JPS6339888B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention applies electron beams, X-rays, ion beams, β-rays,
It is cured by irradiation with high-energy rays such as gamma rays and neutron beams, but it is virtually non-curable when exposed to light irradiation with a wavelength of 300 nm or more, and it is mainly related to so-called negative resist materials that can be processed in a bright room. One of its objectives is to provide resist materials for microfabrication of various devices in the electronics industry, including high-density integrated circuits.
Specifically, a polymer having multiple oxirane rings is reacted with a monomer having one or more ethylenically unsaturated groups and one functional group capable of ring-opening addition to the oxirane rings, and then the remaining unreacted The main component is a solvent-soluble ethylenically unsaturated bond-containing polymer that does not contain an oxirane ring and is obtained by ring-opening the oxirane ring in the presence of a ring-opening agent (excluding hydrogen halides). coating a resist material and an organic solvent solution of the resist material on a substrate surface and drying to form a thin film;
Relating to a method of using a resist material that, after irradiation with high-energy beams such as electron beams, X-rays, and ion beams, dissolves and removes the non-irradiated portions with an appropriate solvent to create a pattern formed by the hardened portions on the surface of the substrate. . The inventors invented a high-energy ray-curable material and have already filed a patent application for this (Japanese Patent Application Laid-Open No. 1989-1999).
No. 29397). That is, the invention relates to a resist material made by reacting a monobasic unsaturated fatty acid with a polymer having two or more oxirane rings, and then opening the remaining oxirane rings with hydrogen halide. A method was employed in which a carboxyl group was used exclusively as a functional group to be added and opened to the oxirane ring of the upper polymer, and then the remaining unreacted oxirane ring was opened. On the other hand, it has excellent adhesion to various substrate surfaces such as nonmetals and nonmetallic compounds such as silicon, silicon oxide, and silicon nitride, metals and metal compounds such as chromium, aluminum, gold, and chromium oxide, and rare earth compounds and rare earth composites. In order to exhibit etching resistance and at the same time have the desired high sensitivity and high resolution, it is necessary to be able to provide a wide variety of resist materials using several methods. The present invention has been completed as a result of continuing research aimed at creating a highly practical resist material that can meet these demands. First, the ethylenically unsaturated group-containing polymer, which is a feature of the present invention, will be explained. Specific examples of polymers having an oxirane ring that serve as starting materials for resist materials include glycidyl acrylate, glycidyl methacrylate 2-vinyloxyethyl glycidyl ether, 2-vinyl thioglycidyl ether, allyl glycidyl ether, vinyl acetate glycidyl ester, Allyl acetate glycidyl ester, 4-glycidyl styrene, 2-allylphenyl glycidyl ether, 4
- Oxirane rings such as allyl phenyl glycidyl ether, 4-vinylbenzoic acid glycidyl ester, 3,4-epoxybutene, 3,4-epoxy-2-methylbutene, 4-vinylcyclohexene oxide, P-divinylstyrene monoxide, and ethylene A homopolymer obtained by so-called vinyl polymerization, or a copolymer obtained by polymerization of two or more types of monomers, and the above-mentioned A monomer having an oxirane ring and an ethylene bond as shown in the example of
Styrene and its derivatives such as styrene without oxirane ring, 2-chlorostyrene, 4-chlorostyrene, 2-vinyltoluene, 4-vinyltoluene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, Alkyl acrylic acid or methacrylic acid such as n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, etc. , cycloalkyl, aryl, or aralkyl esters, as well as acrylic acid or methacrylic acid derivatives such as acrylic nitrile, methacrylic nitrile, acrylic amide, methacrylic amide, vinyl chloride, vinylidene chloride, vinyl fluoride, trifluoride chloride, etc. Binary or ternary polymers with halobinyl monomers such as ethylene, vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone, and vinyl monomers such as acrylonitrile, methacrylnitrile, vinyl acetic acid, and allyl acetic acid can also be used. . Regarding the above-mentioned vinyl monomers without an oxirane ring, there are functional groups such as free carboxyl groups that easily add to and open the oxirane ring, or those having multiple ethylenically unsaturated bonds, such as divinyl sulfone. In this case, since there is a possibility that a general or local crosslinking reaction may occur, its use should be avoided in the synthesis of the oxirane-containing ring polymer that is the starting material for the resist material of the present invention. As a starting material for the resist material of the present invention, the oxirane ring-containing polymer preferably has a number average molecular weight of 10 ³ to 10 ⁶ , and the abundance ratio of monomers containing oxirane rings in the polymer is 10 mol %. , advantageously
It is preferably 30 mol% or more. The oxirane-containing ring polymer is usually easily synthesized by a known so-called vinyl polymerization method, and some specific examples will be given below. Reference example 1 284 g of glycidyl methacrylate (GMA) and 4.85 g of benzoyl peroxide (BPO) in the reaction vessel
g of methyl ethyl ketone held at 50°C.
