JPS6337823B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to novel light- and radiation-sensitive polymer compositions. Conventionally, methods for imparting photosensitivity to polyamic acid, which is a precursor of heat-resistant polyimide, include (a) adding 1 to 5% by weight of dichromate as a photosensitive additive to polyamic acid (USP-3623870); (b) Formula (1)
A mixture of isomers of a dicarboxylic acid dichloride derivative having a photosensitive group shown in and a mixture shown in formula (2)

【formula】

[Formula] (However, R ^* is

【formula】

【formula】) A method of addition polymerizing or polycondensing a polyfunctional cyclic compound to produce a polyamic acid having a photosensitive group in the ester residue (DE-OS2308830). (c) A method of adding to polyamic acid a compound containing a carbon-carbon double bond that can be doubled or polymerized by actinic radiation, an amino group, or a quaternized salt thereof (JP-A-54
-145794) are known. Each of these is applied to a substrate in the form of a varnish dissolved in an appropriate organic solvent, dried to form a coating film, and if necessary, irradiated with ultraviolet rays through an appropriate photomask, developed, and rinsed. The desired relief pattern is obtained. These light-cured and patterned polyamic acid coatings are further subjected to appropriate heat treatment to form heat-resistant polyimide coatings. Polyimide films are used in the semiconductor industry for applications such as insulating layers and passivation layers for solid-state devices, but since these devices generally require extremely fine wiring, polyimide films are fabricated by microfabrication using photoresist. A polyimide film with a relief pattern is formed by chemical etching. For example, a pattern of photoresist is formed on a polyimide layer, then treated with an etchant consisting of hydrazine hydrate and ethylene diamine to form a polyimide relief pattern, and then the photoresist is removed with a photoresist stripper. The resulting polyimide relief pattern is then used for the intended wiring structure. However, these microfabrication processes are extremely complicated as a whole, so in order to simplify this process, a method that can omit the formation of a photoresist film and its peeling process is to expose a polyimide precursor (polyamic acid) to light. There has been a desire for a method that can impart properties and directly microfabricate this coating film with light, and there have been expectations for the development of materials that make this possible. The materials developed for these purposes are those listed in (a), (b), and (c) above.
Among these materials, the materials described in (a) have extremely poor liquid stability when used as varnish, and also have problems with insulation because inorganic ions remain in the polyimide coating of the processing fluid. In the case of the above-mentioned material, the composition consisting of the compound (1) above is viscous and difficult to purify, and even if obtained, it is expensive, and the chlorine ions generated by dehydrochlorination are directly contained in the membrane. Therefore, it is not suitable for semiconductor applications because it may have an adverse effect on reliability. Although the materials described in (c) are materials that have improved these drawbacks, the sensitivity of these materials is still only about several hundred s.mW/cm ² , which is insufficient for practical use. An object of the present invention is to eliminate the above-mentioned drawbacks of the prior art and to provide a light- and radiation-sensitive polymer composition that is inexpensive and has high performance. In particular, the purpose is to improve photosensitivity, which has been insufficient in the past. The novel photosensitive polymer composition provided by the present invention has industrially usable storage stability, and in particular has extremely high sensitivity to light and radiation, making it industrially useful. The polyimide film formed by coating the photosensitive polymer composition of the present invention on a support, exposing it to light, developing it and then heat-treating it has excellent heat resistance and insulation properties, and also has excellent semiconductor reliability. Since it does not contain harmful inorganic salts, it is particularly useful for applications in the semiconductor industry. The present invention will be explained in detail below. The present invention relates to (a) general formula

