JPS6230241A - Photoresist composition - Google Patents

Abstract

PURPOSE:To obtain a photoresist composition superior in antihalation ability, resolution, film retentivity, and adhesion of its coat to a substrate by adding a photocross-linking agent and a specified compound to a cyclized conjugated diene polymer or copolymer. CONSTITUTION:The photoresist composition consisting of the cyclized conjugated diene polymer or copolymer, preferably, such as a cyclized isoprene or butadiene homopolymer, and the photocross-linking agent, preferably, such as an azido type photosensitive material soluble in organic solvents, e.g., 4,4-diazidostilbene, contains as a halation inhibitor the compound represented by the formula shown on the right, such as 5-hydroxy-3-methyl-4-phenylazo-1-phenylpyrazole, thus permiting prebaking conditions not to be affected even in the case of using a substrate high in reflectivity, and an image high in resolution to be obtained with high reproducibility, and yet the adhesion of the photoresist composition to the substrate not to be lowered.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to photoresist compositions. More specifically, the present invention relates to a photoresist composition comprising a cyclized product of a conjugated diene polymer or copolymer (hereinafter simply referred to as a conjugated diene polymer), a photocrosslinking agent, and a specific compound.

b. Conventional Technology Recent advances in integrated circuit manufacturing technology have been remarkable, with the degree of circuit integration increasing at an annual rate of twice as much. Therefore, there is a strong demand to improve not only the manufacturing technology but also the equipment and peripheral materials used, and in the photoresist field, photocrosslinking agents have been added to cyclized products of conjugated diene polymers to create photoresist compositions with excellent handling and high resolution. Photoresist compositions containing the following are known.

However, when using such a photoresist composition on a highly reflective substrate such as aluminum, the light that passes through the resist layer during exposure and is reflected on the substrate surface wraps around the area that is not desired to be exposed (this phenomenon is called halation). ), and as a result, it is not possible to accurately reproduce the fine patterns necessary for manufacturing integrated circuit elements.This phenomenon is particularly noticeable in the stepped structure of the substrate, and is caused by so-called whiskers. There was a problem in that the resolution was lowered due to the formation of a hardened portion called the hardened portion.

In order to solve this problem, methods described in Japanese Patent Publication No. 51-37562 and Japanese Patent Application Laid-open No. 59-214847 have been proposed. These technologies reduce the light transmittance of the photoresist composition coating by adding light-absorbing materials, so-called dyes, to the photoresist composition as antihalation agents, thereby minimizing the amount of light that passes through the substrate during exposure. This is what I am trying to do.

C3 Problems to be Solved by the Invention In the prior art described above, for example, when Oil Yellow (trade name) shown in Japanese Patent Publication No. 51-37562 is used as a light-absorbing material, it reflects on the substrate surface and destroys the photoresist composition coating. The light that passes through is absorbed by the light-absorbing material and is rapidly attenuated, making it possible to prevent a decrease in resolution due to the light going around to areas that are not desired to be exposed.

However, the photoresist composition applied to the substrate needs to be preheated at 80 to 100°C to remove the residual solvent. The problem is that the antihalation effect is greatly affected by the pre-beta processing conditions, such as volatilization from the film and the antihalation effect is not sufficient, resulting in poor reproducibility. In addition, a decrease in the adhesion of the photoresist composition coating to the substrate cannot be avoided, which is a major drawback of the prior art.

Furthermore, if the dye disclosed in JP-A-59-214847 is used as a light-absorbing material, the volatilization during pre-beta and the resulting decrease in the antihalation effect can be eliminated, but the problem with resolution and the substrate of the photoresist composition coating film can be eliminated. The disadvantages are that the adhesion and adhesion of the photoresist composition may decrease, and the photoresist composition coating may peel off from the substrate during development, making it unsuitable for forming the fine patterns necessary for manufacturing integrated circuit devices. Was.

d8 Means for Solving Problems The present inventors have studied ways to improve the above-mentioned drawbacks, and have added a compound of the general formula to a photoresist composition consisting of a cyclized product of a conjugated diene polymer and a photocrosslinking agent to prevent haleysilane. By using a photoresist composition containing the additive as an agent, even when using a substrate with a high reflectance surface, it is not affected by the blebake conditions, and images with good reproducibility and high resolution can be obtained. Furthermore, the inventors discovered that there was no problem in the adhesion of the photoresist composition to the substrate, and based on this finding, they completed the present invention.