The mixture was added to 800 ml and stirred at 50° C. for 5 hours under a nitrogen atmosphere, and then the reaction was continued under reflux for 4 hours. After cooling to room temperature, the mixture was added to 10 g of isopropyl alcohol (IPA) with strong stirring to obtain 240 g of dried polymer poly(glycidyl methacrylate) precipitated (yield: 85%). Epoxy value 660mmol/100g, viscosity η=
13.0cps [25℃, 20% methyl cellosolve acetate (MCA) solution]. Reference Example 2 284 g of GMA and 52 g of styrene were added to 1350 ml of methyl ethyl ketone in a reaction vessel, 7.5 g of BPO was added, and the mixture was reacted for 5 hours at reflux temperature under a nitrogen atmosphere. After cooling, the polymer poly(glycidyl methacrylate-CO) was poured into IPA20 with strong stirring and precipitated.
-Styrene) was separated and dried to obtain 254g (yield 75
%). Epoxy value 533 mmol/100 g, η = 12.0 cps (25
°C, MCA20% solution). Reference example 3 GMA284g, cyclohexyl methacrylate
83.5 g of tetrahydrofuran in a reaction vessel
7.5 g of 2,2-azobis(2,4-dimethylvaleronitrile) was added thereto under a nitrogen atmosphere, and the mixture was reacted at 60° C. for 4 hours. After cooling to room temperature 13
of methyl alcohol under strong stirring to precipitate the polymer poly(glycidyl methacrylate-CO-
Separately dry cyclohexyl acrylate) 277
g (yield 75%). Epoxy value 535 mmol/100 g, η = 12.8 cps (25
°C, MCA20% solution). Reference example 4 217 g of glycidyl acrylate (GA) and 116 g of methyl methacrylate were added to acetone in a reaction vessel.
450ml, add 3.75g of azobis(isobutyronitrile) (AIBN) under nitrogen atmosphere, and heat at 60℃.
Reacted for 20 hours. After cooling, add 2 parts of acetone to the reaction mixture.
After making a homogeneous solution, it was poured into 15% methyl alcohol under strong stirring, the precipitate was separated and dried to form a polymer poly(glycidyl acrylate).
89 g of CO-methyl methacrylate was obtained (yield
79%). Epoxy value 461 mmol/100 g, η = 13.8 cps (25
°C, MCA20% solution). Reference example 5 Dissolve 0.5 g of polyvinylpyrrolidone in 500 ml of water in a pressure-resistant glass autoclave, cool the autoclave with acetone-dry ice cryogen,
Add 142 g of GMA, 31.3 g of vinyl chloride, and 0.6 g of AIBN and fix in a constant temperature shaking device (incubator), 60
After a heating reaction at ℃ for 10 hours, the mixture was allowed to cool. The precipitate was separately dried to obtain 160 g of white powder. Then,
Add the powder to dioxane 2 and dissolve it, then pour it into a large amount of water with stirring to separate the precipitate.
