JP3436045B2 - Method for producing resist composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Used in microfabrication of semiconductors with ultraviolet light and far ultraviolet light
A method for producing a di-type photoresist composition.
You. [0002] 2. Description of the Related Art Generally, compounds having a phenolic hydroxyl group are used.
The compound is converted to a quinonediazidesulfonic acid ester, and the
A resist composition containing steal as a photosensitizer
It is public to form a strike film and use it for semiconductor microfabrication.
Is knowledge. That is, a photosensitive agent having a quinonediazide group
And a composition containing a novolak resin, 300 to 500
quinonediazide group of photosensitizer
A carboxyl group is generated, and the alkali-insoluble
Utilizing the fact that it becomes resoluble, this composition is positive.
Used as a mold resist. This positive resist is
Features superior resolution than negative resist
Is used in the manufacture of various integrated circuits for semiconductors.
Have been. [0003] SUMMARY OF THE INVENTION Positive photoresist
Usually powders the material, especially quinonediazide-based photosensitizers.
It is prepared by charging in body form. For this reason,
Material preparation accuracy (Target of content of each material in resist
Value or the ratio of the measured value to the standard value)
It becomes about ± 0.5%.
In some cases, variations may occur in the dimensions and the like of the blades. Therefore,
Solving these problems, namely improving dimensional accuracy and preparing
It was desired that the accuracy be improved. [0004] It is an object of the present invention to address the problems of the prior art.
To improve the accuracy of raw material charging for positive photoresist.
To improve the dimensional accuracy of the integrated circuit.
It is to produce a resist composition suitable for production. [0005] The inventors of the present invention have conducted intensive studies and have found that
In preparing the strike composition, the ingredients are charged in the form of a solution.
By doing this, it is possible to improve the
This can prevent performance degradation such as dimensional deviation.
And completed the present invention. [0006] That is, the present invention provides a quino
Prepare a diazide photosensitizer in the form of a solution in an organic solvent.
ThePrepared in the form of organic solvent solutionNovolak resin
For producing a resist composition by mixing with
Is provided. Positive photoresist composition
Is added to novolak resins and quinonediazide-based photosensitizers.
In addition, alkali-soluble low molecular weight phenol-based additive
Additives, and this phenolic additive also dissolves in organic solvents.
Prepare and prepare in liquid form. [0007] DESCRIPTION OF THE PREFERRED EMBODIMENTS Resists Produced According to the Invention
The composition is composed of a novolak resin and a quinonediazide-based photosensitive
The type of each of these components is particularly limited
Can be used normally in the resist field.
Wear. The quinonediazide type photosensitizer is usually phenol
Compounds having a hydroxy group and quinonediazidosulfonyl
It is produced by a condensation reaction with a halide. Condensation reaction
The compound having a phenolic hydroxyl group as a raw material is a molecule.
Having at least one phenolic hydroxyl group in it
And especially at least phenolic hydroxyl groups
Those having two are preferred. Has a phenolic hydroxyl group
Examples of the compound represented by the following formulas (I) to (IV)
And the like. [0009] In the formula, m represents a number from 0 to 4,¹ , R
^Two , R^Three , R^Four , R^Five , R⁶ , R⁷ , R⁸ , R⁹ ,
R^Ten, R¹¹, R¹², R¹³And R¹⁴One of (just
And when m = 0, R¹ , R^Two , R^Three , R^Four , R^Five ,
R⁶ , R⁷ , R⁸ , R⁹ And R^TenOne of them) is water
Acid groups, independently of each other, hydrogen, hydroxyl, halogen
, Alkyl, cycloalkyl, alkenyl, aryl
Aralkyl, alkoxy, amino, monoalkyl
Mino, dialkylamino, alkylcarbonylamino,
Alkyl carbamoyl, aryl carbamoyl, alk
Rusulfamoyl, arylsulfamoyl, carboxy
Syl, cyano, nitro, formyl, alkylcarboni
, Alkoxycarbonyl, aryloxycarbonyl
Or an alkylcarbonyloxy, R^Fifteen,
R¹⁶, R¹⁷And R¹⁸Are independently of each other hydrogen, hydroxyl,
Alkyl, cycloalkyl, alkenyl, aryl, a