A polymer whose main component is a repeating unit represented by the formula; (b) a light- and radiation-sensitive additive having an amino group and an aromatic azide group or an aromatic sulfonyl azide group in the same molecule; c) It relates to a light- and radiation-sensitive polymer consisting of a sensitizer and/or an amine having an unsaturated bond, which is added as necessary. The above polyamic acid [ ] can be converted into polyimide by heating or a suitable catalyst, and these polyimides have heat resistance. A polymer whose main component is a repeating unit [ ] is
It may consist only of [ ] or may be a copolymer with other repeating 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 obtained by the final heat treatment. The heat resistance of polyimide is 1 at 250 to 400℃ in a nitrogen atmosphere.
It is desirable that the formed relief pattern is retained even after heating for a long time. It is particularly desirable that the repeating units used in the copolymerization yield heat-resistant polyimides; examples of these can be found in Hara et al., "Current status and trends of heat-resistant polymers" (Journal of Japan Petroleum Institute 17 , 110-120,
(1974). Typical examples include repeating units of polyamideamic acid and polyesteramic acid, but are not limited thereto. In the above polyamic acid formula, R ¹ is a trivalent or tetravalent group having at least two carbon atoms, and is preferably an aromatic ring or an aromatic heterocycle from the viewpoint of the heat resistance of the polyimide. These examples are USP3179614, USP3740305,
No. 2956. As a specific example of R ¹ ,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] (In the formula, the bond represents a bond with a carbonyl group of the polymer main chain, and the carboxyl group is located at the ortho position to the bond.) Examples include, but are not limited to, the following. Further, the polymer of the formula [] may be in the form of a copolymer in which R ¹ is composed of two or more of these types. Especially desirable are

【formula】

[Formula]. R ² is a divalent group having at least two or more carbon atoms, and is preferably an aromatic ring or an aromatic heterocycle from the viewpoint of heat resistance when formed into a polyimide. Examples of these are also shown in the above patent documents. As a specific example of R ² ,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

Typical examples include, but are not limited to, [Formula].
Further, these may have substituents such as amino groups, amide groups, carboxyl groups, sulfonic acid groups, and sulfonamide groups as long as they do not adversely affect the heat resistance of the polyimide. As the polymer containing the repeating unit [] as a main component, those shown in the above patent documents can be used, but particularly preferably used polymers include pyromellitic dianhydride and 4,4'-diaminodiphthalate. enyl ether, pyromellitic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether, pyromellitic dianhydride and 3,3',
4,4'-Benzophenonetetracarboxylic dianhydride and diaminodiphenyl ether and diaminodiphenyl ether-3-carbonamide, pyromellitic dianhydride and 3,3',4,4'-benzophenone tetra Carboxylic dianhydride and 4,4' diaminodiphenyl ether, 4,4' diaminodiphenyl ether-3-carbonamide and bis(3-aminopropyl)tetramethyldisiloxane, pyromellitic dianhydride and 3,3 ',4,
Examples include polyamic acid derived from 4'-benzophenonetetracarboxylic dianhydride, diaminodiphenyl ether, and bis(3-aminopropyl)tetramethyldisiloxane. The polyamic acid whose main component is the repeating unit [ ] is usually obtained by reacting a diamine compound with an acid dianhydride in an approximately equimolar amount as described above, but the reaction solvent used in this case is From the viewpoint of solubility of the polyamic acid, polar solvents are preferably used, and aprotic polar solvents are particularly suitable. As the aprotic polar solvent, N
-Methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N-acetyl-2-pyrrolidone, N-acetyl-ε-caprolactam, 1,3- Typical examples include dimethyl-2-imidazolidinone. The light and radiation sensitivity of the composition according to the present invention can be attributed to the light and radiation sensitivity of the compound having an amino group and an aromatic azide group or an aromatic sulfonyl azide group in the same molecule. The compound [ ] is incorporated into the polymer [ ] by ionic bonding of the amino group with the carboxyl of the polymer [ ]. An aromatic azide group or an aromatic sulfonyl azide group is an azide group with relatively excellent thermal stability, and when exposed to light such as ultraviolet rays, electron beams, or radiation such as X-rays, an active species nitrene is generated, and this active species is quantification, addition to double bonds, hydrogen abstraction reactions, etc. Therefore, the light- and radiation-sensitive additives [] incorporated into the polymer [] undergo the above reaction upon irradiation with light or radiation, and the polymer []
This results in high polymerization, three-dimensional crosslinking, etc., resulting in a difference in solubility in solvents from the unirradiated area, and pattern formation becomes possible. From the viewpoint of productivity, etc., the photo-sensitivity is 0.5, which is the normalized value of the film thickness after development relative to the film thickness of the coating film.
The amount of UV irradiation is 100s.mW/cm ² (500m
It is desirable that the sensitivity be below (value measured at 365 nm using a WXe-Hg lamp) or less. Light and radiation sensitive additives having an amino group and an aromatic azide group or an aromatic sulfonyl azide group in the same molecule include: (Here, X is _-N3 or _-SO2N3 , Y is an alkylene group, and ^R3 , ^R4 , _and ^R5 are hydrogen or an alkyl group having 5 or less carbon atoms.) (Here, X _{is -N3} or _-SO2N3 , ^R3 , ^R4 , ^R5
represents hydrogen or an alkyl group having 5 or less carbon atoms. ) (Here, ^X is _-N3 or _-SO2N3 ^{, R3R4R5} is hydrogen or _an alkyl group having 5 or less carbon atoms, ^R3 is

