relates to actinic radiation-sensitive polymer compositions capable of being used.

(Prior Art) As a photosensitive polyimide composition, a composition in which a compound containing a carbon-carbon double bond and an amino group or a quaternized salt thereof that can be dimerized or polymerized by actinic radiation is added to polyamic acid (for example, a photosensitive polyimide composition) is used. No. 59-52822) or a polyimide precursor composition in which photosensitivity is introduced into polyamic acid with an ester group (for example, USP No. 3957512, US Pat.
P4040831) is known.

However, when such conventional compositions are exposed by a stepper using the G-line of a mercury lamp currently used in the manufacture of semiconductor devices, the residual film rate decreases significantly due to the effects of long wavelength exposure and oxygen desensitization, resulting in a desired film thickness. It is difficult to obtain the desired properties, and the film has the disadvantage of causing roughness during development.

(Problems to be Solved by the Invention) An object of the present invention is to provide an actinic radiation-sensitive polymer composition that can reduce the above-mentioned drawbacks, namely, film thinning and film roughening during exposure with a G-line stepper.

(Means for solving problems) The object of the present invention is achieved by the following configuration.

(1) (a) General formula - [CO-R, -CONH-R2 -NH Co
-(C O O R3 ) n (wherein R1 is a trivalent or tetravalent organic group having at least two or more carbon atoms, R2 is a divalent organic group having at least two or more carbon atoms, R represents hydrogen or an alkali metal counter ion. n is 1 or 2. A compound [2] containing an unsaturated bond and an amino group or a quaternized salt thereof; (c) an aromatic azide compound [3] and/or an aromatic sulfonazide compound [4]; (d) N- An actinic radiation-sensitive polymer composition comprising an allyl glycine compound [5].

In the present invention, the polymer having the structural unit [1] is a polymer having the structure represented by the above general formula and having an imide ring or other cyclic structure by heating or a suitable catalyst (hereinafter referred to as a polyimide polymer). It is possible.

In the above structural unit [1], R is a trivalent or tetravalent organic group having at least two or more carbon atoms. In view of the heat resistance of the polyimide polymer, R1 preferably has a structure in which the bond to the carbonyl group of the main chain of the polymer is directly formed from an aromatic heterocycle. Therefore, as R1,
Contains an aromatic ring or aromatic heterocycle, and has 6 to 3 carbon atoms
A trivalent or tetravalent group of 0 is preferred.

Preferred specific examples of R1 include (wherein, the bond represents a bond between the carbonyl group of the main chain of the polymer, and the carbonyl group of the polymer side chain is located at the ortho position to the bond; The hands are not shown in the above structural formula), but are not limited thereto.

Further, in the bolamer having the structural unit [1], R1 may be composed of only one type among these, or may be a copolymer composed of two or more types.

Particularly desirable as R1 are the above structural units [in which R2 is a divalent organic group having at least two or more carbon atoms, but from the viewpoint of heat resistance when used as a polyimide polymer, It is preferable that the chain has a structure in which the bond to the amide group is directly formed through an aromatic ring or an aromatic heterocycle. Therefore, R2 is preferably a divalent group containing an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms.

(In the formula, the bond represents a bond with an amide group in the main chain). In addition, alkyl groups or aryl groups having 1 to 6 carbon atoms, halogen groups, cyano groups, amino groups, azide groups, carboxyl groups, sulfonamide groups, etc. may be used as long as they do not adversely affect the heat resistance of the polyimide polymer. There is no problem even if it has a nuclear substituent. As a particularly preferred example of those having these nuclear substituents, a borimer having one structural unit may be one in which R2 may be composed of only one type of these, or may be a joint composed of two or more of these. It may also be a polymer.

Furthermore, in order to improve the adhesiveness of the polyimide polymer, it is also possible to copolymerize an aliphatic group having a siloxane bond as R2 within a range that does not reduce the heat resistance. A preferred specific example is C H 3 C H. (CH2)3SiOSt
(CH2)3-CH3 CH. Examples include.

