JP3436782B2 - Positive photoresist composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel positive photoresist composition, and more specifically, it has excellent properties such as sensitivity, resolution, depth of focus and heat resistance and has a suppressed standing wave effect. The present invention relates to a positive photoresist composition having an excellent pattern shape in which the influence of interference between irradiation light and light reflected from a substrate is suppressed.

[0002]

2. Description of the Related Art The degree of integration in the manufacture of semiconductor devices has rapidly increased in recent years, and submicron or half-micron ultrafine pattern processing precision is required in the manufacture of VLSI and the like. Therefore, with respect to the positive photoresist composition used, excellent sensitivity, resolution,
It is desired to have characteristics such as depth of focus and heat resistance.

Further, in the manufacture of VLSI using optical lithography today, there is a demand for the development of a photoresist composition in which the standing wave effect is suppressed in addition to the above-mentioned resist characteristics. However, the fact is that no positive photoresist satisfying all of these requirements has been found so far.

For example, a method of forming a resist pattern using a photoresist having an increased esterification rate of hydroxybenzophenone has been proposed for the purpose of suppressing the in-film multiple reflection effect, the bulk effect, and the standing wave effect (Japanese Patent Laid-Open No. HEI-2).
-971). However, in this positive photoresist, although the in-film multiple reflection effect, the bulk effect, and the standing wave effect can be suppressed to some extent, they are not sufficiently satisfactory, and the sensitivity and resolution are not satisfactory. Therefore, it cannot be applied to the manufacture of today's VLSI devices.

[0005]

Under the circumstances described above, the present invention has excellent characteristics such as sensitivity, resolution, depth of focus and heat resistance, and has a suppressed standing wave effect. The object of the present invention is to provide a positive photoresist composition having an excellent pattern shape in which the influence of the interference between the irradiation light and the reflected light from the substrate is suppressed.

[0006]

Means for Solving the Problems As a result of intensive studies to develop a positive photoresist composition having the above-mentioned preferable properties, the present inventors have found that a specific naphthoquinone-1,1 is added to an alkali-soluble novolac resin. 2-Diazidosulfonic acid ester compounds and specific phenolic compounds
Then, it was found that the object can be achieved by blending a specific polyphenol compound, and the present invention has been completed based on this finding.

That is, the present invention comprises (A) an alkali-soluble novolac type resin and (B) naphthoquinone-1,2-
An ester compound of diazidosulfonic acid, and (C) 2-hi
Droxybenzoic acid ester and (D) polyhydroxy ester
Nzophenones, 1- [1- (4-hydroxypheni
) Isopropyl] -4- [1,1-bis (4-hydro)
[Xyphenyl) ethyl] benzene, tris (hydroxy)
Phenyl) methanes or bis (hydroxyphenyl) a
A positive photoresist composition containing lucans,
And (A) an alkali-soluble novolac type resin, and (B)
Ester of naphthoquinone-1,2-diazide sulfonic acid
Compound and (C ') general formula

[Chemical 2] ( Wherein R is an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, and when n is 2 or more, R may be the same or different) At least one selected , and (D) polyhydroxybenzo
Phenones 1- [1- (4-hydroxyphenyl) ii
Sopropyl] -4- [1,1-bis (4-hydroxyphenyl)
[Ethyl) ethyl] benzene, tris (hydroxyphenyl)
) Methanes or bis (hydroxyphenyl) alkanes
There is provided a positive photoresist composition comprising the like.

In the positive photoresist composition of the present invention, an alkali-soluble novolac type resin is used as the film-forming substance as the component (A). The alkali-soluble novolac resin is not particularly limited, and in the positive photoresist composition, an alkali-soluble novolac resin conventionally used as a film-forming substance, for example, an aromatic hydroxy compound such as phenol, cresol or xylenol and formaldehyde is used. It is possible to use a product obtained by condensing an aldehyde such as, for example, in the presence of an acidic catalyst.

In the composition of the present invention, the alkali-soluble novolac type resin having a weight average molecular weight of 2,000 to 20,000, preferably 5,000 to 15,000, which is obtained by cutting the low molecular weight region, has excellent heat resistance. It is advantageous to obtain the product.