【formula】 【formula】

【formula】

【formula】 【formula】

【formula】

[Formula] represents one group selected from -O- and -CH ₂ -. ) (Here, X represents -N ₃ , -SO ₂ N ₃ , R ⁸ and R ⁹ represent hydrogen or an alkyl group having 5 or less carbon atoms). In particular, the basicity of the amino group is high.

[Formula] is preferable used. in particular

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. The light- and radiation-sensitive additive [] is 0.05 times or more the equivalent weight of the total carboxyl groups in the polymer [],
Desirably, the equivalent amount is 0.4 times or more, and 3
It is preferable that it is blended into the polymer [ ] in a proportion equivalent to a double equivalent or less. If it deviates from this range, it may cause a decrease in photosensitivity or there will be many restrictions on developability. In addition, especially when the blending ratio is large, it has a negative effect on the heat resistance of the polyimide produced after the final heat treatment. The light- and radiation-sensitive material of the present invention is usually used in the form of a varnish in which the polymer [] and the light- and radiation-sensitive additive [] are dissolved in a suitable organic solvent. ]
It is desirable to use a solvent that can dissolve both the additive and the additive [ ], and from this point of view, primarily polar solvents are preferably used, and aprotic polar solvents are more preferably used. Examples of these polar solvents include N-methyl-2-pyrrolidone, N-acetyl-2
-pyrrolidone, N,N-dimethylformamide,
N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N-
Examples include acetyl-ε-caprolactam and dimethylimidazolidinone. These may be used alone or in combination. In addition to the polymer having the formula [] as a main component and additives [], unsaturated amines, sensitizers, adhesion improving agents, etc. may be added to the light- and radiation-sensitive polymer of the present invention as necessary. I can't help it. Sensitizers improve photosensitivity by expanding the sensitive wavelength range of photosensitive groups and efficiently imparting light energy to photosensitive groups. It is added as a reaction partner. Therefore, when both are used, they may be used alone or in combination. The unsaturated amine can be a reaction partner in the addition reaction or hydrogen abstraction reaction with the active species nitrene, and can contribute to polymerization and three-dimensional crosslinking of the polymer. When adding an unsaturated amine, it is desirable to use it at a mixing ratio of 0.1 to 2 times the equivalent of all carboxyl groups in the polymer [], and the total amount of the additive [] and the unsaturated amine is 3.
It is preferable to use an equivalent amount less than twice as much. Outside this range, the developability will be restricted and the heat resistance of the final polyimide product will be adversely affected. Examples of these unsaturated amines are (Here, R ⁹ represents hydrogen or a methyl group, R ¹⁰ represents hydrogen, a lower alkyl group, or a vinyl group, and k+l
=3, k=1 to 3. ) (Here, R ¹¹ represents hydrogen or a phenyl group, R ¹² represents hydrogen or a lower alkyl group, R ¹³ represents a substituted or unsubstituted hydrocarbon group, and R ¹⁴ and R ¹⁵ represent a substituted or unsubstituted alkyl group, respectively. ) (Here, R ¹⁶ represents a substituted or unsubstituted alkyl group.) Specific examples include CH ₂ =CHCH ₂ NH ₂ ,

[Formula] CH ₃ CH=CHCH ₂ NH ₂ ,

【formula】

[Formula] CH ₂ = CHCH = CHCH ₂ NH ₂ , (CH ₂ = CHCH ₂ ) ₂ NH, (CH ₃ CH
= CHCH ₂ ) ₂ NH,

[Formula] (CH ₂ = CHCH ₂ ) ₈ N, (CH ₃ CH = CHCH ₂ ) ₃ N,

[Formula] CH ₂ = CH COOCH ₂ CH ₂ N(CH ₃ ) ₂ , CH ₂ =
CHCOOCH ₂ CH ₂ N(C ₂ H ₅ ) ₂ , PhCH＝CHCOOCH ₂ CH ₂ N(CH ₃ ) ₂ , PhCH＝
CHCOOCH ₂ CH ₂ N (C ₂ H ₅ ) ₂

