JP3443466B2 - Photosensitive resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to an alkali-soluble resin,
The present invention relates to a photosensitive resin composition containing a quinonediazide photosensitive compound and a solvent as main components. For more details,
The present invention relates to a photoresist for forming a highly integrated circuit, which has high resolution, high sensitivity, good heat resistance, and good pattern shape.
The present invention also relates to a pattern forming method using a photosensitive resin composition.

[0002]

2. Description of the Related Art Positive photoresists comprising an alkali-soluble novolak resin and a quinonediazide type photosensitive compound which functions as an alkali dissolution inhibitor are known.
In such a photoresist, in the exposed area, the quinonediazide-based photosensitive compound decomposes to form ketene via carbene, which reacts with moisture inside and outside the system to form indenecarboxylic acid, which easily dissolves in an alkaline aqueous solution. Come to do. On the other hand, in the unexposed area, the solubility of the alkali-soluble novolak resin in the alkali developing solution is inhibited by the quinonediazide photosensitive compound (hereinafter, this effect is referred to as a masking effect), so that it is difficult to dissolve in the alkali developing solution and a high residual film is formed. The rate can be maintained and a fine pattern can be formed with almost no swelling,
It is often used in the manufacture of integrated circuits.

As such a positive type resist, for example, in Japanese Patent Publication No. 62-28457, 2, 3, 4, 4'-
A positive photoresist composition containing a photosensitive component containing naphthoquinonediazide-5 or 4-sulfonic acid tetraester of tetrahydroxybenzophenone is described. In JP-A-62-150245, 1,2-naphthoquinonediazide-5 of 2,3,4,2 ', 6'-pentahydroxybenzophenone is added to an alkali-soluble resin.
A positive-working radiation-sensitive resin composition containing a 1,2-quinonediazide compound such as a sulfonic acid triester is described. JP-A-5-34917 discloses a positive resist composition containing a novolac resin, a quinone diazide sulfonic acid ester of a tetravalent or higher valent phenol compound and a quinone diazide sulfonic acid ester of a trivalent or lower valent phenol compound. JP-A-5-1194
75, 2,3,4,4'-tetrahydroxybenzophenone 1,2-naphthoquinonediazide-5.
Partial esterification product with sulfonic acid and 1,2-naphthoquinonediazide-5 of dihydroxybenzophenone
Radiation-sensitive compositions containing fully esterified products with sulfonic acids and / or partially or fully esterified products of 1,2-naphthoquinonediazide-5-sulfonic acid of trihydroxybenzophenone are described.

By the way, integrated circuits have become highly integrated year by year, and accordingly, the resolution required for resists has become finer. A method for improving the resolution is generally carried out by increasing the amount of photosensitive groups in the resist, but on the other hand, a decrease in sensitivity cannot be avoided. In particular, when a naphthoquinonediazide sulfonic acid ester of hydroxybenzophenone, which has been widely used as a photosensitive compound, is used, the heat resistance is good, but the i-line (wavelength = 365 nm) which has been used in recent years in semiconductor lithography. In the region (2), the absorption of light by the photosensitizer is large, and the decrease in sensitivity becomes more remarkable. Further, since the energy difference of transmitted light between the upper and lower sides of the resist film applied on the wafer is large, the pattern shape becomes a trapezoid, and there is a limit in improving the resolution.

On the other hand, there has been proposed a photoresist containing a photosensitive compound in which a quinonediazide compound, which is a photosensitive component, is bound to a low molecular weight novolak resin different from an alkali-soluble resin, instead of being bound to hydroxybenzophenone. For example, International Publication Number WO90 / 01
726 is a positive photoresist containing a non-photosensitive novolac resin and a photosensitive novolac resin, for example, a 1,2-naphthoquinonediazide-5-sulfonic acid esterified product of a condensate of p-cresol and formaldehyde (average molecular weight 600). Compositions are disclosed. JP-A-4-23
In 0755, an alkali-soluble resin and, for example,
1,2-condensate of m-cresol and acetaldehyde
-A photoresist composition containing a naphthoquinone diazide sulfonic acid esterified product is disclosed. JP-A-5
No. 34916 discloses a photoresist composition containing an alkali-soluble resin and a 1,2-naphthoquinonediazide-5-sulfonic acid esterified product of a condensate of pyrogallol and acetone, for example.

However, there is an increasing demand for improvement in resolution, and in order to meet this demand, if the molecular structure of the novolak resin used in the photosensitive compound is controlled, the above-mentioned masking effect is improved and high resolution is achieved. On the other hand, there is a problem that sensitivity and heat resistance are insufficient. In particular, regarding heat resistance, there is a demand for practically 120 ° C. or higher, and further 125 ° C. or higher. On the other hand, in JP-A-2-108054, an alkali-soluble novolac resin having a standard polystyrene equivalent weight average molecular weight of 4,000 to 20,000 is disclosed.
And a resin B having a standard polystyrene-reduced weight average molecular weight of 200 to 2,000, and a 1,2-quinonediazide sulfonic acid ester of the resin B and, for example, 2,3,4,4'- A positive resist containing a quinonediazide sulfonic acid ester of tetrahydroxybenzophenone is described. However, even when a quinone diazide sulfonic acid ester of a novolac resin and a quinone diazide sulfonic acid ester of hydroxybenzophenone are used together as a photosensitizer, the sensitivity, resolution and heat resistance are insufficient depending on the type of photosensitizer.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive type photosensitive resin having high resolution, good pattern shape, practical sensitivity and high heat resistance, and well balanced performance. To provide a composition. Another object of the present invention is to provide a method for forming a pattern using such a photosensitive composition.

[0008]

In order to solve the above-mentioned problems, the inventors of the present invention have conducted extensive studies, and as a result, as a photosensitive compound, a quinonediazide compound having a low molecular weight different from that of an alkali-soluble resin was used. And a photosensitive compound combined with a novolak resin having a specific structure and a photosensitive compound in which a quinonediazide compound is bonded to hydroxybenzophenone are used in combination, a photoresist containing this photosensitive compound is compared to conventional products. As a result, they have a high resolution and have a good pattern shape, practical sensitivity and high heat resistance, and have reached the present invention.

That is, the gist of the present invention is a photosensitive resin composition containing an alkali-soluble resin, a quinonediazide type photosensitive compound and a solvent, wherein the photosensitive compound has a weight average molecular weight of 600 to 2,200 and the following general formula: A novolac resin (A) represented by (i) or a quinonediazide sulfonic acid esterified product of a novolak resin (B) represented by the following general formula (ii) having a weight average molecular weight of 600 to 2,200 and the following general formula (iii): A photosensitive resin composition comprising a quinonediazide sulfonic acid esterified product of hydroxybenzophenones (C) represented.

[0010]

[Chemical 4]

(In the formula, R ¹ and R ⁴ each represent an alkyl group, R ² represents an alkyl group or an aryl group,
R ³ represents a hydrogen atom or an alkyl group, and u and v each represent an integer of 0 to 3. However, when a plurality of R ^{1 to} R ⁴ are present, they may be the same or different. k and l represent a number of 0 or more, and k: 1 = 1: 9
(10 to 10 is satisfied)

[0012]

[Chemical 5]

(Wherein R ⁵ represents a hydroxyl group or an alkyl group, R ⁶ and R ⁹ each represent a hydrogen atom, an alkyl group or an aryl group, and R ⁷ and R ¹⁰ represent a hydrogen atom or an alkyl group, R ⁸ represents an alkyl group, x represents an integer of 0 to 2, and y represents an integer of 0 to 3. However, R
^{When a} plurality of ^{5 to} R ¹⁰ are present, they may be the same or different. m and n represent a number of 0 or more, and satisfy m: n = 10: 0 to 6: 4)

[0014]

[Chemical 6]

(In the formula, p and q each represent an integer of 0 or more and satisfy 3 ≦ p + q ≦ 6) The present invention will be described in detail below. In the photoresist composition of the present invention, as the alkali-soluble resin, for example, novolac resin, resole resin, polyvinylphenol resin, polyacrylic acid resin or the like can be used. The molecular weight of this alkali-soluble resin is larger than the molecular weight of the novolak resin constituting the photosensitive compound described below, and the two are clearly distinguished. That is, the weight average molecular weight of the alkali-soluble resin (analytical value in terms of polystyrene by gel permeation chromatography) is
It is usually about 3,000 to 20,000.

As the alkali-soluble resin, novolac resin is particularly preferable and is not particularly limited, but examples thereof include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol,
Phenols such as 2,3,5-trimethylphenol or resorcinol, 2-methylresorcinol, 5
-2 or 3 or more phenols or polyhydroxybenzenes selected from polyhydroxybenzenes such as methylresorcinol and pyrogallol, and aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, etc. 1 selected from carbonyl compounds such as aromatic aldehydes, alkyl ketones such as acetone
A novolac resin obtained by polycondensation by heating in the presence of one or more kinds and an acid catalyst such as hydrochloric acid, sulfuric acid, oxalic acid, etc. is preferable.

More preferably, m-cresol and p
A novolac resin obtained by polycondensing two components of cresol, or a three or four component containing 2,5-xylenol and / or 3,5-xylenol therein with formaldehyde and / or acetaldehyde, or m
A mixture of cresol, p-cresol, 2,5-xylenol and resorcinol with formaldehyde and / or
Alternatively, it is a novolac resin obtained by polycondensation with acetaldehyde. m-cresol, p-cresol, 2,5
-Or 3,5-xylenol, and the mixing ratio (molar ratio) of resorcinol is usually 1 to 7: 3 to 7: 0.
It is 5: 0 to 1.

When formaldehyde and acetaldehyde are used together as the carbonyl compound, the mixing ratio is formaldehyde: acetaldehyde = 95-40:
5 to 60 (molar ratio) is preferable, and particularly 90 to 50:10.
-50 (molar ratio) is preferable. Among them, m-cresol: p-cresol: 2,5-xylenol = 3 to 6:
Mixture of 3 to 5: 0 to 3 (molar ratio) and formaldehyde alone or formaldehyde: acetaldehyde = 90
A novolac resin which is a condensate with a mixture of ˜50: 10 to 50 (molar ratio) is preferred.

In the present invention, as the quinonediazide photosensitive compound, a quinonediazide of a novolak resin having a specific structure and having a weight average molecular weight of 600 to 2,200 (hereinafter sometimes referred to as "low molecular weight novolak resin"). It is essential to use both a sulfonated product and a quinonediazide sulfonated product of hydroxybenzophenone. The molecular weight novolak resin constituting the photosensitive compound is represented by the general formula (i) or (ii) shown above, and these are polycondensates of the phenolic compound and the carbonyl compounds constituting the novolac resin.

The novolac resin (A) is represented by the general formula (i) shown above.
The alkyl group represented by R ₁ , R ₂ , R ³ and R ⁴ is a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group and the like. It may have 1 to 4 carbon atoms. Examples of the aryl group represented by R ² include a phenyl group and the like,
u and v represent the integer of 0-3.

In the general formula (i) shown above, R ^{1 to} R ⁴
When there are a plurality of groups represented by, they may be the same or different, but a plurality of R ^{1 to} R ⁴
Are preferably the same. Among them, in the general formula (i) shown above, it is preferable that R ¹ and R ⁴ are the same and are an alkyl group having 1 to 2 carbon atoms, and a methyl group is particularly preferable. R ² is particularly preferably a methyl group, R ³ is particularly preferably a hydrogen atom or a methyl group, and u and v are preferably 1.

The novolak resin (A) is usually obtained by polycondensing an alkyl-substituted monohydric phenol with a carbonyl compound. Examples of such an alkyl-substituted monohydric phenol include m-cresol and p-. Examples thereof include cresol, 3-ethylphenol, 4-ethylphenol and the like. Cresols are preferable, and m-cresol is particularly preferable. Examples of the carbonyl compound include aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde and propionaldehyde, aromatic aldehydes such as benzaldehyde, aliphatic ketones such as acetone, methyl ethyl ketone and diethyl ketone, acetylbenzene and benzophenone. And aromatic ketones. Of these,
Aliphatic aldehydes and aliphatic ketones are preferable, and formaldehyde, acetaldehyde, and acetone are particularly preferable.

However, as is clear from its structure, the novolac resin (A) contains aldehydes or ketones other than formaldehyde as essential components as carbonyl compounds. In the general formula (i), k
And l represent a number of 0 or more, and the constitutional ratio k of the repeating unit:
1 is in the range of 1: 9 to 10: 0. The composition ratio is not particularly limited as long as it is within the above range, but the heat resistance of the resist tends to be particularly good as the ratio of k to 1 is large. On the other hand, as the ratio of 1 to k increases, the pattern shape tends to be particularly good. Therefore, the type and blending ratio of the starting phenolic compound and the carbonyl compound may be selected according to the desired resist performance, and the constitutional ratio k: 1 of the repeating unit in the novolac resin (A) may be adjusted appropriately.

From the viewpoint of resolution and heat resistance, it is preferable that l = 0. When the quinonediazide sulfonic acid ester of the novolac resin (A) is used together with the quinonediazide sulfonic acid ester of the hydroxybenzophenones (C), the pattern shape tends to be good. On the other hand, the novolac resin (B) is represented by the general formula (ii) shown above, wherein the alkyl groups represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each methyl. Examples thereof include those having 1 to 4 carbon atoms which may be linear or branched, such as a group, ethyl group, n-propyl group and i-propyl group. Examples of the aryl group represented by R ⁶ and R ⁹ include a phenyl group.

When there are a plurality of groups represented by R ^{5 to} R ¹⁰ , they may be the same or different, but a plurality of R ^{5 to} R ¹⁰ are preferably the same. R ⁶ and R ⁹ , and R ⁷ and R ¹⁰ may be the same or different, but are preferably the same.
In the general formula (ii) shown above, R ⁶ and R ⁹ are preferably alkyl groups or aryl groups, and R ⁷ and R ¹⁰ are preferably hydrogen atoms or alkyl groups. Of these, R ⁵ is preferably a hydroxyl group or a methyl group, R ⁸ is preferably a methyl group, and
⁶ and R ⁹ are preferably a methyl group or a phenyl group, and R ⁷
And R ¹⁰ is preferably a hydrogen atom or a methyl group, and particularly R
⁵ is a hydroxyl group, R ⁸ is a methyl group, R ⁶ and R
It is preferable that ⁹ is a methyl group, and R ⁷ and R ¹⁰ are hydrogen atoms or a methyl group.

Although x represents an integer of 0 to 2 and y represents an integer of 0 to 3, it is preferable that x is 0 or 1 and y is 1. The novolac resin (B) is usually obtained by polycondensing polyhydroxybenzenes optionally substituted with an alkyl group or an alkyl-substituted monohydric phenol with a carbonyl compound. Examples of the class include resorcinol, 2-
Methylresorcinol, 4-methylresorcinol, 5
-Resorcinols such as methylresorcinol and 2-ethylresorcinol, catechols such as catechol, 3-methylcatechol and 4-methylcatechol, and pyrogallol. Of these, resorcinol, 2-methylresorcinol and pyrogallol are preferable, and pyrogallol is particularly preferable. Examples of the above-mentioned monohydric phenols include m-cresol, p-cresol, 3-ethylphenol, 4-ethylphenol and the like, but cresols are preferable, and among them, m-cresol is preferable.

Examples of carbonyl compounds include aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, aromatic aldehydes such as benzaldehyde, aliphatic ketones such as acetone, methyl ethyl ketone and diethyl ketone, and acetylbenzene. And aromatic ketones such as benzophenone. Of these, acetaldehyde, benzaldehyde and acetone are preferable, and acetaldehyde and acetone are particularly preferable.

However, as is clear from its structure, the novolak resin (B) contains polyhydroxybenzenes as an essential component. Further, m and n represent a number of 0 or more, and in the general formula (ii), the constitutional ratio m: n of the repeating units is in the range of 10: 0 to 6: 4. The structural ratio is
It is not particularly limited as long as it is within the above range, but m with respect to n
The larger the ratio, the better the heat resistance tends to be. Therefore, the kind and blending ratio of the raw material polyhydroxybenzenes, alkyl-substituted monohydric phenols and carbonyl compounds are selected according to the desired resist performance, and the constituent ratio m: n of the repeating units in the novolak resin (B) is adjusted appropriately. do it.

From the viewpoints of sensitivity and heat resistance, it is preferable that R ⁵ represents a hydroxyl group, R ⁶ and R ⁷ represent a methyl group, and n = 0. As a method for producing the novolak resin (A) or (B) having a lower molecular weight than the phenols and the carbonyl compounds as described above, the phenols and the carbonyl compounds are present in the presence of an acidic catalyst according to a known method. Below, a method of polycondensation is adopted. The temperature of the polycondensation reaction is usually about 50 to 200 ° C.

The weight average molecular weight of the novolak resins (A) and (B) (analytical value in terms of polystyrene by gel permeation chromatography) is 600 to
Must be 2,200. When the weight average molecular weights of the novolak resins (A) and (B) are too small, the masking effect is small and a good pattern shape cannot be obtained.
Also, the heat resistance tends to be poor. On the contrary, if it is too large, the masking effect tends to be too large and the sensitivity tends to be poor.

The molecular weight of the novolak resin can be adjusted by controlling the amount of the catalyst used when the ketones are used as the reaction raw material and controlling the amount of the catalyst used when the aldehydes are used. Examples of the quinonediazide sulfonic acid ester of the novolac resin (A) or (B) include 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, and 1,2-naphthoquinonediazide. -5-sulfonic acid, 2,1-naphthoquinonediazide-4-sulfonic acid, 2,1-naphthoquinonediazide-5
-Sulfonic acid, 2,1-naphthoquinonediazide-6-sulfonic acid, 2,1-naphthoquinonediazide-7-sulfonic acid, 2,1-naphthoquinonediazide-8-sulfonic acid and the like esterified products may be mentioned. They may be used together or in combination. Of these, esterified products of 1,2-naphthoquinonediazide-5-sulfonic acid and 1,2-naphthoquinonediazide-4-sulfonic acid are preferable, and 1,2-naphthoquinonediazide-5-sulfonic acid esterified product is particularly preferable. .

The quinonediazide sulfonic acid ester of the novolak resin (A) or (B) can be prepared, for example, according to a conventionally known method such as 1,2-naphthoquinonediazide-5.
Reacting a sulfonyl chloride corresponding to the above quinonediazide sulfonic acid, such as sulfonic acid chloride, with a novolak resin (A) or (B) in an organic solvent in which they are dissolved in the presence of a basic catalyst such as triethylamine at room temperature. It can be manufactured.

The esterification rate of the quinonediazide sulfonic acid ester of the novolak resin (A) or (B), that is, the substitution rate of the quinonediazidesulfonyl group for hydrogen of the hydroxyl group contained in the novolak resin (A) or (B) [ (Quinonediazide sulfonic acid ester compound 1
Number of quinonediazidesulfonyl groups per molecule) x 100 /
(Number of hydroxyl groups per molecule of novolac resin)] is 20 to 8
0% is preferable. If the esterification rate is too high, the masking effect will be too large and the sensitivity will tend to decrease.
On the other hand, if the esterification rate is too low, the masking effect tends to be small, and the pattern shape tends to be poor.

On the other hand, another photosensitive compound of the present invention is a quinonediazide sulfonic acid esterified product of the hydroxybenzophenones (C) represented by the general formula (iii). Examples of the hydroxybenzophenone represented by the general formula (iii) include, for example, 2,3,4,2 ', 3', 4 '.
-Hexahydroxybenzophenone, 2,3,4
Hexahydroxybenzophenones such as 3 ′, 4 ′, 5′-hexahydroxybenzophenone, 2, 3, 4,
2 ', 4'-pentahydroxybenzophenone, 2,
Pentahydroxybenzophenones such as 3,4,2 ′, 3′-pentahydroxybenzophenone and 2,3,4,3 ′, 5′-pentahydroxybenzophenone,
2,3,4,3'-tetrahydroxybenzophenone,
2,3,4,4'-tetrahydroxybenzophenone,
2,4,2 ', 4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxybenzophenone, 2,3,2', 4'-tetrahydroxybenzophenone, 2,5,2 ', 5' -Tetrahydroxybenzophenones such as tetrahydroxybenzophenone, 2,5,3 ', 4'-tetrahydroxybenzophenone, 2,5,3', 5'-tetrahydroxybenzophenone,
Examples thereof include trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone. Among these, compounds of 4 ≦ p + q ≦ 6 in formula (iii) are preferable, and compounds of 5 ≦ p + q ≦ 6 are more preferable. Of these, pentahydroxybenzophenones are preferable, and 2,3,4,2 ', 4'-pentahydroxybenzophenone is particularly preferable.

As the quinone diazide sulfonic acid esterified product of the hydroxybenzophenones (C), the quinone diazide sulfonic acid esterified product as exemplified for the above-mentioned novolac resin (A) or (B) quinone diazide sulfonic acid esterified product is used. Named
1,2-naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid is preferable, and 1,2-naphthoquinonediazide-5- is particularly preferable.
Sulfonic acid is preferred.

The quinonediazide sulfonic acid esterified product of the hydroxybenzophenones (C) can be prepared according to a conventionally known method, for example, 1,2-naphthoquinonediazide-
By reacting a sulfonyl chloride corresponding to the above quinonediazide sulfonic acid such as 5-sulfonic acid chloride and a hydroxybenzophenone (C) in an organic solvent in which they are dissolved in the presence of a basic catalyst such as triethylamine at room temperature. It can be manufactured.

The esterification rate of the quinonediazide sulfonate of hydroxybenzophenones (C) [(number of quinonediazidesulfonyl groups per molecule of quinonediazide sulfonate) × 100 / (number of hydroxyl groups per molecule of hydroxybenzophenone)] Is 50 ~
90% is preferable. If the esterification rate is too high, the masking effect will be too large and the sensitivity will tend to decrease. On the other hand, if the esterification rate is too low, the masking effect tends to be small, and the pattern shape tends to be poor.

In the present invention, a compound in which a quinonediazide-based photosensitive component is bound to a novolak resin (A) or (B) synthesized from the above-mentioned specific raw material and a quinonediazide-based compound to a specific hydroxybenzophenone (C) are used. A compound having a light-sensitive component bound thereto is also used as a light-sensitive compound. The mixing ratio of the former Q-factor Q ₁ and the latter Q-factor Q _{2 in} the photoresist solution is Q.
_A ratio of ₁ : Q ₂ of 1:15 to 15: 1 is preferable,
Furthermore, 1:10 to 10: 1 is preferable, and 1: 5 to 7: 1.
Is particularly preferable. Here, the Q factor means the number of millimoles of quinonediazide sulfonic acid group with respect to 1 g of total solid content in the photoresist liquid. This mixing ratio affects the characteristics as a photoresist, and when the proportion of Q ₁ increases, the resolution tends to improve, while when the proportion of Q ₂ increases, the sensitivity tends to improve. Therefore, according to the desired photoresist performance, the ratio of the Q factor should be within this range.
It is preferable to mix and use each photosensitive compound.

The solvent used in the present invention may be any solvent capable of dissolving the above-mentioned quinonediazide photosensitive compound and alkali-soluble resin, and has a boiling point of 60 to 220 ° C. from the viewpoint of operability during use. Those having a temperature of 120 to 180 ° C. are preferable. These solvents include ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ether alcohols such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, ethyl acetate, acetic acid. Carboxylic acid esters such as butyl and ethyl butyrate, lactones such as γ-butyrolactone, ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and ethyl butyl ketone, cyclic ketones such as cyclopentanone and cyclohexanone, oxalic acid Dibasic acid carboxylic acid esters such as diethyl and diethyl malonate, ethylene glycol diacetate, propylene glycol diacetate Dicarboxylic acid esters of glycol over preparative like, 2-
Oxycarboxylic acids such as methyl hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate. Acid ester, etc.
Examples thereof include ketone esters such as ethyl pyruvate.
Among them, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-from the viewpoint of safety-free solvent, good storage stability, moderate viscosity, and good coating uniformity. Preferred are methyl hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methylamylketone and ethylbutylketone. Even if these solvents are used alone,
Further, two or more kinds can be mixed and used.

The concentration of the alkali-soluble resin in the photoresist composition of the present invention is usually about 1 to 40% by weight. The concentration of the quinonediazide-based photosensitive compound is usually about 0.2 to 35% by weight, preferably 0.2.
It is about 32% by weight. Further, the Q factor of the photoresist composition is usually 0.4 to 0.9. If necessary, a surfactant such as polyoxyethylene ethers and fluorine-based alkyl esters may be added to the photoresist composition of the present invention to improve coating properties such as striations. The addition amount of these is usually 2% by weight or less, preferably 1% by weight or less based on the weight of the photoresist composition. Further, it is possible to add a dye or the like for reducing the influence of irregularly reflected light from the substrate during image transfer, and a sensitizer or the like for improving the sensitivity. The photoresist composition of the present invention can be easily prepared by adding an alkali-soluble resin, a quinonediazide compound and, if necessary, a surfactant and the like to the solvent as described above and mixing them.

As will be described later, the photoresist composition of the present invention can be applied to exposure with light having a wavelength of 330 to 450 nm. As a photosensitive compound, the novolak resin represented by the general formula (i) ( When the quinonediazide sulfonic acid esterified product of A) is used, especially i-line (wavelength = 36
5 nm) When using a quinonediazide sulfonic acid esterified product of the novolak resin (B) represented by the general formula (ii) as a photosensitive compound, i
It is preferably used for line and g-line (wavelength = 436 nm) exposure.

The photosensitive resin composition of the present invention can be applied to various conventionally known applications as the application of the photosensitive resin composition, and is particularly useful as a photoresist for making an integrated circuit. To form a resist pattern using the photoresist composition of the present invention, it is used after undergoing steps such as coating on a substrate, exposure and development according to a known method. The substrate on which the photoresist composition is applied is a semiconductor substrate such as a silicon wafer. A spin coater is usually used for coating the photoresist composition on such a substrate, and the film thickness of the photoresist composition is usually 0.3 to 5 μm.
It is a degree. Usually, after coating the photoresist composition, the substrate is heated on a hot plate or the like, the solvent is removed, and then the substrate is exposed through a mask to print a desired pattern on the substrate. For exposure, g-line (436 nm), i-line (365n)
m) and the like, light having a wavelength of 330 to 450 nm is preferably used. After the exposure, the substrate is optionally heated at about 90 to 120 ° C. for about 60 to 120 seconds and then developed with an alkaline aqueous solution. Examples of the alkaline aqueous solution include inorganic hydroxides such as potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine and di-n-propylamine. Alkaline aqueous solutions of secondary amines, tertiary amines such as triethylamine and trimethylamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and trimethylhydroxyethylammonium hydroxide are preferably used. If necessary, the developer may contain alcohol,
You may add and use a surfactant etc.

[0043]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples as long as the gist thereof is not exceeded. In the following examples, the molecular weight of each novolak resin obtained in Synthesis Examples 1 to 9 of novolac resin was analyzed by gel permeation chromatography, and the result was expressed as a polystyrene-equivalent weight average molecular weight. The esterification rate of each photosensitizer obtained in Photosensitizer Synthesis Examples 1 to 12 was calculated from the charged amount.

Novolac Resin Synthesis Example 1 135.0 g of m-cresol and p were placed in a separable flask.
-Cresol 180.0 g, 2,5-xylenol 15
2.7 g and 15.0 g of oxalic acid dihydrate were added, the internal temperature was raised to 95 ° C. with stirring, heating and refluxing, 273.1 g of 37% formalin aqueous solution was added dropwise, and while maintaining the temperature, 5
The reaction was carried out over time. Then the internal temperature is increased to 18 for 1.5 hours.
Water was distilled off from the system while the temperature was raised to 0 ° C., the internal temperature was further raised to 195 ° C., and unreacted monomers were distilled off under a reduced pressure of 15 Torr to obtain a novolak resin (a). . The molecular weight of the resin was 5,400.

Novolac resin synthesis example 2 m-cresol 237.9 g, p in a separable flask
-Cresol 190.3g, 2,5-xylenol 5
3.8 g, 15.0 g of oxalic acid dihydrate and 1 ml of 35% hydrochloric acid were added, and 31.7 g of 90% acetaldehyde was added dropwise with stirring at room temperature, and then stirring was continued at room temperature for 30 minutes. Then, the internal temperature was raised to 95 ° C., 210.1 g of 37% aqueous formalin solution was added dropwise, and the reaction was carried out for 5 hours while maintaining the temperature. Then the internal temperature is 1.5 hours over 1
Water was distilled off from the system while the temperature was raised to 80 ° C., the internal temperature was further raised to 195 ° C., and unreacted monomers were distilled off under reduced pressure of 10 Torr to obtain a novolak resin (b). . The molecular weight of the resin was 4065. The formaldehyde / acetaldehyde ratio (molar charge ratio) was 8/2.

Novolac Resin Synthesis Example 3 In a eggplant-shaped flask, 324 g of m-cresol and 2 oxalic acid were added.
Hydrate 30 g, 35% hydrochloric acid 3 ml and ethanol 300
90 ml of acetaldehyde 11 was added under stirring at room temperature.
7.5 g was added dropwise, then the oil bath temperature was maintained at 100 ° C., and the mixture was heated under reflux for 5 hours to carry out the reaction. After the reaction,
The reaction solution was diluted with 300 ml of ethanol and then added dropwise to 3 liters of water to precipitate a crystal substance. The resulting precipitate was collected by filtration, washed with 3 liters of water three times, and dried to obtain a novolak resin (c). The molecular weight of the resin is 10
It was 58.

Novolac Resin Synthesis Example 4 475.4 g of m-cresol in a separable flask, 3
A novolak resin (d) was obtained in the same manner as in Novolak Resin Synthesis Example 1 except that 214.1 g of a 7% formalin aqueous solution and 15.0 g of oxalic acid dihydrate were added. The molecular weight of the resin was 750.

Novolac Resin Synthesis Example 5 140.4 g of acetone was added to a separable flask, 50.2 g of pigalol was further added, and the mixture was stirred and dissolved at room temperature. Further, 0.23 g of phosphorus oxychloride (POCl ₃ ) was added, the temperature was raised, the mixture was stirred, and the reaction was conducted for 5 hours while heating under reflux. After completion of the reaction, the reaction solution was cooled to 10 ° C., and the reaction solution was discharged into 3.6 liters of water to precipitate crystals. The obtained precipitate was collected by filtration, washed with water and dried to obtain a novolak resin (e). The molecular weight of the resin was 1250.

Novolak Resin Synthesis Example 6 96.0 g of m-cresol and p- in a separable flask.
Cresol 120.0 g, 2,5-xylenol 27.
1 g and 7.6 g of oxalic acid dihydrate were added, and the internal temperature was raised to 95 ° C. with stirring, heating and refluxing, and a 37% formalin aqueous solution 1
A novolak resin (f) was obtained in the same manner as in Novolak Resin Synthesis Example 1 except that 23.6 g was dropped. The molecular weight of the resin was 6500.

Novolac resin synthesis example 7 108.0 g of m-cresol, 10.0 g of oxalic acid dihydrate, 1 ml of 35% hydrochloric acid and 300 ml of ethanol were added to a round-bottomed flask, and 48.9 g of 90% acetaldehyde was added dropwise under stirring at room temperature. A novolac resin (g) was obtained in the same manner as in Novolak Resin Synthesis Example 3 except for the above. The molecular weight of the resin was 1834.

Novolak Resin Synthesis Example 8 In an eggplant type flask, 86.5 g of m-cresol, 22.0 g of resorcinol, 10.0 g of oxalic acid dihydrate, 35
% Novolak resin (h) was obtained in the same manner as in Novolak Resin Synthesis Example 3 except that 0.5 ml of hydrochloric acid and 100 ml of ethanol were added and 29.5 g of 100% acetaldehyde was added dropwise under stirring at room temperature. The molecular weight of the resin was 905.

Novolak Resin Synthesis Example 9 A novolak resin (j) was obtained in the same manner as in the novolak resin synthesis example 2 except that 475.2 g of m-cresol, 23.8 g of 90% acetaldehyde and 150.8 g of 37% formaldehyde were used. It was The molecular weight of the resin was 620.

Photosensitizer Synthesis Example 1 31.7 g of novolak resin (c) and 26.0 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride were added,
It was dissolved in a mixed solvent of 160 ml of acetone and 44 ml of N-methylpyrrolidone, 10.6 g of triethylamine was added dropwise, and after reacting at room temperature for 2 hours, the reaction solution was filtered to remove triethylamine hydrochloride. The filtrate was added to 1 liter of water, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain a photosensitizer (P-1). The esterification rate of the photosensitizer is 40%.

Photosensitizer Synthesis Example 2 Novolak resin (d) (32.3 g) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (40.2 g) were added,
A photosensitizer (P- was prepared in the same manner as in Photosensitizer Synthesis Example 1) except that it was dissolved in a mixed solvent of 200 ml of acetone and 50 ml of N-methylpyrrolidone, and 16.4 g of triethylamine was added dropwise.
2) was obtained. The esterification rate of the photosensitizer is 55%.

Photosensitizer Synthesis Example 3 12.3 g of 2,3,4,2 ', 4'-pentahydroxybenzophenone and 1,2-naphthoquinonediazide-5
-Sulfonyl chloride (52.1 g) was dissolved in a mixed solvent of 200 ml of 1,4-dioxane and 50 ml of N-methylpyrrolidone, and 23.2 g of triethylamine was added dropwise thereto. 3) was obtained. The esterification rate of the photosensitizer is 84%.

Photosensitizer Synthesis Example 4 7.5 g of novolak resin (e) and 18.7 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride were dissolved in a mixed solvent of 100 ml of acetone and 25 ml of N-methylpyrrolidone to give triethylamine 8 Photosensitizer (P-4) in the same manner as in Photosensitizer Synthesis Example 1 except that 0.3 g was dropped.
Got The esterification rate of the photosensitizer is 50%.

Photosensitizer Synthesis Example 5 12.3 g of 2,3,4,2 ', 4'-pentahydroxybenzophenone and 1,2-naphthoquinonediazide-5
-Sulfonyl chloride (46.5 g) was dissolved in a mixed solvent of 1,4-dioxane (200 ml) and N-methylpyrrolidone (50 ml), and triethylamine (18.9 g) was added dropwise thereto. 5) was obtained. The esterification rate of the photosensitizer is 75%.

Photosensitizer Synthesis Example 6 2,3,4-trihydroxybenzophenone 14.0 g
And 1,2-naphthoquinonediazide-5-sulfonyl chloride (36.8 g) and 1,4-dioxane (107.4).
A photosensitizer (P-6) was obtained in the same manner as in Photosensitizer Synthesis Example 1, except that the solvent was dissolved in a mixed solvent of 2 g of N-methylpyrrolidone and 15.0 g of triethylamine was added dropwise. The esterification rate of the photosensitizer is 75%.

Photosensitizer Synthesis Example 7 45.9 g of novolak resin (g) and 46.3 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride were added,
A photosensitizer (P-7) was obtained in the same manner as in Photosensitizer Synthesis Example 1 except that the solvent was dissolved in a mixed solvent of 240 g of acetone and 65 g of N-methylpyrrolidone, and 18.4 g of triethylamine was added dropwise. The esterification rate of the photosensitizer is 50%.

Photosensitizer Synthesis Example 8 114.8 g of novolak resin (h) and 135.0 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride.
553 g of acetone and 187 g of N-methylpyrrolidone
Of the photosensitizer (P-) in the same manner as in Photosensitizer Synthesis Example 1 except that 54.9 g of triethylamine was dissolved.
8) was obtained. The esterification rate of the photosensitizer is 50%.

Photosensitizer Synthesis Example 9 2,3,4,4'-tetrahydroxybenzophenone 1
6.6 g and 1,2-naphthoquinonediazide-5-sulfonyl chloride 54.4 g were added to 1,4-dioxane 16
A photosensitizer (P-9) was obtained in the same manner as in Photosensitizer Synthesis Example 1 except that the solvent was dissolved in a mixed solvent of 1.5 g and 48.5 g of N-methylpyrrolidone, and 20.5 g of triethylamine was added dropwise. The esterification rate of the photosensitizer is 75%.

Photosensitizer Synthesis Example 10 Gallium (7.32 g) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (21.6 g) were mixed with 1,4-dioxane (160.0 g) and N-methylpyrrolidone (24.0 g).
Of the photosensitizer (P-) in the same manner as in Photosensitizer Synthesis Example 1 except that 8.1 g of triethylamine was added dropwise.
10) was obtained. The esterification rate of the photosensitizer is 100%.

Photosensitizer Synthesis Example 11 Novolak resin (j) (24.9 g) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (32.9 g) were dissolved in a mixed solvent of acetone (152 ml) and N-methylpyrrolidone (40 ml), and triethylamine (12) was added thereto. Photosensitizer (P-1) was prepared in the same manner as in Photosensitizer Synthesis Example 1 except that 9 g was dropped.
1) was obtained. The esterification rate of the photosensitizer was 47%.

Photosensitizer Synthesis Example 12 2,3,4,2 ', 4'-Pentahydroxybenzophenone 22.9 g and 1,2-naphthoquinonediazide-5
-Sulfonyl chloride (70.5 g) was dissolved in a mixed solvent of 1,4-dioxane (240 ml) and N-methylpyrrolidone (65 ml), and triethylamine (27.1 g) was added dropwise thereto. ) Got. The esterification rate of the photosensitizer is 60%. The photosensitizers produced in the above photosensitizer synthesis examples are summarized in Tables 1 and 2.

[0065]

[Table 1]

[0066]

[Table 2]

Photoresist Composition Preparation Example 1 Novolak resin (b) 6.0 as an alkali-soluble resin
46 g and a photosensitive compound (P-1) 2.88 as a photosensitive compound
3 g and 0.271 g of the photosensitizer (P-3) were dissolved in 30.8 g of methyl 3-methoxypropionate, and a fluorine-based surfactant (trade name "Florard" FC-430 Sumitomo 3M Co., Ltd.) 1
A photoresist composition (PR-1) was prepared by adding 00 ppm and filtering through a membrane filter having a pore size of 0.2 μm.
Got

Photoresist Composition Preparation Examples 2 to 22 The same procedure as in Photoresist Composition Preparation Example 1 except that the alkali-soluble resin and the photosensitive compound shown in Table 3 were combined in the proportions shown in Table 3. Photoresist composition (P
R-2) to (PR-22) were obtained.

Examples 1 to 10 and Comparative Examples 1 to 12 Photoresist compositions (PR-1) to (PR-22)
Was patterned by the following patterning methods 1 to 5, and the sensitivity, the limiting resolution, the exposure margin, and the heat resistance were evaluated. The results are shown in Table-4 to Table-9. Incidentally, Table-4 to Table-
The following symbols and terms in 9 respectively have the following meanings.

[0070]

[Table 3] Eth: The minimum exposure amount required to completely dissolve the 1.4 mm square exposed portion of the photoresist film up to the substrate with the alkaline developing solution is indicated by the exposure time E ₀ : 0.5 μm on the mask When the line and space pattern of width (when exposed by i-line) or 0.8 μm width (when exposed by g-line) is 1: 1, by developing after exposure, the exposed and unexposed areas are separated. Line width 0.5 μm (when exposed with i-line) or 0.8 μm (when exposed with g-line)
Shows the amount of exposure that the line and space pattern is finished at 1: 1 without any film thickness reduction. Resolving power: The minimum line and space dimension heat resistance that can be resolved when the amount of exposure is E ₀ . : Maximum temperature at which the pattern of 5 μm line & space is not deformed when the wafer is heated on the hot plate for 5 minutes (measurement is at 5 ° C intervals)

Patterning Method 1 After coating the photoresist composition (PR- 1 to PR-8) on a silicon wafer with a spin coater, 90 ° C.
Remove the solvent by heating on a hot plate for 60 seconds,
A photoresist film having a film thickness of 1.07 μm was formed. This was exposed by a Nikon i-line stepper (NA = 0.50), heated on a 110 ° C. hot plate for 60 seconds, and then placed in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds. Dipped for 2 seconds and developed.

Patterning Method 2 After coating the photoresist composition (PR-9 to PR-12) on a silicon wafer by a spin coater, 80
The solvent was removed by heating for 90 seconds on a hot plate at ℃ to form a photoresist film having a film thickness of 1.03 μm.
This was exposed with a g-line stepper (NA = 0.38) manufactured by GSJ, heated on a hot plate at 120 ° C. for 90 seconds, and then in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. at 60 ° C. Dipped for 2 seconds and developed.

Patterning Method 3 Photoresist Composition (PR-13 to PR-14 and P
R-19 to 22) was applied to a silicon wafer by a spin coater and then heated on a hot plate at 95 ° C. for 60 seconds to remove the solvent, thereby forming a photoresist film having a thickness of 1.03 μm. This was exposed with a g-line stepper (NA = 0.38) manufactured by GSJ, and then immersed in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds to develop.

Patterning Method 4 A photoresist composition (PR-15 to PR-16) was applied to a silicon wafer by a spin coater, and then 9
The same procedure as in Patterning Method 1 was performed except that the solvent was removed by heating for 60 seconds on a 0 ° C. hot plate to form a photoresist film having a film thickness of 1.02 μm.

Patterning Method 5 A photoresist composition (PR-17 to PR-18) was applied to a silicon wafer by a spin coater, and then 9
The same procedure as in Patterning Method 1 was performed except that the solvent was removed by heating on a 0 ° C. hot plate for 60 seconds to form a photoresist film having a thickness of 1.22 μm.

[0076]

[Table 4]

[0077]

[Table 5]

From the results shown in Table 4, even when the quinonediazide sulfonate of novolac resin and the quinonediazide sulfonate of polyhydroxybenzophenone are used in combination, the quinonediazide sulfonate of novolak resin is a compound outside the scope of the present invention. Examples 1 to 4 using the quinonediazide sulfonic acid esterification product of the novolak resin (A) defined in the present invention are significantly improved in the limiting resolution and heat resistance, as compared with Comparative Examples 1 to 4 using Recognize.

[0079]

[Table 6]

From the results shown in Table 5, even when the quinonediazide sulfonate of novolak resin and the quinonediazide sulfonate of polyhydroxybenzophenone are used in combination, the quinonediazide sulfonate of novolak resin is a compound outside the scope of the present invention. It is understood that Examples 5 to 6 using the quinonediazide sulfonic acid esterification product of the novolak resin (B) defined in the present invention are significantly improved in sensitivity and heat resistance as compared with Comparative Examples 5 and 6 using .

[0081]

[Table 7]

From the results shown in Table 6, the sensitivity and the limiting resolution of Example 7 according to the present invention are remarkably improved as compared with Comparative Example 7 in which two kinds of quinonediazide sulfonates of polyhydroxybenzophenone are used in combination. I understand.

[0083]

[Table 8]

From the results shown in Table 7, it can be seen that the limiting resolution of Example 8 according to the present invention was remarkably improved as compared with Comparative Example 8 in which quinonediazide sulfonic acid ester compounds of two types of novolak resins were used in combination. .

[0085]

[Table 9]

From the results of Table 8, as compared with Comparative Example 9 in which the photosensitizer used in combination with the quinonediazide sulfonic acid ester of novolak resin is outside the scope of the present invention, Example 9 according to the present invention has sensitivity, critical resolution and It can be seen that the heat resistance is remarkably improved.

[0087]

[Table 10]

From the results of Table-9, Example 1 according to the present invention
0 is compared with Comparative Example 10 in which the quinonediazide sulfonic acid esterified product of the novolak resin (A) specified in the present invention is used alone and Comparative Example 12 in which two quinonediazide sulfonic acid esterified products of the novolak resin (A) are used in combination. It can be seen that the sensitivity, the limiting resolution and the heat resistance are remarkably improved. Further, Comparative Example 11 in which the quinonediazide sulfonic acid ester of hydroxybenzophenone (C) specified in the present invention is used alone has good sensitivity and heat resistance, but the critical resolution is remarkably inferior. It can be seen that Example 10 has practical sensitivity and heat resistance, and the marginal resolution is remarkably improved.

[0089]

The composition of the present invention has a wavelength of 330 to 4 in particular.
It has a practical sensitivity to irradiation with ultraviolet rays in the range of 50 nm and has a high resolution, and a resist pattern formed using the composition of the present invention has a good pattern shape and high heat resistance. It is particularly useful as a photoresist for making highly integrated circuits.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mineo Nishi, 1-1 Kurosaki Shiroishi, Yawatanishi-ku, Kitakyushu Sanritsu Chemical Co., Ltd. Kurosaki Development Laboratory (72) Koji Nakano 1-1, Kurosaki Shiroishi, Yawatanishi-ku, Kitakyushu Sanryo Chemical Co., Ltd., Kurosaki Development Laboratory (72) Inventor Keisuke Nakano 1-1, Kurosaki Shiroishi, Hachimansai-ku, Kitakyushu City Sanryo Chemical Co., Ltd., Kurosaki Development Laboratory (72) Iwa Matsuo 4-chome, Fushimi-cho, Chuo-ku, Osaka No. 1-1 Sanryo Chemical Co., Ltd. Osaka Branch (56) Reference JP-A-2-108054 (JP, A) JP-A-4-301847 (JP, A) JP-A-6-180500 (JP, A) JP-A-7-28235 (JP, A) JP-A-7-92670 (JP, A) JP-A-64-35435 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/00-7/42

Claims (6)

(57) [Claims] 1. A photosensitive resin composition containing an alkali-soluble resin, a quinonediazide photosensitive compound and a solvent, wherein the photosensitive compound has a weight average molecular weight of 600 to 600.
2,200, a novolak represented by the following general formula (i)
A photosensitive resin composition comprising a resin (A) quinone diazide sulfonate ester compound and a hydroxybenzophenone (C) quinone diazide sulfonate ester compound represented by the following general formula (iii). . [Chemical 1] (In the formula, R ¹ and R ⁴ each represent an alkyl group, and R ^1
2 represents an alkyl group or an aryl group, R ³ represents a hydrogen atom or an alkyl group, u and v are 0 to 3 respectively.
Represents the integer. However, when a plurality of R ^{1 to} R ⁴ are present, they may be the same or different. k
And l represent a number of 0 or more, and k: l = 1: 9 to 10: 0.
Satisfying) (In the formula, p and q each represent an integer of 0 or more, and 3 ≦
p + q ≦ 6 is satisfied) 2. In the formula (i), R ¹ and R ⁴ are the same, an alkyl group having 1 to 2 carbon atoms, R ² is a methyl group, and R ³ is a hydrogen atom or a methyl group. And u and v are 1. The composition of claim 1, wherein 3. In the formula (iii), 5 ≦ p + q ≦ 6.
It is any one of Claim 1 or 2 characterized by these.
A composition according to claim 1. 4. A novolak resin (A) having a quinonediazide sulfonic acid esterification product having a Q ratio of Q ₁ and a hydroxybenzophenone (C) having a quinonediazide sulfonic acid esterification product having a Q ratio of Q ₂ (where the Q ratio is the ratio Q between mmoles of quinonediazide based photosensitive group) to the total solid content 1g in the resist solution _1: Q ₂ is 1: 15-15: any one of claims 1 to 3, characterized in that a 1 The composition according to. 5. The alkali-soluble resin is m-cresol:
p-cresol: 2,5- or 3,5-xylenol:
The composition according to any one of claims 1 to 4 , which is a condensate of resorcinol = 1 to 7: 3 to 7: 0 to 5: 0 to 1 (molar ratio) and a carbonyl compound. 6. The carbonyl compound is formaldehyde alone or formaldehyde: acetaldehyde = 95-
The composition according to claim 5 , which is a mixture of 40: 5 to 60 (molar ratio).