JPS6091349A - Composition for negative type electron ray resist - Google Patents

Abstract

PURPOSE:To obtain electron ray resist havng resistance to dry etching by combining bisphenol an dichlorotriazine. CONSTITUTION:A compsn. for negative type electron ray resist is obtd. by incorporating the polycyanurate obtd. by polycondensation of the bisphenol expressed by the formula I and the 2-substd. -4, 6-dichloro-Sym-triazine expressed by the formula II therein. Ar in the formula I is the group expressed by -C6H4-Q-C6H4- and one or two of the hydrogen atoms of respective benzene rings may be substd. with halogen. Q is the group expressed by -CR<1>R<2>-, -S-, -CR<3>(OH)-. R<1> and R<2> denote respectively a hydrogen atom, lower alkyl group or -CH2CO2H. R<3> denotes a lower alkyl group. R in the formula II denotes -N(CH2CH=CH2)2, -NHCH2CH=CH2, -OCH2CH=CH2, -O-glycidyl.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a negative electron beam resist composition. More specifically, the present invention relates to the general formula HO-Ar-OH (
I) (wherein Ar is a group represented by the formula, X is a logon atom,
n represents Oll or the number 2, q represents eagle, R1 and R2 each represent a hydrogen atom, a lower alkyl group, or -
CH2COOH, R3 represents a lower alkyl group, and the 10H group in formula (I) is bonded to the ortho or para position with respect to the group -Q; General formula, . L-/゛＼. -6el II lul (wherein, R is -N(CH2CH=CH2)2, -NH
CH2CH=CH2, -〇CH2CH=CH2 or -0
A negative-tone electron beam resist composition characterized by containing poly/americate obtained by polycondensation with 2-substituted-4,6-fuchloroS triazine represented by CH2CH-CH2)\1 Regarding.

In recent years, as integrated circuits have progressed from LSI to ultra-LSI, microfabrication technology has come to require submicron processing accuracy. In order to realize these technologies, lithography technology is also transitioning from conventional photolithography to electron beam lithography, and at the same time, the Renost material used in electron beam lithography is also being developed with high sensitivity and high resolution. materials are required.

Furthermore, in recent years, microfabrication technology has been largely shifting toward the use of gas phase, ie, dry processing, and high sensitivity and high resolution resist materials are now required to have plasma dry etching resistance.

The electron beam renost that had been developed previously had high resolution in the case of a square shape, but had the drawbacks of low sensitivity and poor dry etching resistance. On the other hand, in the case of a negative type, the resolution is slightly lower than that of a negative type, but the sensitivity is higher.
It has been shown that polymers with aromatic rings introduced into their structures also have good plasma dry etching resistance. However, it is generally known that introducing an aromatic ring into a polymer structure is advantageous for improving plasma dry etching resistance, but it also reduces sensitivity. In the development of resists, we maintain the high sensitivity characteristic of negative resists,
In addition, it has become an important issue to improve the dry etching resistance by introducing an aromatic ring.

In view of this situation, the present inventors aimed to create a material that can be used in electron beam phosphorography, which is important in submicron processing technology, and has high dry etching resistance. As a result of research on negative-tone electron beam-sensitive resins in which aromatic rings have been introduced, it was found that polycyanurate obtained by polycondensation of the compound of general formula CI) and the compound of general formula (■) is sensitive to electron beams. They found that the resist composition is flexible and suitable for submicron processing, and succeeded in providing a new negative-working electron beam resist composition.

Therefore, the present invention provides a negative electron beam resist characterized by containing polycyanurate obtained by polycondensing the compound of the general formula (I) and the compound of the general formula (Ill). It is.