【formula】

【formula】

Examples include [Formula]. The amount of the sensitizer that is added as necessary is the total weight of the polymer whose main component is [] and the additive [], and if an unsaturated amine is added, the total weight of this is added. It is preferable that the amount is 0.01 to 10% by weight, and if it is used in a larger amount, it will restrict the developability and adversely affect the heat resistance of the final polyimide product. Preferably used sensitizers include, for example, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, benzoquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, and benzophenone. , P,P'-dimethylbenzophenone, Mihiraketone, 2-nitrofluorene, 5-nitroacenaphthene, 4-nitro-
Examples include 1-naphthylamine, anthrone, 1,9-benzanthrone, dibenzalacetone, benzoin ether, and 4,4'-bis(diethylamino)benzophenone. The light- and radiation-sensitive polymer composition of the present invention may contain an appropriate adhesion aid in order to improve the adhesion between the heat-cured film and the support substrate. Examples of adhesion aids that are preferably used include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, oxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. Organosilicon compounds or aluminum monoethylacetoacetate diisopropylate, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum tris (malonic acid ethylate), aluminum diethylacetoacetonate monoisopropylate, aluminum diacetylacetonate Aluminum chelate compounds such as monoisopropylate, aluminum monomethylacetoacetate diisopropylate, aluminum dimethylacetoacetate monoisopropylate, aluminum tris(methylacetoacetate), aluminum monopropylacetoacetate diisopropylate, aluminum dipropylacetoacetate monoisopropylate are cited as typical examples. Examples of the material of the support to which the novel photosensitive polymer composition of the present invention is applied include metals, glass, semiconductors, metal oxide insulators (such as TiO ₂ , Ta ₂ O ₅ ,
_SiO2, etc.) silicon nitride, etc. The light- and radiation-sensitive polymer composition of the present invention can be patterned by conventional microfabrication techniques using light, radiation, and the like. The light and radiation polymer composition can be applied to the support by means such as spin coating using a spinner, dipping, spraying, and printing, which can be appropriately selected depending on the purpose. The thickness of the coating film can be adjusted by the coating means, the solid content concentration of the varnish, and the viscosity. A relief pattern is obtained by irradiating the light and radiation polymer composition according to the present invention, which has formed a coating film on the support, with ultraviolet rays, and then dissolving and removing the unexposed areas with a developer. The light source is not limited to ultraviolet light, but may also be visible light, X-rays, electron beams, etc. The developer contains N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N- which is the solvent of this polymer composition.
dimethylacetamide, dimethyl sulfoxide,
Hexamethylphosphortriamide, dimethylimidazolidinone, etc. alone or methanol,
It can be used as a mixture with a non-solvent of the composition such as ethanol, isopropyl alcohol, benzene, toluene, xylene, etc. The relief pattern formed by development is then washed with a rinse solution to remove the development solvent. Suitable examples of the rinsing liquid include methanol, ethanol, isopropyl alcohol, benzene, toluene, and xylene, which have good miscibility with the developer. The relief pattern polymer obtained by the above treatment is a heat-resistant polyimide precursor, and by heat treatment it becomes a heat-resistant polymer having imide rings and other cyclic groups. The photosensitive polymer composition of the present invention can be used to form passivation films for semiconductors, interlayer insulating films for multilayer integrated circuits, soldering protective films for printed circuits, alignment films for liquid crystals, and the like. Further, by taking advantage of its high heat resistance, it can also be applied as a dry etching resistant photoresist and a dry etching resistant radiation resist. The present invention will be explained below using examples. Example 1 An amine solution was prepared by dissolving 100 g (0.5 mol) of diaminodiphenyl ether in 791 g of N-methyl-2-pyrrolidone under a nitrogen stream. Next, this solution was cooled with ice to maintain the solution temperature at about 15°C, and powdered pyromellitic dianhydride 109 was mixed with stirring.
g (0.5 mol) was added. After the addition was completed, the reaction was further carried out at approximately 15°C for 3 hours until the viscosity reached 60 poise (30