Specific examples of volima whose main components are structural unit [1] include pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 3,3-,4.4-benzophenone 1. lacarboxylic dianhydride and 4,4-diaminodiphenyl ether, 3,3-,4,4. --Biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether, pyromellitic dianhydride and 3,3'-(or 4,t")
) diaminodiphenylsulfone, pyromellitic dianhydride and 3,3-,. L4'-benzophenonetetracarboxylic dianhydride and 3,3'-(or 4,4')diaminodiphenylsulfone, 3,3',4.4-benzophenonetetracarboxylic dianhydride and 3 , 3'-(or 1,4') diaminodiphenylsulfone, 3,3-,4.4"-biphenyltetracarboxylic dianhydride and 3,3'-(or 4,4") diaminodiphenylsulfone , pyromellitic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3-,4.4-benzophenonetetracarboxylic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3 ".4.4-Biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3",4,. 4=-benzophenonetetracarboxylic dianhydride and paraphenylene diamine, 3, 3-. 4.
4--Biphenyltetracarboxylic dianhydride and paraphenylenediamine, pyromellitic dianhydride and 3,3
”,4.4゛-benzophenonetetracarboxylic dianhydride and veraf 22 diamine, pyromellitic dianhydride and 3,4.4゛-benzophenonetetracarboxylic dianhydride and paraphenyl dianhydride Diamine, 3,3=,4.4=-diphenyl ether tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether, 3,3-,4.4'-diphenyl ether tetracarboxylic dianhydride Preferably used are polyamic acids synthesized from anhydride and paraphenylene diamine, pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, bis(3-aminopropyl)tetramethyldisiloxane, and the like.

For a polymer having one structural unit, l'l'ff
It may consist only of JA unit [1], or
It may also be a copolymer or blend with other structural units. The type and amount of structural units used in the copolymerization are desirably selected within a range that does not significantly impair the heat resistance of the polyimide polymer obtained by the final heat treatment.

In the present invention, unsaturated bonds and amino groups that can be dimerized or polymerized by actinic radiation or their . As the compound [2] containing a primary salt, a compound containing a carbon-carbon double bond and an amino group or a quaternized amino group in one molecule is used.

As compound [2], at least one compound represented by the following general formula [A], [B] or [C] or a quaternized salt thereof is preferably used.

General formula [A] (where R1o represents hydrogen or a methyl group,
n+I=3, n=1-3).

Preferred specific examples include CH3/ゝR8 (where R4 is hydrogen or a phenyl group, R is hydrogen or a lower alkyl group having 1 to 6 carbon atoms, and R6 is a substituted or unsubstituted carbon having 2 to 12 carbon atoms). hydrogen group, R7 and R8 each represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms), \C H3 \ CH2 CH,, \C H3 (R 9 represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms) 6) and the general formula [C] CH2 = CH-CH2 NH2, (CH2 = CH-CH2 -> -2NH, etc., but are not limited to these.

From the viewpoint of actinic radiation sensitivity, amino compounds having an acrylic or methacrylic group as an unsaturated group are particularly desirable.

In the case of a compound in which the amino group is not quaternized, it is desirable to combine the structural unit [1] with R3 being hydrogen. In the case of a compound in which the amino group is quaternized, it is desirable that R3 of the structural unit [1] be combined with an alkali metal ion or an ammonium ion.

The amount of compound [2] is 0.05% of the total ruboxy group (or its salt) of Volima whose main component is structural unit [1].
equivalent or more, preferably 0. It is preferable that it is mixed with the polymer in a range of 3 equivalents or more and 2 equivalents or less. If it is outside this range, the photosensitivity may deteriorate or the permissible range of development conditions such as development time and temperature may become narrow, so care must be taken.