The cyclized product of the conjugated diene polymer used in the present invention is a cyclized product of a polymer or copolymer having a repeating structural unit represented by the following formula in the polymer chain.

V-drop-C-R mushroom・Specific examples of the repeating structural unit include cis-1
, 4-butadiene unit, trans-1,4-butadiene unit, cis-1,4-isoprene unit, trans-1,
4-isoprene unit, cis-1,4-pentadiene unit, trans-1,4-pentadiene unit, 1.4-2-
phenylbutadiene unit, 1,2-butadiene unit, 3
, 4-isoprene unit, 1.2-pentadiene unit, 3
Examples of unsaturated monomer units that can form a copolymer together with 4-2-phenylbutadiene units include vinyl aromatic units such as styrene and α-methylstyrene; Examples include group compound units, olefin units such as ethylene, propylene, and isobutylene.

As the cyclized products of these conjugated diene polymers, cis-
1,4-isoprene unit, trans-1°4-isoprene unit, 3.4-isoprene unit, cis-1,4-butadiene unit, trans-1°4-butadiene unit, 1,
A cyclized product of a polymer or copolymer having 2-butadiene units is preferred, and a cyclized product of a homopolymer of isoprene or butadiene is particularly preferred. Although not limited, preferably 5 to 95%, particularly preferably 10 to 90%
%, most preferably 15-50%. Note that the amount of remaining double bonds is expressed as follows. (*: Measured by NMR) The photocrosslinking agent used in the present invention is an azide-based photosensitive substance soluble in an organic solvent, such as 4. 4'-diazidostilbene, p-phenylenebisazide, 4.4'-diazidobenzophenone, 4.4'-diazidodiphenylmethane, 4. 4'-Diazidochalcone, 2,6-bis(
4'-azidobenzal)cyclohexanone, 2.6-
Bis(4'-azidobenzal)-4-methylcyclohexanone, 4°4'-diazidodiphenyl, 4.4'
-diazide-3.3'-dimethyldiphenyl, 2.7-
Examples include diacid fluorene. However, the photocrosslinking agent is not limited to these, and any photocrosslinking agent that is effective in combination with the cyclized product used in the present invention can be used. These photocrosslinking agents are preferably used by adding 0.1 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, per 100 parts by weight of the cyclized product of the conjugated diene polymer. be done.