℃ solution (A) was obtained. 2.34 g (0.01 mol) of 2-(N,N-dimethylamino)ethyl paraazidobenzoate was dissolved in 10 g of solution (A), and then filtered under pressure using a 5 μm pore filter. The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 90° C. for 30 minutes to obtain a coating film of 2.6 μm. This coating film was flat and even, and adhered well to the substrate. This coating was closely covered with a striped mask and exposed to ultraviolet light using a 500W Xe-Hg lamp. The intensity of ultraviolet rays on the exposed surface was 25 mW/cm ² in the wavelength range of 365 nm. After exposure, it was developed with a mixture of 4 volumes of dimethylacetamide and 1 volume of ethanol, and then washed with a rinse solution (ethanol) to obtain a relief pattern. The change in residual film thickness over time is measured, and the residual film thickness is normalized by the coating film thickness.
Sensitivity is 18s.mW/cm ² with the exposure amount giving 0.5 as sensitivity.
I got it. A relief pattern with sharp end faces was obtained by exposure at an exposure dose of 72 s.mW/cm ^{2 ,} which is four times the sensitivity. Even when this pattern was heated at 400°C for 60 minutes, no blurring of the pattern was observed. Example 2 1.17 g (0.05 mol) of 2-(N,N-dimethylamino)ethyl paraazidobenzoate in 10 g of solution (A),
0.28 g (0.05 mol) of allylamine was added, and the same operations as in Example 1 were carried out to prepare a solution, apply, dry, expose, develop, and rinse. The sensitivity was 20 s.mW/cm ² , and the pattern resolution and heat resistance were equivalent to those obtained in Example 1. Examples 3 to 35 For Examples 3 to 35, Tables 1 to 6 show the preparation ratio of samples, conditions such as reaction solvent and developer, and results of coating properties, sensitivity, heat resistance, etc., and other reaction conditions, The operation was performed as shown below. As shown in Examples 1 to 6, about 15
A diamine compound was dissolved in an aprotic polar solvent at °C to prepare a diamine solution. Under a nitrogen stream and stirring, the acid dianhydride ground into powder was added while keeping the reaction temperature at about 15°C. After the addition of the acid dianhydride was completed, the reaction was continued at 15° C. for 3 hours to prepare a polyamic acid solution. A photosensitive additive was added to the prepared polyamic acid solution, and when unsaturated amines and sensitizers were added, they were further added to the above solution and dissolved to form a homogeneous solution. Then, the mixture was filtered under pressure using a 5 μm pore filter to prepare a photosensitive polymer composition. Photosensitive additive columns in Tables 1, 3, and 5 and Tables 2, 4,
In the unsaturated amine column of No. 6, the equivalent to the polymer COOH indicates the number of equivalents of the additive added to the total carboxyl groups of the polyamic acid. The weight percent shown in the sensitizer column of Tables 2, 4, and 6 refers to the total weight of diamine, acid dianhydride, light- and radiation-sensitive additives, unsaturated amine, and sensitizer. Gradually by weight
It is multiplied by 100. The light- and radiation-sensitive polymer composition prepared as described above is spin-coated onto various substrates using a spinner.
The film was then heat-dried at 90°C for 30 minutes to form a coating film, which was then irradiated with ultraviolet rays using a 500WXe-Hg lamp through a striped photomask, developed, rinsed (with ethanol), and cured at 350°C for 1 hour. Sensitivity was defined as good if the exposure amount (observed at 365 nm) giving a value of 0.5 (observation at 365 nm) was obtained by normalizing the film thickness after development with the coating film thickness, and if it was less than 100 s.mW/cm ² it was considered poor. Heat resistance
After curing at 350° C. for 1 hour, those with a weight loss of 1% or less after heating at 300° C. for 1 hour and no blurring of the formed pattern were considered good, and those with more than that were judged as poor.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Examples 36 to 40 Examples 36 to 40 are shown in Tables 7 and 8, showing the conditions such as sample preparation ratio, reaction solvent, developer, etc., and the results of coating properties, sensitivity, heat resistance, etc. The reaction conditions and operations were carried out as shown in Examples 3 to 35 to prepare light and radiation polymer compositions. The polymer composition prepared as described above was spin-coated onto a substrate, and then heated and dried at 90° C. for 30 minutes to form a coating film. This sample was irradiated with an electron beam at an accelerating voltage of 15 KV in a vacuum, with different irradiation doses depending on the location.
The irradiated area was made insolubilized and developed with a developing solvent. Next, an electron sensitivity curve was obtained, which plots the change in film thickness after development depending on the irradiation dose. Sensitivity was defined as the irradiation dose that gave a value of 0.5 when the film thickness after development was normalized to the coated film thickness, and a irradiation dose of 6×10 ^-6 coulombs/cm ² or less was considered good, and anything above this was considered poor. Heat resistance was evaluated as good if the pattern did not become blurred when heated at 350°C.