In the composition of the present invention, an ester compound of naphthoquinone-1,2-diazide sulfonic acid is used as the photosensitive component of the component (B). Examples of the ester compound of naphthoquinone-1,2-diazidesulfonic acid include naphthoquinone-1,2-diazito-5-sulfonic acid or naphthoquinone-1,2-diazito-4-sulfonic acid, and the following (a) Examples of complete esterified products or partially esterified products with the compounds (1) to (3) are included.

(A) Polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone. (B) 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene.

(C) Tris (4-hydroxyphenyl)
Methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,3 5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4
-Hydroxyphenylmethane, bis (4-hydroxy-
2,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3 4-dihydroxyphenylmethane, bis (4-hydroxy-2,
Tris (hydroxyphenyl) methanes such as 5-dimethylphenyl) -3,4-dihydroxyphenylmethane.

(D) bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane,
Bis (3-cyclohexyl-4-hydroxyphenyl)
-2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5 -Cyclohexyl-4-hydroxy-
2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-
Methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl)-
3-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2- Hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, bis (5-
Cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl)-
Bis (cyclohexylhydroxyphenyl) -hydroxyphenylmethanes such as 3,4-dihydroxyphenylmethane.

(E) 2- (2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2 -(2 ', 4'-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4'
-Hydroxyphenyl) propane, bis (2,3,4-
Tri-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) bis such as methane (hydroxyphenyl
Nil) alkanes.

(F) Phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, partially esterified or partially etherified gallic acid Compounds with hydroxyl groups such as.

As the component (B), for the purpose of improving sensitivity, resolution, heat resistance, and depth of focus range characteristics, in particular, the compounds (a) to (f) and naphthoquinone-1,2 are used.
-Ester compounds with diazide sulfonic acid can be used in appropriate combination according to the purpose, and particularly, those having excellent resist properties include (b) to (e).
At least 1 selected from ester compounds of each compound of naphthoquinone-1,2-diazide sulfonic acid
Species or this, and the compound of (a) and naphthoquinone-1,
A combination with an ester compound with 2-diazide sulfonic acid is preferred.

Among the compounds (a) to (f), particularly preferable compounds among the compounds (a) are 2,3,4-trihydroxybenzophenone, 2,3,4.
4,4'-tetrahydroxybenzophenone is a compound of bis (4-hydroxy-3,5
-Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxy Phenylmethane, bis (4-hydroxy-2,5
-Dimethylphenyl) -3,4-dihydroxyphenylmethane is represented by bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -in the compound (d) above.
2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-
4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane and bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane are mentioned respectively, and the above-mentioned examples (b) And the compounds of (e) are mentioned.

The component (B) in the composition of the present invention includes the polyhydroxybenzophenones and 1- [1- (4
-Hydroxyphenyl) isopropyl] -4- [1,1
-Bis (4-hydroxyphenyl) ethyl] benzene,
Or the above-mentioned tris (hydroxyphenyl) methanes,
The bis (cyclohexyl-hydroxyphenyl) - hydroxyphenyl methanes, the bis (hydroxy-phenylene
Le) alkanes are condensed with naphthoquinone- (1,2) -diazide- (2) -4-sulfonyl halide or naphthoquinone- (1,2) -diazide- (2) -5-sulfonyl halide to give a complete ester. It can be produced by esterification or partial esterification. This condensation reaction is usually carried out in an insoluble solvent such as dioxane in the presence of a basic condensing agent such as triethanolamine, alkali carbonate or alkali hydrogen carbonate.

The component (B) in the composition of the present invention is based on the total number of moles of hydroxyl groups of the compounds (a) to (f).
Naphthoquinone-1,2-diazide- (2) -5-sulfonic acid chloride or naphthoquinone-1,2-diazide- (2) -4 in a molar number of 50% or more, preferably 60% or more
-Esterified products obtained by reacting sulfonic acid chloride (average degree of esterification: 50% or more, preferably 60% or more) are particularly preferable because they have high sensitivity and high resolution.

The photosensitive component of the component (B) is the alkali-soluble novolac type resin 100 of the component (A).
5 to 200 parts by weight, preferably 16 to 10 parts by weight
It is desirable to mix in the range of 0 parts by weight. If the amount is less than 5 parts by weight, an image faithful to the pattern cannot be obtained and the transferability is deteriorated. If it is more than 200 parts by weight, the homogeneity of the formed resist film is deteriorated and the resolution is deteriorated. There is a tendency.

In the composition of the present invention, the component (C) or the component (C ') is selected from 2-hydroxybenzoic acid ester or a phenolic compound represented by the general formula (I) . At least one kind is used. This 2-hi
The Dorokishi acid, such as 2-hydroxybenzoic acid methyl, 2-hydroxybenzoic acid ethyl, 2-hydroxybenzoic acid butyl, 2-hydroxybenzoic acid amyl, 2-hydroxybenzoic acid hexyl, 2-hydroxybenzoic acid benzyl, 2 -Octyl hydroxybenzoate ,
2-hydroxybenzoic acid dodecyl etc. are mentioned. The alkyl group in these compounds may be linear or branched. These may be used alone or in combination of two or more.
Of these, particularly 2-hydroxy-benzoic acid benzyl (benzyl salicylate) are preferred.

The phenolic compound represented by the general formula (I) is an alkylphenol, and specific examples thereof include 2-methylphenol, 3-methylphenol, 4-methylphenol and 2,3-dimethylphenol. 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-
Dimethylphenol, 3,5-dimethylphenol, 2
-Ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,3,4-trimethylphenol,
2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 3,4,5-
Trimethylphenol, 2-isopropyl-3-methylphenol, 2-isopropyl-4-methylphenol, 2-isopropyl-5-methylphenol, 2-isopropyl-6-methylphenol, 3-isopropyl-2-methylphenol, 3- Isopropyl-4-methylphenol, 3-isopropyl-5-methylphenol, 4-isopropyl-2-methylphenol, 5-isopropyl-2-methylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl -
5-methylphenol, 2-tert-butyl-6-methylphenol, 3-tert-butyl-2-methylphenol, 3-tert-butyl-5-methylphenol, 4-tert-butyl-5-methylphenol, 4
-Tert-butyl-2-methylphenol, 4-te
rt-butyl-3-methylphenol, 5-tert-
Butyl-2-methylphenol, 2-sec-butylphenol, 3-sec-butylphenol, 4-sec
-Butylphenol, 2-n-butyl-4-methylphenol, 2-n-butyl-5-methylphenol, 2-
n-Butyl-6-methylphenol, 4-n-butyl-
2-methylphenol, 4-n-butyl-3-methylphenol and the like can be mentioned. These may be used alone or in combination of two or more.
It may be used in combination with 2-hydroxybenzoic acid ester . Among these, particularly preferred is 2-te.
rt-Butyl-4-methylphenol, 2-tert-
Butyl-6-methylphenol, 2-tert-butyl-5-methylphenol and 4-tert-butyl-5
-Methylphenol.

In the composition of the present invention, by blending the component (C) or the component (C '), the sensitivity becomes high, the standing wave effect is suppressed, and an excellent pattern shape is obtained. The phenolic compound as the component (C) or the component (C ′) is the alkali-soluble novolac type resin 10 as the component (A).
0 to 10 parts by weight, preferably 2 to 5 parts by weight
It is desirable to mix in the range of parts by weight. This blend amount is 2
If it is less than part by weight, the suppression of the standing wave effect is insufficient, and
If it exceeds 5 parts by weight, the heat resistance tends to decrease, and if it exceeds 10 parts by weight, the heat resistance as well as the depth of focus characteristics deteriorate.

In [0024] The present invention compositions, polyhydroxy benzophenones as the component (D) in order to further increase the sensitivity, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4 -Hydroxyphenyl) ethyl] benzene, or tris (hydroxyphenyl) methanes, bis (hydroxyphenyl) alkanes
It is necessary to add. This makes it possible to provide a practical photoresist composition which is excellent in sensitizing effect, has high sensitivity, and has a small dimensional change amount with respect to the exposure amount.

Further, in the composition of the present invention, other sensitizers such as mercaptooxazole, mercaptobenzoxazole, mercaptooxazoline, and mercaptobenzo may be used as desired within a range that does not impair the objective. Thiazole, benzoxazoline, benzothiazolone, mercaptobenzimidazole, urazole, thiouracil, mercaptopyrimidine, imidazolone and their derivatives can be used in combination.

One of these sensitizers may be used,
Two or more kinds may be used in combination, and the mixing ratio thereof is usually 0.1 to 30 parts by weight, preferably 0.5 to 25 parts by weight with respect to 100 parts by weight of the alkali-soluble novolac type resin.
It is selected within the range of parts by weight. If this amount is less than 0.1 parts by weight, the sensitizing effect will not be sufficiently exerted, and if it exceeds 30 parts by weight, the sensitizing effect will not be obtained in spite of the amount, which is rather uneconomical and not preferable. The optimum amount thereof is appropriately selected depending on the kind of the photosensitive component.

Further, in the composition of the present invention, as an auxiliary agent for improving the resolution and the residual film rate, if desired.
The same isocyanurate compound can also be blended.
Examples of this isocyanurate compound include 1,
3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
1,3,5-Tris (4-tert-butyl-3-hydroxy-2,6-diethylbenzyl) isocyanurate, 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) Isocyanurate and the like can be mentioned. These may be used alone or in combination of two or more, and the mixing ratio thereof is usually 0.5 to 15 parts by weight, preferably 1 to 100 parts by weight of the alkali-soluble novolac type resin. .0-1
It is selected in the range of 0 parts by weight.

The composition of the present invention further comprises, if necessary, a compatible additive such as an additional resin, a plasticizer, a stabilizer or a developed image for improving the performance of the resist film. A commonly used one such as a coloring agent for making it visible can be added and contained.

The composition of the present invention comprises the above-mentioned alkali-soluble novolac type resin (A), a photosensitive component (B) and a phenolic compound (C) or (C ').
It is preferable to dissolve the polyphenol compound of the component (D) and various additive components used as desired in a suitable solvent to be used in the form of a solution.

Examples of such a solvent include acetone,
Ketones such as methyl ethyl ketone, cyclohexanone and methyl isoamyl ketone; polyhydric alcohols such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol or diethylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and Derivatives thereof; cyclic ethers such as dioxane; and esters such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate. it can. These may be used alone or in combination of two or more.

About the preferred method of using the composition of the present invention 1
As an example, first, on a support such as a silicon wafer, the component (A), the component (B), the component (C) or the component (C ′), and an additive component used if necessary are as described above. Apply a solution dissolved in a suitable solvent with a spinner, etc., dry it to form a photosensitive layer, and then use a light source that emits ultraviolet light, such as a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an arc lamp, a xenon lamp. , Exposure through a required mask pattern, or irradiation while scanning with an electron beam. Then add this to a developer, eg 1
When it is immersed in a weak alkaline aqueous solution such as a 10 wt% tetramethylammonium hydroxide aqueous solution, the exposed portion is dissolved and removed, and an image faithful to the mask pattern can be obtained.

[0032]

The positive photoresist composition of the present invention comprises
It has excellent characteristics such as sensitivity, resolution, depth of focus, and heat resistance, and suppresses the standing wave effect, and can give a resist pattern with an excellent cross-sectional shape, and especially semiconductors such as IC and LSI. It is suitably used as a resist for ultra-fine processing in the manufacture of devices.

[0033]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The physical properties of the photoresist composition were determined as follows. (1) Sensitivity: The sample was applied onto a silicon wafer using a spinner and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a film thickness of 1.05 μm. A reduction projection exposure apparatus NSR-1755i7A (manufactured by Nikon Corporation, NA =
0.50) for 0.1 second to 0.01 second, and then developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 1 minute, washed with water for 30 seconds and dried. At this time, the minimum exposure time at which the film thickness of the exposed portion after development was 0 was measured as the sensitivity in millisecond (ms) unit. (2) Resolution: The resolution is shown by the limiting resolution in the exposure amount for reproducing the mask pattern of 0.5 μm.

(3) Heat resistance: A resist pattern having a pattern line width of 5 μm formed on a silicon wafer was subjected to 125 ° C., 130 ° C., 135 ° C.
The temperatures at which the resist pattern is deformed when baked on a hot plate for 5 minutes at temperatures of 140 ° C. and 140 ° C. are shown.

(4) Pattern shape: A cross-sectional shape of a resist pattern having a width of 0.4 μm is SEM
(Scanning Electron Microscope) Observed by a photograph, the side surface is cut almost vertically and the effect of standing waves is suppressed ◎
The sample was slightly tapered, but the effect of the standing wave was suppressed, and the sample was marked with ◯, and the sample with the side surface being wavy and showing the effect of the standing wave was marked with x.

(5) Depth of focus width: The minimum EOP (line and space of 0.4 μm is formed on a one-to-one basis) using a reduction projection exposure apparatus NSR-1755i7A (manufactured by Nikon Corporation, NA = 0.50). Exposure time) was used as a reference exposure amount, and the focus was vertically shifted in the exposure amount, exposure and development were performed, and an SEM photograph of a resist pattern obtained was observed. From the SEM photograph, the maximum value (μm) of defocus that yields a 0.4 μm rectangular resist pattern was taken as the depth of focus width. 1.2 or more was represented as A, 0.8 or more and 1.1 or less as B, and 0.4 or more and 0.7 or less as C.

Production Example 1 m-cresol and p-cresol in a weight ratio of 40: 6
The mixture was mixed at a ratio of 0, formalin was added to the mixture, and the cresol novolac resin obtained by condensation by an ordinary method using an oxalic acid catalyst was subjected to a fractionation treatment to cut the low molecular weight region to obtain a weight average molecular weight of 6000. A cresol novolac resin was obtained.

Production Example 2 m-cresol and p-cresol in a weight ratio of 40: 6
The mixture was mixed at a ratio of 0, formalin was added to the mixture, and the cresol novolac resin obtained by condensation by an ordinary method using an oxalic acid catalyst was subjected to a fractionation treatment to cut the low molecular weight region to obtain a weight average molecular weight of 12,000. A cresol novolac resin was obtained.

Production Example 3 m-cresol and p-cresol in a weight ratio of 60: 4
The mixture was mixed at a ratio of 0, formalin was added to the mixture, and the cresol novolac resin obtained by condensation by an ordinary method using an oxalic acid catalyst was subjected to a fractionation treatment to cut the low molecular weight region to obtain a weight average molecular weight of 6000. A cresol novolac resin was obtained.

Example 1 100 parts by weight of the cresol novolac resin obtained in Preparation Example 1, 1.0 mol of 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-
20 parts by weight of esterification reaction product with 3.5 mol of sulfonyl chloride, 1.0 mol of bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane and naphthoquinone-1,2-diazide -
6 parts by weight of esterification reaction product with 2.0 mol of 5-sulfonyl chloride, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene 20 parts by weight, 1, 3,
5-tris (4-tert-butyl-3-hydroxy-
After dissolving 1.2 parts by weight of 2,6-dimethylbenzyl) isocyanurate and 2 parts by weight of benzyl salicylate in 350 parts by weight of ethylene glycol monoethyl ether acetate, this was filtered using a membrane filter having a pore size of 0.2 μm. A photoresist composition was prepared. Table 1 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus and pattern shape of this product.

Comparative Example 1 A photosensitive composition was obtained in the same manner as in Example 1 except that benzyl salicylate was not added.
Table 1 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus and pattern shape of this product.

Examples 2 to 5 Esterification reaction of 1.0 mol of 2,3,4,4'-tetrahydroxybenzophenone with 3.5 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride in Example 1 Amount of product, bis (5-cyclohexyl-4-
The amount of the esterification reaction product of 1.0 mol of hydroxy-2-methylphenyl) -2-hydroxyphenylmethane and 2.0 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride and the addition amount of benzyl salicylate A photoresist composition was obtained in the same manner as in Example 1, except that the composition was changed as shown in Table 1. Table 1 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus and pattern shape of this product .

[0043]

[Table 1]

[Note] (1) m / p ratio: blending weight ratio of m-cresol and p-cresol, the same applies hereinafter (2) BP-1: 2,3,4,4'-tetrahydroxybenzophenone 1 mol Esterification product of naphthoquinone-1,2-diazide-5-sulfonyl chloride (3.5 mol) and so on (3) TP-1: bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxy 1 mol of phenylmethane and naphthoquinone-1,2-diazide-
Esterification product with 2 moles of 5-sulfonyl chloride, the same as below (4) BP-1 / TP-1: compounding weight ratio of BP-1 and TP-1, same as below (5) component (B) and component (C) The parts by weight of (A)
The value is based on 100 parts by weight of the component. Same as below

Example 6 100 parts by weight of the cresol novolac resin obtained in Preparation Example 1, 1.0 mol of 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-
26 parts by weight of esterification reaction product with 3.5 mol of sulfonyl chloride, 1- [1- (4-hydroxyphenyl)
Isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene 20 parts by weight, 1,3,5-
Tris (4-tert-butyl-3-hydroxy-2,2
After dissolving 1.2 parts by weight of 6-dimethylbenzyl) isocyanurate and 2 parts by weight of benzyl salicylate in 350 parts by weight of ethylene glycol monoethyl ether acetate, this was filtered using a membrane filter having a pore size of 0.2 μm to obtain a photoresist. A composition was prepared. Table 2 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus and pattern shape of this product.

[0046] In Comparative Example 2 Example 6, except that no addition of benzyl salicylate, in the same manner as in Example 6, to obtain a photosensitive composition.
Table 2 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus and pattern shape of this product.

Example 7 100 parts by weight of the cresol novolac resin obtained in Preparation Example 1, bis (5-cyclohexyl-4-hydroxy-2-)
26 parts by weight of an esterification reaction product of 1 mol of methylphenyl) -2-hydroxyphenylmethane and 2.0 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride, 1- [1- (4-hydroxyphenyl) Isopropyl] -4- [1,1-bis (4-hydroxyphenyl)]
Ethyl] benzene 20 parts by weight, 1,3,5-tris (4
-Tert-Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate (1.2 parts by weight) and benzyl salicylate (2 parts by weight) were dissolved in ethylene glycol monoethyl ether acetate (350 parts by weight), and the resulting solution had a pore size of 0. A photoresist composition was prepared by filtering with a 2 μm membrane filter. Table 2 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus and pattern shape of this product.

[0048] In Example 8 Example 7, except for changing 4.5 parts by weight the amount of benzyl salicylate, in the same manner as in Example 7, to obtain a photoresist composition. Sensitivity, resolution about this thing,
Table 2 shows the heat resistance, the depth of focus, and the physical properties of the pattern shape.

[0049] In Example 9 Example 7, except for using a cresol novolak resin obtained in Production Example 3 in the same manner as in Example 7, to obtain a photoresist composition. Table 2 shows the sensitivity, resolution, heat resistance, depth of focus and physical properties of the pattern of this product.
Shown in.

[0050]

[Table 2]

Examples 10 to 13 A photoresist composition was prepared in the same manner as in Example 1 except that the types and amounts of the component (B) and the component (C) were changed as shown in Table 3. Got Table 3 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus, and pattern shape of this product.

[0052] In Comparative Example 3 Example 10, except that no addition of 4-hydroxybenzoic acid benzyl, in the same manner as in Example 10, to obtain a photosensitive composition. Table 3 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus, and pattern shape of this product.

[0053]

[Table 3]

[Note] (1) BP-2: 1 mol of 2,3,4-trihydroxybenzophenone and naphthoquinone-1,2-diazide-5-
Esterification product with 2.5 mol of sulfonyl chloride (2) TP-2: 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene 1 mol Of naphthoquinone-1,2-diazide-5-sulfonyl chloride (3 mol) (3) TP-3: bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane (1 mol) and naphthoquinone- Esterification product of 1,2-diazido-5-sulfonyl chloride (2 mol) (4) TP-4: bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane (1 mol) and naphthoquinone-1,2 -Diazide-5-sulfonyl chloride esterified with 2 mol

Examples 14 to 18 Esterification reaction of 2,3,4,4'-tetrahydroxybenzophenone with 1.0 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride in Example 1 Amount of product and bis (5-cyclohexyl-4
The amount of the esterification reaction product of 1.0 mol of -hydroxy-2-methylphenyl) -2-hydroxyphenylmethane and 2.0 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride is shown in Table 4. Except that benzyl salicylate was replaced with 2-tert-butyl-4-methylphenol in the amounts shown in Table 4, a photoresist composition was obtained in the same manner as in Example 1. Table 4 shows the sensitivity, resolution, heat resistance, depth of focus, and physical properties of the pattern shape of this product.

[0056] In Example 19 Example 14, the type and amount of the component (B), except that changed as shown in Table 4, to obtain a photoresist composition in the same manner as in Example 14. Table 4 shows the sensitivity, resolution, heat resistance, depth of focus and physical properties of the pattern of this product.
Shown in.

[0057]

[Table 4]

Example 20 100 parts by weight of cresol novolac resin obtained in Preparation Example 1, bis (5-cyclohexyl-4-hydroxy-2-)
Methylphenyl) -2-hydroxyphenylmethane 1.
Esterification reaction product of 0 mol with 2.0 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride 26
20 parts by weight of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1,3,5-tris (4-tert-) Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 1.2 parts by weight and 2
-Tert-Butyl-4-methylphenol 2 parts by weight with ethylene glycol monoethyl ether acetate 35
After being dissolved in 0 part by weight, this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a photoresist composition. Table 5 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus and pattern shape of this product.

[0059] In Comparative Example 4 Example 20, except that no addition of 2-tert-butyl-4-methylphenol, in the same manner as in Example 20, to obtain a photosensitive composition. Table 5 shows the physical properties of the sensitivity, resolution, heat resistance, depth of focus and pattern shape of this product.

[0060]

[Table 5]

Example 21 100 parts by weight of the cresol novolac resin obtained in Preparation Example 1, bis (5-cyclohexyl-4-hydroxy-2-)
Methylphenyl) -2-hydroxyphenylmethane 1.
10 parts by weight of an esterification reaction product of 0 mol and 2.0 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride (average degree of esterification 67%), bis (4-hydroxy-3,5-dimethylphenyl) ) -3,4-Dihydroxyphenylmethane 1.0 mol and naphthoquinone-1,2
-Diazide-5-sulfonyl chloride 10 parts by weight of esterification reaction product with 3.5 mol (average degree of esterification 88%) and 2- (2,3,4-trihydroxyphenyl)
-2- (2 ', 3', 4'-trihydroxyphenyl)
10 parts by weight of an esterification reaction product (average esterification degree: 67%) of 1.0 mol of propane and 4 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride, bis (4
-Hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane 25 parts by weight, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 1.6 Part by weight and 3.1 parts by weight of benzyl salicylate were dissolved in 350 parts by weight of ethylene glycol monoethyl ether acetate, and this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a photoresist composition. Table 6 shows the sensitivity, resolution, heat resistance, depth of focus, and physical properties of the pattern shape of this product.

Example 22 In Example 21 , the photosensitive component was bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-
1.0 mol of hydroxyphenylmethane and naphthoquinone-
Esterification reaction product with 2.0 mol of 1,2-diazide-5-sulfonyl chloride (average degree of esterification 67%)
15 parts by weight of bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane (1.0 mol) and naphthoquinone-1,2-diazide-5-sulfonyl chloride (2.5 mol) A photoresist composition was obtained in the same manner as in Example 21 , except that 30 parts by weight of the esterification reaction product (average degree of esterification: 63%) was used. Table 6 shows the sensitivity, resolution, heat resistance, depth of focus, and physical properties of the pattern shape of this product.

[0063]

[Table 6]

Front page continued (72) Inventor Nobuo Tokutake 150 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Tokyo Ohka Kogyo Co., Ltd. (72) Hidekatsu Ohara 150, Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Tokyo Ohka Kogyo Co., Ltd. (72) Inventor Toshinasa Nakayama 150 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Tokyo Ohka Kogyo Co., Ltd. (56) Reference JP-A-6-43649 (JP, A) JP-A-5-333540 (JP, A) JP-A-58-80636 (JP, A) JP-A-1-133045 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (12)

(57) [Claims] 1. An (A) alkali-soluble novolac type resin, (B) an ester compound of naphthoquinone-1,2-diazide sulfonic acid, and (C) a 2-hydroxybenzoic acid ester.
Stell and (D) polyhydroxybenzophenones, 1
-[1- (4-hydroxyphenyl) isopropyl]-
4- [1,1-bis (4-hydroxyphenyl) ethyl
Lu] benzene, tris (hydroxyphenyl) methanes
Alternatively, a positive photoresist composition containing a bis (hydroxyphenyl) alkane . 2. The component (B) is 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4).
-Hydroxyphenyl) ethyl] benzene, tris (hydroxyphenyl) methanes, bis (cyclohexylhydroxyphenyl) -hydroxyphenylmethanes and
The positive photoresist composition according to claim 1, which is at least one selected from ester compounds of naphthoquinone-1,2-diazide sulfonic acids of bis (hydroxyphenyl) alkanes. 3. The component (B) comprises at least one selected from ester compounds of naphthoquinone-1,2-diazide sulfonic acids of polyhydroxybenzophenones, and 1
-[1- (4-hydroxyphenyl) isopropyl]-
4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, tris (hydroxyphenyl) methanes, bis (cyclohexylhydroxyphenyl) -hydroxyphenylmethanes and bis (hydroxyphenyl)
2. The positive photoresist composition according to claim 1, wherein the positive photoresist composition is at least one selected from ester compounds of naphthoquinone-1,2-diazide sulfonic acids of alkanes. 4. Tris (hydroxyphenyl) methanes are bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane and bis (4-hydroxy-2,5-dimethylphenyl) -2- Claimed to be hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane. Item 4. A positive photoresist composition according to Item 2 or 3. 5. Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -containing bis (cyclohexylhydroxyphenyl) -hydroxyphenylmethanes
2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-
Positive type according to claim 2 or 3, which is 4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane or bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane. Photoresist composition. 6. A bis (hydroxyphenyl) alkane is 2- (2,3,4-trihydroxyphenyl) -2.
-(2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2-
(2 ', 4'-dihydroxyphenyl) propane, 2-
The (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, bis (2,3,4-trihydroxyphenyl) methane or bis (2,4-dihydroxyphenyl) methane. Positive photoresist composition. 7. A polyhydroxybenzophenone compound,
2,3,4-trihydroxybenzophenone or 2,
The positive photoresist composition according to claim 3, which is 3,4,4'-tetrahydroxybenzophenone . 8. The 2-hydroxybenzoic acid ester is 2-
Positive photoresist composition according to claim 1, wherein the hydroxybenzoic acid benzyl. 9. The content of the component (C) is the same as that of the component (A) 10.
2 to 10 parts by weight with respect to 0 parts by weight.
9. The positive photoresist composition as described in any one of 8 above. 10. An (A) alkali-soluble novolac type resin, (B) an ester compound of naphthoquinone-1,2-diazide sulfonic acid, and (C ') a general formula: ( Wherein R is an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, and when n is 2 or more, R may be the same or different) At least one selected , and (D) polyhydroxybenzo
Phenones 1- [1- (4-hydroxyphenyl) ii
Sopropyl] -4- [1,1-bis (4-hydroxyphenyl)
[Ethyl) ethyl] benzene, tris (hydroxyphenyl)
) Methanes or bis (hydroxyphenyl) alkanes
A positive photoresist composition containing the followings: 11. The component (C ′) is 2-tert-butyl-4-methylphenol, 2-tert-butyl-6-
Methylphenol, 2-tert-butyl-5-claim 1 is at least one selected from among methylphenol and 4-tert-butyl-5-methylphenol
0. The positive photoresist composition as described in 0 . 12. (C ') content of the component, according to claim 10 which is 2 to 10 weight parts per 100 weight parts component (A)
Or the positive photoresist composition as described in 11 above.