JPH0348250A - Positive type resist composition - Google Patents

Abstract

PURPOSE:To improve sensitivity, resolution, residual film rate, heat resistance, and preservable stability by incorporating the quinone diazide sulfonate of a specific compd. as a photosensitive agent into the above compsn. CONSTITUTION:The quinone diazide sulfonate of the compd. expressed by formula I is incorporated as the photosensitive agent into the compsn. In the formula I, R<1> to R<4> denote H, halogen, 1 to 4C alkyl group, alkenyl group or hydroxyl group; R<5>, R<6> denote H, halogen or 1 to 4C alkyl group; R<7> to R<10> denote H or 1 to 4C alkyl group. The positive type resist compsn. which is excellent in various characteristics, such as sensitivity, resolution, residual film rate, heat resistance, and preservable stability, and is suitable for fine working of particularly <=1mum is obtd. in this way.

Description

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

(Conventional technology) 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 it with light.
Semiconductor devices are formed using lithography technology, which is then developed to form a negative or positive image.

Conventionally, negative resists made of cyclized polyisoprene and bisazide compounds have been known as resist compositions for forming semiconductor devices.

However, since this negative resist is developed with an organic solvent, it swells significantly and has limited resolution, so it has the disadvantage that it cannot be used in the manufacture of highly integrated semiconductors. on the other hand,
In contrast to this negative-tone resist composition, positive-tone resist compositions have excellent resolution and are considered to be fully compatible with higher integration of semiconductors.

Currently, positive resist compositions commonly used in this field are composed of a novolank resin and a quinonediazide compound.

However, conventional positive resist compositions lack sensitivity,
Satisfactory results have not always been obtained regarding various properties such as resolution, residual film rate, heat resistance, and storage stability, and there is a strong desire to improve performance. (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 for Solving the Problem) This object of the present invention is to provide a positive resist composition containing an alkali-soluble phenol resin and a photosensitizer, in which a quinone diazide of a compound represented by the following general formula (1) is used as the photosensitizer. This is achieved by a positive resist composition characterized by containing a sulfonic acid ester.

Rl-R'. H, halogen, 01-C4 alkyl group, alkenyl group or hydroxyl group R'. R'. H, halogen or C1 to C4 alkyl group R7 to RI6;} {or CI to C4 alkyl The alkali-soluble phenol resin used in the basic invention includes, for example, condensation reaction products of phenols and aldehydes, phenols Examples include condensation reaction raw materials of and ketosi, vinylphenol polymers, isopropenylphenol polymers, and hydrogenation reaction products of these phenol resins.

Specific examples of phenols used here include monohydric phenols such as phenol, cresol, xylenol, ethylphenol, probylphenol, butylphenol, and phenylphenol; phenols and the like.

Specific examples of aldehydes used here include formaldehyde, acetaldehyde, benzaldehyde, and terephthalaldehyde.

Specific examples of ketones used here include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, and the like.

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 precepts include acrylic acid derivatives, methacrylic acid derivatives,
Examples include styrene derivatives, maleic anhydride, maleic acid imide derivatives, vinyl acetate, and acrylonitrile.

Further, the isopropenylphenol-based 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 ξ-do derivatives, vinyl acetate, acrylonitrile, and the like.

These hydrogenation reactions of phenolic resins can be carried out by any known method, including dissolving the phenolic resin in an organic solvent and introducing hydrogen in the presence of a homogeneous or heterogeneous hydrogenation catalyst. This can be achieved by doing. These alkali-soluble phenolic resins can be used alone, or two or more types can be used in combination. Positive-type resist of the present invention}Jl precepts include, if necessary,
To improve developability, storage stability, heat resistance, etc., for example, copolymers of styrene and acrylic acid, methacrylic acid, or maleic anhydride, copolymers of alkenes and maleic anhydride, and vinyl alcohol polymers. , vinylpyrrolidone polymer, rosin, shellac, etc. can be added. The amount added is the above alkali-soluble phenol resin 1
0 to 50 parts by weight, preferably 5 to 2 parts by weight
It is 0 parts by weight.

The photosensitizer used in the present invention has the general formula (1
) is not particularly limited as long as it is a quinonediazide sulfonic acid ester of the compound represented by. Specific examples include 1,2-penzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2, Examples include compounds such as 1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, and other sulfonic acid esters of quinonediazide derivatives.

General formula (!) As a specific example of the compound shown in teeth, These include:

CE Shil (22) (24) (26) (27) (28) (29) (31) (32) (33) (34) (35) (36) The photosensitizer in the present invention has the formula -i ( It is possible to form a compound by an esterification reaction between the compound shown in 1) and a quinonediazide sulfonic acid compound, and it is described in "Photosensitive Polymer" (1980) by Gentaro Nagamatsu and Hideo Inui, Kodansha (Tokyo), etc. They can be combined according to the usual methods.

The photosensitizers in the present invention can be used alone, or two or more types can be used in combination. The compounding amount of the photosensitizer is 1 to 100 parts by weight, preferably 3 to 40 parts by weight, based on 100 parts by weight of the resin. If it is less than 1 part by weight, it will be impossible to form a pattern, and if it exceeds 100 parts by weight,
Development residues are more likely to occur.

The positive resist composition of the present invention is used by dissolving it in a solvent, and examples of the solvent include acetone, methyl ethyl ketone,
Ketones such as cyclohexane, cyclopentanone, cyclohexanol, n-propyl alcohol. ．． is
Alcohols such as o-propyl alcohol and n-butyl alcohol, ethylene glycol dimethyl ether,
Ethers such as ethylene glycol diethyl ether and dioxane, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, proyl formate, butyl formate, proyl acetate, butyl acetate, methyl probionate, ethyl propionate, methyl acetate, Esters such as ethyl acetate, methyl lactate, ethyl lactate, cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate,
Cellosolve esters such as proyl cellosolve acetate and butyl cellosolve acetate, propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, diethylene glycol heptanomethyl 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,
Examples include polar solvents such as dimethylformamide and N-methylacetamide.

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, SL-IJ ation inhibitors, and plasticizers, if necessary. can.

As the developer for the positive resist composition of the present invention, an aqueous alkali solution is used, and specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, propylaminol, etc. Primary amines such as diethylamine, tertiary amines such as dipropylamine, trimethylamine, triethylamine, diethylethanolamine,
Alcohol amines such as triethanolamine ξ, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxydimethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, etc. can be mentioned.

Furthermore, if necessary, add methanol or
Appropriate amounts of water-soluble organic solvents such as ethanol, propanol, 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.

Nopolafuku Resin 100 obtained by mixing Taiho flaming 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.
30 parts of a quinonediazide compound in which 80% or more of the 10H groups of the compound GO+ are esters of 1,2-naphthoquinonediazide-5-sulfonic acid are dissolved in 320 parts of ethyl cellosol acetate. A resist solution was prepared by filtering through a 1 μm Teflon filter.

After applying the above resist solution onto a silicone wafer using a coater, it was baked at IOO°C for 90 seconds to a thickness of 1.1
A 7 μm resist film was formed. g v this wafer
Exposure was performed using an A-step 7per NSR-1505G6E (manufactured by Nikon Corporation, NA=0.54) and a test reticle. Next, a positive pattern was obtained by developing with a 2.38% aqueous tetramethylammonium hydroxide solution at 23° C. for 1 minute using the Huttle 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 1.15μ when measured using a film thickness meter Alpha Step 200 (manufactured by Tenco).
It was m.

Furthermore, the wafer with this pattern formed thereon was subjected to dry ethoching equipment DEM-45 IT (manufactured by Nichiden Anelva Co., Ltd.) at a power of 300 W, a pressure of 0.03 Torrs, a gas CF4/H=3/1, and a frequency of 1. 5 6MHz
When etching was performed, it was observed that only the areas where there was no pattern were etched.

After coating the resist solution of Example 1 on a silicon wafer with a coater, it was baked at 80° C. for 90 seconds to give a thickness of 1.
A 2 μm resist film was formed. This wafer was exposed using a g-line stepper NSR-1505G6E and a test reticle. Next, this wafer is
FEB (POSTEXPOSURE) at 10℃ for 60 seconds
After baking, the film was developed using a 2.38% aqueous solution of tetramethylammonium hydroxide at 23° C. for 1 minute using 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 observed with a film thickness meter Alpha Stethop 200 and was found to be 1.20 μm.

Novolafuku is obtained by mixing m-cresol, p-cresol, and 3.5-xylenol in a molar ratio of 50:20:30, adding formalin to the mixture, and condensing the mixture in a conventional manner using an oxalic acid catalyst. 100 parts of the resin, 33 parts of a quinonediazide compound in which 85% or more of the 10H groups of the compound αω are esters of 1,2-naphthoquinonediazide-5-sulfonic acid are dissolved in 300 parts of ethyl lactate. A resist solution was prepared by filtering through a 1 μm Teflon filter.

After applying the above resist solution onto a silicone wafer using a coater, it was baked at 100°C for 90 seconds to a thickness of 1.1
A 7 μm resist film was formed. This wafer was passed through a g-line stepper NSR-1505G6E (NA=0
．． 54) and a test reticle. Next, a positive pattern was obtained by developing with a 2.38% aqueous tetramethylammonium hydroxide 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 Stemp 200 and was found to be 1.16 μm.

Arrow 41 Raw± Copolymer of vinylphenol and styrene (mole ratio 6:4
) 100 parts, 80% or more of the 1〇H groups of the compound αφ are 1.2
-28 parts of a quinonediazide compound, which is naphthoquinonediazide-5-sulfonic acid ester, was dissolved in 320 parts of ethyl cellosolve acetate. A 1 μm Teflon filter was used to prepare a liquid solution. After applying the above resist solution onto a silicone wafer using a coater, it was baked at 100°C for 90 seconds to a thickness of 1.1
A 7 μm resist film was formed. This wafer was passed through a g-line stepper NSR-1505G6E (NA=0
．． 54) and a test reticle. Next, a positive pattern was obtained by developing with a 2.38% aqueous tetramethylammonium hydroxide 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 1.10 μm.

100 parts of a copolymer of isopropenylphenol and styrene (molar ratio 7=3), compound αω, quinonediazide compound 28 in which 80% or more of the αω-10H groups are 1,2-naphthoquinonediazide-5-sulfonic acid ester A resist solution was prepared by dissolving one part in ethyl cellosolve acetate slO and filtering through a 0.1 μm Teflon filter.

After applying the above resist solution onto a silicone wafer using a coater, the resist solution was betatized at 100°C for 90 seconds to a thickness of 1.
A 17 μm resist film was formed. This wafer was subjected to a g-ray stethoper NSR-1505G6E (NA=0
．． 54) and a test reticle. Next, a positive pattern was obtained by developing with a 2.38% aqueous tetramethylammonium hydroxide 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 1.10 JIIl. Novolac resin 100 obtained by mixing m-cresol and p-cresol at a molar ratio of 426, adding formalin to this, and condensing the mixture in a conventional manner using an oxalic acid catalyst.
30 parts of a quinonediazide compound in which 85% or more of the 10H groups of the compound αω are esters of 1,2-naphthoquinonediazide-4-sulfonic acid were dissolved in 300 parts of diglyme and filtered through a 0.1 μm Teflon filter. A resist solution was prepared.

After applying the above resist solution onto a silicone wafer using a coater, it was baked 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 an i-line stepper - ALS WAFERSTEP2142.
Exposure was performed using a test reticle and a test reticle.

Next, a positive pattern was obtained by developing with a 2.38% aqueous tetramethylammonium hydroxide 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 1.15 μm.

Lost 1! [- Copolymer of vinylphenol and styrene (molar ratio 6:4
) 100 parts, 60% or more of -OH groups of compound QI are 1.2
-30 parts of a quinonediazide compound, which is a naphthoquinonediazide-5-sulfonic acid ester, was dissolved in 300 parts of diglyme and filtered through a 0.1 μm Teflon filter to prepare a resist solution.

After applying the above resist solution onto a silicone wafer with a coater, it was baked at 100°C for 90 seconds to a thickness of 1.2 cm.
A 0 μm resist film was formed. This wafer is processed using i-line stethoscope ALS WAFERSTEP2142i.
(NA=0.5 4) and a test reticle were used for exposure. Next, a positive pattern was obtained by developing with a 2.38% aqueous tetramethylammonium hydroxide 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 1.15 μm.

104i Novorasoc 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.
28 parts of a quinonediazide compound in which 70% or more of the 10H groups of compound αQ are esters of 1,2-naphthoquinonediazide-5-sulfonic acid were dissolved in 320 parts of ethyl cellosolve acetate lactate and filtered with a 0.1 μm Teflon filter. A furnace-filtered resist solution was prepared.

After applying the above resist solution onto a silicone wafer using a coater, it was baked at 100°C for 90 seconds to a thickness of 1.1
A 7 μm resist film was formed. gvA this wafer
Styva NSR 15'0506E (NA=0.5
4) and a test reticle were used for exposure. Next 2
．． A positive pattern was obtained by developing with a 38% aqueous tetramethylammonium hydroxide 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 0.45μ 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.

A novolac resin 100 is obtained by mixing raw m-cresol and p-cresol at a molar ratio of 4 to 6, adding formalin to the mixture, and condensing the mixture in a conventional manner using an oxalic acid catalyst.
20 parts of a quinonediazide compound in which 60% or more of the 10H groups of compound (26) are esters of 1,2-naphthoquinonediazide-5-sulfonic acid were dissolved in 300 parts of ethyl lactate and filtered with a 0.1 μm Teflon filter. A furnace-filtered resist solution was prepared.

After applying the above registration solution onto a silicone wafer using a coater, it was baked at 100°C for 90 seconds to give a thickness of 1,1
A 7 μm resist film was formed. This wafer was subjected to a g-line temperer NSR-1505G6E (NA=0
．． 54) and a test reticle. Next is 2.38% tetramethylammonium hydroxide water? A positive pattern was obtained by developing with 8 liquids 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 1.15μ steel.

100 parts of hydrogenation reaction product of raw O vinylphenol polymer (hydrogenation rate 35%), 85% or more of the αω-1〇H groups of the compound are 1,2-naphthoquinonediazide-4 sulfonic acid ester Add 30 parts of quinonediazide compound to 3 parts of diglyme
Dissolved in 0.00 parts. A resist solution was prepared by filtering through a 1 μm Teflon filter.

After applying the above resist solution onto a silicone wafer using a coater, the resist solution was betatized at 100°C for 90 seconds to a thickness of 1.0
A 0 μm resist film was formed. Excimer laser device C292, which 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 Stethop 200 and was found to be 0.95 μm. 100 parts of hydrogenation reaction product of vinyl phenol polymer on left salmon (hydrogenation rate 30%), compound Q (If -0} 159
28 parts of a quinonediazide compound of which 0% or more is 1.2-naphthoquinonediazide-4-sulfonic acid ester was dissolved in 300 parts of diglyme and coated with a 0.1 μm Teflon Fino Letter; A solution was prepared.

After applying the above resist solution onto a silicone wafer using a coater, it was baked at 100°C for 90 seconds to a thickness of 1.0
A 0 μm resist film was formed. This wafer was exposed using a test mask of an ultraviolet irradiation device PLA-5 2 1 FA (manufactured by Canon Inc.). 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 U plate 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; H, halogen, alkyl group, alkenyl group or hydroxyl group of C_1~C_4 R^5, R^6; H, halogen or C_1~ C_4 alkyl group R^7 to R^1^0; H or C_1 to C_4 alkyl group