As the bisphenol type compound of the general formula (■),
For example, bisphenol A, 4,4'-thionophenol, phenolphthalein, diphenolic acid, bis-
(2-hydroxy-5=chlorophenyl) sulfide,
212'-methylenebis-(4-chlorophenol),
Bithionol, 3,4-bis(p-hydroxyphenyl)-3,4-hexanediol, 2,3-bis(p-
Hydroxyphenyl)-2,3-butanol is mentioned. The compounds of the general formula (2-substituted 4,6-fuchloro-S-trianone type) include 2-diallylamino-4,6-cyclos-)ryanone, 2-allylamino-4,6-nochloro-triazine , 2-substituted 4,6-dichloro-6-triazine, 2-glycidyloxy-4,6-cycloS-trianone, etc.
-) ' Methods for synthesizing J anone-type compounds are described, for example, in the Journal of the American Chemical Society, Vol. 73 (1951), p. 2981, and U.S. Patent No. 3,127,399 (1964 )It is described in).

Examples of solvents used in the compositions of the invention include:
N,N-trimethylformamide, cyclohexanone, 4
- Methylcyclohexanone, chloroform, etc.
These may be used alone or in mixtures.

When using the composition of the present invention, it is applied onto a target substrate such as Sl or SiO2 by a spin coating method, baked in an open environment, and then irradiated with an electron beam. The irradiated substrate is then developed with a solvent such as N,N-methylformamide, cyclohexanone, methyl ethyl ketone, acetone, or chloroform, and rinsed with a solvent such as a lower alcohol. Further, after development and baking, a desired material, such as Sl or 5102, is etched, thereby making it possible to carry out desired high-precision microfabrication.

The present invention will be described in more detail below with reference to synthesis examples of the constituent substances of the compositions of the present invention and examples of the compositions of the present invention, but the present invention is not limited to these Examples.

Synthesis Example 1 Synthesis of polycondensate of diphenolic acid and 2-aziloquine-4,6-nochloros-)rianone 2-aryloquine/-
3.12 of 4+6-dichloro-〇-trianone was dissolved in 32.5 mJ of nitrobenzene, and diphenolic acid 4
．． A sodium hydroxide aqueous solution containing 31F and 1 ml of a cationic surfactant (a solution of 1.35f of sodium hydroxide dissolved in 50we of water) was quickly added at 6 to 7°C, and the temperature was kept constant. Stirring was continued for 5 hours.

After the reaction was completed, the reaction solution was neutralized, and the precipitated polymer was dissolved in acetone and dropped into methanol to precipitate it. Next, the precipitated polymer was separated from P, washed with methanol, taken out, dried, diphenolic acid and 2-aziloquine-4
, 6-dichloro-8-triazine was obtained.

Synthesis example 2 4.4'-thionophenol and 2-noarylamino4
Synthesis of polycondensate with ,6-sochloro-e-triazine 31 of 2-diallylamino-4,6-nochloro-e-trianone and 2.77 of 4,4'-thionophenol were dissolved in 35 ml of nitrobenzene. Cationic surfactant 1 vtl dissolved in sodium hydroxide aqueous solution (
A solution of 0.52 f of sodium hydroxide dissolved in 20.5 mJ of water) was quickly added at 50°C, and the mixture was stirred for 30 minutes while keeping the temperature constant.

Next, the temperature of the reaction solution was raised to 80 °C, and an aqueous sodium hydroxide solution (a solution of 0.52 f of sodium hydroxide dissolved in 5.5 m/! of water) was added again, and while keeping the temperature constant, Stir for hours. After the reaction is complete, the reaction solution is completely neutralized, the nitrobenzene layer is dropped into methanol to precipitate the polymer, separated by f, washed with methanol, taken out and dried, 4.
4'-thionophenol and 2-diallylamino-4,6
A polycondensate with -dichloro-5-)rhanone was obtained.