For example, the compound having the general formula 5-hydroxy-3-methyl-4-phenylazo- 1-phenylpyrazole, 5-acetoxy-3-methyl-4-phenylaso21-phenylpyrazole, 5-trimethylsiloxy-3-methyl-4-phenylazo-1-phenylpyrazole, 5-hydroxy-3-methyl-4- 1)-) Gluazo-1-phenylpyrazole, 5-hydroxy-3
-Methyl-4-m-)gluazo-1-phenylpyrazole, 5-hydroxy-3-methyl-4-o-)gluazo-1-phenylpyrazole, 5-hydroxy-3-methyl-4-(3',4 '-dimethylphenylazo)-1-
Phenylpyrazole, 5-hydroxy-3-methyl-4
-p-chlorophenyla/'-1-phenylpyrazole, 5-hydroxy-3-methyl-4-p-bromophenylazo-1-phenylpyrazole, 5-hydroxy-3
-Methyl-4-p-nitrophenylazo-1-phenylpyrazole, 5-hydroxy-3-ethyl-4-phenylazo-1-phenylpyrazole, 5-hydroxy-3
-n-propyl-4-phenylazo-1-phenylpyrazole, 5-hydroxy-3-1so -propyl-4
-phenylazo-1-phenylpyrazole, 5-hydroxy-3-methyl-4-phenylazo-1-p-)lylpyrazole, 5-hydroxy-3-methyl-4-phenylazo-1-m-tolyruvirazole, 5- hydroxy-
3-Methyl-4-phenylazo-1-0-)lylpyrazole, 5-hydroxy-3-methyl-4-phenylazo-1-(4',5'-dimethylphenylpyrazole), 5-hydroxy-3-methyl- 4-Phenylazo-
1-p-chlorophenylpyrazole, 5-hydroxy-
3-Methyl-4-phenylazo-1-p-bromophenylpyrazole, 5-hydroxy-3-methyl-4-phenylazo-1-p-nitrophenylpyrazole, 5-hydroxy-3-methyl-4-phenylazo-1- naphthylpyrazole, 5-hydroxy-3-n-butyl-4-
Phenylazo-1-phenylpyrazole, 5-hydroxy-3-tert-butyl-4-phenylazo-1-phenylpyrazole, 5-hydroxy-3-cyclohexyl-4-phenylazo-1-phenylpyrazole, 5-
Hydroxy-3-chloromethyl-4-phenylazo-1
-Phenylpyrazole, 5-hydroxy-3-trimethylsilylmethyl-4-phenylazo-1-phenylpyrazole, 5-hydroxy-3-p-chlorophenyl-4
-phenylazo-1-phenylpyrazole, 5-methoxy-3-methyl-4-phenylazo-1-phenylpyrazole, 5-ethoxy-3-methyl-4-phenylazo-1-phenylpyrazole, 5-methoxyethoxy-3
-ethyl-4-phenylazo-1-phenylpyrazole, 5-trifluoroacetoxy-3-isopropyl-4
-phenylazo-1-phenylpyrazole, 5-hydroxy-3-vinyl-4-(4'-chlorophenylazo)
-1-phenylpyrazole, 5-methoxy-3-allyl-4-phenylazo-1-(4'-7'romophenylpyrazole), 5-)samethylsiloxy-3-isoprenyl-4-(4'-di trophenylazo)-1-phenylpyrazole, 5-phenoxy-3-acetylyl-4-
Phenylazo-1-(4'-anispyrazole), 5
-benzyloxy-3-cinnamyl-4-phenylazo-
1-(4'-anispyrazole), 5 tert
-butoxy-3-methyl-4-phenylazo-1-phenylpyrazole, and the like.

These are preferably added in an amount of 0.1 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, per 10.0 parts by weight of the cyclized product of the conjugated diene polymer. If the amount added is less than 0.1 part by weight, the effect of the addition is small, and if it is added in excess of 10 parts by weight, defects such as a low residual film rate after development may occur.

A sensitizer can also be added to the photoresist composition of the present invention. Examples of the sensitizer include benzophenone, anthraquinone, l,2-naphthoquinone, 1,4-naphthoquinone, 2-methylanthraquinone, benzanthrone, violanthrone, 9-anthraaldehyde, benzyl, p,p'-tetramethylazimino benzophenone,
Carbonyl compounds such as chloranil, aromatic hydrocarbons such as anthracene and chrysene, nitrobenzene, p-dinitrobenzene, 1-nitronaphthalene, p-nitrodiphenyl, 2-nitronaphthalene, 2-nitrofluorene, 5-nitroacenaphthene, etc. Nitro compounds, nitroaniline, 2-chloro-4-nitroaniline, 2.
6-') Chloro-4-nitroaniline, 5-nitro-2
Examples include nitrogen compounds such as -aminotoluene and toteracyanoethylene, and sulfur compounds such as diphenyl sulfide.

Storage stabilizers can also be added to the photoresist compositions of the present invention, such as hydroxyaromatic compounds such as hydroquinone, methoxyphenol, pt-butylcatechol, quinones such as benzoquinone, p-torquinone, p-xyquinone, etc. amines such as phenyl-α-naphthylamine, p,p′-”diphenylphenylenediamine, dilaurylthiodibrobionate, 4,4
-thiobis(6-t-butyl-3-methylphenol,
2.2-thiobis(4-methyl-6-t-butylphenol), 2-(3,5-di[-butyl-4-hydroxyanilino)-4,6-bis(N-octylthio)-
Sulfur compounds such as s-triazine can be used.