As the aromatic azide compound [3] in the present invention, a compound in which an azide group is directly bonded to an aromatic ring is used. The aromatic ring herein refers to a benzene ring, a naphthalene ring, and other fused rings. These aromatic rings are lower (
It may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a carboxyalkyl group, a nitro group, a halogen group, a carboxyl group, a carboxyester group, or a secondary or tertiary amino group. , also 10~-C
O- -SO2--CH2--CH=CH
It may be bonded to another aromatic ring which is unsubstituted or substituted with the above-mentioned substituent via a divalent group such as -CH=CH-Co-. Therefore, the number of carbon atoms is usually 6
-30, preferably 6-21.

Specifically, aromatic monoazide compounds such as U are preferably used, but are not limited thereto.

Only one type of aromatic monoazide compound [3] may be used, or two or more types may be used in combination.

The amount of aromatic monoazide [31] is based on the structural unit [
The total amount is 0.1 per the weight of the polymer whose main component is 1.
It is desirable to add % by weight or more, more preferably 0.0% by weight or more based on the weight of the polymer. It is preferable to add it in a proportion of 5% by weight or more and 30% by weight or less.

If it is outside this range, it may not have an adverse effect on the developability or stability of the composition, so it is preferable to be careful.

As the aromatic sulfonazide compound [4] in the present invention, a compound in which a sulfonazide group is directly bonded to an aromatic ring is used. The aromatic ring herein refers to a benzene ring, a naphthalene ring, or other condensed rings. These aromatic rings include lower (1 to 6 carbon atoms) alkyl groups, alkoxy groups, carboxyalkyl groups,
- May be substituted with a substituent such as an oral group, a halogen group, a carboxyl group, a carboxy ester group, a secondary or tertiary amino group, and 10- -CO-SO, -
-CI2 - -CH=CH-- -CH=C
It may be bonded to another aromatic ring which is unsubstituted or substituted with the above-mentioned substituent via a divalent group such as H--Co. Therefore, the number of carbon atoms is usually 6 to 30, preferably 6 to 21.

Specifically, aromatic monosulfone azide compounds such as CONH2 are preferably used, but are not limited thereto. Only one type of aromatic sulfonazide compound [4] may be used, or two or more types may be used in combination.

The amount of aromatic sulfonazide [4] is based on the structural unit [1
] is preferably added in a total amount of 0.1 weight % or more based on the weight of the polymer whose main component is 0.5 weight % or more and 30 weight % or less based on the weight of the polymer. is good.

If it is outside this range, it may adversely affect the developability and stability of the composition, so care must be taken.

When using compounds [3] and [4] together, [3] and [
4] is the structural unit [I. ] is preferably added in a total amount of 0.1% by weight or more, more preferably 0.5% by weight or more based on the weight of the volima, which is the main component.
It is preferable to add it in a proportion of ~30% by weight. If it is outside this range, it may adversely affect the developability and stability of the composition, so care must be taken.

N-allylglycine [5] used in the present invention is a compound in which an aromatic ring is directly bonded to the nitrogen atom of glycine, and the aromatic ring herein refers to a benzene ring, a naphthalene ring, an anthracene ring, , naphthoquinone ring, anthraquinone ring, etc., and these aromatic rings include lower (1 to 6 carbon atoms) alkyl groups, alkoxy groups, nitro groups, halogen groups, carboxyl groups, carboxyester groups, 2
It may be substituted with a substituent such as a class or tertiary amine group, and 101 groups, -CO one group, S02 one group, -
It may be bonded to another aromatic ring which is unsubstituted or substituted with the above-mentioned substituent via a divalent group such as one CH2 group or one -CH=CH group.

Specifically, N-allylglycines such as N-phenylglycine and N-naphthylglycine are preferably used, but are not limited thereto.

The amount of N-allylglycine [5] to be added is preferably at least 0.05% by weight and at most 1096% by weight based on the weight of the volima whose main component is structurally medium [1]. If it is out of this range, it may adversely affect the developability and stability of the composition, so care must be taken.