Synthesis Example 3 Synthesis of polycondensate of diphenolic acid and 2-diallylamino-4,6-nochloro-s-triano/2-diallylamino-4,6%-dichloro-S-trianone (13.22 ml) was added to 153 ml of toluene. Dissolve,・
To this, a sodium hydroxide aqueous solution (a solution of 6.87 sodium hydroxide dissolved in 90 ml of water) containing 15.4 f of diphenolic acid and 3.5 ml of a cationic surfactant was quickly added at 70°C. The mixture was stirred for 4 hours while keeping the temperature constant. After the reaction was completed, the reaction solution was neutralized, the precipitated polymer was dissolved in acetate, and the solution was dropped into n-hegetane to precipitate the polymer. Next, the precipitated polymer was separated from P, washed with n-hebutane, taken out and dried to obtain a polycondensate of diphenolic acid and 2-diallylamino-4,6-dichloro-5-)riazine. Synthesis Example 4 4.4'-thiodiphenol and 2-allyloxy-4,6
-Synthesis of polycondensate with dichloro-s-triazine 2-allyloxy-4,6-dichloro-8-triazine 3
．． Dissolve 82 in 33 ml of nitrobenzene and add 4,
4'-thionophenol 37 and cationic surfactant 6
．． Quickly add 5 ml of sodium hydroxide aqueous solution (sodium hydroxide l) A solution of 1.23 f of rum dissolved in 130 ml of water at 6 to 7°C, and keep the temperature constant for 5 hours. Stirring was performed.

After the reaction is completed, the reaction solution is neutralized, and the nitrobenzene layer is dropped into methanol to precipitate the polymer, which is washed with methanol, taken out and dried, and 4,4'-thionophenol and 2- Allyloxy-4,6-dichloro-
A polycondensate with S-trianone was obtained.

Synthesis Example 5 Bis-(2-hydroxy-5-chlorophenyl) sulfide and 2-diallylamino-4,6-dichloro-5-)
Synthesis of polycondensate with riazine 2-diallylamino-4
, 6-nochloro-8-triazo/3ri and bis-(2-hydroxy-5-chlorophenyl) sulfite 3.59 wo = ).

Sodium hydroxide dissolved in 35 ml of benzene and 0.8 ml of a cationic surfactant dissolved therein) Rum water soluble RI (a solution of 0.52 ml of sodium hydroxide dissolved in 26 rnl of water) was heated at 50°C. The mixture was added quickly and stirred for 9 minutes while keeping the temperature constant. Next, the reaction solution is FM)'
The temperature was raised to 50°C, and an aqueous sodium hydroxide solution (a solution of 0.57 sodium hydroxide dissolved in 19.8 m# of water) was added again, and the mixture was stirred for 5 hours while keeping the temperature constant. After the reaction was completed, the reaction solution was neutralized, and the nitrobenzene layer was dropped into methanol to precipitate the polymer. After separation, the polymer was washed with methanol, taken out, dried, and bis-(2-hydroxy-5-chlorophenyl ) A polycondensate of sulfide and 2-diallylamino-4,6-dichloro-8-triazine was obtained.

Synthesis Example 6 Synthesis of polycondensate of bisphenol A and 2-diallylamino-4,6-nochloro-s-trianone 2-diallylamino-4,6-dichloro-〇-triazine 3f and bisphenol A 2.8 f onitrobenze 724 A sodium hydroxide aqueous solution (a solution in which 0.52 f of sodium hydroxide was dissolved in 20.4 rrrl of water) in which 0.82 ml of a cationic surfactant was dissolved was quickly added at 50°C. Stirring was performed during addition while keeping the temperature constant.

Next, the temperature of the reaction solution was raised to 80°C, and an aqueous sodium hydroxide solution (a solution of 0.5 J of sodium hydroxide dissolved in 5.3 ml of water) was added again, and the temperature was kept constant for 5 hours. Stirred. After the reaction is completed, the reaction solution is neutralized, and the nitrobenzene layer is dropped into methanol to precipitate the polymer.
After separation, the mixture was washed with methanol, taken out, and dried to obtain a polycondensate of bisphenol A and 2-diallylamino-4,6-dichloro-s-)riadi/.

