JPH0229652A - Photoresist composition - Google Patents

Abstract

PURPOSE:To provide the compsn. having a high glass transition temp. (Tg) and high O2RIE resistance by adopting a polysiloxane structure and further, using a specific silicone polymer. CONSTITUTION:This compsn. consists of the alkaline soluble siloxane compd. contg. the units expressed by the formulas I, II in the molecule and a photosensitive body which is the esterified matter of a polyhydroxy compd. and 1,2- naphthoquinonediazide-4-sulfonyl chloride and/or 1,2-naphthoquinonediazide-5- sulfonyl chloride. In the formulas I, II, X is one kind selected from a group of a carboxyl group, etc.; R1-R5 denote a group selected from a group of hydrogen and those having general formula of -Y-R6. A positive photoresist having high sensitive to UV rays is obtd. in this way and since the compsn. contains the silicon, the resistance to oxygen plasma is high and the compsn. is usable as the upper layer resist of two-layered resists.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photoresist composition with high oxygen plasma resistance that can be reproduced with high precision.

[Prior art and its problems]

Conventionally, resist materials for high-energy radiation have been used for pattern formation in LSI processing processes. Among these, fluorine-containing methacrylate polymer is known to have high sensitivity (IXIO-'C/c+fl) as a positive resist (Patent No. 1034536). has the disadvantage of low plasma processing resistance in LSI processing.

On the other hand, chloromethylated polystyrene (CMS), which is a negative resist, is known as a resist with high sensitivity and high plasma processing resistance (Patent No. 1107695).
issue). However, with this negative resist, as the film thickness increases, the resolution decreases and it is not possible to form fine patterns.Therefore, in order to solve this drawback, the resist should be multilayered instead of Ill. Accordingly, a method of forming a thick and fine pattern with a high shape ratio has been proposed. That is, after forming a thin film of resist material as the first layer, high energy is irradiated to the second layer resist material, and the first layer organic polymer is oxygen plasma etched ( 0!RIB) to obtain a pattern with a high shape ratio (B, J,
Lin, 5o-1id 5tate'Techno1
．． For example, Hatzakis et al. [M, Hatzakis et a
l, Proc, 1nt, 1. Conf, Microl
ithography (1981)).

However, this negative resist material has a glass transition temperature (
There is a problem that Tg) is low. This is because when the Tg is low, problems occur such as easy adhesion of dust to the resist, difficulty in controlling the film thickness, and deterioration of developability due to pattern deformation during development.

In this way, the resist material has a high Tg and 0. A material with high RIE resistance is required.

Furthermore, in order to form a high-resolution pattern, an alkaline development type non-swelling resist is required.

(Means for Solving the Problems) Therefore, in this invention, a silicone polymer is adopted that has a polysiloxane structure to increase the 0□RIE resistance, and also has a high Tg by introducing a large number of phenyl groups into the side chain. By using this, the above problems are solved.

The present invention is implemented by one type selected from the group of carboxyl groups, represented by the following formulas (1) and (II) or substituted hydrocarbon groups, which may be the same or different, RI+Rz,
R: 1, R4 and R3 are the same or different and represent hydrogen and a type of group selected from the group consisting of -Formula-'1-Rh. ), a polyhydroxy compound, and 1,2-naphthoquinonediazide-5-sulfonyl chloride and/or 1,2-naphthoquinonediazide-4-
This is a positive photoresist composition characterized by comprising a photosensitive material which is an esterified product with sulfonyl chloride.

Here, R represents a hydrocarbon group and a substituted hydrocarbon group,
Preferably an alkyl group having 1 to 6 carbon atoms, OH, -3H,
-NHt, C0OH,CN.

SOi H, -Sow NHz, R' CNH-^ R' So, NH-, an alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group, an aromatic hydrocarbon group having 6 to 15 carbon atoms, -OH, -3H, -NH,.

C0OH, -CN, -3OzH, 5OtNH! .

R' -CNH- ^ R' So, NH-, an aromatic hydrocarbon group having 6 to 15 carbon atoms substituted with an alkoxy group (here, R' is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms) group, or a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms).

Further, R6 represents a hydroxyl group, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and preferably a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or -OH.

-SH,NHt, C0OH, -CN, -3O3
H.