An example of the method for producing the composition of the present invention will be explained. First, a diamine compound and an acid dianhydride are reacted in a solvent to obtain a polymer containing the structural unit [1] as a main component. Next, add compounds [2] and [3] and/or [4] and [5] to this solution.
], and can be manufactured by dissolving and blending other additives as necessary. In addition, as the above-mentioned polymer, a solid polyamic acid polymer or a polymer separated and purified from the solution after the reaction may be redissolved and used.

As the solvent used in the above production method, polar solvents are preferably used from the viewpoint of solubility of the volima, and aprotic polar solvents are particularly suitable. Non-propylene polar solvents include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorotriamide, γ-
Ptyrolactone and the like are preferably used. As other additives, a sensitizer, a copolymer monomer, or an adhesion improver to the substrate may be included as long as the sensitivity and heat resistance are not significantly reduced.

In addition, when the compounding amount of compound [4] is 0.5 to 1-0% by weight, as a sensitizer, Mihira ketone, 4,4--
Bis(diethylamino)penzophenone and the like are preferably used. The actinic radiation sensitivity of the composition of the invention can be further improved by adding a sensitizer. As the copolymerizable monomer, monomaleimide, polymaleimide, or substituted products thereof are preferred.

In addition, in order to further improve photosensitivity, organic groups such as N-phenyldiethanolamine having an al]-alic hydroxyl group on the amino group and aromatic groups in which a ketonic C=0 is not directly bonded to the aromatic group are used. It is also preferred to add secondary or tertiary amino compounds.

Next, a method for using the composition of the present invention will be explained.

The compositions of the present invention can be patterned using well-known microfabrication techniques using actinic radiation.

First, the composition of the present invention is coated on a suitable support. Application methods include spin coating using a spinner, spray coating using a spinner, dipping, printing, and roll coating.
Possible methods include tinging. The coating film thickness can be adjusted by the coating means, solid content concentration, and viscosity of the composition.

Examples of the material of the support to which the composition of the present invention is applied include metals, glass, semiconductors, metal oxide insulators, and silicon nitride.

In order to improve the adhesion between the coating film of the composition of the present invention or the polyimide film after heat treatment and the support, an adhesion aid may be used as appropriate.

As adhesion aids, oxypropyl l, rimel l, xysilane, γ-glycidoxypyl [limethoxysilane,
Organosilicon compounds such as γ-aminopropyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane, or aluminum such as aluminum heptanoethyl acetoacetate diisopropylene silane and aluminum tris(acetylacetonate-1). Chelate compounds or titanium bis(acetylacenate)
Titanium chelate compounds such as are preferably used.

Next, the composition of the present invention, which has become a coating film on the support, is irradiated with actinic radiation in a desired pattern.
Examples include beams, electron beams, ultraviolet rays, visible light, etc., but ultraviolet rays and short-wavelength visible rays, that is, those in the wavelength range of 200 to 500 nm are preferred.

Next, a relief pattern is obtained by dissolving and removing the unirradiated areas with a developer. An appropriate developer is selected depending on the structure of the volima.

The developer contains N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, etc., which are the solvents of this composition. It can be used alone or as a mixture with a non-solvent of composition such as methanol, ethanol, isoprobilal]-ol, water, methyl carbitol, ethyl carbitol, toluene, xylene and the like. In many cases, ammonia water or other alkaline aqueous solutions can also be used.

Development can be carried out by spraying the above-mentioned developer onto the coated film surface, immersing it in the developer, or applying ultrasonic waves while immersing it.

It is desirable that the relief pattern formed by development is then washed with a rinsing solution.

As the rinsing agent, methanol, ethanol, isoprobil alcohol, butyl acetate, etc., which have good miscibility with the developer, are preferably used.