Synthesis Example 7 Synthesis of polycondensate of bisphenol A and 2-allyloxy-4+ 6-cyclos-triazine 3.17 ml of 2-aryloxy-7-4,6-dichloro-8-triazine was dissolved in 32.5 ml of nitrobenzea. Add 3.42 r of bisphenol A and 6.3 ml of cationic surfactant to this.
An aqueous solution of sodium hydroxide (a solution in which 1.26 ml of sodium hydroxide was dissolved in 125 ml of water) was quickly added at 7°C, and the mixture was stirred for 5 hours while keeping the temperature constant. After the reaction is completed, the reaction solution is neutralized, and the nitrobenzene layer is dropped into acetone to precipitate the polymer, which is separated from each other and washed with acetone, taken out, dried, and bisphenol A and 2-acroquine-4,6-dichloro A polycondensate with O-s-) riazine was obtained.

Synthesis Example 8 Bisphenol A and 2-acroquine-4,6-dichloro
-B-) Synthesis of epoxidized polycondensate with liapolyne Polycondensate 27 of bisphenol A and 2-acroquine-4,6-dichloro-s-triazine synthesized according to Synthesis Example 7 was added to chloroporm 50 Ill. Dissolved, added 0.57 m-chloroperbenzoic acid, and stirred at 50°C for 1 hour. After the reaction is completed, the reaction solution is dropped into methanol to precipitate the polymer, which is washed with methanol and then taken out and dried to obtain bisphenol A and 2-allyloki/-4,
An epoxidized product of a polycondensate with 6-dicoulor S-triazine was obtained.

Synthesis Example 9 Phenolphthalein and 2-diallylamino-4,6-
Synthesis of polycondensate with dichloro-s-triazine 2-diallylamino-4,6-dichloro-S-triazine 32 and phenolphthalein 3,9f were dissolved in 35 ml of nitrobenzene, and a cationic surfactant was added to the solution. 0
．． 8 ml of a sodium hydroxide aqueous solution (a solution of 0.77 r of sodium hydroxide dissolved in 20.4 ml of water) was quickly added at 10° C. and stirred for 1 hour while keeping the temperature constant.

Next, the temperature of the reaction solution was raised to a leap degree of °C, and a sodium hydroxide water bath was applied! (
A solution of 0.779 sodium hydroxide dissolved in 5.3 ml of water) was added again and stirred for 5 hours while keeping the temperature constant. After the reaction is completed, the reaction solution is neutralized, and the nitrobenzene layer is dropped into methanol to precipitate the polymer, which is separated from each other, washed with methanol, taken out and dried, and phenolphthalein and 2-diallylamino-4,6- A polycondensate with dichloro-5-)riazine was obtained.

Example 1 A polycondensate of diphenolic acid and 2-aryloki'y-4,6-dichloro-s-triazine synthesized according to Synthesis Example 1 was dissolved in cyclohexanone to prepare a solution having a concentration of 12 wt%. Next, this solution was applied to a film thickness of 0.5 μm on a silicon wafer by spin coating, baked in an oven at 85°C for 10 minutes, and then exposed to an electron beam using an electron beam irradiation device with an acceleration voltage of 15 KV. Irradiated. After irradiation, the film was developed using N,N-dimethylformamide and rinsed with Inglobil alcohol.

The sensitivity of this product to electron beams is 2.
5 μc/crn”.

Example 2 A polycondensate of 4,4'-thiodiphenol and 2-diallylamino-4,6-dichloro-s-triazine synthesized according to Synthesis Example 2 was dissolved in cyclohexanone to form a solution with a concentration of 12 wt%. Prepared.

Next, using this solution, the coating operation, baking operation, and electron beam irradiation were performed in the same manner as in Example 1, followed by development using N,N-dimethylformamide, and rinsing with isoglobil alcohol. . The sensitivity of this material to electron beams was 0.85 pc/crn2 when 50% film remained.