Furthermore, the photoresist composition of the present invention may contain other antihalation agents, such as 1,3-diphenylpyrazoline, 1,3
．． 5-triphenylpyrazoline, ■-phenyl-3-m
-) Riluvirazoline, 1-m-) Dyl-3-phenylpyrazoline, 1-phenyl-3-p-bromophenylpyrazoline, 1.3-di-m-tolylpyrazoline, 1.3-
Diphenyl-5-methylpyrazoline, 1,5-diphenyl-3-p-tolylpyrazoline, 1.5-diphenyl-
3-1)-Methoxyphenylpyrazoline, 1.5-diphenyl-3-p-ethoxyphenylpyrazoline, 1.5
-diphenyl-p-phenoxyphenylpyrazoline, 1
．． 5-diphenyl-3-(p-phenyl)phenylpyrazoline, 1,5-diphenyl-(p-ethoxy-m-methyl)phenylbirapurine, 1-phenyl-3,5-di(p-chlorophenyl)phenylpyrazoline Zorin, 1゜3
-diphenyl-5-p-methoxyphenylbirapurine,
1-phenyl-3-p-methoxyphenyl-5-p-tolylpyrazoline, 1-phenyl-3-p-tolyl-5-
Methoxyphenylpyrazoline, 1-phenyl-3,5-
Di(p-methoxyphenyl)pyrazoline, ■, 5-diphenyl-3-α-naphthylpyrazoline, 1,5-diphenyl-3-β-naphthylpyrazoline, 1.3,4.5-
Tetraphenylpyrazoline, 1,3.5.5. -tetraphenylpyrazoline, 1.3.4-)diphenylpyrazoline, 1. 5-') Aliphatic nitrogen-containing compounds such as phenyl-3-styrylpyrazoline, 1-β-naphthyl to 3-styryl-5-phenylpyrazoline, l-phenyl-3-chlorostyryl-5-phenylviraprine, 4 -Methyl-7-dinithylaminocoumarin, 3-phenyl-7-
Acetylaminocoumarin, 3-p-)Lilu-7-acetylaminocoumarin, 3-phenyl-4-methyl-7-dinithylaminocoumarin, 3-p-)Lilu-7-diethylaminocoumarin, 3-p-methoxyphenyl-4 - Aromatic esters such as ethyl-7-dinithylaminocoumarin, 2,6-bis(4'-dimethylaminobenzal)
Cyclohexanone, 2゜6-bis(4'-dimethylaminobenzal)-4-methylcyclohexanone, 2,6-
Bis(4'-diethylaminobenzal)cyclohexanone, 2゜6-bis(4'-diethylaminobenzal)-
4-Methylcyclohexanone, 2,6-bis(4'-
dipropylaminobenzal) cyclohexanone, 2.6
-bis(4'-dipropylaminobenzal)-4-
Methylcyclohexanone, 2.6-bis(4'-dimethylaminobenzal)-4-ethylcyclohexanone, 2
,6-bis(4'-diethylaminobenzal)-4
-Ethylcyclohexanone, 2,6-bis(4'-dipropylaminobenzal)-4-ethylschif-11hetosanone, 2.6-bis(4'-dimethyl゛)'minobenzal)-4-propylhexanone, 2.6 -Bis(4'
-diethylaminobenzal)-4-propylhexanone, 2.6-bis(4'-dibrobylaminobenzal)-4-propylhexanone, 2.6-bis(4'-aminobenzal)cyclohexanone, 2゜6- Screw (4'
-aminobenzal)-4-methylcyclohexanone, 2
．． 6-bis(4'-aminobenzal)-4-ethylcyclohexanone, 2゜6-bis(4'-aminobenzal)-4-propylcyclohexanone, 1.3-bis(4
′ -aminobenzal)acetone, 1,3-bis(4′
-dimethylaminobenzal)acetone, l,3-bis(
4'-diethylaminobenzal)acetone, 1°3-bis(4'-dipropylaminobenzal)acetone, 2.
4-bis(4'-aminobenzal)pent-3-one, 2.4-bis(4'-dimethylaminobenzal)pent-3-one, 2.4-bis(4'-diethylaminobenzal)pent-3-one 3-one, 2,4-bis(4'-
dipropylaminobenzal) pent-3-one, 2,6
-bis(3'-diethylaminobenzal)cyclohexanone, 2,6-bis(3'-diethylaminobenzal)-4-methylcyclohexanone, 2,6-bis(3'
-diethylaminobenzal-4-ethylcyclohexanone, 1,3-bis(3'-diethylaminobenzal)acetone, 2,4-bis(3'-diethylaminobenzal)pent-3-one and other nitrogen-containing aliphatic and Aromatic carbonyl compounds and the like can be used.