Repeatedly, 135 g of dried poly(glycidyl methacrylate-CO-vinyl chloride) was obtained (yield 78
%). Epoxy value 613 mmol/100 g, η = 16.3 cps (25
°C, dioxane 20% solution). Reference example 6 130 g of 4-glycidylstyrene, 42 g of 4-chlorostyrene, and 800 g of dioxane with 3.2 g of BPO added.
ml and reacted for 5 hours at 70°C in a reaction vessel under nitrogen atmosphere. After cooling, add IPA8 with strong stirring.
The precipitate was dried to obtain 120 g of poly(4-glycidylstyrene-CO-4-chlorostyrene) (yield: 69%). Epoxy value 443 mmol/100 g, η = 8.5 cps (25
°C, MCA15% solution). Reference Example 7 143 g of GMA and 50 g of 4-vinylstyrene monoxide were added to 600 ml of tetrahydrofuran containing 3.4 g of AIBN, and the mixture was heated in a reaction vessel under a nitrogen atmosphere for 50 g.
The reaction was allowed to take place at ℃ for 12 hours. IPA10 with strong stirring after cooling
The precipitate poured into the solution was separately dried to obtain 180 g of poly(glycidyl methacrylate-CO-4-vinylstyrene monoxide) (yield: 93%). Epoxy value 695 mmol/100 g, η = 13.2 cps (25
°C, MCA 12% solution). Reference Examples 8 to 10 Three types of poly(glycidyl methacrylate-CO-methyl methacrylate) were synthesized by the following methods. A mixture of equal weights of xylene and methyl ethyl ketone was mixed to the same weight as the total amount of GMA and methyl methacrylate, and the mixture was placed in an ampoule and cooled with a cryogen. After purging the air in the ampoule with nitrogen, the process was repeated four times. Thereafter, the ampoule was sealed and reacted for 8 hours in an incubator maintained at 80°C. After cooling, cut the ampoule and mix the polymer solution with an equal weight mixture of xylene and methyl ethyl ketone for 10 minutes.
The precipitated polymer was diluted twice, then added to 10 times the volume of methyl alcohol, and the precipitated polymer was dried separately. In addition,
GMA and methyl methacrylate were commercially available products treated in a conventional manner to remove the polymerization inhibitor.

[Table] The above synthesis method was based on the GMA technical data of NOF Corporation. For the purpose of introducing an ethylenically unsaturated bond into the polymer by utilizing the oxirane ring of the above-mentioned oxirane-containing ring polymer, a monomer having a functional group and an ethylenically unsaturated group capable of ring-opening addition to the oxirane ring is used. Make your body work. In this case, it is usually desirable that the number of functional groups having oxirane ring addition activity is one. In general, when a monomer containing two or more functional groups is used, as expected, a crosslinking reaction occurs due to addition to the oxirane ring, resulting in a product that is unsuitable as a raw material for resist materials. I can't.
However, there are 2 ethylenically unsaturated groups in the monomer.
There is no problem with the presence of more than one ethylenically unsaturated group, and it has been found that there are cases in which a monomer having one ethylenically unsaturated group gives better results. As functional groups capable of ring-opening addition to the oxirane ring, haloacyl groups, hydroxyl groups, sulfhydryl groups and secondary amino groups can be used for the purposes of this invention. Specific examples of monomers that can be used to introduce ethylenically unsaturated bonds into the oxirane-containing ring polymer are given below. Monomers having a haloacyl group as a functional group that is added to the oxirane ring by ring opening include acrylic acid chloride, methacrylic acid chloride, methylvinyl acetate chloride, allyl acetate chloride, isopropenylacetate chloride, 3-allylpropionic acid chloride,
Allyl phenyl acetate chloride, allyl benzyl acetate chloride, monomethyl maleic chloride, monoethyl maleic chloride, monoisopropyl maleic chloride, monomethyl fumaric acid chloride, monoethyl fumaric acid chloride, monoisopropyl fumaric acid chloride, monomethyl itaconic acid chloride, Examples include the same structure in which the above-mentioned acid chloride is converted into acid bromide. This type of functional group acts on the oxirane ring and mainly forms vic chloroester or vic bromo ester. When having a hydroxyl group as a functional group, two types of groups can be used: alcoholic and phenolic. First, monomers with alcoholic hydroxyl groups include allyl alcohol, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, and pentaerythritol triacrylate. , pentaerythritol trimethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-vinylbenzyl alcohol, 4-allylbenzyl alcohol, and the like. Monomers with phenolic hydroxyl groups include 4-hydroxystyrene, 2-hydroxystyrene, 3-hydroxystyrene, 2-allylphenol, 3-allylphenol, 2-methyl-6-allylphenol, 2-allyl -4-methylphenol, 1-allyl-2-naphthol,
Eugenol, 4-allylanisole, 3-allylanisole, 2,6-diallylphenol,
2,6-diallyl-p-cresol, 2,4,6
-Triarylphenol etc. are mentioned as an example. This type of functional group is added to the oxirane ring,
Gives vic hydroxy ether. Monomers having a sulfhydryl group as a functional group include allyl mercaptan, mercaptobutene-2, mercaptobutene-3, mercaptopentene-4, mercaptopentene-1, 2-vinylthiophenol, 3-vinylthiophenol, 2-
Examples include allylthiophenol.
In this case, the adduct to the oxirane ring is a vic hydroxythioether. Monomers having a secondary amino group as a functional group include N-methylallylamine, diallylamine, N-methylaminoethyl acrylate, N-
Methylaminoethyl methacrylate, N-propylaminomethyl acrylate, N-propylaminomethyl methacrylate, N-propylaminoethyl acrylate, N-propylaminoethyl methacrylate, N-benzylallylamine, N-
Examples include allylaniline, N-allyl-2-toluidine, and many other secondary amines having ethylenically unsaturated bonds; these amines add to the oxirane ring to form vic tertiary amino alcohols. In this case, however, as is well known, the tertiary amine acts as a curing catalyst for the epoxy resin by opening the oxirane ring, so the glycidyl-containing polymer itself may be completely or locally cured. It is expected that this will depend on the selection of the monomer having a secondary amino group as a functional group and the reaction conditions. However, by appropriate selection of the polymer, the monomer having a secondary amino group, and the reaction conditions, it is possible to prevent gelation by a mechanism similar to that of epoxy resin curing. In addition, monomers with aldehyde or ketone groups as functional groups, such as acrolein, crotonaldehyde, allyl acetaldehyde, or methyl vinyl ketone, divinyl ketone, diallyl ketone, etc., add to the oxirane ring to form an acetal. No suitable resist material of the invention was found. Further, as functional groups, there are cyano groups, urea, and urethane derivatives, but similar to the case of aldehyde or ketone groups, no suitable materials have been obtained. In addition, specific examples of monomers that can be used to synthesize the oxirane-containing ring polymer and monomers that can be used to introduce ethylenically unsaturated bonds into the oxirane-containing ring polymer are explained below. This is not intended to limit the content of the present invention. Using a monomer having a functional group with addition activity to the oxirane ring as shown in the examples above,
By introducing an ethylenically unsaturated bond into an oxirane-containing ring polymer, a polymer having an ethylenically unsaturated bond can be obtained. The rate of introduction naturally depends on the chemical properties of the monomer having a functional group and the oxirane-containing ring polymer, as well as the reaction conditions. However, it is generally known that it is practically impossible to add a monomer having a functional group to all oxirane rings in a polymer to open the rings. In this case, the oxirane rings remaining unreacted reduce the storage stability of the resist material, resulting in development residue after high-energy irradiation, and disadvantages such as poor edge sharpness of the formed pattern. was recognized. Therefore, after introducing an ethylenically unsaturated group into the oxirane ring, we applied a ring-opening agent (excluding hydrogen halide) that opens and eliminates the remaining end-reacted oxirane ring, and found that the stability was extremely good. A resist material was obtained which gives a pattern with excellent resolution and no development residue. Hydrogen sulfide and hydrogen cyanide are advantageously used as ring-opening agents of this type;
The oxirane ring opens to produce halohydrin, vic hydroxythiol, and cyanohydrin, respectively. Also, chloric acid, perchloric acid, bromic acid, perbromic acid,
Halogen oxyacids such as iodic acid and periodic acid also serve as ring-opening agents, and in this case mainly consist of vic diol. In addition, it is also possible to use a Grignard reagent, ammonia nitric acid, boron trifluoride, particularly a boron trifluoride acetic acid adduct, and the like. However, in the case of Griard's reagent, it does not react with ethylenically unsaturated bonds, but acts on ester bonds, so it cannot be used, for example, in polymers with haloacyl groups and ethylenically unsaturated bonds introduced therein. In this case, alcohol is produced from the oxirane ring.