Represents aralkyl or alkoxy; [0011] Where R^{twenty one}, R^{twenty two}, R^{twenty three}, R^{twenty four}, R^{twenty five}, R
²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴
And R³⁵One of them is hydroxyl and the others are independent of each other
Hydrogen, hydroxyl, halogen, alkyl, cycloalkyl
Alkenyl, aryl, aralkyl, alkoxy,
Amino, monoalkylamino, dialkylamino, al
Kill carbonyl amino, alkyl carbamoyl, aryl
Rucarbamoyl, alkylsulfamoyl, aryls
Rufamoyl, carboxyl, cyano, nitro, holmi
, Alkylcarbonyl, alkoxycarbonyl, ant
Oxycarbonyl or alkylcarbonyloxy
And R³⁶Is hydrogen, hydroxyl, alkyl, cycloalkyl
Alkenyl, aryl, aralkyl or alkoxy
Represents si; [0013] Where R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R
⁴⁶, R⁴⁷, R⁴⁸And R⁴⁹Are independent of each other, hydrogen, water
Acid group, halogen, alkyl, cycloalkyl, alkenyl
, Aryl, aralkyl, alkoxy, amino, mono
Alkylamino, dialkylamino, alkylcarboni
Ruamino, alkylcarbamoyl, arylcarbamoy
, Alkylsulfamoyl, arylsulfamoy
, Carboxyl, cyano, nitro, formyl, al
Killcarbonyl, alkoxycarbonyl, aryloxy
Represents cyclocarbonyl or alkylcarbonyloxy; [0015] Where R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R
⁵⁶And R⁵⁷Two of them are hydroxyl groups and the rest are independent of each other
Hydrogen, hydroxyl, halogen, alkyl, cycloalkyl
Alkenyl, aryl, aralkyl, alkoxy,
Amino, monoalkylamino, dialkylamino, al
Kill carbonyl amino, alkyl carbamoyl, aryl
Rucarbamoyl, alkylsulfamoyl, aryls
Rufamoyl, carboxyl, cyano, nitro, phor
Mill, alkylcarbonyl, alkoxycarbonyl,
Reeloxycarbonyl or alkylcarbonyloxy
Represents R⁵⁸And R⁵⁹One is a hydroxyl group and the other is water
A hydrogen atom, a hydroxyl group or an alkyl having 1 to 4 carbon atoms;⁶⁰
And R⁶¹One of which is alkyl, alkenyl, cycloa
Alkyl or aryl;⁶⁰And R⁶¹On the other hand,
R⁶², R⁶³And R⁶⁴Are independently of each other hydrogen,
, Cycloalkyl, alkenyl, aryl, aralkyl
, Alkoxy, amino, monoalkylamino, dial
Killamino, alkylcarbonylamino, alkylcar
Bamoyl, arylcarbamoyl, alkylsulfamo
Yl, arylsulfamoyl, carboxyl, shea
No, nitro, alkylcarbonyl, alkoxycarbonyl
, Aryloxycarbonyl or alkyl carbonyl
Represents Roxy or R⁶⁰And R⁶¹Together
And R⁶²And R⁶³Come together and join
Forming a cycloalkane ring having 5 to 8 carbon atoms together with carbon atoms
To achieve. In the above formulas (I) to (IV), halogen
Can be fluorine, chlorine, bromine, iodine, etc.
Alkyl (alkyl alkyl
When alkyl is bonded to another group such as bonyl
And alkoxy (including alkoxycarbonyl)
Including the case where alkoxy is further bonded to another group)
It may have about 1 to 10 carbon atoms, and may be a cycloalkyl
Can have from about 5 to 8 carbon atoms and
Can have about 2 to 10 carbon atoms. Aryl
(Aryl is another group such as arylcarbamoyl
) Is typically phenyl or
Naphthyl, which is a hydroxyl group or a group having 1 to 4 carbon atoms.
And may be substituted with
Is typically benzyl, phenethyl, naphthyl
Tyl, naphthylethyl, etc.
Substituted with an acid group or alkyl having about 1 to 4 carbon atoms
You may. The compounds included in the formula (I) include, for example,
Examples include the following: 4- (2,3,4-trihydroxybenzyl)
Le) phenol, 2,5- or 2,6-dimethyl-4- (2,3,4-
Trihydroxybenzyl) phenol, 2,3,5- or 2,3,6-trimethyl-4-
(2,3,4-trihydroxybenzyl) phenol, 4- or 3- [1- (2,3,4-trihydroxyf
Enyl) -1-methylethyl] phenol, 4- or 3- [1- (2,4-dihydroxyphenyl)
-1-methylethyl] phenol, 4- or 3- [1- (2,4-dihydroxy-3-me
Tylphenyl) -1-methylethyl] phenol, 4- [1- (2,4-dihydroxyphenyl) -1-me
Tyl ethyl) resorcinol, 4- [1- (2,3,4-trihydroxyphenyl)-
1-methylethyl] pyrogallol, 4- [1- (2,4-dihydroxy-5-t-butylphenyl)
Enyl) -1-methylethyl] phenol, 2,6-bis (2-hydroxy-5-methyl
Rubenzyl) -4-methylphenol, 2,6-bis (4-hydroxy-3,5- or -2,
5-dimethylbenzyl) -4-methylphenol, 2,6-bis (2-hydroxy-3,5-dimethylben
Jill) -4-methylphenol, 2,6-bis (2,4-dihydroxybenzyl) -4-
Methylphenol, 2,6-bis (2,3,4-trihydroxybenzyl)
-4-methylphenol, 1,3-dihydroxy-4,6-bis [1- (4- also
Is 3-hydroxyphenyl) -1-methylethyl] benne
Zen, 1,3-dihydroxy-2-methyl-4,6-bis [1
-(4- or 3-hydroxyphenyl) -1-methyl
Ethyl] benzene, 4,4'-methylenebis [2- (4-hydrido)
Roxybenzyl) -3,6-dimethylphenol], 4,4'-methylenebis [2- (4-hydroxy-2,
5- or -3,5-dimethylbenzyl) -3,6-di
Methylphenol], 4,4'-methylenebis [2- (2-hydroxy-5-
Methylbenzyl) -3,6-dimethylphenol], 2,2'-methylenebis [6- (4-hydroxy-3-
Methylbenzyl) -4-methylphenol], 4,4'-methylenebis [2- (4-hydroxy-3-
Or 2-methylbenzyl) -3,6-dimethylphen
Nord), 4,4'-methylenebis [2- (2,4-dihydroxy
Benzyl) -3,6-dimethylphenol], 4,4'-methylenebis [2- (4-hydroxy-3-
Or 2-methylbenzyl) -6-methylphenol
Le), 4,4'-methylenebis [2- (4-hydroxybenzyl)
Ru) -6-methylphenol], 4,4'-methylenebis [2- (2-hydroxy-5-
Methylbenzyl) -6-methylphenol], 4,4'-methylenebis [2- (4-hydroxy-2,
5- or -3,5-dimethylbenzyl) -6-methyl
Phenol), 1- [1,1-bis (4-hydroxyphenyl) ethyl
L] -4- [1- (4-hydroxyphenyl) -1-me
Tylethyl] benzene, 2,4-bis [2-hydroxy-3- (4
-Hydroxy-2,3,6-trimethylbenzyl) -5
-Methylbenzyl] -3,5,6-trimethylphenol
, 2,6-bis [4-hydroxy-3- (4-hydroxy
-3- or -2-methylbenzyl) -2,5-dimethyl
Rubenzyl] -4-methylphenol, 2,6-bis [4-hydroxy-3- (4-hydroxy
−2,6-dimethylbenzyl) -2,5-dimethylben
Zyl] -4-methylphenol, 2,6-bis [4-hydroxy-3- (2-hydroxy
-5-methylbenzyl) -2,5-dimethylbenzyl]
-4-methylphenol, 2,6-bis [4-hydroxy-3- (2-hydroxy
Benzyl) -2,5-dimethylbenzyl] -4-methyl
Phenol, 2,6-bis [4-hydroxy-3- (2-hydroxy
-4,5-dimethylbenzyl) -2,5-dimethylben
Zyl] -4-methylphenol, 1,4-bis [1- {4-hydroxy-3- (4-hydrido)
Roxybenzyl) -5-methylphenyl {-1-methyl
Ethyl] benzene, 1,4-bis [1- {4-hydroxy-3- (2-hydrido)
Roxy-5-methylbenzyl) phenyl {-1-methyl
Ethyl] benzene, 4,4'-methylenebis [2- {4-hydroxy-3-
(2,4-dihydroxybenzyl) -5-methylbenzyl
Ru-3,6-dimethylphenol] and the like. As the compound included in the formula (II), for example,
Examples include the following: 4,4 ', 4 "-trihydroxytrife
Nil methane, 3,4 ', 4 "-trihydroxytriphenylmethane, 3 ", 4,4 ', 4" -tetrahydroxy-3,3',
5,5'-tetramethyltriphenylmethane, 2 ", 3", 4,4 ', 4 "-pentahydroxy-3,
3 ', 5,5'-tetramethyltriphenylmethane, 2 ", 4,4'-trihydroxy-2,2 ', 5,5'
-Tetramethyltriphenylmethane, 2,2 ', 2 "-trihydroxy-4,4', 5,5 '
-Tetramethyltriphenylmethane, 5,5'-di-t-butyl-3 ", 4,4 ', 4" -te
Trahydroxy-2,2'-dimethyltriphenylmeta
, 5,5'-di-t-butyl-3 ", 4,4 ', 4" -te
Trihydroxy-2,2'-dimethoxytriphenylmethyl
Tongue, 5,5'-dicyclohexyl-3 ", 4,4 ', 4" -te
Trahydroxy-2,2'-dimethyltriphenylmeta
, 5,5'-diisopropyl-3 ", 4,4 ', 4" -te
Trahydroxy-2,2'-dimethyltriphenylmeta
, 5,5'-dicyclohexyl-3 ", 4,4 ', 4" -te
Trihydroxy-2,2'-dimethoxytriphenylmethyl
Tongue, 5,5'-diisopropyl-3 ", 4,4 ', 4" -te
Trihydroxy-2,2'-dimethoxytriphenylmethyl
Tongue, 5,5'-dicyclohexyl-2 ", 4,4 ', 5" -te
Trahydroxy-2,2'-dimethyltriphenylmeta
, 5,5'-diisopropyl-2 ", 4,4 ', 5" -te
Trahydroxy-2,2'-dimethyltriphenylmeta
, 5,5'-dicyclohexyl-2 ", 4,4 ', 5" -te
Trihydroxy-2,2'-dimethoxytriphenylmethyl
Tongue, 5,5'-diisopropyl-2 ", 4,4 ', 5" -te
Trihydroxy-2,2'-dimethoxytriphenylmethyl
Tongue, 2 ", 4,4'-, 3", 4,4'- or 4,4 ',
4 "-trihydroxy-3,3 ', 5,5'-tetrame
Tyltriphenylmethane, 4,4 ', 4 "-trihydroxy-3" -methoxy-
3,3 ', 5,5'-tetramethyltriphenyl meta
, 5,5'-dicyclohexyl-2 ", 4,4'-trich
Droxy-2,2'-dimethyltriphenylmethane, 5,5'-diisopropyl-2 ", 4,4'-trihydride
Roxy-2,2'-dimethyltriphenylmethane, 4,4 ', 4 "-trihydroxy-3-methoxytrif
Phenylmethane and the like. The compounds included in the formula (III) include, for example,
Examples include the following: 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 3-trihydroxybenzophenone, 2,2 ', 4-trihydroxybenzophenone, 2,2 ', 5-trihydroxybenzophenone, 2,3,3'-trihydroxybenzophenone, 2,3,4'-trihydroxybenzophenone, 2,3 ', 4-trihydroxybenzophenone, 2,3 ', 5-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4 ', 5-trihydroxybenzophenone, 2 ', 3,4-trihydroxybenzophenone, 3,3 ', 4-trihydroxybenzophenone, 3,4,4'-trihydroxybenzophenone, 2,4,4'-trihydroxy-3-methylbenzofe
Non, 2,3,3 ', 4'-tetrahydroxybenzopheno
, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzopheno
, 2,2 ', 3,4-tetrahydroxybenzophenone, 2,2 ', 3,4'-tetrahydroxybenzopheno
, 2,2 ', 5,5'-tetrahydroxybenzopheno
, 2,3 ', 4', 5-tetrahydroxybenzopheno
, 2,3 ', 5,5'-tetrahydroxybenzopheno
, 2,2 ', 4,4'-tetrahydroxy-3,3'-dimethyl
Tylbenzophenone, 2,2 ', 3,4,4'-pentahydroxybenzofe
Non, 2,2 ', 3,4,5'-pentahydroxybenzofe
Non, 2,2 ', 3,3', 4-pentahydroxybenzofe
Non, 2,3,3 ', 4,5'-pentahydroxybenzofe
Non, 2,3,3 ', 4,4', 5'-hexahydroxyben
Zofenone, 2,2 ', 3,3', 4,5'-hexahydroxyben
Zofenone and the like. The compounds included in the formula (IV) include, for example,
Examples include the following: 2,4,4-trimethyl-2 ', 4', 7
-Trihydroxyflavan, 2,4,4-trimethyl-2 ', 3', 4 ', 7,8-
Pentahydroxyflavan, 2,3 ', 4,4,8-pentamethyl-2', 4 ', 7
-Trihydroxyflavan, 4- (1 ', 2', 3 ', 4', 4'a, 9'a-hex
Sahydro-6'-hydroxyspiro [cyclohexane-
1,9'-Xanthen] -4'a-yl) resorcinol
, 4- (1 ', 2', 3 ', 4', 4'a, 9'a-hex
Sahydro-6'-hydroxy-5'-methylspiro [
Chlorohexane-1,9'-xanthen] -4'a-yl)
-2-methylresorcinol, 4- (1 ', 2', 3 ', 3'a, 9', 9'a-hex
Sahydro-6'-hydroxyspiro [cyclopentane-
1,9'-cyclopenta [b] chromene] -3'a-yl)
Resorcinol and the like. A compound having such a phenolic hydroxyl group
The compound reacts with condensation with quinonediazide sulfonyl halide.
It is esterified by the reaction and becomes a photosensitizer. Used here
Quinonediazidosulfonyl halide is usually o-quinone
Diazidosulfonyl halide, for example, 1,2-
Naphthoquinonediazide-4- or -5-sulfonylha
Ride, 1,2-benzoquinonediazide-4-sulfoni
Lehalide and the like. This condensation reaction is generally carried out in an organic solvent.
It is. As the organic solvent to be used, for example, tetrahydro
Ethers such as furan and dioxane, N, N-dim
Amides such as tylformamide, dimethyl sulfoxide
Water-miscible solvents such as sulfoxides such as sides
Or an aliphatic carbon such as n-hexane or n-heptane.
Hydrogens, alicycles such as cyclohexane and cyclopentane
Formula hydrocarbons, aromatic carbons such as toluene and xylene
Hydrogens, halogens such as dichloromethane and chloroform
Aliphatic hydrocarbons, chlorobenzene and dichloroben
Halogenated aromatic hydrocarbons such as zen, ethyl acetate
And esters such as butyl acetate and amyl acetate, methyl
Ketones such as isobutyl ketone and 2-heptanone,
Ethylene glycol monomethyl ether acetate or d
Tylene glycol monoethyl ether acetate, professional
Pyrene glycol monomethyl ether acetate, professional
Like pyrene glycol monoethyl ether acetate
Soluble in water such as glycol ether esters
Medium. Each of these reaction solvents is used alone
Or a mixture of two or more. Also
This condensation reaction is carried out in the presence of a dehydrohalogenating agent.
You. As the dehydrohalogenating agent, for example, triethyl
Aliphatic amines such as amines, cyclic such as pyridine
Amines, inorganic bases such as sodium bicarbonate, etc.
Used. After completion of the reaction, an acid such as acetic acid is usually added.
In addition, the excess dehydrohalogenating agent is neutralized. In the present invention, a quinonediazide-based photosensitive
Agent in the form of a solution in an organic solvent, and then
Mix with resin. To do so, use the phenolic
Compounds having hydroxyl group and quinonediazidosulfonylhala
The condensation reaction with
The salt of the dehydrohalogenating agent formed in the subsequent neutralization is removed.
The quinonediazide-based photosensitizer into a solution of the organic solvent.
After the condensation reaction, another organic solvent is added for solvent exchange.
Quinonediazide-based photosensitizer
A method of obtaining a solution of the added organic solvent can be adopted.
You. The quinonediazide-based photosensitizing agent
The solvent solution must be mixed with the novolak resin before mixing
It is desirable that halogen ions and the like have been removed.
To do so, the quinonediazide-based photosensitizer is separated from water.
It is preferable to prepare an organic solvent solution and wash with water. Wash with water
Organic solvent solution of non-diazide type photosensitizer with sufficient amount of water
It can be done by mixing, stirring and separating.
You. If necessary, repeat washing with an appropriate amount of water several times.
You can also return. Compounds having phenolic hydroxyl groups
Reaction between the product and quinonediazide sulfonyl halide
If performed in an organic solvent that separates from water, neutralize and remove
The salt of the hydrogenating agent is removed by filtration or the like, and then water is removed.
In addition, washing is performed by stirring. Also,
Compounds having an enolic hydroxyl group and quinonediazide sulf
Condensation reaction with phonyl halide in an organic solvent miscible with water
If neutralization is performed, the salt of the dehydrohalogenating agent is filtered off after neutralization.
An organic solvent that is removed by excess and then separated from water and
Add water, stir, and separate to separate this water.
Quinonediazide-based photosensitizers
It is possible to adopt a method of exchanging the medium and washing with water. Organic solvent for dissolving quinonediazide-based photosensitizer
Is a solvent for the resist composition, for example, water and
Release ketones and glycol ether esters
Preferably it is. Quinonediazide
An organic solvent solution of the photosensitizer is obtained.
In order to remove moisture contained in
Concentration is generally performed to achieve the concentration required for production.
Is preferred. The other component of the resist composition,
Volak resins are usually phenolic compounds and aldehydes.
Is obtained by condensation in the presence of an acid catalyst.
You. Phenolic compounds used as raw materials for novolak resins
Thus, for example, o-, m- or p-cresol,
2,5-, 3,5- or 3,4-xylenol, 2,
3,5-trimethylphenol, 2-t-butyl-5-
Examples include methylphenol and t-butylhydroquinone.
I can do it. Also, it is the other raw material of novolak resin.
Formaldehyde, acetaldehyde
Aliphatic aldehydes such as aldehydes and glyoxal,
And like benzaldehyde, salicylaldehyde
Aromatic aldehydes. One or two of these phenolic compounds
At least one species and one or more aldehydes
By condensing in the presence of a medium, the novolak resin
can get. Acid catalysts such as hydrochloric acid, sulfuric acid and phosphoric acid
Inorganic acids, oxalic acid, acetic acid, p-toluenesulfonic acid
Organic acids, divalent metal salts such as zinc acetate, etc.
Can be The condensation reaction can be performed according to a conventional method.
For example, run at a temperature in the range of 60 to 120 ° C for about 2 to 30 hours.
Will be In addition, even if the reaction is carried out in bulk,
May be performed. The resulting novolak resin is, for example,
Perform another operation such as gel permeation chromatography
-(GPC) (using UV 254 nm detector)
Turn: less than 900 in terms of polystyrene equivalent molecular weight
Of the unreacted phenolic compound
25% or less of the total pattern area excluding the
It is more preferable that the content be 20% or less. According to the present invention, the novolak resin is also an organic resin.
Prepare in the form of a solution of a solvent and use the quinonediazide-based
Mixed with the organic solvent solution of the agentYou.Dissolve novolak resin
Organic solvents are also solvents for resist compositions.
Is preferred. Separation operation as described above for novolak resin
If so, then perform a solvent exchange operation if desired
Novolak tree as a solution of any organic solvent
Fat can be obtained. In the present invention, the resist composition may further comprise a molecule.
Low molecular weight phenol based on alkali soluble at an amount of 900 or less
Additives, for example, reduce phenolic hydroxyl groups in the molecule
With a polyhydric phenol compound with twoYou.this
When blending such a low molecular weight phenolic additive,
This additive is also prepared in the form of a solution of an organic solvent, and
Quino prepared in the form of volak resin and organic solvent solution
Mix with benzodiazide photosensitizerYou.For example, in solid form
The intended additives are dissolved in a suitable organic solvent.
Or in the form of a solution. Organic solvents used here
The agent is also preferably a solvent for the resist composition.
New The solvent of the resist composition is adjusted to an appropriate drying speed.
Gives a uniform and smooth coating after the solvent evaporates
Things are good. Such solvents include, for example,
Lenglycol monomethyl ether acetate and ethyl
Glycol monoethyl ether acetate, propylene
Such as glycol monomethyl ether acetate
Recol ether esters, cyclohexanone and 2-
Ketones such as heptanone, n-amyl acetate
Esters and the like. These solvents
These can be used alone or as a mixture of two or more.
You. If necessary, ethyl lactate or γ-butyrolact
May contain small amounts of water-miscible organic solvents such as
it can. Quinone di prepared in the form of a solution in an organic solvent
Azide-based photosensitizers are used for novolak resins and
Additional solvents, and optionally low molecular weight
By mixing with phenolic additives, resist
It becomes a composition. The resist composition thus prepared is
If necessary, other ingredients such as dyes, Novola
Small amounts of additives other than
Can also be. In the resist composition produced according to the present invention,
The composition ratio of each component is not particularly limited.
Can be a value that is usually adopted. Its composition
The ratio is based on the type of quinonediazide-based photosensitizer and low molecular weight
It varies depending on the presence or absence of a knol-based additive.
Is based on the total solids content of the resist composition.
Quinonediazide-based photosensitive resin
The agent is in the range of about 10 to 50% by weight and has a low molecular weight.
About 3-40% by weight when using phenolic additives
It is. [0041] The present invention will be described in more detail with reference to the following examples.
However, the present invention is not limited to these examples.
It is not limited. The part and density display in the example are
Unless otherwise specified, it is based on weight. Reference Example (Production of Novolak Resin) In a four-necked flask, 148.5 parts of m-cresol, p-co
121.5 parts of resole, 252 methyl isobutyl ketone
Parts, 10% oxalic acid aqueous solution 37.0 parts and 90% acetic acid aqueous solution
Charge 84.8 parts of the solution, and stir while heating in an oil bath at 100 ° C.
Then, 129.5 parts of 37.0% formalin was dropped in 40 minutes.
And then allowed to react for an additional 15 hours. Next, wash and dehydrate
And methyl isobut containing 42.3% of novolak resin
466 parts of a chill ketone solution were obtained. Polystyrene by GPC
The weight average molecular weight in terms of len was 4,300. Remove 450 parts of this solution from the bottom
Charged to Suko, and further added methyl isobutyl ketone 909.6
And 996.1 parts of n-heptane at 60 ° C.
After stirring for 0 minutes, the mixture was allowed to stand and separated. Obtained by liquid separation
380 parts of 2-heptanone was added to the lower
Evaporator for isobutyl ketone and n-heptane
To remove the novolak resin in 2-heptanone.
A liquid was obtained. Weight average molecule in terms of polystyrene by GPC
The molecular weight is 9,000, which is 900 or less in terms of polystyrene equivalent molecular weight.
The area ratio in the lower area is 14% of the total pattern area.
there were. Preparation Example 1 (Production of Photosensitive Agent Solution) The following formula (a) [0045] 4- (1 ', 2', 3 ',
4 ', 4'a, 9'a-Hexahydro-6'-hydroxy
C-5'-methylspiro [cyclohexane-1,9'-
Xanthene] -4'a-yl) -2-methylresorcino
1 mol of 1,2-naphthoquinonediazide-5-sul
2.72 liters of dioxane in 2 moles of honyl chloride
And completely add 2.4 mol of triethylamine to the solution.
1,2-naphthoquinonediazide-5-sulfonyl
The reaction was continued until no chloride was detected. End of reaction
After completion, 0.6 mol of acetic acid was added and the mixture was stirred for 1 hour.
The precipitate (amine salt) was filtered. 2-Heptano in the filtrate
Wash with 6 liters of ion-exchanged water and 3 liters
Then, a treatment for removing metals and chloride ions was performed. After liquid separation,
Take out the 2-heptanone layer, the solid content becomes about 20%
To give a 2-heptanone solution of the photosensitizer. Preparation Examples 2 to 6 (production of another photosensitive agent solution) In place of the compound of formula (a) used in Preparation Example 1,
4,4'-methylenebis [2- (4-
Hydroxybenzyl) -3,6-dimethylphenol]
(Formula (b): Preparation Example 2), 2,4,4-trimethyl-
2 ', 4', 7-trihydroxyflavan (the following formula (c):
Preparation Example 3), 2,3,4,4'-tetrahydroxyben
Zofenone (the following formula (d): Preparation Example 4), 4,4'-methyle
Bis [2- (2-hydroxy-5-methylbenzyl)
-3,6-dimethylphenol] (Formula (e): Preparation Example
5) or 2,6-bis [4-hydroxy-3- (2-
(Hydroxy-5-methylbenzyl) -2,5-dimethyl
Benzyl] -4-methylphenol (Formula (f): Preparation Example
6) The same procedure as in Preparation Example 1 was carried out except that the same molar amount was used.
Cropping, containing each photosensitizer at about 20% concentration.
-A heptanone solution was obtained. [0048] Preparation Example 7 (Preparation of photosensitive solution by another method)
Build) The same 4- (1 ′, 2 ′, 3 ′,
4 ', 4'a, 9'a-Hexahydro-6'-hydroxy
C-5'-methylspiro [cyclohexane-1,9'-
Xanthene] -4'a-yl) -2-methylresorcino
1 mol of 1,2-naphthoquinonediazide-5-sul
2 mol of honyl chloride in 4 liters of 2-heptanone
And completely add 2.4 mol of triethylamine to the solution.
1,2-naphthoquinonediazide-5-sulfonyl
The reaction was continued until no chloride was detected. End of reaction
After completion, 0.6 mol of acetic acid was added and stirred for 1 hour.
The residue (amine salt) was filtered. Deionized water 3 in the filtrate
Add liters and wash to remove metals and chloride ions.
Was done. After liquid separation, the solid content of the 2-heptanone layer was about 2%.
Concentrate to 0%, as in Preparation Example 1
To give a 2-heptanone solution of the photosensitizer. Preparation Examples 8 to 12 (Preparation of another photosensitive agent solution) 4- (1 ', 2', 3 ', 4', 4 'used in Preparation Example 7
a, 9'a-Hexahydro-6'-hydroxy-5'-
Methyl spiro [cyclohexane-1,9'-xanthe
] -4'a-yl) -2-methylresorcinol
Instead, the same 4,4 ′ as used in Preparation Examples 2 to 6, respectively.
-Methylenebis [2- (4-hydroxybenzyl)-
3,6-dimethylphenol] (Preparation Example 8), 2,4
4-trimethyl-2 ', 4', 7-trihydroxyfura
Bang (Preparation Example 9), 2,3,4,4'-tetrahydroxy
Cibenzophenone (Preparation Example 10), 4,4'-methyle
Bis [2- (2-hydroxy-5-methylbenzyl)-
3,6-dimethylphenol] (Preparation Example 11), or
2,6-bis [4-hydroxy-3- (2-hydroxy
-5-methylbenzyl) -2,5-dimethylbenzyl]
4-Methylphenol (Preparation Example 12) in the same molar amount
Except for using, the same operation as in Preparation Example 7 was performed.
About 20% of the same photosensitive agent as obtained in Preparation Examples 2 to 6
A 2-heptanone solution containing the same in concentration was obtained. Preparation Example 13 (Comparison: Production of Powder Photosensitive Agent) The same 4- (1 ′, 2 ′, 3 ′,
4 ', 4'a, 9'a-Hexahydro-6'-hydroxy
C-5'-methylspiro [cyclohexane-1,9'-
Xanthene] -4'a-yl) -2-methylresorcino
1 mol of 1,2-naphthoquinonediazide-5-sul
2 moles of honyl chloride, 4.72 liters of dioxane
Completely dissolved in toluene, and the solution contains 2.4 mol of triethylamine.
Is added dropwise to give 1,2-naphthoquinonediazide-5-sulfo.
The reaction was continued until no nyl chloride was detected. Anti
After completion of the reaction, 0.6 mol of acetic acid was added, and the mixture was stirred for 1 hour.
The precipitate (amine salt) was filtered with. Filtrate is 1% aqueous acetic acid
The precipitate is filtered into the solution, and the filtrate is ion-exchanged.
Wash thoroughly with water replacement and remove metal and chlorine ions.
Was. This is dried to obtain a powdered photosensitizer.
Was. Preparation Examples 14 to 18 (Comparison: Different powder photosensitizers)
Manufacturing of) The 4- (1 ′, 2 ′, 3 ′, 4 ′,
4'a, 9'a-Hexahydro-6'-hydroxy-
5'-Methylspiro [cyclohexane-1,9'-oxa
Content] -4'a-yl) -2-methylresorcinol
Instead of the same as those used in Preparation Examples 2 to 6,
4,4'-methylenebis [2- (4-hydroxybenzyl)
Ru) -3,6-dimethylphenol] (Preparation Example 14),
2,4,4-trimethyl-2 ', 4', 7-trihydro
Xiflavan (Preparation Example 15), 2,3,4,4'-tet
Lahydroxybenzophenone (Preparation Example 16), 4,4 '
-Methylenebis [2- (2-hydroxy-5-methylbe
Ndyl) -3,6-dimethylphenol] (Preparation Example 1
7) or 2,6-bis [4-hydroxy-3- (2
-Hydroxy-5-methylbenzyl) -2,5-dimethyl
Benzyl] -4-methylphenol (Preparation Example 18)
The same operation as in Preparation Example 13 was performed, except that the same molar amount was used.
As a result, each photosensitive agent was obtained in the form of a powder. Preparation Example 19 (Production of phenolic additive solution)
Build) 2.5 mol of 2,6-xylenol in 400 g of methanol
Solution containing 1 mole of salicylaldehyde and
0.2 mol of sulfonic acid, salicylaldehyde
Stir until no longer detectable. After the reaction, ion exchange
200 g of water exchange was added, and crystals were sufficiently precipitated, followed by filtration.
did. The filtrate was rinsed with a 60% aqueous methanol solution.
And dissolved in 500 g of 2-heptanone and ion-exchanged water
The metal was removed by washing. Next, water is less than 0.1%
Concentration and 2-heptanone preparation so that
Again, the final concentration of the reaction product will be 25%
I adjusted it. Thus, it has the structure of the following formula (g)
4,4 '-(2-hydroxybenzylidene) di-2,
A solution of 6-xylenol in 2-heptanone was obtained. [0054] Preparation Example 20 (Another phenolic additive solution
Manufacturing of) Starting materials are 1.2 mol of resorcinol and cyclohexanone.
The same operation as in Preparation Example 19 was performed except that the amount was changed to 1 mol.
Thus, 4- (1 ′, 2 ′, 3 ′,
4 ', 4'a, 9'a-Hexahydro-6'-hydroxy
Cispiro [cyclohexane-1,9'-xanthene]-
4'a-yl) 2-F containing 25% resorcinol
A phthalone solution was obtained. [0056]Preparation Examples 21 and 22 (Alternative phenolic
Production of additive solution) Commercially available 1, having the structure of the following formula (i) or (j) respectively
1-bis (4-hydroxyphenyl) cyclohexane
(Preparation Example 21) or 9,9-bis (4-hydroxyphenyl)
Enyl) fluorene (Preparation Example 22) to 2-heptanone
After dissolving and washing with water, the same operation as in Preparation Example 19 was performed.
2-Heptanone solution containing 25% of each compound
I got [0058] Preparation Example 23 (Another phenolic additive solution
Manufacturing of) P-Isopropenylphenol in 400 g of toluene
A mixture containing 2.1 mol and 1 mol of 2-methylresorcinol
0.02 mol of a 1% hydrochloric acid aqueous solution is added to the solution,
Stirred for hours. After the completion of the reaction, the solid was filtered and washed with toluene.
After rinsing, it was dissolved in 2-heptanone. After washing
Performs the same operation as in Preparation Example 19 to convert the structure of the following formula (k) to
4,6-bis [1- (4-hydroxyphenyl) having
-1-methylethyl] -2-methylresorcinol
A 2-heptanone solution containing 5% was obtained. [0060] Preparation Example 24 (Another phenolic additive solution
Manufacturing of) The starting material was resorcinol 2.1 mol and 2,2'-m-phenyl.
Other than changing to 1 mol of enylene bis (2-propanol)
Was subjected to the same operation as in Preparation Example 23, to give the structure of the following formula (l).
1,3-bis [1- (2,4-dihydroxy)
Phenyl) -1-methylethyl] benzene containing 25%
A 2-heptanone solution was obtained. [0062] Preparation Example 25 (Comparison: Addition of powder phenol type)
Production of agents) 2.5 mol of 2,6-xylenol in 400 g of methanol
Solution containing 1 mole of salicylaldehyde and
0.2 mol of sulfonic acid, salicylaldehyde
Stir until no longer detectable. After the reaction, ion exchange
200 g of water exchange was added, and crystals were sufficiently precipitated, followed by filtration.
did. The filtrate was rinsed with a 60% aqueous methanol solution.
And a mixture of 200 g of ethyl acetate and 500 g of toluene
Dissolve and wash with ion exchanged water to remove metal
Was. After concentrating until the ethyl acetate concentration is 5% or less,
Add ene only by distillation to precipitate enough crystals and filter.
Was. The filtrate is dried to have the structure of the above formula (g)
4,4 '-(2-hydroxybenzylidene) di-2,6
-Xylenol was obtained as a powder. Preparation Example 26 (comparative: another powdered phenolic
Production of additives) Starting materials are 1.2 mol of resorcinol and cyclohexanone.
The same operation as in Preparation Example 25 was performed except that the amount was changed to 1 mol.
Thus, the 4- (1 ′, 2 ′, 3 ′,
4 ', 4'a, 9'a-Hexahydro-6'-hydroxy
Cispiro [cyclohexane-1,9'-xanthene]-
4'a-yl) resorcinol was obtained as a powder. Preparation Example 27 (comparative: another powdered phenolic
Production of additives) P-Isopropenylphenol in 400 g of toluene
A mixture containing 2.1 mol and 1 mol of 2-methylresorcinol
0.02 mol of a 1% hydrochloric acid aqueous solution is added to the solution,
Stirred for hours. After the completion of the reaction, the solid was filtered and washed with toluene.
After rinsing, 200 g of ethyl acetate and 500 g of toluene
g of the mixture, washed with ion-exchanged water,
Removal was performed. Concentrate until the ethyl acetate concentration is 5% or less
After shrinking, toluene was added only by distillation to precipitate enough crystals.
And filtered. The filtrate is dried to obtain the structure of the above formula (k).
4,6-bis [1- (4-hydroxyphenyl)
L) -1-methylethyl] -2-methylresorcinol
Was obtained as a powder. Preparation 28 (comparative: another powdered phenolic
Production of additives) The starting material was resorcinol 2.1 mol and 2,2'-m-phenyl.
Other than changing to 1 mol of enylene bis (2-propanol)
Was subjected to the same operation as in Preparation Example 27 to give the structure of the above formula (l).
1,3-bis [1- (2,4-dihydroxy)
Phenyl) -1-methylethyl] benzene as powder
Obtained. Example 4,4 'having the structure of the above formula (e) obtained in Preparation Example 5
-Methylenebis [2- (2-hydroxy-5-methylbe
Benzyl) -3,6-dimethylphenol]
Prepare 7 parts of a solution of zidosulfonic acid ester in terms of solid content.
4- having the structure of the above formula (h) obtained in Preparation Example 20
(1 ', 2', 3 ', 4', 4'a, 9'a-hexahi
Dro-6'-hydroxyspiro [cyclohexane-1,
9'-Xanthen] -4'a-yl) resorcinol
3.1 parts by weight of the solution in terms of solid content, before being obtained in Preparation Example 21
1,1-bis (4-hydroxy having a structure of the formula (i)
A solution of phenyl) cyclohexane was converted to a solid content of 1.1.
Parts and 2-heptanone, and then obtained in Reference Example.
Prepared novolak resin solution with weight average molecular weight of 9,000
10.13 parts in terms of solid content were charged and stirred. 2-hepta
Non was adjusted to be 60 parts in total. After homogenization,
After microfiltration, a positive photoresist was obtained. The above operation is repeated several times to basically
Multiple lots of the same positive photoresist were manufactured. Each
After applying these lots to a silicon wafer and drying
Exposure through a predetermined mask, development with an alkaline developer
Thus, a positive pattern was formed. As a result, each
The positive pattern obtained from the lot has dimensions of 0.35 ±
It was within the standard of 0.015 μm. Raw material preparation
The accuracy should be kept within ± 0.15% of the target value.
Was completed. Obtained in Preparation Examples 1 to 12 and 19 to 24
Even when various combinations are made using the components
Almost the same results as in the example were obtained,
Was. Comparative Example 4, having the structure of formula (e) obtained in Preparation Example 17;
4'-methylenebis [2- (2-hydroxy-5-methyl
Benzyl) -3,6-dimethylphenol]
7 parts of diazidesulfonic acid ester (powder), Preparation Example 2
4- (1 ', having the structure of the formula (h) obtained in
2 ', 3', 4 ', 4'a, 9'a-hexahydro-
6'-hydroxyspiro [cyclohexane-1,9'-
Xanthene] -4'a-yl) resorcinol (powder)
3.1 parts of a commercially available 1,1-biamine having a structure of the above formula (i)
S (4-hydroxyphenyl) cyclohexane (powder)
1.1 parts and 2-heptanone
Of the novolak resin with a weight average molecular weight of 9,000
The liquid was charged with 10.13 parts in terms of solid content and stirred. 2-he
The amount of phthalone was adjusted to be 60 parts in total. Homogenization
Thereafter, the resultant was subjected to microfiltration to obtain a positive photoresist. The above operation is repeated several times to basically
Multiple lots of the same positive photoresist were manufactured. Each
After applying these lots to a silicon wafer and drying
Exposure through a predetermined mask, development with an alkaline developer
Thus, a positive pattern was formed. As a result, each
The positive pattern obtained from the lot has dimensions of 0.35 ±
It was distributed at 0.02 μm. Also, the accuracy of raw material preparation is
It was ± 0.5% of the target value. [0072] According to the present invention, a positive photoresist is provided.
Of raw materials can be improved, and then
It is possible to improve the dimensional accuracy of the formed resist pattern.
Can be. Therefore, the method of the present invention requires accuracy.
Production of positive photoresists that are used
It is particularly useful for forming a resist pattern.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claim 1] A method for producing a resist composition comprising a novolak resin and a quinonediazide-based photosensitizer dissolved in a solvent, wherein the quinonediazide-type photosensitizer is dissolved in an organic solvent solution. In the form of a solution of organic solvent
And the resist composition further contains an alkali-soluble low molecular weight phenolic additive, and the phenolic additive is also prepared in the form of a solution of an organic solvent and mixed with other components. Characterized by the fact that
A method for producing a resist composition.