The photoresist composition of the present invention is usually used as a solution in an organic solvent such as meta-xylene, mixed xylene, or toluene, and the solid content concentration at this time is generally 5 to 30% by weight.

e. Examples The present invention will now be explained in more detail with reference to Examples and Comparative Examples; however, the present invention is not limited to these Examples unless the gist of the invention is exceeded.

Example 1 Cis-1,4-polyisoprene cyclized product (2,6-bis(4'-azidobenzal) as a photocrosslinking agent in the remaining dichloromethane)
Cyclohexanone 0.55g, 2 as storage stabilizer,
0.11 g of 2'-methylenebis(4'-methyl-6-t-butylphenol) and 4. 4'-thiobis(2,6-di-t-butylphenol) 0.11g
, a predetermined amount of 5-hydroxy-3-ethyl-4-(P-)lylazo)-1-phenylpyrazole as an antihalation agent and 88.0 mj of xylene! A photoresist composition was prepared by mixing the following.

The photoresist composition thus prepared was coated to a thickness of 0.2
The film thickness after drying is 1.0μ on a silicon wafer with a step structure of 0.7μ■ on which a μm aluminum layer is vapor-deposited.
It was coated by rotating using a spinner so that the color was -. Then, it was dried for 90 seconds on a hot plate kept at 120°C, and then an ultra-high pressure mercury lamp was used at a light intensity of 50 W/rrf.
Resolution test chart Exposure through a chrome mask and print the image. V[L
OPf! After immersing and developing for 1 minute using RM-600 (trade name), rinsing for 1 minute with n-butyl acetate,
I observed the printed image.

The results are shown in Table-1.

FIG. 1 is an explanatory diagram of the state in which light reflected from the substrate surface goes under the light-shielding part during exposure of the photoresist, where l is the mask, 2 is the mask light-shielding part, 3 is the mask light-transmitting part, 4 is the incident light, 5 is the light that has gone under the mask light shielding part, 6 is the photoresist, 7 is the slope in the step structure part,
8 indicates a substrate.0 The length of the photosensitive area in Table 1 is the length of the photosensitive area exposed to light 5 in FIG. 1, measured from the slope 7.

Example 2 As an antihalation agent, the compounds listed in Experiment Nos. 3 to 8 in Table 1 were used instead of 5-hydroxy-3-ethyl-4-(p-)lylazo)-1-phenylpyrazole. The test was conducted in the same manner as in Example 1.

The results are shown in Table-1.

Example 3 As experiment numbers 9 to 10, Example I (experiment numbers 1 to 2
) using the same photoresist composition, and instead of the silicon wafer with the aluminum layer deposited, a silicon wafer with a 0.7μ silicon thermal oxide film was used.
In the same manner as in Example 1, the image was printed, developed and rinsed, then heat treated in nitrogen at 150°C for 0 minutes, and
IF (49% aqueous solution)/NH,F (40χ aqueous solution)/
Etching was performed at 25° C. for 30 minutes using an etchant consisting of a mixture of water and 1/6/10 (volume ratio). The side etch (a phenomenon in which the bottom of the photoresist composition coating is etched due to the etchant surrounding the film) of the samples in Experiment Nos. 9 and 10 were all 1.8 to 1.9.
It was μ steel and had excellent adhesion between the photoresist composition coating and the substrate.

The results are shown in Table-2.

Table 2 Example 4 As experiment numbers 11 to 16, Example 2 (experiment numbers 3 to 8
) The test was conducted in the same manner as in Example 3, except that the composition described in Example 3 was used. In both cases, the side etch is 1.8 to 1.9.
μm, and it was confirmed that the adhesive property was good.

The results are shown in Table-2.

Example 5 As experiment numbers 17 to 18, Example 1 (experiment numbers 1 to 18)
Using the same photoresist composition as in 2), 0.13 μ-
A silicon wafer coated with a silicon thermal oxide film was spin-coated using a spinner so that the thickness after drying was 1.0μ.Then, it was dried for 90 seconds on a hot plate kept at each temperature. The image was printed using an ultra-high pressure mercury lamp at a light intensity of 50 W/n through a test chart chrome mask.

Next item developer solution Toshite JsRDEVELOPHRM-60
After spray developing for 10 seconds using 0 (product name),
Spray rinsed with n-butyl acetate for 10 seconds, observed the printed image, and determined the peeling rate during development.

The results are shown in Table-3. The peeling rates in Experiment Nos. 17 and 18 were all low (and the adhesion between the photoresist composition coating and the substrate was excellent).

Example 6 As experiment numbers 19 to 24, Example 2 (experiment numbers 3 to 8)
) The test was conducted in the same manner as in Example 5, except that the composition described in Example 5 was used. It was confirmed that both had a low peeling rate and good adhesion. The results are shown in Table-3.

Table 3 Comparative Example 1 A photoresist composition was prepared by removing the antihalation agent from the photoresist composition used in Example 1.

The photoresist composition thus prepared was applied to a silicon wafer on which an aluminum layer had been deposited in the same manner as in Example 1, and exposed for 3.0 seconds to print an image, develop, and rinse. As a result, the resolution in flat areas is 2.
9μ-, but the length of the photosensitive area due to the wraparound of light to the light-shielding portion at the step portion was 7μ- or more.

Comparative Example 2 A photoresist composition in which 0.55 g of Oil Yellow was added as an antihalation agent to the photoresist composition used in Comparative Example 1, and a compound represented by the following structural formula was added as an antihalation agent to the photoresist composition used in Comparative Example 1. A photoresist composition was prepared by adding 0.55 g of 1,2-dinaphthylmethylidenehydrazine.

Using the photoresist composition thus prepared, an image was printed and developed in the same manner as in Example 1.

The results are shown in Table 4.

Table 4 Comparative Example 3 The same photoresist composition as in Comparative Example 2 was used, but instead of a silicon wafer on which an aluminum layer was deposited, 0.7μ
An image was printed and developed in the same manner as in Comparative Example 2 using a silicon wafer having a silicon thermal oxide film of -. Then 1
Heat treatment was performed in nitrogen at 50° C. for 30 minutes, and etching was performed using the same etchant as in Example 3 at 25° C. for 30 minutes. The side etch of this product was 3.0 μ- in all cases.

Comparative Example 4 Using the same photoresist composition as in Comparative Example 2, an image was printed, developed and rinsed in the same manner as in Example 5, and the peeling rate was determined. The results are shown in Table-5.

Table 5 f1 Effects of the Invention The photoresist l = composition of the present invention has excellent antihalation performance, excellent resolution, residual film rate, and adhesion and adhesion of the photoresist composition coating film to the substrate. There is almost no peeling of the resist during use, and therefore, the resist composition of the present invention can be suitably used in the manufacture of integrated circuit devices.

[Brief explanation of drawings]

No. 11E is an explanatory diagram of how light reflected on the substrate surface goes around under the light shielding part during exposure of the photoresist. DESCRIPTION OF SYMBOLS 1... Mask, 2... Mask light-shielding part, 3... Mask light-transmitting part, 4... Incident light, 5...
. . . Light that has gone under the mask light-shielding portion, 6. Photoresist, 7. Slope in the stepped structure, 8. Substrate.

Claims (1)

[Claims] (1) Cyclized products of conjugated diene polymers or copolymers include photocrosslinking agents and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [Here, R^1 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl is a substituent selected from a group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, and a trialkylsiloxy group, and R^2 is a substituent selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. R^3 is a substituent selected from a hydrogen atom, an alkyl group and an aryl group,
R^4, R^5, R^6, R^7, and R^8 are hydrogen atoms, alkyl groups, halogen atoms, nitro groups, alkenyl groups, aryl groups, alkynyl groups, hydroxyl groups,
It is an aromatic ring formed by a substituent selected from an alkoxy group, an aryloxy group, or an acyloxy group, or by adjacent substituents. ] A photoresist composition containing a compound represented by: