JPS60198536A - High energy ray-sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. enhanced in sensitivity by adding at least one kind of specified org. compd. in a polymer soln. contg. a polymer or copolymer made from a halogenated monomer represented by a specified formula. CONSTITUTION:The present high energy ray-sensitive resin is obtained by preparing a polymer soln. contg. a polymer or copolymer made from a halogenated monomer represented by the formula (X1 is H, halogen, 1-4C straight optionally halogenated alkyl; X2, Y, Z are each H, halogen, or 1-4C alkyl; and R is an aromatic or hetero ring), and adding at least one kind of compd. selected form aniline homologues, N-alkylanilines, arylamines, amines having amino groups on the side chains, and condensed ring type amino compds. to this soln.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polymer solution for semiconductor manufacturing, which is made by adding an organic compound that exhibits a sensitizing effect to a polymer solution that is sensitive to high-energy rays such as X-rays, electron beams, or ion beams. A high energy ray sensitive resin composition obtained by adding a seed organic compound to an energy ray sensitive resin composition.

(1) Aniline, acetanilide, anthranilic acid,
O1m+Aniline homologs such as p-nitroaniline and chloraniline (2) N-alkylanilines such as methylaniline, Michler's ketone, p-dimethylaminobenzoic acid, and p-dimethylaminobenzaldehyde (3) Diphenylamine, p-aminodi7 Arylamines such as phenylamine and triphenylamine (4) Amines having an amino group in the side chain such as benzylamine and β-phenethylamine (5) Or m,p
- Aromatic diamines such as phenylenediamine and p-aminoacetanilide (6) Fused cyclic amino compounds such as naphthylamine (7) Virol, imidazole, N-vinylcarbasol, and polyvinylcarbaso/Int.

In recent years, semiconductor integrated circuits have become increasingly dense. Conventionally, these have been mainly created through a processing process in which a photosensitive polymer material called photoresist is irradiated with ultraviolet rays, but as circuit patterns have become finer and more precise, they have been created by light diffraction and interference. The limits of resolution are becoming apparent.

In contrast, exposure methods using X-rays or electron beams, which have shorter wavelengths, have attracted attention as technologies that can form fine patterns, and have already been put into practical use in some cases.

However, with these high-energy rays, the energy absorption efficiency of resist materials is generally low, and as a result, exposure requires a long time, resulting in a disadvantage that sufficient throughput cannot be obtained.

As a result of extensive studies, the present inventors discovered that by adding one kind of organic solvent-soluble additive to a high-energy radiation-sensitive composition prepared by dissolving a polymer having a halogenated group in its structure in an organic solvent. He discovered scales with improved sensitivity and completed the present invention.

That is, the present invention provides (where X is hydrogen, halogen, a straight chain halogenated alkyl having 1 to 4 carbon atoms, or a straight chain alkyl having 1 to 4 carbon atoms, Xt*Y, and Z is hydrogen.

Represents halogen or halogenated alkyl having 1 to 4 carbon atoms. Furthermore, R represents an aromatic ring or a heterocycle) At least one member selected from the group consisting of the following (1) to θ is added to a polymer solution containing a polymer or copolymer obtained from a halogen-containing monomer represented by The present invention provides a high-energy ray-sensitive resin composition containing an organic compound of the present invention.

(1) Aniline, acetanilide, anthranilic acid,
09m, p-nitroaniline, chlorua (2) N-alkylanilines such as methylaniline, Michler's ketone, p-dimethylaminobenzoic acid, p-dimethylaminobenzaldehyde (3) Diphenylamine, p-aminodiphenylamine, triphenylamine, etc. Arylamines (4) Amines having an amino group in the side chain such as benzylamine and β-7enetelamine (5101m* p-
7 Aromatic diamines such as enylene diamine and p-aminoacetanilide (6) Fused cyclic amino compounds such as naphthylamine (7) Heterocyclic compounds such as hyrol, imidazole, N-vinylcarbazole, and polyvinylcarbazole (8) Pyridoxamine Heterocyclic amines (9) such as
Benzoic acid compounds such as p-methoxybenzoic acid and p-amyloxybenzoic acid θQ Anthraquinone compounds such as anthraquinone and 5-chloroanthraquinone Aromatic nitro compounds such as 5-nitroacenaphthene 61 Hexanediamine, N-methyl Alicyclic amine compounds such as dichlorohexylamine and dichlorohexylamine There are no strict limitations on the molecular weight and solution concentration of the polymer or copolymer containing the above general formula in its structure, but the molecular weight is determined by the organic solvent. It can be used as a photosensitive polymer as long as it can be dissolved in and form a film by ordinary means, but in general, it can be used as a photosensitive polymer.
000.000 is used. If the solution is >5 degrees
It is generally about 4 oz (w/V).

Examples of the organic solvent for forming such a photosensitive polymer solution include alcohols such as methylcellosolp and ethylcellosolp, ketones such as acetone, methylethylketone, and methylimbutylketone, ethyl acetate, n-propyl acetate, n-amyl acetate, Ester compounds such as isoamyl acetate and ethyl acetate cellosolve, alkyl halides such as carbon tetrachloride and tetrachloroethane, heterocyclic compounds such as tetrahydrofuran and pyrrole, and benzene.

Examples include aromatic compounds such as toluene, xylene, and monochlorobenzene, and alicyclic compounds such as cyclohexane.

In the present invention, as the specific compound added as a sensitizer, any compound can be used regardless of whether it is a low molecule or a polymer as long as it is soluble in the organic solvent for dissolving the photosensitive polymer. Compounds listed in (1) to 0 are suitable.

The amount of these organic compounds added does not need to be particularly strictly limited, but is preferably about 1 to 50% by weight based on the photosensitive polymer.

Furthermore, these specific compounds have been pre-contained with kercols such as methanol, ethanol, n-propatool, isopropatool, n-butanol, and glycerin, ethers such as diethyl ether, fatty acids such as acetic acid and acetic anhydride, and their derivatives. It can also be used after being dissolved in a solvent. By applying the thus obtained photosensitive composition of the present invention to a substrate, exposing it to radiation such as X-rays, γ-rays, radiation, and developing it, the composition may lose other properties. It was revealed that the sensitivity was significantly improved without any problems, and the gamma value was also excellent.

The present invention will be explained below with reference to examples, but the present invention is not limited to these examples.

Example 1 A xylene solution of partially chloromethylated polystyrene with a chloromethylation rate of 50 cm and a molecular weight of 40,000 (manufactured by Toyo Dentatsu Kogyo Co., Ltd.,
Various additives were added to OMB-gx (trade name:
0℃! IO minutes) and electron beam irradiation (acceleration voltage zoxv).

The unexposed resist layer was developed with a mixture of inamyl acetate and ethyl cellosolve (mixing ratio 20:80), rinsed with isopropanol, and the film thickness was measured to create a sensitivity curve.

The exposure amount at the remaining 11q rate of 50chi is expressed as sensitivity,
When looking at the effects of the additives, the results shown in the table were obtained.

The sensitizing effect of the additive is clear from this table.

Example 2 Partially chloromethylated polystyrene with a chloromethylation rate of 15 cm and a molecular weight of 110,000 (manufactured by Toyo Soda Kogyo Co., Ltd., trade name: ays)
-DU) and 109 of this with 12 g of potassium bromide at 50. / of N,N dimethylamide and stirred (4
Time) Various additives were added to a xylene solution of partially bromomethylated polystyrene obtained by dropping methanol, and the solution was coated on a silicon wafer in the same manner as in Example 1. This material was irradiated with soft X-rays (target, Rh, wavelength 4.6K), and the relative sensitivity was determined in the same manner as in Example 1, and the results shown in the following table were obtained.

Example 5 Poly(2-vinylnaphthalene) 59 was dissolved in 50 ml of chloromethyl methyl ether, 1 ml of stannous chloride was added, and after stirring overnight, the reaction solution was poured into a large amount of methanol.
The obtained chloromethylated polyvinylnaphthalene precipitate was dried and made into a xylene solution.

This material was coated and irradiated with an electron beam in the same manner as in Example 1, and the results are shown in the following table.

Example 4 Polyvinylcarbazole 169 and chlorobenzene 250
d and mixed with pyridine 100d.

Dissolved. After adding bromine 109 and stirring for 30 minutes, ethanol from Daikei was poured, and the resulting precipitate was dissolved in chlorobenzene. This product was applied in the same manner as in Example 1.

As a result of electron beam exposure and development, the following relative sensitivity was obtained.

Example 5 Polystyrene (manufactured by Toyo Uta Kogyo, standard polystyrene, F
-4) Dissolve 59 in 100 me of methylene chloride,
After adding 100 me of thihydrochloric acid, an organic electrolytic reaction using a platinum electrode was performed. After the reaction is complete, pour in Daisuke's methanol,
The resulting precipitate was filtered and dried.

The thus obtained chlorinated polystyrene was dissolved in xylene together with various additives, and then coated and exposed in the same manner as in Example 1 to obtain the results shown in the following table.

Claims (1)

[Scope of Claims] The following general formula (where X is hydrogen, halogen, a straight chain halogenated alkyl having 1 to 4 carbon atoms, or a straight chain alkyl having 1 to 4 carbon atoms, Z is hydrogen; represents a halogen or a halogenated alkyl having 1 to 4 carbon atoms; and R represents an aromatic ring or a heterocycle) A polymer solution containing a polymer or copolymer obtained from a halogen-containing monomer 111++, 11 ru request, Lmo@n'l: P h :Wd I-J' -1
'l J-/l, group/I-J- heterocyclic compounds (8) Heterocyclic amines such as pyridoxamine (9)
Benzoic acid compounds such as p-methoxybenzoic acid p-Amyloxybenzoic acid Anthraquinone compounds such as anthraquinone and 3-chloro-anthraquinone Aromatic nitro compounds such as 5-nitroacenaphthene 62 Hexanediamine, N-methyl dichlorohexyl 2) The high-energy ray-sensitive resin composition according to claim 1, wherein the high-energy ray source is an X-ray, an electron beam, or an ion beam.