The relief pattern polymer obtained by the above treatment is a precursor of a heat-resistant polyimide polymer,
Heat treatment results in a heat-resistant polymer having imide rings and other cyclic structures. The heat treatment is usually carried out at a temperature in the range of 135 to 400° C. while increasing the temperature stepwise or continuously.

The actinic radiation-sensitive polymer composition of the present invention can be used for semiconductor passivation films, passivation film buffer films, interlayer insulating films for multilayer integrated circuits, interlayer insulating films and surface protection films for hybrid integrated circuits, and printed circuits. It is used to form soldering protection films, alignment films for liquid crystals, interlayer insulation films for mounting boards, etc. Furthermore, it can be used as a highly heat-resistant photoresist for metal adhesion and dry etching processes.

It can be applied to other known uses of polyimide.

[Effects of the Invention] As described above, the present invention provides a compound containing a bolymer mainly composed of the structural unit [1], an unsaturated bond that can be dimerized or polymerized by actinic radiation, and an amino group or a quaternized salt thereof [
2], an aromatic azide compound [3] and/or an aromatic sulfone azide compound [4], and N-allylglycine [
It is composed of an actinic radiation-sensitive composition consisting of
High sensitivity can be obtained by line exposure.

[Example] Next, embodiments of the present invention will be described based on Examples.

Example 1 4,4'-diaminodiphenyl sulfide 207.65
g, 9.94 g of 1.3-bis(3-aminopropyl)tetramethyldisiloxane was dissolved in 1530 g of N-methyl-2-pyrrolidone to prepare an amine solution. Add 213.76 g of pyromellitic anhydride to this amine solution,
The reaction was carried out at 50°C for 3 hours to obtain a volima solution (A) of 130 boads at 25°C. This polymer solution (A) was mixed with 370 g of ethyl aminoethyl methacrylate, and then 17.25 g of 4-azidobenzalacetophenone, N
- A solution of 17.25 g of phenylglydine dissolved in 250 g of N-methyl-2-pyrrolidone was mixed and filtered.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then heated at 90°C and 95°C using a vacuum suction tube type hot plate (Model SCW636, manufactured by Dainippon Screen Co., Ltd.).
Drying was carried out for 3 minutes each. The film thickness of this coating is 10
It became μm. Next, the coating film was set in an exposure machine (Canon Inc. 1 LA-501F), and the gray scale (
Kodak Photographic step ta
Bullet No. 2 (21 steps) and a filter (Y-43 manufactured by Toshiba Glass) for 2 minutes. The intensity of the ultraviolet rays at this time is 5 mW/am2 (436n
n+). The development was done using N-methylhyde IJF (7
Immersion development was performed using a mixed solvent of 0 parts) and xylene (30 parts) t7). Development was continued for an additional 30 seconds immediately after the unexposed areas were dissolved. It was then rinsed with isopropanol for 20 seconds and spun dry on a spinner. When the film thickness after development was measured, it was 8. It was 0 μm (film reduction amount = 2.0 μm). After this, 200℃, 350℃
The film was heat-treated at 30° C. for 30 minutes each, and the pattern was observed using an optical microscope. It showed a good pattern with no film roughening at an exposure dose of 250 mJ or more.

Example 2 192.2 g of 4,4'-diaminodiphenyl ether,
1. 9.94 g of 3-bis(3-aminopropyl)tetramethyldisiloxane was dissolved in 189 g of N-methyl 2-pyrrolidone.
0 g to prepare an amine solution. 315.1 g of penzophenone tetracarboxylic anhydride was added to this amine solution.
was added and reacted at 50°C for 3 hours to obtain a polymer solution (B) of 150 bores at 25°C. This Volima solution (I3
) was mixed with 370 g of diethylaminoethyl methacrylate, and then 8.63 g of N-phenyldiethanolamine was added to
g,4-azidobenzalacetophenone 11.25g,
17.25g of N-phenylglycine was converted into N-methyl-2-
A solution dissolved in 250 g of pyrrolidone was mixed and filtered.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 80° C. for 1 hour.