Example 3 A polycondensate of diphenolic acid and 2-diallylamino-4,6-dichloro-8-triacinth synthesized according to Synthesis Example 3 was dissolved in cyclohexanone to prepare a solution having a concentration of 12 wt%. Next, using this solution, coating operation, baking operation, and electron beam irradiation were performed in the same manner as in Example 1, followed by development using cyclohexanone and rinsing with isopropyl alcohol. The sensitivity of this material to electron beams was 2.7 μc/crX when there was a large amount of 5O remaining film.

Example 4 A polycondensate of 4,1'-thiodiphenol and 2-allyloxy-4,6-dichloro-8-triazine synthesized according to Synthesis Example 4 was dissolved in cyclohexanone to a concentration of 12
A solution of wtZ was prepared. Next, using this solution, coating operation, baking operation, and electron beam irradiation were performed in the same manner as in Example 1, followed by development using N,N-dimethylformamide, and rinsing with isopropyl alcohol.

This material showed good sensitivity to ID electron beams.

Example 5 Bis-(2-hydroxy-5) synthesized according to Synthesis Example 5
-chlorophenyl)sulfitodo2-diallylamino-
A polycondensate with 4,6-dichloro-s-triazine was dissolved in cyclohexanone to prepare a solution having a concentration of 12 wt%. Next, using this solution, coating operation, baking operation, and electron beam irradiation were performed in the same manner as in Example 1.
-Developed using dimethylformamide and rinsed with isopropyl alcohol. This product showed good sensitivity to electron beams.

Example 6 A polycondensate of bisphenol A and 2-diallylamino-4,6-dichloro-8-triazine synthesized according to Synthesis Example 6 was dissolved in chloroform to prepare a solution having a concentration of 12 wt%. Next, using this solution, coating operation, baking operation, and electron beam irradiation were performed in the same manner as in Example 1, followed by development using N,N-dimethylformamide and rinsing with isopropyl alcohol. The sensitivity of this material to electron beams is 6.6μc/c when 50% film remains.
It was m2.

Example 7 A polycondensate of bisphenol A and 2-allyloxy-4,6-dichloro-s-triazine synthesized according to Synthesis Example 7 was dissolved in chloroform to prepare a solution having a concentration of 12 wt%. Next, using this solution, coating operation, baking operation, and electron beam irradiation were performed in the same manner as in Example 1, followed by development using chloroform and rinsing with isopropyl alcohol. This one is good against electron beams,
showed sensitivity.

Example 8 The agiquinated polycondensate of bisphenol A and 2-acroquine-4,6-dichloro-s-triazine synthesized according to Synthesis Example 8 was dissolved in cyclohexanone to prepare a solution with a concentration of 12 wt%. Next, using this solution, coating operation, baking operation, and electron beam irradiation were performed in the same manner as in Example 1, followed by development using N,N-dimethylformamide, and rinsing with isopropyl alcohol. The sensitivity of this material to electron beams was 4.0 μC/cm2 when 50% film remained.

Example 9 Phenolphthalein synthesized according to Synthesis Example 9 and 2-
Polycondensate f with diallylamino-1,6-dichloro-s-t') azine: A 12 wt% solution was prepared by dissolving in N,N-dimethylformamide. Next, using this solution, coating operation, baking operation, and electron beam irradiation were performed in the same manner as in Example 1, and then development was performed using N,N-dimethylformamide, and 1 ml of isopropyl alcohol was used. This one showed good sensitivity to electron beams.

Claims (1)

[Claims] 1) General formula, HO-Ar-OH (1) (wherein Ar is a group represented by the formula, X is a halogen atom, n
represents a number of 0.1 or 2, R3 represents a hydrogen atom, a lower alkyl group, or -CH3COO)1, R3 represents a lower alkyl group, and the (assumed to be bonded at the oron position or para position) and the general formula, (wherein R is
-N(CH3CH=CH2)2, -NHCH2CH=C
1. A negative electron beam Renost composition comprising a polycyanurate obtained by polycondensation with 2-substituted-4,6-dichloro-S triazine represented by H2. 2) The negative electron beam Renost composition according to claim 1, wherein Ar in the general formula (■) is a group selected from OHOH.