-Sow NHz, R' CNH, R'
5OzN) (-^ Alkyl group having 1 to 6 carbon atoms substituted with alkoxy group etc., aromatic hydrocarbon group having 6 to 15 carbon atoms, -OH, -SH
, -NH, -COOH, -CN.

SOs H, SO2NHt, R' CNH
-^ R' SO, NH-, an aromatic hydrocarbon group having 6 to 15 carbon atoms substituted with an alkoxy group (here, R' is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a carbon represents a substituted or unsubstituted aromatic group of numbers 6 to 15).

R? 1RIO to R11 represent substituted or unsubstituted aliphatic and aromatic hydrocarbon groups, preferably having 1 to 6 carbon atoms.
Alkyl group, -OH, -3H, -NH,.

-COOH, -CN, -3Os H, -3ot N) (
Z.

R' -CNH, R' SOiNH- ^ Alkyl group having 1 to 6 carbon atoms substituted with alkoxy group etc., aromatic hydrocarbon group having 6 to 15 carbon atoms, OH, -3H,
NHt, C0OH, -CN.

SOs H, -Sow NHz, R'
CNH-^ R' SO, NH-, an aromatic hydrocarbon group having 6 to 15 carbon atoms and substituted with an alkoxy group (here, R' is a carbon number 1
~6 substituted or unsubstituted alkyl groups, or 6 carbon atoms
~15 substituted or unsubstituted aromatic groups).

R,, R, represents a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, preferably an alkylene group having 1 to 6 carbon atoms, -OH, -3)! , -NH,.

COOH, CN, S Ox H, S Ot N
Ht.

R' -CNH-, R' 5ChNH-^ Alkylene group having 1 to 6 carbon atoms substituted with an alkoxy group, etc., divalent aromatic hydrocarbon group having 6 to 15 carbon atoms, -0H
, -3H, -NH,, -COOH.

-CN, -3O3H, -3oNH,.

R' -CNH-, R' 5OzNH-^ A divalent aromatic hydrocarbon group having 6 to 15 carbon atoms substituted with an alkoxy group, etc. (here, R' is a substituted or unsubstituted group having 1 to 6 carbon atoms) represents an alkylene group, or a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 15 carbon atoms).

Moreover, it is more preferable that the binder contains 50% by weight or more of the compounds represented by formulas [I] and [■].

Hereinafter, the photoresist composition of the present invention will be explained in detail.

Since the siloxane polymer of the present invention has a polysiloxane structure as the main chain of the polymer, it has very high O, RIE resistance and is advantageous for forming fine patterns with high aspect ratios. In addition, although it has a polysiloxane structure, since many phenyl groups are present in the side chains, the Tg is higher than room temperature and it can be used as a resist. Furthermore, since a hydrophilic group such as a carboxyl group is introduced into the phenyl group, the polymer is soluble in an alkaline aqueous solution.

Therefore, by adding the orthonaphthoquinone compound to the siloxane polymer, it can be used as a positive photoresist composition. That is, the Si-containing polymer represented by formula (1) or formula (II) is treated with 1,2-naphthoquinonediazide-5-sulfonic acid and/or 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound. A photoresist composition to which a certain photosensitive material is added exhibits positive resist properties because upon irradiation with ultraviolet (υV), the orthonaphthoquinone compound in the irradiated area changes to the corresponding indenecarboxylic acid, and the irradiated area is removed by alkaline development.

In this photoresist composition, the orthonaphthoquinone compound plays a role as a dissolution inhibitor for the resist in an alkaline solution, and the amount of the orthonaphthoquinone compound added is usually in the range of 5 to 30% by weight. 5% by weight
If it is less than 30% by weight, it will not be possible to suppress the dissolution of the polymer compound in an alkaline developer, and alkaline development will not be possible, and if it exceeds 30% by weight, Si as a resist material will
The content decreases, and the oxygen plasma resistance decreases, which is disadvantageous. Generally, a preferable addition amount is about 20% by weight.

One formula used in the present invention! A method for producing a siloxane polymer containing a unit represented by is a cyclic phenylsiloxane such as hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, etc. using an alkali metal hydroxide such as potassium hydroxide or an alkali metal alkyl such as butyl lithium. There is a method of carrying out ring-opening polymerization with a compound and modifying the obtained polydiphenylsiloxane.