The film thickness of this coating film was 10 μm. Next, this coating film was exposed under the same conditions as in Example 1. Then, immersion development was performed using a mixed solvent of N-methylpyrrolidone (70 parts) and methanol (30 parts).

Development was continued for an additional 30 seconds immediately after the unexposed areas were dissolved. It was then rinsed with isopropanol for 20 seconds and spun dry on a spinner. When the film thickness after development was measured, it was 8.5 μm (film reduction amount: 1.5 μm
). Thereafter, the film was heat-treated at 200° C. and 350° C. for 30 minutes each, and the pattern was observed using an optical microscope. At an exposure dose of 150 mJ or more, a good pattern with no film roughness was shown.

Example 3 207.6 g of 4,4′-diaminodiphenyl sulfide
, 1.94 g of 3-bis(3-aminopropyl)tetramethyldisiloxane was added to 1 N-methyl-2-pyrrolidone.
890 g to prepare an amine solution. Add 315% of penzophenonetetracarboxylic anhydride to this amine solution.
Add 7g, react at 50°C for 3 hours, and react at 25°C for 13
A Volima solution (C) with 0 boas was obtained. This Volima solution (
C) was mixed with 370 g of diethylaminoethyl methacrylate, and then 10.0 g of N-phenyldiethanolamine was added.
3g,4-azitobenzalacetophenone 20.6gS
A solution of 20.6 g of N-phenylglycine dissolved in 300 g of N-methyl-2-pyrrolidone was mixed and filtered.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and dried in the same manner as in Example 1.

The thickness of the resulting coating film was 10 μm. Next, this coating film was exposed under the same conditions as in Example 1. The development was carried out by immersion development using a mixed solvent of N-methylpyrrolidone (70 parts) and xylene (30 parts).

Development was continued for an additional 30 seconds immediately after the unexposed areas were dissolved. It was then rinsed with isopropanol for 20 seconds and spun dry on a spinner. When the film thickness after development was measured, it was 8.5 μm (film reduction ji: 1.5
μm). Thereafter, the film was heat-treated at 200° C. and 350° C. for 30 minutes each, and the pattern was observed using an optical microscope. At an exposure dose of 200 mJ or more, a good pattern with no film roughness was shown.

Example 4 370 g of diethylaminoethyl methacrylate were mixed into the same solution (B) obtained in Example 2, followed by 8.63 g of N-phenyldiethanolamine, 8.66 g of 4-azidobenzalacetophenone. 3-sulfonylazidobenzoic acid 17.25g, N-phenylglycine 1
A solution of 7.25 g dissolved in 250 g of N-methyl-2-pyrrolidone was mixed and filtered.

The resulting solution was spin-coated onto a silicon wafer using a spinner, and then dried at 80°C for 1 hour.

The film thickness of this coating film was 10 μm. Next, after exposure under the same conditions as in Example 1, N-methylpyrrolidone (70
Immersion development was performed using a mixed solvent of 1 part) and methanol (30 parts). The development time starts immediately after the unexposed area dissolves,
Development was continued for an additional 30 seconds. It was then rinsed with isopropanol for 20 seconds and spun dry on a spinner. When the film thickness after development was measured, it was 8.7 μm (film reduction: 1.3 μm). After this, 30℃ at 200℃ and 350℃
The film was heat-treated for minutes at a time, and the pattern was observed using an optical microscope. It showed a good pattern with no film roughening at an exposure dose of 200 mJ or more.

Example 5 192.2 g of 4,4'-diaminodiphenyl ether,
1.9.94 g of 3-bis(3-aminopropyl)tetramethyldisiloxane was mixed with 189 g of N-methyl 2-pyrrolidone.
0 g to prepare an amine solution. 315.7 g of penzophenone tetracarboxylic anhydride was added to this amine solution.
was added and reacted at 50°C for 3 hours to obtain a polymer solution (A) of 150 bores at 25°C. This Volima solution (A)
was mixed with 370 g of diethylaminoethyl methacrylate, and then 8.63 g of N-phenyldiethanolamine.
A solution of 17.25 g of , 3-sulfonylazidobenzoic acid and 17.25 g of N-phenylglycine dissolved in 250 g of N-methyl-2-pyrrolidone was mixed and filtered.

Next, a coating film (10 μm) was formed and exposed under the same conditions as in Example 2, and then N-methylpyrrolidone (7 μm) was formed and exposed to light.
Immersion development was performed using a mixed solvent of 0 parts) and methanol (30 parts). Development was continued for an additional 30 seconds immediately after the unexposed areas were dissolved. It was then rinsed with isopropanol for 20 seconds and spun dry on a spinner. When the film thickness after development was measured, it was 8.0 μm (film reduction: 2.0 μm). After this, 200°C, 350°C
The film was heat-treated for 30 minutes at a time, and the pattern was observed using an optical microscope.The exposure shop showed a good pattern with no film roughness when the volume was 250 ml or more.

Comparative example 1 4,4-diaminodiphenyl sulfide 207.65
An amine solution was prepared by dissolving 9.94 g of g,1,3-bis(3-aminopropyl)tel-ramethyldisiloxane in 1530 g of N-methyl-2-pyrrolidone. To this amine solution was added 213.76 g of anhydrous bilomelyl 1 acid, and the mixture was reacted at 50°C for 3 hours to obtain a polymer solution (A) of 130 boads at 25°C. 370 g of diethylaminoethyl methacrylate was mixed with this Bolima solution (A),
Next, 10.3 g of N-phenyldiethanolamine14
A solution of 20.6 g of -azidobenzalacetophenone dissolved in 300 g of N-methyl-2-pyrrolidone was mixed and filtered.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 90°C and 95°C for 3 minutes each using the vacuum adsorption type plate of Example 1 to form a film with a thickness of 10 μm. A coating film was obtained.

Next, this coating film was exposed to light in the same manner as in Example 1, and then immersion development was performed. When the film thickness after development was measured, it was 5.4 μm (film reduction: 4.6 μm).

Thereafter, heat treatment was performed at 200° C. and 350° C. for 30 minutes each, and the pattern was observed using an optical microscope, but film roughness occurred even at an exposure dose of 600 [111].

Comparative Example 2 4,4″-diaminodiphenyl ether 192.2g,
1. 9.94 g of 3-bis(3-aminopropyl)tetramethyldisiloxane was dissolved in 18 g of N-methyl-2-pyrrolidone.
90g to prepare an amine solution. Add 315.7 ml of penzophenonetetracarboxylic anhydride to this amine solution.
g and reacted at 50°C for 3 hours, and at 25°C for 15 hours.
A polymer solution (B) with 0 bores was obtained. This polymer solution (
B) was mixed with 370 g of diethylaminoethyl methacrylate, and then mixed with a solution of 20.6 g of Michlerken 1.n dissolved in 250 g of N-methyl-2-pyrrolidone.
Filtered.

Claims (1)

[Claims] (1) (a) General formula -[CO-R_1-CONH-R_2-NH]-(CO
OR_3)n (However, in the formula, R_1 is a trivalent or tetravalent organic group having at least two or more carbon atoms, R_2 is a divalent organic group having at least two or more carbon atoms, and R_3 is hydrogen or an alkali. (b) an unsaturated bond that can be dimerized or polymerized by actinic radiation, and an amino a compound containing a group or a quaternized salt thereof [2]; (c) an aromatic azide compound [3] and/or an aromatic sulfonazide compound [4]; (d) an N-allylglycine compound [5] An actinic radiation-sensitive polymer composition comprising: