JP3449826B2 - Positive photoresist composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive positive type.
For photoresist compositions, especially high
With image power, wide defocus latitude, and high heat resistance
The photoresist composition for microfabrication.
You. [0002] Positive photoresists according to the present invention are semi-conductive.
Conductor wafer, glass, ceramics or metal
Spin coating or roller coating on the substrate
It is applied to a thickness of ３3 μm. Then, heat and dry,
Circuit patterns and the like are exposed to ultraviolet light through an exposure mask.
After printing and development, a positive image is formed. Furthermore this
By etching with a positive image as a mask,
The pattern can be processed on the board. Typical
Applications include semiconductor manufacturing processes for ICs, liquid crystals, and thermal
Manufacture of circuit boards such as ridges and other photofabrication
And the like. [0003] As a positive photoresist composition,
Generally, alkali-soluble resin (for example, novolak resin)
A set containing a naphthoquinonediazide compound as a photosensitive material
The product is used. Naphthoquinone di used for photosensitive materials
The azide compound itself dissolves in the alkali
It acts as a dissolution inhibitor to reduce dissolution,
Decomposition by irradiation produces alkali-soluble substances.
It works to increase the alkali solubility of filter oil resin.
Peculiar in point and because of this large property change to light
It is particularly useful as a photosensitive material for a positive photoresist. [0004] Further, Novolat resin as a binder is
It can be dissolved in alkaline aqueous solution without swelling.
When using the generated image as a mask for etching
Gives high resistance especially to plasma etching
Therefore, it is particularly useful for this application. For example, "Novolak type
Phenolic resin / naphthoquinonediazide-substituted compound "
USP-3,666,473, USP-4,11
5,128 and USP-4,173,470, etc.
The most typical composition is "cresol-forma
Novolak resin consisting of aldehyde / trihydroxybenz
Zofenone-1,2 naphthoquinonediazidosulfonic acid
An example of "Ester" is Thompson's "Introduction
Woo Micro Lithography "(LF Thomp
son "Introduction to Micro"
lithography ") (ACS Publishing, No. 21)
9, No. 9, pp. 112-121). Further, Japanese Patent Application Laid-Open No. 6-242601 discloses
Is a phenolic compound (pheno
, M- / p-cresol, xylenol) and fragrance
Aliphatic aldehydes (benzaldehyde, hydroxybenzure
Aldehydes) in the presence of an acid catalyst.
Without isolating the low molecular weight obtained
Novola obtained by condensation with toluene and formaldehyde
Resin is described. And this novolak tree
Fatty oil containing o-naphthoquinonediazide compound
Resolution, profile, sensitivity, depth of focus and tolerance
Excellent balance of various properties such as heat and no scum
It is described that a photosensitive resin composition can be obtained. [0006] Also, USP-5,266,440
Means aromatic aldehydes (benzaldehyde, salicyl
Aldehydes) and phenols (phenol, m- / p
-Cresol, xylenol, naphthol, bispheno
) And, if necessary, a condensate of formaldehyde
O-quinonediazide compound to a novolak resin
Included photoresist compositions are described. This
Photoresist composition has excellent heat resistance
Having. Further, Japanese Patent Application Laid-Open No. 2-84414 discloses that
Novolak resins include phenolic compounds (Phenol
M- / p-cresol), formaldehyde and
Novolak resin composed of nohydroxy aromatic aldehyde
Is described. And formaldehyde and mono
Mixtures of aldehydes containing hydroxyaromatic aldehydes
Novolak resin is prepared from, heat resistance,
Positive photosensitive resist with high resolution can be obtained
Is described. [0008] However, such as ultra LSI
In the manufacture of semiconductor substrates, line widths of 1 μm or less
Processing of ultra-fine patterns is required. For such uses
In particular, high resolution, defocus latitude
Wide and high heat resistance, high enough to accurately capture the shape of the exposure mask
High sensitivity from the viewpoint of pattern shape reproduction accuracy and high productivity
Photoresist is required.
The reality is that mold photoresist cannot cope. [0009] Therefore, the object of the present invention is particularly a semiconductor device.
In the manufacture of body devices, (1) high resolution
Positive photoresist composition, (2) wide defocus
A positive photoresist composition having a lattice,
(3) The positive resist is excellent in heat resistance.
A photoresist composition. Means for Solving the Problems The present inventors have made the above-mentioned various features.
As a result of intensive studies with attention to the
By using a volak resin and a quinonediazide compound
And found that the above objectives could be achieved.
Based on this, the present invention has been completed. That is, the present invention
The object can be achieved by the following configuration. Phenolization represented by the following general formula (1)
And formaldehyde and the following general formula (2)
Obtained by condensing an aromatic aldehyde compound
Lucari soluble resin, 1,2-quinonediazide compound
A positive photoresist composition comprising: Embedded image Here, R ₁ ~ R _Three : May be the same or different, hydrogen atom, hydroxyl
Group, halogen atom, alkyl group, cycloalkyl group,
Alkoxy, alkenyl, aryl, aralkyl
Group, alkoxycarbonyl group or arylcarboni
R group, R _Four ~ R ₈ : May be the same or different, hydrogen atom, hydroxyl
Group, formyl group, halogen atom, alkyl group, cycloa
Alkyl group, alkoxy group, alkenyl group, aryl group,
Aralkyl group, -NHCO-R ₉ , -NHCOO-
R ₉ , -NHCONH-R ₉ , -CONH-R ₉ , -C
ONHCO-R ₉ , R ₉ : Alkyl group, cycloalkyl group, alkenyl group,
An aryl group or an aralkyl group. Where R _Four ~ R ₈ At least one of the
-NHCO-R ₉ , -NHCOO-R ₉ , -NHCON
HR ₉ , -CONH-R ₉ , -CONHCO-R ₉ Or
One of the substituents selected from That is, the present invention relates to an alkali-soluble resin.
And a phenolic compound represented by the general formula (1)
Muraldehyde and aromatic alde represented by the general formula (2)
Alkali-soluble resin obtained by condensation with
High resolution and wide defocus
Positive that has both heat resistance and high heat resistance
A mold photoresist can be provided. According to the present invention
Positive-type photoresists, especially those that require heat resistance,
It can be suitably used for a ly etching treatment. Hereinafter, the present invention will be described in detail. In the general formula (1), R ₁ ~ R _Three At
Halogen atom is chlorine atom, bromine atom or iodine
Atoms are preferred, and chlorine atoms are more preferred. Alkyl group
As methyl, ethyl, propyl, n-butyl
Group, isobutyl group, sec-butyl group or t-butyl
Alkyl groups having 1 to 4 carbon atoms, such as
ル is more preferred in terms of sensitivity. As a cycloalkyl group
Cyclopropyl, cyclopentyl, cyclohexyl
Butyl and cyclooctyl are preferred, and cyclohexyl is preferred.
Is more preferred. Methoxy as the alkoxy group
Group, ethoxy group, hydroxyethoxy group, propoxy
Group, hydroxypropoxy group, isopropoxy group, n-
Butoxy, isobutoxy, sec-butoxy
An alkoxy group having 1 to 4 carbon atoms such as t-butoxy group
Are preferred, and methoxy and ethoxy are more preferred.
No. Alkenyl groups include vinyl, propenyl,
C 2 -C 4 alkyl, such as a ril or butenyl group
Nyl group is preferable, and vinyl group and allyl group are more preferable.
No. Aryl groups include phenyl, xylyl, tol
An yl group or a cumenyl group is preferred, and a phenyl group is more preferred.
Is more preferable. Aralkyl groups include benzyl and phenene
A tyl or cumyl group is preferred, and a benzyl group is more preferred.
preferable. Methoxyca as the alkoxycarbonyl group
A rubonyl group or an ethoxycarbonyl group is preferred,
A methoxycarbonyl group is more preferred. Aryl carb
As the nyl group, a benzoyloxy group is preferable. Also,
R ₁ ~ R _Three May be the same or different. Change
Further, the substitution position of each substituent is not particularly limited. Phenols represented by the above general formula (1)
More specific examples of phenol, o-cresol
Cresols such as m-cresol and p-cresol
, 2,5-xylenol, 3,5-xylenol,
3,4-xylenol, 2,3-xylenol, 2,4
Xylenol such as xylenol, 2,6-xylenol
, O-ethylphenol, m-ethylphenol,
p-ethylphenol, pt-butylphenol, etc.
Alkylphenols, o-methoxyphenol, m-
Methoxyphenol, p-methoxyphenol, o-d
Toxicphenol, m-ethoxyphenol, p-ethoxy
Xyphenol, 3,5-dimethoxyphenol, 2-
Methoxy-4-methylphenol, o-propoxyfe
Knol, m-propoxyphenol, p-propoxyf
Enol, o-butoxyphenol, m-butoxyfe
Alkoxypheno such as phenol and p-butoxyphenol
, 2,3,5-trimethylphenol, 3,4
5-trimethylphenol, 2,3,6-trimethylphenol
Trimethylphenols such as enol, o-vinylphenol
Knol, m-vinylphenol, p-vinylphenol
, O-allylphenol, m-allylphenol, p
Alkenyl phenols such as allyl phenol, o-
Phenylphenol, m-phenylphenol, p-phenyl
Arylphenols such as phenylphenol, o-ben
Zylphenol, m-benzylphenol, p-benzyl
Aralkylphenols such as ruphenol, o-methoxy
Cicarbonylphenol, m-methoxycarbonylphen
Alcohols such as phenol and p-methoxycarbonylphenol
Oxycarbonylphenols, o-benzoyloxyf
Enol, m-benzoyloxyphenol, p-ben
Arylcarbonylpheno such as zoyloxyphenol
, O-chlorophenol, m-chlorophenol
, Halogenated phenols such as p-chlorophenol
, Catechol, resorcinol, hydroquinone, furo
Polyhydroxybens such as loglucinol and pyrogallol
Can show zens, etc., but are not limited to these
is not. Also, methylolated phenols, such as
For example, use of bishydroxymethyl-p-cresol
Can also be. Among these, phenol, cresol
, Xylenols and trimethylphenols are preferred.
M-cresol, p-cresol, o-cresol
2,5-xylenol, 3,5-xylenol,
3,4-xylenol, 2,3-xylenol, 2,6
-Xylenol, 2,3,5-trimethylphenol
More preferred. The above-mentioned phenol compounds are two or more kinds.
It can be mixed and used. Combination in that case
Is a mixture of two kinds of m-cresol and p-cresol,
Or m-cresol and 2,3-xylenol
A mixture of m-cresol, p-cresol,
Three mixtures of 2,3-xylenol are preferred. this
Preferred mixing ratios of the mixtures are shown below. Two kinds of m-cresol and p-cresol
In the mixture, m-cresol: 30 mol% or more and less than 90 mol% p-cresol: 10 mol% or more and less than 70 mol%, more preferably m-cresol: 40 mol% or more and less than 80 mol% p-cresol: 20 mol% And less than 60 mol%. M-cresol and 2,3-xylenol
M-cresol: 30 mol% or more and less than 90 mol% 2,3-xylenol: 10 mol% or more and less than 70 mol%, more preferably m-cresol: 40 mol% or more and less than 80 mol% 2, 3-xylenol: not less than 20 mol% and less than 60 mol%. M-cresol, p-cresol, 2,3
M-cresol: 40 mol% or more and less than 80 mol% p-cresol: 1 mol% or more and less than 40 mol% 2,3-xylenol: 1 mol% or more and less than 60 mol%, more preferably, m-cresol: 50 mol% or more and less than 70 mol% p-cresol: 1 mol% or more and less than 30 mol% 2,3-xylenol: 10 mol% or more and less than 50 mol% More preferably, m-cresol: 50 mol% or more Less than 70 mol% p-cresol: 1 mol% or more and less than 10 mol% 2,3-xylenol: 10 mol% or more and less than 40 mol%. Further, a phenol compound of the general formula (1)
Can be used in combination with other phenol compounds. example
For example, JP-A-5-181270 and JP-A-5-32360
4, JP-A-5-249666, JP-A-5-2326
No. 96, JP-A-60-164740, JP-A-5-32
3605, JP-A-4-226458, JP-A-5-1
No. 88590 and JP-A-7-72623.
Polyphenol having 2 to 5 aromatic rings described therein
It can be used in combination with a class. These polyphenols
The combination ratio is based on the phenol compound of the general formula (1).
30 mol% or less, preferably 20 mol% or less
Is preferred. In the general formula (2), R _Four ~ R ₈ At
Halogen atom is chlorine atom, bromine atom or iodine
Atoms are preferred, and chlorine atoms are more preferred. Alkyl group
As methyl, ethyl, propyl, n-butyl
Group, isobutyl group, sec-butyl group or t-butyl
Alkyl groups having 1 to 4 carbon atoms, such as
ル is more preferred in terms of sensitivity. As a cycloalkyl group
Cyclopropyl, cyclopentyl, cyclohexyl
Butyl and cyclooctyl are preferred, and cyclohexyl is preferred.
Is more preferred. Methoxy as the alkoxy group
Group, ethoxy group, hydroxyethoxy group, propoxy
Group, hydroxypropoxy group, isopropoxy group, n-
Butoxy, isobutoxy, sec-butoxy
An alkoxy group having 1 to 4 carbon atoms such as t-butoxy group
Are preferred, and methoxy and ethoxy are more preferred.
No. Alkenyl groups include vinyl, propenyl,
C 2 -C 4 alkyl, such as a ril or butenyl group
Nyl group is preferable, and vinyl group and allyl group are more preferable.
No. Aryl groups include phenyl, xylyl, tol
An yl group or a cumenyl group is preferred, and a phenyl group is more preferred.
Is more preferable. Aralkyl groups include benzyl and phenene
A tyl or cumyl group is preferred, and a benzyl group is more preferred.
preferable. Further, -NHCO-R ₉ , -NHCOO-
R ₉ , -NHCONH-R ₉ , -CONH-R ₉ , -C
ONHCO-R ₉ Can be mentioned. However,
In the general formula (2), R _Four ~ R ₈ At least one of
Is -NHCO-R ₉ , -NHCOO-R ₉ , -NHC
ONH-R ₉ , -CONH-R ₉ , -CONHCO-R
₉ Must be chosen from. If so, these substitutions
The number of substituents on the group is not limited, but is preferably 3 or less,
One is more preferable, and one is most preferable. Ma
Further, the substitution position is not limited, and CHO-
Any position of o-position, m-position and p-position with respect to
Noh. Note that R ₉ Is an alkyl group, a cycloalkyl group,
An alkenyl group, an aryl group or an aralkyl group
And specific examples of each substituent are the above-mentioned R _Four ~ R ₈ Listed in
Is the same as An aromatic aldehyde represented by the general formula (2)
More specific examples of the classes are shown below, which are used in the present invention.
The compounds that can be used are not limited to these. Embedded image Embedded image A phenol represented by the general formula (1):
Formaldehyde and an aromatic alcohol represented by the general formula (2)
The mixing ratio with aldehydes fully demonstrates the effects of the present invention.
Use only the amount of aromatic aldehydes required to
Phenol of general formula (1)
Aromatic aldehydes of the general formula (2)
It is preferred that the amount of the compounds is less than 40 mol%. In particular, one
More preferred mixing ratio of the aromatic aldehydes of the general formula (2)
The ratio is 0.1 mol% or more and less than 30 mol%, and 1 mol
% Or more and less than 20 mol% is more preferable. [0030] The present invention uses formaldehyde as an essential component.
And an aromatic aldehyde represented by the general formula (2)
However, formaldehyde is a formaldehyde precursor,
For use in the form of paraformaldehyde, trioxane, etc.
Can also be. As a third component, acetoaldehyde
Hyd, furfural, benzaldehyde, hydroxybe
Nudsaldehydes, crotonaldehyde, chloroaceto
Aldehydes and the like can also be used. Also, Hormua
Rudealdehyde is a phenolic compound represented by the general formula (1)
20 to 150 mol% for 100 mol%
Preferably, more preferably 50 to 120 mol%.
No. As the acidic catalyst used in the condensation reaction, hydrochloric acid,
Sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and sulfur
Acids and the like can be used, among which oxalic acid and p-
Toluenesulfonic acid is preferred. Also, use these together
Can also be used. Novolak resin comprising the above components of the present invention
Has a weight average molecular weight of 3,000 to 20,000, preferably
Is 4000 to 18000, more preferably 5000 to 1
It is preferably in the range of 6000. Less than 3000
Is large in film loss after development of unexposed areas, exceeding 20,000
If this is not the case, the developing speed will be reduced and the sensitivity will be reduced.
The novolak resin of the present invention removes and removes low molecular weight components.
Is most effective when the molecular weight after
I do. As a method for removing low molecular weight components of novolak resin
Are disclosed in JP-A-60-45238, JP-A-60-97347,
60-140235, 60-189439, 64-
14229, JP-A-1-276131 and 2-6091
5, 2-275555, 2-282745, 4-
101147, 4-122938, etc.
Techniques such as fractional precipitation, fractional lysis, column chromatography
Scum, heat-resistant
It is more preferable because the performance such as the property is improved. Low minutes to remove
The amount of the molecular weight component is preferably 20% by weight to 70% by weight,
0% to 60% by weight is more preferred. Here, the weight average molecular weight is gel permeation.
Polystyrene equivalent value of Chillon Chromatography (GPC)
Is defined by Also, the degree of dispersion of novolak resin
(The ratio of the weight average molecular weight Mw to the number average molecular weight Mn, that is, M
w / Mn) is 1.5 to 4.0, preferably 1.8 to 3.0.
5, more preferably 2.0 to 3.3. More than 4
In addition, performance such as sensitivity, heat resistance, and profile is impaired.
On the other hand, if it is less than 1.5, it is high in synthesizing a novolak resin.
Unsuitable due to lack of practical reality
It is off. Alkali-soluble resins that can be used
Although it is not particularly limited as long as it is compatible with the resin,
Styrene, acetone-pyrogallol resin, acetone-
Resorcinol resin is preferred because it does not degrade heat resistance
No. In the present invention, 1,2-naphtho is used as a photosensitive material.
Use quinonediazidosulfonyl esters.
And the like have the following polyhydroxy compound and 1,2-naph
Toquinonediazide-5- (and / or-4-) sulfoni
Is esterified with ruchloride in the presence of a basic catalyst.
It is obtained by doing. Examples of polyhydroxy compounds include 2,2
3,4-trihydroxybenzophenone, 2, 4, 4 '
-Trihydroxybenzophenone, 2,4,6-Trich
Droxybenzophenone, 2,3,4-trihydroxy
-2'-methylbenzophenone, 2,3,4,4'-te
Trahydroxybenzophenone, 2, 2 ', 4,4'-te
Trahydroxybenzophenone, 2, 4, 6, 3 ', 4'
-Pentahydroxybenzophenone, 2, 3, 4, 2 ',
4'-pentahydroxybenzophenone, 2,3,4,
2 ', 5'-pentahydroxybenzophenone, 2,4,
6, 3 ′, 4 ′, 5′-hexahydroxybenzophenone,
2,3,4,3 ', 4', 5'-Hexahydroxybenzofu
Polyhydroxybenzophenones such as enone, 2,3,4-trihydroxyacetopheno
2,3,4-trihydroxyphenylpentyl keto
2,3,4-trihydroxyphenylhexyl keto
Polyhydroxyphenyl alkyl ketones such as bis (2,4-dihydroxyphenyl) methyl
Tan, bis (2,3,4-trihydroxyphenyl) meth
Tan, bis (2,4-dihydroxyphenyl) propane
-1, bis (2,3,4-trihydroxyphenyl) p
Bis such as lopan-1, nordihydroguaiaretic acid
((Poly) hydroxyphenyl) alkanes, 3,4,5-trihydroxybenzoic acid
Pill, phenyl 2,2,3,4-trihydroxybenzoate,
Poly, such as phenyl 3,4,5-trihydroxybenzoate
Hydroxybenzoic acid esters, bis (2,3,4-trihydroxybenzo)
Yl) methane, bis (3-acetyl-4,5,6-tri)
Hydroxyphenyl) -methane, bis (2,3,4-to
Rehydroxybenzoyl) benzene, bis (2,4,6)
-Bis (poly) such as trihydroxybenzoyl) benzene
Hydroxybenzoyl) alkane or bis (polyhydro
(Xybenzoyl) aryls, ethylene glycol-di (3,5-dihydride)
Roxybenzoate), ethylene glycol-di (3,
Alkylenes such as 4,5-trihydroxybenzoate)
Di (polyhydroxybenzoates), 2,3,4-biphenyltriol, 3,
4,5-biphenyltriol, 3,5,3 ', 5'-bi
Phenyltetrol, 2,4,2 ', 4'-biphenyl
Troll, 2, 4, 6, 3 ', 5'-biphenylpenteau
2,4,6,2 ', 4', 6'-biphenylhexoxo
2,3,4,2 ', 3', 4'-biphenylhexoxo
Polyhydroxybiphenyls such as 4,4'-thiobis (1,3-dihydroxy
B) Bis (polyhydroxy) sulfide such as benzene
2,2 ', 4,4'-tetrahydroxydiph
Bis (polyhydroxyphenyl) ether such as enyl ether
2,2 ', 4,4'-tetrahydroxydiph
Bis (polyhydroxyphenyl) such as enyl sulfoxide
B) Sulfoxides, 2,2 ', 4,4'-diphenylsulfone
Bis (polyhydroxyphenyl) sulfones such as tris (4-hydroxyphenyl) meta
4,4 ', 4 "-trihydroxy-3,5,3', 5 '
-Tetramethyltriphenylmethane, 4, 4 ', 3'',
4 ''-tetrahydroxy-3,5,3 ', 5'-tetrame
Tiltriphenylmethane, 4, 4 ', 2 ", 3", 4 "-
Pentahydroxy-3,5,3 ', 5'-tetramethylto
Refenylmethane, 2,3,4,2 ', 3', 4'-hexa
Hydroxy-5,5'-diacetyltriphenyl meta
2,3,4,2 ', 3', 4 ', 3'',4''-octahydr
Roxy-5,5'-diacetyltriphenylmethane,
2, 4, 6, 2 ', 4', 6'-hexahydroxy-5,
Polyhydrides such as 5'-dipropionyltriphenylmethane
Roxytriphenylmethanes, 3,3,3 ', 3'-tetramethyl-1,
1'-spirobi-indane-5,6,5 ', 6'-tetro
3,3,3 ', 3'-tetramethyl-1,1'-s
Pyrobi-indane-5,6,7,5 ', 6', 7'-hexo
All, 3, 3, 3 ', 3'-tetramethyl-1, 1'-
Spirobi-indan-4,5,6,4 ', 5', 6'-hex
Sool 3,3,3 ', 3'-tetramethyl-1,1'
-Spirobi-indane-4,5,6,5 ', 6', 7'-f
Polyhydroxyspirobi-indanes such as xool; 3,3-bis (3,4-dihydroxyphenyl);
Nyl) phthalide, 3,3-bis (2,3,4-trihydride)
Roxyphenyl) phthalide, 3 ', 4', 5 ', 6'-tetra
Hydroxyspiro [phthalide-3,9'-xanthene]
Polyhydroxyphthalides such as morvon, quercetin, rutin, etc.
Dyes, α, α ′, α ″ -tris (4-hydroxy
Phenyl) 1,3,5-triisopropylbenzene,
α, α ′, α ″ -tris (3,5-dimethyl-4-hydrid
Roxyphenyl) 1,3,5-triisopropylbenze
Α, α ', α "-tris (3,5-diethyl-4-
Hydroxyphenyl) 1,3,5-triisopropyl
Senzen, α, α ′, α ″ -tris (3,5-di-n-pro
Pyr-4-hydroxyphenyl) 1,3,5-triiso
Propylbenzene, α, α ′, α ″ -tris (3,5-
Diisopropyl-4-hydroxyphenyl) 1,3,5
-Triisopropylbenzene, α, α ', α "-tris
(3,5-di-n-butyl-4-hydroxyphenyl)
1,3,5-triisopropylbenzene, α, α ′,
α "-tris (3-methyl-4-hydroxyphenyl)
1,3,5-triisopropylbenzene, α, α ′,
α "-tris (3-methoxy-4-hydroxyphenyl
Le) 1,3,5-triisopropylbenzene, α,
α ', α "-tris (2,4-dihydroxyphenyl)
1,3,5-triisopropylbenzene, 1,3,5-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Benzene, 1,3,5-tris (5-methyl-2-hydrido
Roxyphenyl) benzene, 2,4,6-tris (3
5-dimethyl-4-hydroxyphenylthiomethyl) me
Styrene, 1- [α-methyl-α- (4′-hydroxy
Phenyl) ethyl] -4- [α, α'-bis (4 "-
Droxyphenyl) ethyl] benzene, 1- [α-methyl
-Α- (4'-hydroxyphenyl) ethyl] -3-
[Α, α'-bis (4 "-hydroxyphenyl) ethyl
L] benzene, 1- [α-methyl-α- (3 ′, 5′-
Dimethyl-4'-hydroxyphenyl) ethyl] -4-
[Α, α'-bis (3 ", 5" -dimethyl-4 "-hydrido
Roxyphenyl) ethyl] benzene, 1- [α-methyl
-Α- (3′-methyl-4′-hydroxyphenyl) e
Tyl] -4- [α ′, α′-bis (3 ″ -methyl-4 ″
-Hydroxyphenyl) ethyl] benzene, 1- [α-
Methyl-α- (3′-methoxy-4′-hydroxyphenyl
Nil) ethyl] -4- [α ′, α′-bis (3 ″ -meth
Xy-4 "-hydroxyphenyl) ethyl] benzene,
1- [α-methyl-α- (2 ′, 4′-dihydroxy
Enyl) ethyl] -4- [α ', α'-bis (4 "-
Droxyphenyl) ethyl] benzene, 1- [α-methyl
-Α- (2 ′, 4′-dihydroxyphenyl) ethyl
] -3- [α "α'-bis (4" -hydroxy
Nyl) ethyl] benzene and the like.
A polyhydroxy compound described in the official gazette, p-bis (2,3,4-trihydroxybe)
Nzoyl) benzene, p-bis (2,4,6-trihydrido)
Roxybenzoyl) benzene, m-bis (2,3,4-
Trihydroxybenzoyl) benzene, m-bis (2,
4,6-trihydroxybenzoyl) benzene, p-bi
(2,5-dihydroxy-3-bromobenzoyl) be
Senzen, p-bis (2,3,4-trihydroxy-5-
Methylbenzoyl) benzene, p-bis (2,3,4-
Trihydroxy-5-methoxybenzoyl) benzene,
p-bis (2,3,4-trihydroxy-5-nitrobe
Nzoyl) benzene, p-bis (2,3,4-trihydride)
Roxy-5-cyanobenzoyl) benzene, 1, 3, 5
-Tris (2,5-dihydroxybenzoyl) benze
1,3,5-tris (2,3,4-trihydroxy
Benzoyl) benzene, 1,2,3-tris (2,3,
4-trihydroxybenzoyl) benzene, 1,2,4
-Tris (2,3,4-trihydroxybenzoyl) be
Senzen 1,2,4,5-tetrakis (2,3,4-to
Rehydroxybenzoyl) benzene, α, α'-bis
(2,3,4-trihydroxybenzoyl) -p-xy
Ren, α, α ', α'-tris (2, 3, 4-trihydr
Roxybenzoyl) mesitylene, 2,6-bis- (2′-hydroxy-
3 ′, 5′-dimethyl-benzyl) -p-cresol,
2,6-bis- (2'-hydroxy-5'-methyl-be
Benzyl) -p-cresol, 2,6-bis- (2′-
Droxy-3 ', 5'-di-t-butyl-benzyl)-
p-cresol, 2,6-bis- (2′-hydroxy-
5'-ethyl-benzyl) -p-cresol, 2,6-
Bis- (2 ', 4'-dihydroxy-benzyl) -p-
Cresol, 2,6-bis- (2'-hydroxy-3 '
-T-butyl-5'-methyl-benzyl) -p-crezo
, 2,6-bis- (2 ', 3', 4'-trihydro
Xy-5'-acetyl-benzyl) -p-cresol,
2,6-bis- (2 ′, 4 ′, 6′-trihydroxy-
Benzyl) -p-cresol, 2,6-bis- (2 ′,
3 ', 4'-trihydroxy-benzyl) -p-crezo
, 2,6-bis- (2 ', 3', 4'-trihydro
(Xy-benzyl) -3,5-dimethyl-phenol,
4,6-bis- (4'-hydroxy-3 ', 5'-dimethyl
Tyl-benzyl) -pyrogallol, 4,6-bis-
(4′-hydroxy-3 ′, 5′-dimethoxy-benzyl)
) -Pyrogallol, 2,6-bis- (4′-hydroxy
C-3 ', 5'-dimethyl-benzyl) -1,3,4-
Trihydroxy-phenol, 4,6-bis- (2 ′,
4 ', 6'-trihydroxy-benzyl) -2,4-di
Methyl-phenol, 4,6-bis- (2 ′, 3 ′,
4'-trihydroxy-benzyl) -2,5-dimethyl
-Phenol and the like. In addition, phenolic resins such as novolak resin
Low nuclei can also be used. Further, the following polyhydroxy compounds are
It can also be used. Embedded image Embedded image The esterification reaction of the photosensitive material is carried out in a predetermined amount.
Polyhydroxy compound and 1,2-naphthoquinonediadi
Do-5- (and / or -4-) sulfonyl chloride
Dioxane, acetone, tetrahydrofuran, methyl
Tylketone, N-methylpyrrolidone, chloroform,
Lichloroethane, trichloroethylene or dichloro
Dissolve in a solvent such as ethane, and add a basic catalyst such as
Thorium, sodium carbonate, sodium bicarbonate, bird
Ethylamine, N-methylmorpholine, N-methylpipe
Condensation by dropping azine, 4-dimethylaminopyridine, etc.
Let it. The product obtained is purified after washing with water and dried. In a usual esterification reaction, the esterification
Mixtures with different numbers of esterifications and esterification positions are obtained.
Select the synthesis conditions or the structure of the polyhydroxy compound.
By doing so, only specific isomers can be selectively
It can be made into tellurium. Esterification rate in the present invention
Is defined as the average value of this mixture. The esterification ratio thus defined is based on the ratio
Polyhydroxy compound and 1,2-naphthoquinone
Diazido-5- (and / or-4-) sulfonyl chloride
Can be controlled by the mixing ratio with the metal. That is, the added 1,
2-naphthoquinonediazide-5 (and / or -4-)
Substantially all sulfonyl chlorides undergo esterification reactions.
So that in order to obtain a mixture with the desired esterification rate
May be adjusted by adjusting the molar ratio of the raw materials. If necessary, 1,2-naphthoquinonedia
Zid-5-sulfonyl chloride and 1,2-naphthoquinone
Also used in combination with diazide-4-sulfonyl chloride
it can. The reaction temperature in the above method is usually -2.
The temperature is 0 to 60 ° C, preferably 0 to 40 ° C. The photosensitive compound synthesized by the method as described above
The product, when used as a resin composition, alone or
Two or more types are mixed and used in an alkali-soluble resin.
However, the compounding amount is 100 parts by weight of Novorak resin.
5 to 150 parts by weight, preferably 20 to 10 parts by weight of the compound
0 parts by weight. If this usage ratio is less than 5 parts by weight, the remaining film
Rate is remarkably reduced.
And the solubility in solvents decreases. The composition of the present invention may be further dissolved in a developer.
For promotion, it may contain a polyhydroxy compound
it can. Preferred polyhydroxy compounds include fu
Knols, resorcin, phloroglucin, 2, 3, 4-
Trihydroxybenzophenone, 2, 3, 4, 4'-te
Trahydroxybenzophenone, 2, 3, 4, 3 ',
4 ', 5'-hexahydroxybenzophenone, aceto
N-pyrogallol condensation resin, phlorogluside, 2, 4,
2 ', 4'-biphenyl tetrol, 4,4'-thiobi
(1,3-dihydroxy) benzene, 2, 2 ', 4,
4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfo
Oxide, 2,2 ', 4,4'-tetrahydroxydiphen
Nilsulfon, tris (4-hydroxyphenyl) meth
Tan, 1,1-bis (4-hydroxyphenyl) cyclo
Hexane, 4,4 '-(α-methylbenzylidene) bis
Phenol, α, α ', α "-tris (4-hydroxy
Enyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl) -1
-Ethyl-4-isopropylbenzene, 1,2,2-to
Lis (hydroxyphenyl) propane, 1,1,2-to
Lis (3,5-dimethyl-4-hydroxyphenyl) p
Lopan, 2,2,5,5-tetrakis (4-hydroxy
Phenyl) hexane, 1,2-tetrakis (4-hydro
Xyphenyl) ethane, 1,1,3-tris (hydroxy
(Ciphenyl) butane, para [α, α, α ', α'-tet
Lakis (4-hydroxyphenyl)]-xylene and the like
I can do it. These polyhydroxy compounds are quinones
100 parts by weight of diazide compound, usually 100 parts by weight
Parts by weight, preferably 5 to 70 parts by weight or less.
Can be Photosensitive material of the present invention and alkali-soluble novola
Ethylene glycol is used as a solvent for dissolving the acrylic resin.
Lumonomethyl ether, ethylene glycol monoethyl
Ether, methyl cellosolve acetate, ethyl celloso
Lube acetate, diethylene glycol monomethyl acrylate
Ter, diethylene glycol monoethyl ether, pro
Pyrene glycol methyl ether acetate, propylene
Glycol propyl ether acetate, toluene,
Xylene, methyl ethyl ketone, cyclohexanone, 2
-Ethyl hydroxypropionate, 2-hydroxy-2
-Ethyl methylpropionate, ethyl ethoxyacetate,
Ethyl droxyacetate, 2-hydroxy-3-methylbutamate
Methyl ester, methyl 3-methoxypropionate,
Ethyl ethoxypropionate, 3-ethoxypropionic acid
Ethyl, methyl 3-ethoxypropionate, pyruvate
Methyl, ethyl pyruvate, ethyl acetate, butyl acetate,
Propylene glycol monomethyl ether propionate
Can be used. These organic solvents are used alone
Or a combination of two or more. Further, N-methylformamide, N, N-
Dimethylformamide, N-methylacetamide, N,
N-dimethylacetamide, N-methylpyrrolidone, di-
High boiling such as methylsulfoxide and benzylethyl ether
Point solvents can be mixed and used. In the positive photoresist composition of the present invention,
Is to further improve the applicability of striations etc.
In addition, a surfactant can be blended. As a surfactant
For example, polyoxyethylene lauryl ether,
Lioxyethylene stearyl ether, polyoxyethylene
Rencetyl ether, polyoxyethylene oleyl A
Polyoxyethylene alkyl ethers such as
Oxyethylene octyl phenol ether, polyoxy
Polyoxyethanes such as ethylene nonyl phenol ether
Tylene alkyl allyl ethers, polyoxyethylene
・ Polyoxypropylene block copolymers, Sorbi
Tan monolaurate, sorbitan monopalmitate,
Rubitan monostearate, sorbitan monooleate
Sorbitan trioleate, sorbitan tristearate
Sorbitan fatty acid esters such as
Tylenesorbitan monolaurate, polyoxyethylene
Sorbitan monopalmitate, polyoxyethylene sol
Bitane monostearate, polyoxyethylene sorbita
Trioleate, polyoxyethylene sorbitan tri
Polyoxyethylene sorbitan fatty acids such as stearate
Nonionic surfactants such as esters, Eftop EF
301, EF303, EF352 (Shin-Akita Chemical Co., Ltd.)
Products), MegaFuck F171, F173 (Dainippon Ink
Co., Ltd.), Florado FC430, FC431 (Sumitomo
3M Co., Ltd.), Asahi Guard AG710, Sir
Freon S-382, SC101, SC102, SC10
3, SC104, SC105, SC106 (Asahi Glass (
Co., Ltd.) and organosiloxanes
Polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Luic or methacrylic (co) polymerized polyflow N
o. 75, No. 95 (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
Manufactured). Distribution of these surfactants
The total amount depends on the amount of the alkali-soluble resin and key in the composition of the present invention.
2 weight per 100 weight parts of nondiazide compound
Parts by weight, preferably 1 part by weight or less. These surfactants may be added alone.
It can also be added in several combinations
Wear. The positive photoresist composition of the present invention
As a developer, sodium hydroxide, potassium hydroxide,
Sodium carbonate, sodium silicate, sodium metasilicate
Inorganic alkalis such as ammonium and aqueous ammonia, ethylamido
Primary amines such as n-propylamine, diethylamine, etc.
Secondary amines such as min, di-n-butylamine,
Tertiary amines such as tylamine and methyldiethylamine;
Dimethylethanolamine, triethanolamine, etc.
Alcohol amines, tetramethylammonium hydro
Oxide, tetraethylammonium hydroxide, coli
Quaternary ammonium salts such as pyrrole, pyrrole, piperidine, etc.
Use of aqueous solutions of alkalis such as cyclic amines
Can be. In addition, isopro
Alcohols such as pill alcohol, nonionic surfactant
Can be used by adding an appropriate amount of a surfactant such as a surfactant.
You. In the positive photoresist composition of the present invention,
Mixes light absorbers, cross-linking agents, adhesion aids, etc. as necessary
Can be The absorber absorbs halation from the substrate
The purpose of prevention and to enhance the visibility when applied to a transparent substrate
It is added as needed for the purpose. For example, "Industrial colors
Technology and market ”(CMC Publishing) and dye handbook (organic synthesis
Commercially available light absorbing agents described in Seikagaku Kyokai, for example, CIDe
sperse Yellow 1,3,4,5,7,8,13,23,31,49,50,51,54,56,
60,64,66,68,79,82,88,90,93,102,114 and 124, CIDis
perse Orange 1,5,13,25,29,30,31,44,57,72 and 73,
CIDisperse Red 1,5,7,13,17,19,43,50,54,58,65,72,
73,88,117,137,143,199 and 210, CIDisperse Viole
t 43, CI Disperse Blue 96, CI Fluorescent Bright
ening Agent 112, 135 and 163, CISolvent Yellow 1
4,16,33 and 56, CISolvent Orange 2 and 45, CI
Solvent Red 1,3,8,23,24,25,27 and 49, CIigment
Green 10, CIPigment Brown 2, etc.
Can be. The light absorbing agent is usually 100 alkali-soluble resins.
100 parts by weight or less, preferably 50 parts by weight based on parts by weight
Or less, more preferably 30 parts by weight or less.
You. The crosslinking agent affects the formation of a positive image.
It is added in a range that does not exist. The purpose of adding the crosslinking agent is mainly
Sensitivity adjustment, improved heat resistance, improved dry etching resistance, etc.
It is. Examples of crosslinkers include melamine, benzoguana
Formaldehyde acts on min, glycoluril, etc.
Compound, or its alkyl-modified product or epoxy compound
Substances, aldehydes, azide compounds, organic peroxides, hex
Samethylene tetramine and the like can be mentioned. these
Is 10 parts by weight with respect to 100 parts by weight of the photosensitive agent.
, Preferably less than 5 parts by weight. Frame
If the amount of the crosslinking agent exceeds 10 parts by weight, the sensitivity is lowered, and
Cam (resist residue) is generated, which is not preferable.
No. The adhesion assistant is mainly used for adhesion between the substrate and the resist.
Resist, especially in the etching process.
It is added for the purpose of preventing peeling. Concrete example
Are trimethylchlorosilane, dimethylvinyl
Lorosilane, methyldiphenylchlorosilane, chloroform
Chlorosilanes such as dimethyldimethylchlorosilane,
Tylmethoxysilane, dimethyldiethoxysilane, methyl
Rudimethoxysilane, dimethylvinylethoxysilane,
Diphenyl dimethoxysilane, phenyl triethoxy
Alkoxysilanes such as orchids, hexamethyldisilaza
, N, N'-bis (trimethylsilyl) urea,
Tyltrimethylsilylamine, trimethylsilylimida
Silazanes such as sol, vinyltrichlorosilane, γ-
Chloropropyltrimethoxysilane, γ-aminopropyl
Rutriethoxysilane, γ-glycidoxypropyl tri
Silanes such as methoxysilane, benzotriazole,
Nzoimidazole, indazole, imidazole, 2-
Mercaptobenzimidazole, 2-mercaptobenz
Thiazole, 2-mercaptobenzoxazole, back
Sol, thiouracil, mercaptoimidazole, mel
Heterocyclic compounds such as captopyrimidine and 1,1-dimethyl
Urea such as chill urea and 1,3-dimethyl urea, or
Ourea compounds can be mentioned. These adhesion aids are alkali-soluble resins.
Usually less than 10 parts by weight, preferably 100 parts by weight, preferably
It is blended in a proportion of less than 5 parts by weight. The above-mentioned composition for a positive photoresist is precisely prepared.
Substrates such as those used in the manufacture of integrated circuit devices (eg, silicon
Con / silicon dioxide coating, glass substrate, ITO substrate, etc.
Suitable application of spinner, coater, etc. on transparent substrate
After pre-baking after application by a method, pass through a predetermined mask
Exposure and post-heating if necessary (PEB: Post ExposureBak
e), developing, rinsing and drying
A resist can be obtained. The present invention is also used for PS plate
Can be Hereinafter, examples of the present invention will be described.
It is not limited to these. In addition,% is the other finger
Unless otherwise specified, it indicates% by weight. EXAMPLES Synthesis of Novolak Resin (1) Synthesis of Novolak Resin (a-1) 113.55 g of m-cresol, 4.8 of p-cresol
7 g, 2,3-xylenol 49.48 g and 4-a
Stirrer 24.48 g of Cetamide Benzaldehyde
500 mL three-neck with flow cooling tube and thermometer
Oxalic acid dihydrate is charged in a flask and stirred at 90 ° C.
5.67 g were added. After 30 minutes, raise the bath temperature to 130 ° C
And stir for an additional 9.5 hours to reflux the contents.
Was. Next, formalin aqueous solution (37.15%)
15 g was dropped over 30 minutes. Add 4 more reaction mixture
Time refluxed. Then, 3-ethoxypropyl
After adding 20 g of ethyl onoate, the reflux condenser was leached.
Replace with a condenser and raise the bath temperature to about 2 hours.
Increase the temperature to 00 ° C to remove unreacted formalin, water, etc.
Was. After 1 hour of normal pressure distillation, 1 mmHg
The pressure was reduced to remove unreacted monomers and the like. Vacuum distillation
Took two hours. Molten alkali-soluble novola
The resin was returned to room temperature and collected. Novolak tree obtained
The weight average molecular weight of the fat is 3260 (polystyrene equivalent)
there were. 100 g of this novolak resin is added to 1000 g of
Dissolve in seton and add 1000 g of n-hexane with stirring
After further stirring at room temperature for 30 minutes, the mixture was allowed to stand for 1 hour. Upper layer
After decanting the remaining lower layer,
-Solvent is distilled off using an evaporator and solid novolak
(A-1) was obtained. Obtained novolak resin (a-1)
Has a weight average molecular weight of 5720 (in terms of polystyrene),
The dispersion was 2.3. (2) Novolak resins (a-2) to (a-
Synthesis of 10) Monomers described in Table 1 and aldehyde compounds in the specification
(A), (b), (d) or (n) is charged in a predetermined amount,
Otherwise, polymerization and fractionation were carried out in the same manner as in Example (1).
(A-3) to (a-10) were obtained. (Table 1
Medium monomer charge indicates molar ratio, total monomer charge
Was 1.5 mol in total. The amount of aldehyde charged is
Shown in mol% based on the monomer charge (1.5 mol)
Was. [Table 1] [Table 2] (3) Synthesis of novolak resin (a-11) 2,2'-dihydroxy-5,5'-dimethyldiphenyl
14.27 g of methane, 5.41 g of o-cresol,
198.53 g of 2,3-xylenol, 2,3,5-to
Limethylphenol 68.10 g, 2,6-xylenol
24.43 g and 4-acetamidobenzaldehyde
Weigh 40.80 g with a stirrer, reflux condenser and thermometer.
Charge into a 1 L three-necked flask and add 3-ethoxy
50 g of ethyl cypropionate were added. Mix 90
9.46 g of oxalic acid dihydrate was added under stirring at ℃.
After one hour, raise the bath temperature to 130 ° C and stir for another 30 hours.
The contents were refluxed. Then oxalic acid dihydrate
After the addition of 9.46 g of product again, the reaction mixture was
Time refluxed. Then, formalin aqueous solution
(37.30%) 221.40 g are added and at 130 ° C.
Let reflux for 12 hours and add 3-ethoxypropionic acid
25 g of ethyl were added. Let it reflux for another 6 hours
25 g of ethyl 3-ethoxypropionate was added again.
Was. Next, take the reflux condenser into the Liebig condenser.
Change the bath temperature to 200 ℃ over about 1 hour,
Formalin, water and the like were distilled off. It takes 3 hours to evaporate
Was. When heating is stopped and the internal temperature drops to 180 ° C
620 g of ethyl lactate is slowly dropped with novolak lactic acid
An ethyl solution was obtained. The obtained novolak resin (a-1)
The weight average molecular weight of 1) is 3270 (polystyrene conversion).
Calculation) and the degree of dispersion was 2.2. (4) Novolak resins (b-1) to (b-
2) Preparing the monomers and aldehydes described in Synthesis Table 2 in predetermined amounts,
Otherwise, polymerization and fractionation were carried out in the same manner as in Example (1).
(B-1) to (b-2) were obtained. [Table 3] (Table 2 shows the molar ratio of the charged monomers.
The total amount of charged monomers was 1.5 mol. Also, Al
The amount of the aldehyde added depends on the amount of the monomer (1.5 mol)
It is shown in mol% with respect to. Synthesis of Photosensitive Material (5) Synthesis of Photosensitive Material (S-1) Compound (1) shown in Table 3 (62.9 g, 1,2-naphthoxy)
53.7 g of nondiazide-5-sulfonyl chloride,
Charge 800 mL of Seton into a three-necked flask and dissolve uniformly.
I understand. Then, gradually add 21.2 g of triethylamine.
The mixture was dropped and reacted at 25 ° C. for 3 hours. 1% reaction mixture
Pour into 3 L of hydrochloric acid aqueous solution, filter the resulting precipitate, wash with water,
Drying was performed to obtain a photosensitive material (S-1). (6) Synthesis of Photosensitive Material (S-2) Compound (2) shown in Table 3 53.8 g, 1,2-naphthoki
53.7 g of nondiazide-5-sulfonyl chloride,
Charge 800 mL of Seton into a three-necked flask and dissolve uniformly.
I understand. Then, gradually add 21.2 g of triethylamine.
The mixture was dropped and reacted at 25 ° C. for 3 hours. 1% reaction mixture
Pour into 3 L of hydrochloric acid aqueous solution, filter the resulting precipitate, wash with water,
Drying was performed to obtain a photosensitive material (S-2). (7) Synthesis of Photosensitive Material (S-3) Compound (3) shown in Table 3 56.5 g, 1,2-Naphthoki
53.7 g of nondiazide-5-sulfonyl chloride,
Charge 800 mL of Seton into a three-necked flask and dissolve uniformly.
I understand. Then, gradually add 21.2 g of triethylamine.
The mixture was dropped and reacted at 25 ° C. for 3 hours. 1% reaction mixture
Pour into 3 L of hydrochloric acid aqueous solution, filter the resulting precipitate, wash with water,
Drying was performed to obtain a photosensitive material (S-3). [Table 4] (8) Preparation of positive photoresist composition
The novolak resin (a-) obtained in the above (1) to (4)
1) to (a-11) and (b-1) to (b-2), above
The photosensitive materials (S-1) to (S-) obtained in the above (5) to (7)
3), solvents (Y-1) to (Y-4) and shown in Table 4.
Table 5 shows the polyhydroxy compounds (P-1) to (P-3).
After mixing at the indicated ratio to obtain a uniform solution, the pore size was 0.10μ.
Filter using a micro filter of m
A composition was prepared. This photoresist composition is
On a silicon wafer using a vacuum cleaner
After drying on a hot plate at 90 ° C. for 60 seconds, the film thickness was 1.
A 02 μm resist film was obtained. [Table 5] [Table 6] The film was subjected to a reduction projection exposure apparatus (a reduction lens manufactured by Nikon Corporation).
Exposure using a small projection exposure apparatus NSR-2005i9C).
After that, PEB was performed at 110 ° C. for 60 seconds, and 2.38%
1 minute with tetramethylammonium hydroxide aqueous solution
It was developed, washed with water for 30 seconds and dried. Gain in this way
Scans the resist pattern of the silicon wafer
The resist was evaluated by observation with a microscope. Table 6 shows the results
Show. The sensitivity is 0.4mm, which reproduces the mask pattern.
Defined as the reciprocal of the amount of light, relative to the sensitivity of Comparative Example 1.
Indicated by The resolution is 0.40 μm.
It shows the critical resolution at the exposed exposure. Defocus
Latitude is 0.40μm resist in effective sensitivity
The width of the focal point where the pattern is separated without film loss
The cross section was observed with a microscope and evaluated. 0.50μm heat resistance
At the temperature at which the edge of the line pattern starts to become round.
did. [Table 7] As described above, according to the present invention, the positive
Photoresist compositions have high resolution, wide
-Resistants who have and can obtain
Because the image is excellent in heat resistance, the semiconductor device manufacturing process
And the like can be suitably used for microfabrication.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-10348 (JP, A) JP-A-2-84414 (JP, A) JP-A-5-204146 (JP, A) JP-A 64-64 48849 (JP, A) JP-A-5-150450 (JP, A) JP-A-57-31674 (JP, A) JP-A-7-36068 (JP, A) JP-A-6-124479 (JP, A) JP-A-6-228038 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claim 1] An alkali obtained by condensing a phenol compound represented by the following general formula (1) with formaldehyde and an aromatic aldehyde compound represented by the following general formula (2): A positive photoresist composition comprising a soluble resin and a 1,2-quinonediazide compound. Embedded image Here, R _{1 to} R ₃ may be the same or different and are a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group or an arylcarbonyl group. And R _{4 to} R ₈ may be the same or different, and represent a hydrogen atom, a hydroxyl group, a formyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group,
Aralkyl group, -NHCO-R _9, -NHCOO-
_{R 9, -NHCONH-R 9,} -CONH-R 9, -C
ONHCO-R _9, R _9: alkyl group, a cycloalkyl group, an alkenyl group,
An aryl group or an aralkyl group. However, at least one of R _{4 to} R ₈ is:
_{-NHCO-R 9, -NHCOO-R} 9, -NHCON
HR ₉ , —CONH—R ₉ , or any of the substituents selected from —CONHCO—R ₉ .