JPH02296247A - Positive type resist composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a positive resist composition, and more particularly, to a positive resist composition for microfabrication necessary for manufacturing semiconductor devices, magnetic bubble memory devices, integrated circuits, etc. The present invention relates to a resist composition.

(Prior art) When manufacturing semiconductors, a resist is applied to the surface of a silicon wafer to create a photoresist film, and a latent image is formed by irradiating the film with light.
Semiconductor elements are formed by lithography technology in which the image is then developed to form a negative or positive image.

Conventionally, as a resist composition for forming a semiconductor element, a negative resist composed of cyclized polyisoprene and a bisazide compound is known.

However, since this negative resist is developed with an organic solvent, it has a drawback that it cannot be used in the manufacture of highly integrated semiconductors because it swells significantly and has a limited resolution. on the other hand,
In contrast to this negative resist composition, a positive resist composition has excellent resolution and is therefore considered to be able to sufficiently cope with high integration of semiconductors.

At present, positive resist compositions commonly used in this field are composed of a novolak resin and a quinonediazide compound.

However, conventional positive resist compositions lack sensitivity,
Satisfactory results have not always been obtained with respect to various properties such as resolution, residual film rate, heat resistance, and storage stability, and improvements in performance are strongly desired.

(Objects to be Solved by the Invention) The objects of the present invention are to solve the above-mentioned drawbacks of the prior art, improve sensitivity,
The object of the present invention is to provide a positive resist composition that has excellent properties such as resolution, residual film rate, heat resistance, and storage stability, and is particularly suitable for microfabrication of 1 μm or less.

[Means to solve the problem]

This object of the present invention is to provide a positive resist composition containing an alkali-soluble phenolic resin and a photosensitizer, which is characterized in that it contains a quinonediazide sulfonic acid ester of a compound represented by the following Funato (I) as the photosensitizer. This is achieved by using a positive resist composition.

R1-R4; Hydrogen, halogen, alkyl group or alkoxy group 5≦m+n≦6 Examples of the alkali-soluble phenolic resin used in the present invention include condensation reaction products of phenols and aldehydes, phenols and ketones, etc. Examples include condensation reaction products of , vinylphenol polymers, isopropenylphenol polymers, and hydrogenation reaction products of these phenol resins.

Here, specific examples of phenols used include phenol, cresol, xylenol, ethylphenol,
-valent phenols such as propylphenol, butylphenol, phenylphenol, resorcinol,
Pyrocatechol, hydroquinone, bisphenol A1
Examples include polyhydric phenols such as pyrogallol.

Here, specific examples of the aldehydes used include formaldehyde, acetaldehyde, benzaldehyde, terephthalaldehyde, and the like.

Here, specific examples of ketones used include acetone,
Examples include methyl ethyl ketone, diethyl ketone, and diphenyl ketone.

These condensation reactions can be carried out according to conventional methods.

Moreover, the vinylphenol-based polymer is selected from a homopolymer of vinylphenol and a copolymer of vinylphenol and a copolymerizable component.

Specific examples of copolymerizable components include acrylic acid derivatives, methacrylic acid derivatives, styrene derivatives, maleic anhydride, maleic acid imide derivatives, vinyl acetate, acrylonitrile, and the like.

The isopropenylphenol polymer is selected from a homopolymer of isopropenylphenol and a copolymer of isopropenylphenol and a copolymerizable component.

Specific examples of copolymerizable components include acrylic acid derivatives, methacrylic acid derivatives, styrene derivatives, maleic anhydride, maleic acid imide derivatives, vinyl acetate, acrylonitrile, and the like.

The hydrogenation reaction of these phenolic resins can be carried out by any known method, in which the phenolic resin is dissolved in an organic solvent and hydrogen is released in the presence of a homogeneous or heterogeneous hydrogenation catalyst. This can be achieved by introducing

These alkali-soluble phenolic resins may be used alone, or two or more types may be used in combination.

If necessary, the positive resist composition of the present invention may contain, for example, a copolymer of styrene and acrylic acid, methacrylic acid, or maleic anhydride, in order to improve developability, storage stability, heat resistance, etc. Copolymers of alkenes and maleic anhydride, vinyl) Li 7 alcohol polymers, vinylpyrrolidone polymers, rosin, shellac, and the like can be added. The amount added is 0 to 50 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the alkali-soluble phenol resin.
~20 parts by weight.

The photosensitizer used in the present invention has the general formula (I)
It is not particularly limited as long as it is a quinonediazide sulfonic acid ester of a compound represented by the formula. As a specific example, the ester moiety is 1.2benzoquinonediazide-4
-Sulfonic acid ester, 12-naphthoquinonediazide-
4-sulfonic acid ester, ■, 2-naphthoquinonediazide-5-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, and other sulfonic acids of quinonediazide derivatives Examples include compounds such as esters.

Specific examples of the compound represented by general formula (1) include the following.

The photosensitizer in the present invention can be synthesized by an esterification reaction of a compound represented by Funato (I) and a quinonediazide sulfonic acid compound, and is described in "Photosensitive Polymers" by Gentabe Nagamatsu and Hideo Inui. (1980) Kodansha (Tokyo) and others.

The photosensitizers in the present invention can be used alone, or two or more types can be used in combination. The amount of the photosensitizer to be blended is 1 to 100 parts by weight, preferably 3 to 40 parts by weight, based on 100 parts by weight of the resin.

If the amount is less than 1 part by weight, it will be impossible to form a pattern;
If the amount exceeds 0.00 parts by weight, afterimages tend to remain.

The positive resist composition of the present invention is used after being dissolved in a solvent, and examples of the solvent include acetone, methyl ethyl ketone,
Ketones such as cyclohexanone, cyclopentanone, cyclohexanol, n-propyl alcohol, 1so-
Alcohols such as propyl alcohol and n-butyl alcohol, ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, propyl formate, butyl formate, acetic acid Esters such as propyl, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate, cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate and other cellosolve esters propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, diethylene glycol monomethyl ether,
Diethylene glycols such as diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, halogenated hydrocarbons such as trichloroethylene, aromatic hydrocarbons such as toluene and xylene, dimethylacetamide, dimethylformamide, N - Polar solvents such as methylacetamide, etc. can be mentioned.

These may be used alone or in combination of two or more.

The positive resist composition of the present invention may contain compatible additives such as surfactants, storage stabilizers, sensitizers, anti-striation agents, and plasticizers, if necessary.

As the developer for the positive resist composition of the present invention, an alkaline aqueous solution is used. Specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, propylamine, etc. Primary amines, tertiary amines such as diethylamine and dipropylamine, tertiary amines such as trimethylamine and triethylamine, alcohol amines such as diethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide , trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and other quaternary ammonium salts.

Furthermore, if necessary, add methanol or
Appropriate amounts of water-soluble organic solvents such as ethanol, propatool, and ethylene glycol, surfactants, storage stabilizers, resin dissolution inhibitors, and the like can be added.

(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in the examples are based on weight unless otherwise specified.

Novolak resin 100 obtained by mixing m-cresol and p-cresol at a molar ratio of 6:4, adding formalin to this, and condensing it using an oxalic acid catalyst in a conventional manner.
20 parts of a quinonediazide compound in which 95% or more of the -○H groups of compound (1) are esters of 1.2-naphthoquinonediazide-5-sulfonic acid were dissolved in 320 parts of ethyl cellosolve acetate and filtered with a 0.1 μm Teflon filter. A resist solution was prepared by filtration.

After applying the above resist solution onto a silicon wafer with a coater, it was baked at 100°C for 90 seconds to a thickness of 1.1
A 7 μm resist solution was formed. This wafer was placed in a g-line stepper N5R-1505G6E manufactured by Kon Co., Ltd., NA=
Exposure was carried out using a reticle for TES I.0.54). Next, a positive pattern was obtained by developing with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23°C for 11 minutes using the paddle method.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.45 μm were resolved. The film thickness of the pattern is 1.15 μm when measured with a film thickness meter Alpha Step 200 (manufactured by Tenco).
Met.

Furthermore, the wafer with this pattern formed thereon was etched using a dry etching device DEM-45IT (manufactured by Nikkei Anelva Co., Ltd.).
using a power of 300 W, a pressure of 0.03 Torr, and a gas of CF4/H=3/1. When etching was performed at a frequency of 13.56 MHz, it was observed that only the areas where there was no pattern were etched.

After applying the resist solution of Example 1 on a silicon wafer with coke, it was plated at 80°C for 90 seconds to give a thickness of 1.
．． A resist film of 2 μm was formed. This wafer was exposed using a g-line stencil N5R-1505G6E and a test reticle.

This wafer was then subjected to PEB (PO) at 110'C for 60 seconds.
5T f! XPO3IIRE BA) [ING) II
After that, the film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23° C. for 11 minutes by the paddle method to obtain a positive pattern.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.40 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 1.20 μm.

It was obtained by mixing m-cresol, p-cresol, and 3,5-xylenol in a molar ratio of 50:20:30, adding formalin to this, and condensing it using an oxalic acid catalyst in a conventional manner. 100 parts of novolac resin, -〇H of compound (1)
A resist solution was prepared by dissolving 25 parts of a quinonediazide compound in which 85% or more of the groups are esters of L2-naphthoquinonediazide-5-sulfonic acid in 300 parts of ethyl lactate and filtering the solution with a 0.1 μm Teflon filter.

After applying the above resist solution onto a silicon wafer using a coater, it was betatized at 100"C for 90 seconds to a thickness of 1.1
A resist film of 7 μm was formed. This wafer was exposed using a g-line stencil N5R-1505G6E (NA=0.54) and a test reticle. Next 2.38
% tetramethylammonium hydroxide aqueous solution
A positive pattern was obtained by development using the paddle method at .degree. C. for 1 minute.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.45 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 1.16 μm.

Fruit 11” (a combination of vinylphenol and styrene (molar ratio 6:4)
100 parts, 95% or more of -〇H groups of compound (1) are 1,2
- Naphthoquinone diazide - 18 parts of a quinone diazide compound, which is an ester of 5-sulfonic acid, was dissolved in 320 parts of ethyl cellosolve acetate and filtered through a 0.1 μm Teflon filter to prepare a resist solution.

After applying the above resist solution onto a silicon wafer using a coater, it was betatized at 100"C for 90 seconds to a thickness of 1.1".
A resist film of 7 μm was formed. This wafer was exposed using a g-line stencil N5R-1505G6E (NA=0.54) and a test reticle. Next 2.38
% tetramethylammonium hydroxide aqueous solution
A positive pattern was obtained by developing at °C for 31 minutes using the paddle method.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.45 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 1.10 μm.

Implementation Health i 100 parts of isopropenylphenol and styrene copolymer (molar ratio 7:3), quinonediazide compound in which 80% or more of the OH groups of compound (1) are esters of 1,2-naphthoquinonediazide-5-sulfonic acid A resist solution was prepared by dissolving 25 parts in 310 parts of ethyl cellosolve acetate and filtering through a 0.1 μm Teflon filter.

After applying the above resist solution onto a silicon wafer with a coater, it was baked at 100°C for 90 seconds to a thickness of 1.1
A resist film of 7 μm was formed. This wafer was exposed using a g-line stepper N5R-1505G6E (NA=0.54) and a test reticle. Next 2,38
% tetramethylammonium hydroxide aqueous solution
A positive pattern was obtained by development using the paddle method at .degree. C. for 1 minute.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.45 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 1.10 μm.

Implementation ±■ Novolac resin 100 m-cresol and p-cresol were mixed at a molar ratio of 420, formalin was added thereto, and the mixture was condensed in a conventional manner using an oxalic acid catalyst.
19 parts of a quinonediazide compound in which 85% or more of the -○H groups of compound (1) are esters of 1,2-naphthoquinonediazide-4-sulfonic acid were dissolved in 300 parts of diglyme and filtered with a 0.1 μm Teflon filter. A resist solution was prepared.

After applying the above resist solution onto a silicon wafer using a coater, it was betatized at 100"C for 90 seconds to a thickness of 1.2
A resist film of 0 μm was formed. This wafer is transferred to i-line stepper ALS WAFER3TEP 2142i.
(NA-0,54 manufactured by GCA) and a test reticle were used for exposure. Next, a positive pattern was obtained by developing with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23°C for 11 minutes using the paddle method.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.45 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 1.15 μm.

Spiky spots 1 Copolymer of vinylphenol and styrene (mole ratio 6:4
), 20 parts of a quinonediazide compound which is an ester of 2-naphthoquinonediazide-5 sulfonic acid, and 300 parts of diglyme.
Dissolve in a portion of the ifl
A resist solution was prepared.

After applying the above resist solution onto a silicon wafer using a coater, it was betatized at 100°C for 90 seconds to a thickness of 1.2
A resist film of 0 μm was formed. This wafer is transferred to i-line stepper ALS WAFER3TEP 2142.
Exposure was performed using a test reticle and a test reticle. Next, a positive pattern was obtained by developing with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23°C for 11 minutes using the paddle method.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.45 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 1.15 μm.

Novolac resin 100 obtained by mixing m-cresol and p-cresol at a molar ratio of 6:4, adding formalin to this, and condensing the mixture in a conventional manner using an oxalic acid catalyst.
22 parts of a quinonediazide compound in which 85% or more of the -○H groups of compound (7) are esters of 1,2-naphthoquinonediazide-5-sulfonic acid were dissolved in 320 parts of ethyl cellosolve acetate and filtered with a 0.1 um Teflon filter. A resist solution was prepared by filtration.

After applying the above resist solution onto a silicon wafer using a coater, it was betatized at 100°C for 90 seconds to a thickness of 1.1
A resist film of 7 μm was formed. This wafer was exposed using a g-line stepper N5R-1505G6E (NA=0.54) and a test reticle. Next 2.38
% tetramethylammonium hydroxide aqueous solution
'C: A positive pattern was obtained by development using the 5-paddle method for 1 minute.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.45 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 1.15 μm.

Novolak resin 100% obtained by mixing m-cresol and p-cresol at a molar ratio of 426, adding formalin to this, and condensing it using an oxalic acid catalyst in a conventional manner.
20 parts of a quinonediazide compound in which 80% or more of the -○H groups of compound (8) are esters of 1,2-naphthoquinonediazide-5-sulfonic acid are dissolved in 300 parts of ethyl lactate and filtered with a 0.1 μm Teflon filter. A resist solution was prepared.

After applying the above resist solution onto a silicon wafer using a coater, it was betatized at 100°C for 90 seconds, and the H was 1.1.
A resist film of 7 μm was formed. This wafer was exposed using a g-line stencil N5R-1505G6E (NA=0.54) and a test reticle. Next 2.38
% tetramethylammonium hydroxide aqueous solution
A positive pattern was obtained by development using the paddle method at .degree. C. for 1 minute.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.45 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 1.15 μm.

Implementation ± Above■ 100 parts of hydrogenation reaction product of vinylphenol polymer (hydrogenation rate 35%), 85% or more of the OH groups of compound (1) are esters of 1,2-naphthoquinonediazide-4-sulfonic acid A resist solution was prepared by dissolving 30 parts of a quinone diazide compound in 300 parts of diglyme and filtering the solution through a 0.1 μm Teflon filter.

After applying the above resist solution onto a silicon wafer using a coater, it was baked at 100°C for 90 seconds to a thickness of 1.0
A resist film of 0 μm was formed. Excimer laser device C292 sealed this wafer with krypton/fluorine.
6 (manufactured by Hamamatsu Photonics) and a test mask. Next, a positive pattern was obtained by developing with a tetramethylammonium hydroxide aqueous solution at 23°C for 1 minute using the paddle method.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.45 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 0.95 μm.

100 parts of hydrogenation reaction product (hydrogenation rate: 30%) of vinyl phenol polymer on fire, quinonediazide in which 90% or more of the OH groups of compound (1) are esters of 1,2-naphthoquinonediazide-4-sulfonic acid. A resist solution was prepared by dissolving 18 parts of the compound in 300 parts of diglyme and filtering the solution through a 0.1 μm Teflon filter.

After coating the above resist solution on a silicon wafer with coke, it was betatized at 100°C for 90 seconds to a thickness of 1.0
A resist film of 0 μm was formed. This wafer was exposed to light using a far ultraviolet irradiation device PLA-521FA (manufactured by Canon) and a test mask. Next, a positive pattern was obtained by developing with a tetramethylammonium hydroxide aqueous solution at 23°C for 1 minute using the paddle method.

When the patterned wafer was taken out and observed under an electron microscope, lines and spaces of 0.40 μm were resolved. The film thickness of the pattern was measured with a film thickness meter Alpha Step 200 and was found to be 0.92 μm.

(Effects of the Invention) The resist composition of the present invention has excellent properties such as sensitivity, resolution, residual film rate, heat resistance, and storage stability, and is therefore particularly suitable for microfabrication of 1 μm or less.

Claims (1)

[Claims] (1) A positive resist composition containing an alkali-soluble phenol resin and a photosensitizer, which is characterized by containing a quinonediazide sulfonic acid ester of a compound represented by the following general formula (I) as the photosensitizer. Resist composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) R^1~R^4; Hydrogen, halogen, alkyl group or alkoxy group 5≦m+n≦6