Alternatively, instead of using cyclic phenylsiloxane alone, it may be copolymerized with tetramethyltetraphenylcyclotetrasiloxane, octamethylcyclotetrasiloxane, or the like. In addition, especially when it is desired to form a pattern with high resolution, a monodisperse polymer with a uniform molecular weight is preferable. A desired monodisperse polymer can be obtained.

A unit represented by formula (■) used in the present invention or general formula (1)
As a method for producing a quioxane polymer containing both units represented by and (It), there is a method of modifying a phenylsilsesquioxane polymer easily obtained by hydrolyzing a silaf compound.

Modification methods for the polydiphenylsiloxane and phenylsilsesquioxane polymers used in the present invention can be roughly divided into two methods. First, the first modification is to convert the synthesized polydiphenylsiloxane and phenylsiloxane polymer into
For example, ulμ, Frdel Craft in the presence of catalyst
Acetylation modification is performed by reaction. In some cases, the second modification is carried out by further carrying out carboxylation or hydroxylation modification by oxidation or reduction reaction. This is a method of denaturing as follows.

' + R+5COOH-→ -5t-OCOR
+e+ RI4S+( 1 → -5t-3R+q + Rz.N) 1 1 → -5i-NRz.

II 〃 + Rt+NCQ -→ ~5t-OCN
)IRz+' + RztSOzNCO-5t-OC
NH3OtRB [R14~2. : Represents a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, preferably an alkyl group having 1 to 6 carbon atoms, -OH, -5H.

-NN,,-COO)(.

CN, S 03H, -S OzN Ht.

R' -CNH-, R' So□NH-^ Alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group, aromatic hydrocarbon group having 6 to 15 carbon atoms, -O)! , -3
l(, -Nl(,, -〇〇〇H.

-CN, -3o, H, -3O,NH,.

R' CNH-, R' SO2NH-^ Aromatic hydrocarbon group having 6 to 15 carbon atoms substituted with an alkoxy group, etc. (here, R' is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or (represents a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms) The photosensitive materials used in the present invention include the following polyhydroxy compounds having three or more active hydrogens in one molecule; .2-naphthoquinonediazide-5-sulfonyl chloride and/or 1,2-naphthoquinonediazide-
At least one naphthoquinone diazide compound obtained by a condensation reaction with 4-sulfonyl chloride is used.

Examples of such polyhydroxy compounds include polyhydroxybenzophenone having three or more hydroxyl groups in one molecule, such as 2,3.4-)lihydroquine benzophenone, 2,4.6-1-lyhydroquinone, and Hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,
3,4.4'-tetrahydroxybenzophenone, 2,
4.2',4'-tetrahydroxybenzophenone,
3.4,5.4'-tetrahydroxybenzophenone,
2,3,4.2', 4'-pentahydroxybenzophenone, 3,4.5.2', 3'-pentahydroxybenzophenone, 2,3,4.3', 5'-pentahydroxybenzophenone, 2, 3,4.3',4'
, 5'-hexahydroxybenzophenone, 3,4,5
．． 2',4',6'-hexahydroxybenzophenone, 2,3.4.4'-tetrahydroxy-2'-methylbenzophenone, 2,3,4.4'tetrahydroxy-6-methylbenzophenone, 2. 3,4.3'
, 5'-pentahydroxy-4'-ethoxybenzophenone, 3,4.5.2', 3'-pentahydroxy-
4'-acetoxybenzophenone, 3,4,5.3'
, 4'-bentahydroxy-2'-ethoxybenzophenone, 2.3,4.3', 4', 5'-hexahydroxy-61-isopropylbenzophenone, 2,3,
4.4'-tetrahydroxy-3'-chlorobenzophenone, 2,3,4.2'tetrahydroxy-4'-bromomethylbenzophenone, 3,4,5.4'-tetrahydroxydi-2'-nitrobenzophenone, 2.3.3'
, 5'-tetrahydroxy-4,4'-di(trimethylsilyloxy)benzophenone, etc. can be used.

In addition, polyhydroxy compounds obtained by reacting polyhydroxybenzenes with aldehydes or ketones in the presence of an acidic catalyst, such as 2,3,4.2'
, 3', 4'-hexahydroxydiphenylmethane, 2,4.6.2', 4', 6'-hexahydroxydiphenylpropane, 2,3.4.2', 3',
4'-hexahydroxytriphenylmethane or the like can be used.

Similarly, polyhydroxybenzoic acid esters having three or more aromatic hydroxyl groups in one molecule, such as hydroquinone mono(3,4,5-dihydroxybenzoate), phloroglucin mono(3,45-trihydroxy benzoate), phloroglucin-tri(3,4,5
-trihydroxybenzoate), phloroglucin tri(2,4-dihydroxybenzoate), ethylene diglycoluge (3,4,5-trihydroxybenzoate), polyethylene glycoluge (3,4,5-trihydroxybenzoate), etc. You can also do that. Similarly, flavonoid pigments having four or more hydroxyl groups in one molecule, such as quercetin, myrin, morin, astilbin, rutin, and quercitonin, can also be used. Similarly, condensed products such as purbrogalin, tetrahydroxytetralin-1-one, biphenyls such as diresorcinol, diphenylsulfones such as bis(2,4-dihydroxyphenyl)sulfone, and bis(2,3,4-)dihydroxy Biphenyl ethers such as phenyl) ether, biphenyl sulfides such as bis(2,3,4-trihydroxyphenyl) sulfide, and spiro compounds such as bis(dihydroxy spiroindane) and bis(trihydroxy spirochroman) are used. You can also do that. Furthermore, low-nuclear substances of phenolic resins such as novolac resins can be used. Compounds in which a part of the group having active hydrogen in the molecule is silylated can be used, and oligomers or low-nucleated substances of poly(hydroxyphenylsiloxane) or poly(hydroxyphenylsilsesquioxane) can be used for this. You can also do it.

Moreover, a compound having a primary or secondary amino group can be used instead of a hydroxyl group, and examples of such compounds include 2.3.4-1-lihydroxy-11-aminobenzophenone, 2,3.4- ) IJ Hydroxy-1
Examples include 1-monomethylaminobenzophenone.

These active hydrogen compounds are usually used as photosensitive materials by esterifying all or part of their active hydrogen groups with 1,2-nafurquinonediazide, sulfonyl chloride, or the like. A plurality of these photosensitive materials may be mixed, or a photosensitive material containing a compound having two or less active hydrogen groups per molecule may be used.

In addition to these photosensitizers, the photoresist composition of the present invention may contain a sensitizer, an additive for image reversal, or a film property improver, if necessary. As the sensitizer, nitrogen-containing heterocyclic compounds having active hydrogen, such as imidazole, benzimidazole, thiazole, benzthiazole, triazole, imidacillin, hydantoin, thiohydantoin, pyrazolone, and oxazolidinedione, are used. Additionally, a compound having a basic group such as an amino group may be added, or US Pat.
Additives disclosed in European Patent No. 1321, European Patent No. 178594, etc. can be added, and in such a method, a negative mode image can be formed by performing heat treatment and full-surface exposure treatment after exposure. can. Various alkali-soluble resins can be further added to the resist composition of the present invention in order to improve the physical properties of the film. Tokukai Showa 6
0-228522, Japanese Patent Publication No. 61-502219, Japanese Patent Publication No. 61-84642, etc., silicon-containing alkali-soluble phenolic resins are added to improve heat resistance, adhesion, brittleness, etc. Membrane physical properties can be improved. Further, the mixture of these resins can also function as a means for adjusting the alkali solubility of the alkali-soluble polysiloxane or polysilsesquioxane of the present invention.

Solvents used in the present invention include ketones such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethers such as dioxane and ethylene glycol dimethyl ether, and methyl cellosolve. Cellosolve esters such as acetate and ethyl cellosolve acetate, fatty acid esters such as butyl acetate, methyl lactate, and ethyl lactate 1! , 1,1.2-trichloroethylene, and other halogenated hydrocarbons; and highly polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethylformamide, and dimethylsulfoxide. These solvents can be used alone or in combination.

The photoresist composition of the present invention may optionally contain a dye,
Plasticizers, adhesion aids, surfactants, etc. can be blended. Specific examples include dyes such as methyl violet, crystal violet, and malachite green, stearic acid, acetal resin, phenoxy resin,
Plasticizers such as alkyd resins, hexamethyldisilazane,
There are adhesion aids such as chloromethylsilane and surfactants such as nonylphenoxy poly(ethyleneoxy)ethanol and octylphenoxypoly(ethyleneoxy)ethanol.

The developing solution for the photoresist composition of the present invention includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; Amines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy An aqueous solution of an alkali such as a quaternary ammonium salt such as hydrogen chloride, or a cyclic amine such as virol or piperidine can be used. Furthermore, appropriate amounts of alcohols and surfactants may be added to the aqueous alkali solution.

Next, a method of forming a pattern using the photoresist composition of the present invention will be described.

First, a film of an organic polymer material is formed on a substrate such as silicon, and the photoresist composition of the present invention is applied thereon to form a two-layer structure. Then, after heat treatment, the photoresist composition is irradiated with light to make only the irradiated area soluble in a developing solvent, and then the photoresist composition in the irradiated area is removed by development. Next, the photoresist composition in the non-irradiated area was used as a mask,
A pattern is formed by etching away the underlying organic polymer material by dry etching using oxygen gas. The above-mentioned organic polymer material may be any material as long as it can be etched by oxygen plasma, but aromatic-containing polymers are preferred in order to increase resistance when dry etching the substrate using this as a mask after pattern formation. .

Production examples will be shown below, but the present invention is not limited thereto.

(Production Example 1) In a 300 ml flask equipped with a stirrer, a thermometer, and a dropping funnel, 15 g of anhydrous aluminum chloride and 50 III of acetyl chloride are placed and stirred. Next, the molecular weight is 7800
A solution of 5 g of polyphenylsilsesquioxane dissolved in 50 d of acetyl chloride was gradually added dropwise. Temperature 25°
Hydrogen chloride is generated as the reaction progresses. After reacting for 3 hours, the mixture was cooled and the hydrochloric acid contents were poured into ice water. Stir well to decompose the aluminum chloride, make sure the ice water is acidic, and filter out the precipitated polymer. Wash thoroughly with dilute hydrochloric acid and water, and finally dry in a vacuum dryer. The molecular weight of the obtained polymer was 7,900.

The infrared absorption spectrum showed carbonyl group absorption at 1670C1m-', and the NMR showed methyl group absorption at δ2.4, confirming acetylation. The acetylation rate at this time was 60% based on NMR.

(Production Example 2) Add 25 d of stannic chloride and 5 ld of acetic anhydride to a 300 d flask equipped with a stirrer, thermometer, and dropping funnel and stir.Next, dissolve 6 g of diphenylsilanediol in 50 ml of acetic anhydride. was gradually added dropwise.Acetylated polysiloxane was obtained in the same manner as in Production Example 1.

The molecular weight of the obtained polymer was 1500, and the acetylation rate was 42%.

(Production Example 3) 6 g of acetylated polyphenylsilsesquioxane obtained in Production Example 1 was added to 10% of an aqueous solution of sodium hypochlorite.
0 d and reflux for 12 hours. When the resulting clear liquid is made acidic by adding hydrochloric acid, a precipitate forms. A yellowish white solid was obtained by filtration. In the infrared absorption spectrum, the absorption of the carbonyl group of 1670C1+-' disappeared and 1
Carboxyl group absorption was observed at 700 cm-', indicating that carboxylation occurred. Yield 70%.

(Production Example 4) 6 g of acetylated polydiphenylsiloxane obtained in Production Example 2 was added to 100% of an aqueous solution of 10% sodium hypochlorite.
d and reflux for 12 hours. Thereafter, carboxylation was carried out in the same manner as in Production Example 3. Yield 65%.

The carboxylated products obtained in Production Examples 3 and 4 were soluble in alkaline aqueous solutions, methanol, and ethanol, and insoluble in other organic solvents.

(Production Example 5) 5 g of acetylated polyphenylsilsesquioxane obtained in Production Example 1 was dissolved in 100% tetrahydrofuran, 3 g of LipZH was added thereto, and refluxed for 3 hours. After the reaction was completed, 5% hydrochloric acid was added. A yellowish white solid was obtained. Yield 55%.

In the infrared absorption spectrum of the product, 16
The carbonyl absorption of 70C1-' disappeared, and 3100-3
Absorption due to OH group is seen near 400 cm-',
I can confirm that it has been refunded.

(Production Example 6) Acetylated polydiphenylsiloxane 5 obtained in Production Example 2
Dissolve g in 100d of tetrahydrofuran, add 3g to this
of Li 1tl H, was added and refluxed. After the reaction was completed, the mixture was poured into ice water containing 5% hydrochloric acid to obtain a yellowish white solid. Yield 66%.

The polymers obtained in Production Examples 5 and 6 were soluble in alkaline aqueous solutions and alcohols such as methanol.

(Production Example 7) Acetylated polydiphenylsiloxane was produced in the same manner as in Production Example 1, except that polydiphenylsiloxane (molecular weight 10,000) obtained by ring-opening polymerization of cyclic siloxane was used instead of polyphenylsilsesquioxane. I got it.

(Production Example Day) Propionylated polyphenylsilsesquioxane was obtained in the same manner as in Production Example 1, using propionyl chloride instead of acetyl chloride.

(Production Example 9) A propionylated polyphenylsiloxane was obtained in the same manner as in Production Example 7 using propionyl chloride instead of acetyl chloride.

(Production Example 10) 5 g of acetylated polyphenylsilsesquioxane obtained in Production Example 1 0.08 g of trimethylsilyl chloride
was dissolved in 20 ae of tetrahydrofuran and reacted at room temperature for 2 hours. Thereafter, it was reprecipitated with 100 d of n-hexane, filtered, and dried to obtain trimethylsiloxy-modified acetylated polyphenylsilsesquioxane.

(Production Example 11) 5 g of acetylated polysiloxane obtained in Production Example 2, P
- 0.5 g of hydroxybenzyl alcohol.

0.8 g of dicyclohexylcarposiimide was dissolved in 50% of tetrahydrofuran and refluxed for 3 hours.

After the reaction was completed, it was reprecipitated into 200 d of n-hexane, filtered and dried to obtain p-hydroxybenzyloxy-modified acetylated polysiloxane.

(Production Example 12) 5 g of carboxylated polyphenylsilsesquioxane obtained in Production Example 3, 0.3 g of P-toluenesulfoisocyanate, and 0.01 g of dibutyltin dilaurate were dissolved in dioxane 50- and heated to 80°C. After completion of the reaction, the reaction mixture was reprecipitated into 200 d of n-hexane, filtered and dried to obtain P-) luenesulfoisocyanate-modified carboxylated polyphenylsilsesquioxane.

(Production Example 13) 5 g of carboxylated polysiloxane obtained in Production Example 4
, 0.46 g of -P-hydroxybenzoic acid, and 0.69 g of dicyclohexylcarposiimide were dissolved in 50 ml of tetrahydrofuran, and refluxed for 4 hours. After the reaction is complete,
After reprecipitating into 200-g of n-hexane, filtering and drying, a p-hydroxybenzoyloxy-modified carboxylated polysiloxane was obtained.

(Production Example 14) 5 g of hydroxylated polyphenylsilsesquioxane obtained in Production Example 5, 1 g of hydroxythiophenol, and 1.5 g of dicyclohexylcarposiimide were dissolved in 50 W of tetrahydrofuran, and refluxed for 5 hours. 6. Reaction completed. After that, reprecipitation in 200 d of n-hexane, filtration, washing with water,
After drying, a p-hydroxythiol-modified hydroxylated polyphenylsilsesquioxane was obtained.

(Production Example 15) 5 g of hydroxylated polysiloxane obtained in Production Example 6
0.7 g of Sm-aminophenol was dissolved in 30 d of tetrahydrofuran and reacted at 40°C for 3 hours. After completion of the reaction, it was reprecipitated into 500 d of water, filtered, and dried to obtain aminophenol-modified hydroxylated polysiloxane. Ta.

(Production Example 16) 5 g of acetylated polydiphenylsiloxane obtained in Production Example 7 and 0.4 g of dimethylsilylmethyl-p-HCH30 were dissolved in 2011 rl of tetrahydrofuran,
After 2 hours of reaction at 40"C, 200"
After reprecipitation in n-hexane, filtration, and drying, a substituted silyl-modified acetylated polydiphenylsiloxane was obtained.

(Production Example 17) Propionylated polyphenylsilsesquioxane obtained in Production Example 8 5g1 diphenylmethylsilane 0.04
After the completion of the reaction, it was reprecipitated into 200 d of n-hexane, filtered and dried to obtain diphenylmethylsilyl-modified propionylated polyphenylsilsesquisane. Ta.

〔Example〕

Example 1 Ol
A photoresist composition containing 20% by weight of the photoresist represented by 1 OH (1) to (9) was applied to a silicon wafer to a thickness of about 0.2 CI, and prebaked at 80'C for 20 minutes.

After Bribeta, Canon's mask aligner (PLA) was used.
-501F) and was exposed to ultraviolet light. After exposure, each film was developed with a developing solution (tetramethylammonium hydroxide 2.38% by weight in water), and the irradiation amount at which the residual film in the irradiated area became 0 was defined as the sensitivity.

The resolution was determined by measuring the minimum pattern size that can be resolved in a line and space pattern.

Table 1 Comparative Example 1 Cis(1,3 7-tetrahydroxy) 1.3,5,7-tetraphenylcyclotetra Sensitivity and resolution are shown in Table 1.

Example 2 HPR-206 resist (manufactured by Hunt) was coated on a silicon wafer to a thickness of 2 CI, and heated at 200° C. for 30 minutes to insolubilize it. The resist material used in Example 1 was applied on top of this HPR resist at approximately 0.2C by the same operation as in Example 1.
It was coated to a thickness of 1 and prebaked at 80°C for 20 minutes. After prebaking, ultraviolet irradiation and development were performed in the same manner as in Example 1, and the mask pattern was transferred onto the HPR resist. Thereafter, the IPR resist was etched using a parallel plate sputter etching apparatus (using oxygen gas as an etchant gas and the resist pattern as a mask).

By etching for 15 minutes under the conditions of RF power of 0.2 W/aa and O□ gas pressure of 20 mTorr, the HPR resist in the portions not covered by the resist pattern completely disappeared.

0.5 C for any resist material used in Example 1
An I-line and space pattern was formed with a thickness of about 2 CI.

1 part by weight of siloxane, polyphenylsilsesquioxane (Oiens I 1linois, Glass
Re5in GR-950) 19 parts by weight and commercially available positive photoresist 0FPR-800 (Tokyo Ohka) 16
0 parts by weight were mixed to prepare a resist solution. Using this liquid, resist properties were evaluated in the same manner as in Example 1.

The sensitivity is as low as 90 mJ/c1i, and the film loss during etching is less than 0.1 μm in this example with no dimensional change, whereas it is large at 0.5 μm, and the 1 μm line is 0.8 μm.
The dimensions had changed to μm.

(Effects of the Invention) As explained above, the photoresist composition of the present invention in which a positive photosensitive agent is added to an alkali-soluble siloxane polymer becomes a positive photoresist that is highly sensitive to ultraviolet light. Further, since the photoresist composition of the present invention contains silicon, it has high resistance to oxygen plasma, and therefore can be used as an upper layer resist of a two-layer resist. For this reason, 0.5C, which could not be achieved with conventional resist materials,
It has the advantage that fine patterns smaller than I can be formed with a high aspect ratio.

Claims (1)

[Claims] (1) The following general formulas [I] and [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] {However, X is ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲Mathematical formulas, chemical formulas, tables, etc.▼ (R represents a hydrocarbon group or a substituted hydrocarbon group.) is a type selected from the group of carboxyl groups, and may be the same or different, R_1 ,
R_2, R_3, R_4 and R_5 are the same or different and represent hydrogen and a type of group selected from the group consisting of the general formula -Y-R_6. } [-Y-; single bond, -O-, -S-, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲mathematical formula, chemical formula, etc.
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, R_6; hydroxyl group, substituted or unsubstituted aliphatic and aromatic hydrocarbon groups R_7 to R_1_3; substituted or unsubstituted aliphatic and aromatic hydrocarbon groups l, m, n and p are 0 or a positive integer. Indications l and m never become 0 at the same time. ] An alkali-soluble siloxane polymer containing at least one unit represented by in the molecule, a polyhydroxy compound, and 1,2-naphthoquinonediazide-5-sulfonyl chloride and/or 1,2-naphthoquinonediazide-4-
A positive photoresist composition comprising a photosensitive material which is an esterified product with sulfonyl chloride.