In the case of ammonia, an amino alcohol is generated and the ring is opened. Nitric acid mainly gives vic hydroxy nitrate to open the ring, but the properties of the product vary from synthesis batch to batch, making control difficult. Boron trifluoride is used as an adduct of organic acids such as acetic acid, but as expected, it produces crosslinked insoluble components, and the soluble components also have a wide molecular weight distribution. In this case, even when used as a soluble component and a resist material, the storage stability is poor and the practical value is slightly inferior. In addition, when introducing an ethylenically unsaturated group into an oxirane-containing ring polymer, even when using a haloacyl group as a functional group, an excess amount of ethylenically unsaturated group and functional A monomer having a functional group is allowed to react according to a conventional method. In addition, in reactions that utilize groups other than haloacyl groups as functional groups for introducing ethylenically unsaturated groups, after the unsaturated group introduction reaction is completed, a ring-opening agent is added to the reaction mixture to eliminate the oxirane ring, and then It is advantageous to take steps to separate the products. The above ethylenically unsaturated bond introduction reaction and the residual oxirane ring opening reaction in which a ring opening agent is applied are carried out in a solvent that is inert to the reaction components. It is also desirable that this type of solvent is a good solvent for the reaction composition and reaction products. Practical examples include esters such as methyl cellosolve acetate, ethyl cellosolve acetate, acetic acid esters, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, ethers such as dioxane, tetrahydrofuran,
dimethylformamide, dimethyl sulfoxide,
It is selected from aprotic polar solvents such as hexamethylphosphoramide depending on the type of reaction composition and reaction conditions. Note that in the reaction of introducing an ethylenically unsaturated group into the oxirane ring, it is often advantageous to use a catalyst suitable for the type of reaction. Specific examples of catalysts of this type are given in the Examples. The reaction products are usually separated by pouring them into a non-solvent. Further, the ring-opening agent added in excess is removed by washing with water. The reaction product obtained by the method described above is vacuum dried, preferably at a temperature not exceeding 80° C., to obtain a resist material. Incidentally, it is already known that the oxirane-containing ring polymer itself, which is the starting material for the resist material of the present invention, can be cured by irradiation with high-energy rays such as electron beams. However, the resist material of the present invention is 10 to 20 times more sensitive to high-energy rays than the oxirane-containing ring polymer used as the starting material, and has excellent resolution and stability, which are the most important properties of resist materials for microfabrication. It has been confirmed that it is extremely superior.