【table】

[Table] Experiments using a method of adding carbon-carbon double bonds and amino groups or quaternized salts thereof that can be dimerized or polymerized by actinic radiation to a polymer whose main component is polyamic acid (Japanese Unexamined Patent Publication No. 145794-1982) The results are shown below as a comparative example. Comparative Example 1 Diaminodiphenyl ether 110 under nitrogen flow
g was dissolved in 278 g of N-methylpyrrolidone to prepare an amine solution. Pyromellitic dianhydride 120
g was dispersed in 308 g of dimethylacetamide to obtain a polyamic acid solution (B). 50 g of solution (B), a solution of 1.15 g of mihiraketone dissolved in 30 g of dimethylacetamide, and 10.2 g of diethylaminoethyl methacrylate (0.055 mol,
10g (equivalent to all carboxyl groups of polyamic acid)
The solution dissolved in dimethylacetamide was mixed to obtain a homogeneous solution, and then filtered under pressure using a 5 μm pore filter. The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 100° C. for 5 minutes to obtain a coating film of 2 μm. This coating film was closely covered with a striped mask and irradiated with ultraviolet light using a 500W Xe-Hg lamp. The UV intensity on the exposed surface is 25m in the wavelength range of 365nm.
It was warm at W/ ^cm2 . After exposure, it was developed with a mixed solvent of dimethylformamide (5 volumes) and methanol (2 volumes) and washed with ethanol to obtain a relief pattern. This pattern was maintained even after heating to 400°C for 60 minutes. The photosensitivity was 310 s.mW/cm ² , which was less than 1/10 of the composition shown in Example 1 (18 s.mW/cm ² ). Comparative Example 2 50 g of solution (B), a solution in which 1.15 g of Mihiraketone was dissolved in 30 g of dimethylacetamide, and a solution in which 12 g of dimethylaminoethyl cinnamate (0.055 mol, equivalent to the total carboxyl group of polyamic acid) was dissolved in 10 g of dimethylacetamide. The mixture was mixed to obtain a homogeneous solution, which was then filtered under pressure using a 5 μm pore filter. The obtained solution was spin-coated onto a silicon wafer using a spinner and dried at 100°C for 5 minutes to obtain a coating film of 2.2 μm. A relief pattern was obtained by exposure, development, and rinsing under the same conditions as those shown in Comparative Example 1. This pattern was maintained even after heating at 400° C. for 60 minutes, but the photosensitivity was 1500 s.mW/cm ² , which was 1/15 lower than all the compositions examined in the present invention. The light- and radiation-sensitive polymer composition of the present invention is characterized by being a photosensitive material that provides a heat-resistant resin and extremely high light- and radiation-sensitivity, as it is a system free of inorganic ions, etc. that meets the requirements of the semiconductor industry. The point is that it is a photosensitive material that has properties. Its photosensitivity is about 10 to 10 s.mW/cm ² , and carbon-carbon double bonds that can be dimerized or polymerized by actinic radiation are added to the known polymers whose main component is polyamic acid. The method of adding amine with several hundred s.m
W/cm ² , the sensitivity has been improved by more than an order of magnitude.

Claims (1)

[Claims] 1 (a) A polymer whose main component is a repeating unit represented by the general formula [Formula] (wherein R ¹ is a trivalent or tetravalent group having at least two or more carbon atoms) , R ² is a divalent group having at least 2 or more carbon atoms, n is 1 or 2), and (b) general formula [Here, X _{is -N3} or _-SO2N3 , ^R3 , ^R4 , ^R5
is hydrogen or an alkyl group having 5 or less carbon atoms, m is 1 or 0, and when m is 1, L is [formula] (however, Y represents an alkylene group) or [formula] (however, R ⁸ is [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] represents one group selected from -O-, CH ₂ -] in the same molecule A light- and radiation-sensitive additive having an amino group and an aromatic azide group or an aromatic sulfonyl azide group, and (c) a sensitizer and/or an amine having an unsaturated bond added as necessary. A light- and radiation-sensitive polymer composition.