A comparative example with starting materials is described in Example 1. Resist materials are usually used in the form of a solution in a volatile good solvent, and examples of this type of solvent include chloroform, dichloroethylene, and chloroform, in addition to the solvent used for the reaction of introducing unsaturated groups into oxirane-containing ring polymers. Haloalkanes such as carbon chloride, hydroxyl solvents such as methyl cellosolve and ethyl cellosolve can be used alone or in combination. The concentration of the resist material solution varies depending on the properties of the polymer, conditions of use, etc., but is usually in the range of 5 to 30% by weight. The resist material solution is applied to the surface of a silicon wafer, chrome mask substrate, or other workpiece using a spin coater, and then heated and dried to form a good film with a thickness of about 3000 Å and no pinholes. Of course, depending on the purpose of use, it is possible to form a film with a thickness of 10,000 Å or more. The coating is further heated at a temperature below 120°C, for example 30°C.
It may be heated for about a minute to remove any remaining traces of solvent in the coating and may be reheated to improve adhesion to the workpiece surface. This operation is known as pre-baking. Next, electron beam, X-ray, ion beam, β-ray, γ-ray
When irradiated with high-energy radiation such as radiation or neutron beams, the irradiated areas harden and become insolubilized. When washed and developed with an appropriate solvent, the non-irradiated areas dissolve and a pattern of hardened resist film is formed on the surface of the workpiece. be done. Methods known in the art are applied to this type of pattern forming method. After development, so-called post-baking, which is a heat treatment in the range of 100 to 250° C., can be performed in order to further strengthen the resist film. Various operations such as chemical etching, dry etching, doping, ion milling, metal vapor deposition, etc. can be performed on the workpiece using the resist pattern subjected to the above-described processing. Resist materials used for such purposes are subject to practical considerations such as stability of the resist material itself, sensitivity to high-energy rays, contrast, presence or absence of development residue, cut of resist pattern edges, resolution, heat resistance, and etching resistance. are evaluated for their characteristics. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 10 g of poly(glycidyl methacrylate-CO-cyclohexyl methacrylate) obtained in Reference Example 3
60ml of methyl cellosolve acetate in the reaction vessel
14 g of 2,6-diallylphenol and 1 g of tributylamine were added thereto, and the mixture was reacted at 80 to 90° C. under a nitrogen atmosphere for 8 hours with stirring. Next, after cooling to room temperature, hydrogen sulfide was introduced to open the unreacted oxirane ring. The end point of the ring-opening reaction was determined by measuring the epoxy value. After removing excess hydrogen sulfide by blowing nitrogen, 120 ml of methyl cellosolve acetate was added to the reaction solution to form a homogeneous solution, which was then poured into isopropyl alcohol 1 with strong stirring. The precipitate that formed was washed with another isopropyl alcohol and dried under vacuum at 60°C. Polymer diallyl phenol ether
13.4g was obtained. A thin film of the above resist material was formed on a substrate for producing a chrome mask and irradiated with an electron beam to obtain the following measurement results. D ^0.5 _g = 7.5×10 ^-7 Coul/cm ² , γ = 1.8, 0.5 μ line and space was resolved. Next, the above 0.5μ line and space pattern was post-baked at 220℃ for 30 minutes, immersed in a chrome etch solution (a mixture of 17g of cerium ammonium nitrate, 5ml of 70% hydrogen peroxide, and 100ml of water) at 22℃, washed with water, and dried. , a mask with good defension was obtained. Example 2 Poly(glycidyl methacrylate) of Reference Example 5
CO-vinyl chloride) 8g of the polymer of Reference Example 3
Example 3 except that 10g was added instead of 10g.
The reaction was carried out in exactly the same manner as above, followed by post-treatment to obtain 11 g of diallyl phenol ether as a polymer. The following results were obtained by electron beam irradiation. A single line of D ^0.5 _g =4×10 ⁻⁷ Coul/cm ² , γ=1.0, and 0.5 μ was resolved. Example 3 Put 600ml of tetrahydrofuran into a reaction container,
15.5 g of poly(glycidyl methacrylate-CO-4-chlorostyrene) of Reference Example 6 was dissolved in this, 0.1 g of p-methoxyphenol and 8 g of diallylamine were added, and the mixture was heated to reflux under a nitrogen atmosphere.
The reaction was stirred for hours. After cooling, ammonia was blown into the reaction solution to open unreacted oxirane rings.
Next, the reaction solution was poured into isopropyl alcohol from step 2, and after standing still, the precipitate was separated, and the slurry was poured into water, stirred, washed with water again, washed with ethyl alcohol, dried under vacuum at 50°C, and prepared with diallylamine. Obtained 17g. The results of electron beam irradiation of the above resist material were as follows. A single line of D ^0.5 _g = 3×10 ⁻⁶ Coul/cm ² , γ = 0.8, and 0.6 μ was resolved. Example 4 After reacting poly(glycidyl methacrylate) and 3-vinylthiophenol, the reaction mixture was poured into methyl alcohol 2 with strong stirring, the precipitate was collected, and the wet cake was treated again with methyl alcohol 2 to remove the precipitate. Separated. Add the wet cake as it is to 600 ml of dioxane to dissolve the precipitate, and add 6 g of periodic acid HIO _{3.2H 2} O and water.
10ml of the mixture was added and stirred at 20°C for 4 hours. Next, the above solution was poured into methyl alcohol from step 4, the precipitate was separated, thoroughly washed with water, and vacuum dried at 60°C.
I got g. The results of electron beam irradiation were as follows. D ^0.5 _g = 4.3×10 ^-7 Coul/cm ² , γ = 1.0, 2 μ line and space was resolved.

Claims (1)

[Claims] 1. A polymer having a plurality of oxirane rings is reacted with a monomer having one or more ethylenically unsaturated groups and one functional group capable of opening the oxirane rings, and then the remaining An electron beam characterized in that the main component is a solvent-soluble ethylenically unsaturated group-containing polymer obtained by ring-opening an unreacted oxirane ring in the presence of a ring-opening agent (excluding hydrogen halides); A resist material that is cured by irradiation with high-energy rays such as X-rays, ion beams, and gamma rays, but is substantially non-curable by irradiation with light having a wavelength of 300 nm or more. 2 Homopolymers and copolymers of monomers having an ethylenically unsaturated bond and an oxirane ring, or the monomers have substantially no reactivity with the oxirane ring under polymerization reaction conditions via an ethylene bond. 2. The resist material according to claim 1, wherein the copolymer with a monomer having no group and having an ethylenically unsaturated bond is a polymer having a plurality of oxirane rings. 3. A monomer having an ethylenically unsaturated bond and an oxirane ring, and a monomer having an ethylenically unsaturated bond and having no group that is substantially reactive with the oxirane ring under polymerization reaction conditions via an ethylene bond. In the case of a copolymer with a monomer having an ethylenically unsaturated bond and an oxirane ring
The resist material according to claims 1 and 2, which has a content of 10 mol % or more. 4 Monomers having one or more ethylenically unsaturated bonds and one functional group capable of ring-opening addition to the oxirane ring, where the functional group is a haloacyl group, hydroxyl group, sulfhydryl group, or secondary amino group. The resist material according to claim 1, which is a base. 5 Adding a monomer having one or more ethylenically unsaturated groups and one functional group capable of ring-opening and addition to the oxirane ring to a polymer having a plurality of oxirane rings, Hydrogen sulfide, hydrogen cyanide,
The resist material according to claim 1, which uses a strong inorganic acid or ammonia having oxidizing properties of halogen oxygen acids. 6. Dissolve the resist material according to claim 1 in an organic solvent, apply it to the surface of a solid substrate on which a pattern is to be formed, dry it, remove the solvent, form a thin film, and apply it to an electron beam, After irradiation with high-energy rays such as X-rays, ion beams, and gamma rays, the non-irradiated portions are dissolved and removed using an appropriate solvent, and the resist material is used to create a pattern formed by the hardened portions on the surface of the substrate. Law.