JPH0844053A - Positive radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. excellent especially in focus latitude, excellent also in sensitivity, resolution, heat resistance and pattern shape and very useful as a positive type resist for production of an integrated circuit considered to be more highly integrated in future. CONSTITUTION:This radiation sensitive resin compsn. contains an alkali-soluble resin and a quinonediazido compd. The alkali-soluble resin is obtd. by bringing m-cresol, at least one among 2,3-xylenol, 3,4-xylenol and 2,3,5-trimethylphenol and at least one kind of aldehyde represented by the formula into a polycondensation reaction. In the formula, R is alkylene, alkenylene, cycloalkylene, polycyclo-alkylene, arylene or aralkylene and l is 0 or 1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a positive type radiation sensitive resin composition. More specifically, ultraviolet rays, far ultraviolet rays, X
The present invention relates to a positive-type radiation-sensitive resin composition suitable as a resist for producing an integrated circuit having an extremely high degree of integration, which is sensitive to radiation such as rays, electron beams, molecular beams, γ rays, synchrotron radiation, and proton beams.

[0002]

2. Description of the Related Art Conventionally, positive type resists have been widely used in the field of fine processing such as manufacturing of integrated circuits because a high resolution resist pattern can be obtained. In recent years, with the progress of higher integration of integrated circuits, development of positive resists capable of forming resist patterns with higher resolution has been strongly promoted.

In such fine processing, a radiation irradiation device typified by a reduction projection exposure machine (stepper) is usually used to irradiate the positive resist with radiation through a predetermined mask pattern (hereinafter referred to as "exposure"). After that, a resist pattern is formed by development, and one of the means for improving the resolution is to increase the numerical aperture (NA) of the stepper lens.

In general, in the stepper as described above, the relation between the depth of focus (DOF) and the numerical aperture is expressed by the following Rayleigh's equation. DOF = k × λ / (NA) ² (where k is a constant, λ is the wavelength of the radiation) The focus depth is a focus allowance that can form a dimension-controlled resist pattern even if the focus shifts in the optical axis direction. It is a measure of sex. Therefore, as is clear from the above equation, when the numerical aperture is increased, the depth of focus, that is, the focus allowance is significantly reduced. Therefore, in order to cope with a stepper having a large numerical aperture, a positive resist having excellent focus tolerance is required.

However, since the conventional positive type resist is practically used near the resolution limit,
In particular, when forming a fine pattern of the order of 0.3 to 0.4 μm, when the focal point is displaced in the optical axis direction, the pattern shape is deformed, the difference between the pattern line width and the design line width becomes large, and the developability is improved. There is a demand for improvement of focus allowance because a phenomenon of significantly lowering occurs.

On the other hand, in JP-A-6-59445,
A resin obtained by condensing m-cresol, p-cresol and / or 3,5-xylenol with an aldehyde under an acidic catalyst, as a photosensitive resin composition which gives a positive resist having high resolution and high heat resistance. , A standard polystyrene-reduced weight average molecular weight of 1,000 to 5,000 is removed from the low molecular weight component, an alkali-soluble novolac resin, a photosensitive resin containing tris (4-hydroxyphenyl) methane and a 1,2-naphthoquinonediazide compound. In the composition, a photosensitive resin composition in which the aldehyde is glyoxal is proposed. However, the composition has not yet improved the focus acceptance.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive type radiation sensitive resin composition excellent in various performances, and particularly to provide a fine resist pattern of the order of 0.3 to 0.4 μm. An object of the present invention is to provide a positive radiation-sensitive resin composition having excellent focus tolerance when formed. Another object of the present invention is to provide a positive type radiation sensitive resin composition which is excellent in sensitivity, resolution, developability and the like, and is also excellent in heat resistance of the resulting resist and its pattern shape.

[0008]

According to the present invention, (1)
(I) m-cresol and (ii) at least one dimethyl or trimethylphenol selected from the group consisting of 2,3-xylenol, 3,4-xylenol and 2,3,5-trimethylphenol, or at least one thereof Of dimethyl or trimethylphenol and other phenols (excluding m-cresol) and (iii) the following formula (1)

Embedded image (In the formula (1), R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 10 carbon atoms. Group, substituted or unsubstituted polycycloalkylene group having 7 to 12 carbon atoms, 6 to 18 carbon atoms
Substituted or unsubstituted arylene group or having 8 to 8 carbon atoms
18 substituted or unsubstituted aralkylene groups,
Is 0 or 1. ), An alkali-soluble resin obtained by polycondensation of at least one aldehyde represented by the formula (1) or a combination of the at least one aldehyde and another aldehyde, and (2) a quinonediazite compound. The positive-type radiation-sensitive resin composition is provided to achieve the above object of the present invention.

The present invention will be described in detail below, and the purpose, constitution and effect of the present invention will be apparent.

Alkali-Soluble Resin The alkali-soluble resin (hereinafter referred to as “resin (A)”) used in the positive-type radiation-sensitive resin composition of the present invention includes (i) m-cresol and (ii) 2, At least one dimethyl or trimethylphenol (hereinafter referred to as "phenol (a)") or phenol selected from the group consisting of 3-xylenol, 3,4-xylenol and 2,3,5-trimethylphenol. A combination of (a) with other phenols (hereinafter referred to as "phenols (c)") (however, excluding m-cresol) (hereinafter referred to as "mixed phenols (b)"). And (iii) at least one aldehyde represented by the formula (1) (hereinafter, referred to as “aldehyde (a)”) or aldehyde (a) Aldehydes other than that (hereinafter, referred to as "aldehyde (c)".) A combination of (hereinafter referred to as "mixed aldehyde (b)".) And the a resin obtained by polycondensation reaction.

In the mixed phenols (b), the phenols (c) which can be combined with the phenols (a) include

(1) Examples of phenols (c) having one hydroxyl group include (i) phenol, o-cresol, p-cresol,
o-ethylphenol, m-ethylphenol, p-ethylphenol, on-propylphenol, mn
-Propylphenol, pn-propylphenol,
o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, o-t-butylphenol, m-t-butylphenol, p-t-butylphenol , Pn-pentylphenol, pt-pentylphenol, p-
n-hexylphenol, pt-hexylphenol, pn-heptylphenol, pt-heptylphenol, pn-octylphenol, pt-octylphenol, pn-nonylphenol, pt-
Nonylphenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,5-xylenol, 5-isopropyl-3-methylphenol, 2-n
-Butyl-5-methylphenol, 2-t-butyl-5
-Methylphenol, 2,5-di-n-butylphenol, 2,5-di-sec-butylphenol, 2,5-di-t-butylphenol, (poly) alkyl-substituted phenol such as 3,4,5-trimethylphenol Kind;

(Ii) o-allylphenol, m-allylphenol, p-allylphenol, o-1-propenylphenol, m-1-propenylphenol, p-
(Poly) alkenyl-substituted phenols such as 1-propenylphenol, o-2-propenylphenol, m-2-propenylphenol and p-2-propenylphenol;

(Iii) (poly) cycloalkyl-substituted phenols such as o-cyclopentylphenol, m-cyclopentylphenol, p-cyclopentylphenol, o-cyclohexylphenol, m-cyclohexylphenol and p-cyclohexylphenol;

(Iv) (poly) aryl-substituted phenols such as o-phenylphenol, m-phenylphenol, p-phenylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol;

(V) (poly) such as o-benzylphenol, m-benzylphenol, p-benzylphenol
Aralkyl substituted phenols;

(Vi) o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, on-propoxyphenol, mn
-Propoxyphenol, pn-propoxyphenol, o-isopropoxyphenol, m-isopropoxyphenol, p-isopropoxyphenol, on
-Butoxyphenol, mn-butoxyphenol,
pn-butoxyphenol, ot-butoxyphenol, mt-butoxyphenol, pt-butoxyphenol, on-pentyloxyphenol, m-
n-pentyloxyphenol, pn-pentyloxyphenol, on-hexyloxyphenol, m
-N-hexyloxyphenol, pn-hexyloxyphenol, on-heptyloxyphenol,
m-n-heptyloxyphenol, pn-heptyloxyphenol, 3-methoxy-4-methoxyphenol, 3-ethoxy-4-methoxyphenol, 3-methoxy-4-ethoxyphenol, 3-ethoxy-4-
(Poly) alkoxyl-substituted phenols such as ethoxyphenol;

(Vii) o-phenoxyphenol, m
-(Poly) aryloxy-substituted phenols such as phenoxyphenol and p-phenoxyphenol;

(Viii) (poly) aralkyloxy-substituted phenols such as o-benzyloxyphenol, m-benzyloxyphenol and p-benzyloxyphenol;

(Ix) o-acetylphenol, m-acetylphenol, p-acetylphenol, on-n-
Propionylphenol, mn-propionylphenol, pn-propionylphenol, on-butyrylphenol, mn-butyrylphenol, pn
-(Poly) acyl-substituted phenols such as butyrylphenol, pn-pentanoylphenol, pn-hexanoylphenol;

(X) Methyl salicylate, ethyl salicylate, n-propyl salicylate, methyl 3-hydroxybenzoate, ethyl 3-hydroxybenzoate, n-propyl 3-hydroxybenzoate, methyl 4-hydroxybenzoate, 4-hydroxy (Poly) alkoxycarbonyl-substituted phenols such as ethyl benzoate and propyl 4-hydroxybenzoate;

Examples of (2) phenols (c) having two hydroxyl groups include (i) catechol, resorcinol, hydroquinone,
3-methylcatechol, 4-methylcatechol, 2-methylresorcinol, 4-methylresorcinol, methylhydroquinone, 3-ethylcatechol, 4-ethylcatechol, 2-ethylresorcinol, 4-ethylresorcinol, ethylhydroquinone, n-propylhydroquinone , Isopropylhydroquinone, t-butylhydroquinone, 4-n-hexylresorcinol,
4-hexanoylresorcinol, 3,5-dimethylcatechol, 2,5-dimethylresorcinol, 2,3-diethylhydroquinone, 2,5-dimethylhydroquinone, 3,5-diethylcatechol, 2,5-diethylresorcinol, 2,5 5-diethylhydroquinone, 3,5-
Diisopropylcatechol, 2,5-diisopropylresorcinol, 2,3-diisopropylhydroquinone, 2,5-diisopropylhydroquinone, 3,5-di-t-butylcatechol, 2,5-di-t-butylresorcinol, 2,3- Di-t-butyl hydroquinone,
(Poly) alkyl-substituted dihydric phenols such as 2,5-di-t-butylhydroquinone;

(Ii) Bisphenols such as bisphenol-A and bisphenol-E;

Examples of (3) phenols (c) having three or more hydroxyl groups include (i) pyrogallol, phloroglucinol, 1,2,4-
In addition to benzenetriol, methyl gallate, ethyl gallate, n-propyl gallate, n-butyl gallate,
(Poly) hydroxycarbonyl-substituted phenols such as n-pentyl gallate, n-hexyl gallate, n-heptyl gallate, and n-octyl gallate;

(Ii) 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (4-hydroxyphenyl) butane And other tris (phenol) s.

These phenols (c) can be used alone or in combination of two or more.

The mixed phenols (b) preferably contain the phenols (a) in an amount of 5 mol% or more, particularly 10 mol% or more.

The proportion of m-cresol in all phenols used including m-cresol is preferably 5 to 95 mol%, particularly preferably 10 to 90 mol%.

Phenols (a) together with m-cresol
Alternatively, the aldehydes to be polycondensed with the mixed phenols (b) are the aldehydes (a) represented by the formula (1) or the aldehydes (a) and the aldehydes (c).
It is a mixed aldehyde (b) in combination with. The mixed aldehydes (b) contain the aldehydes (a) in an amount of preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 10 to 90 mol%.

Here, in the above formula (1), R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, or a substituted group having 5 to 10 carbon atoms. Or an unsubstituted cycloalkylene group, a substituted or unsubstituted polycycloalkylene group having 7 to 12 carbon atoms, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, or a substituted or unsubstituted aralkylene having 8 to 18 carbon atoms Indicates a group.

Examples of the substituted or unsubstituted alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene,
Examples thereof include octylene, nonylene, decylene and the like. Examples of the substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms include ethenylene, propenylene, butenylene, butadienylene, hexatrienylene and the like. Examples of the substituted or unsubstituted cycloalkylene group having 5 to 10 carbon atoms include cyclopentylene, cyclohexylene, cyclooctylene and the like. Examples of the substituted or unsubstituted polycycloalkylene group having 7 to 12 carbon atoms include a divalent bicycloalkylene group obtained by removing two hydrogen atoms from bicycloalkane such as norbornane and camphane. Examples of the substituted or unsubstituted arylene group having 6 to 18 carbon atoms include phenylene, naphthylene, anthranylene and the like. Examples of the substituted or unsubstituted aralkylene group having 8 to 18 carbon atoms include xylylene and benzenebisethylene.

The substitution in R means that the hydrogen atom of the divalent organic group is substituted with an alkyl group, an alkoxyl group, a halogen atom, a nitro group, an amino group, a silyl group, a trialkylsilyl group or the like. Show.

Further, preferred specific examples of the aldehydes (a) represented by the above formula (1) include (1) glyoxal (when l is 0 in the formula (1)); (2) malonaldehyde and succin. Aldehyde, glutaraldehyde, hexanedial, heptanedial,
Octane Diar, Nonan Giard, Decandial,
Undecandial, etc. (in the formula (1), when 1 is 1 and R is an alkylene group having 1 to 10 carbon atoms);

(3) 2-butenedial, 2-pentenedial, 2-hexenedial, etc. (in the formula (1), when 1 is 1 and R is an alkenylene group having 2 to 10 carbon atoms); (4) Cyclopentane dicarbaldehyde, cyclohexane dicarbaldehyde, norbornane dicarbaldehyde,
Camphandicarbaldehyde etc. (in the formula (1), when 1 is 1 and R is a cycloalkylene group having 5 to 10 carbon atoms or a polycycloalkylene group having 7 to 12 carbon atoms); (5) 1,4-benzene Examples thereof include diacetaldehyde and the like (in the formula (1), 1 is 1 and R is an aralkylene group having 8 to 18 carbon atoms).

Of these aldehydes (a), glyoxal, malonaldehyde, succinaldehyde,
Glutaraldehyde and the like are particularly preferable, and glyoxal is most preferable. These aldehydes (a) can be used alone or in combination of two or more.

The aldehydes (c) include formaldehyde, benzaldehyde, acetaldehyde,
Propylaldehyde, phenylacetaldehyde, α-
Phenylpropyl aldehyde, β-phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-
Nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-ethylbenzaldehyde, m-ethylbenzaldehyde, p-ethylbenzaldehyde, on
-Propylbenzaldehyde, mn-propylbenzaldehyde, pn-propylbenzaldehyde, o-
Examples thereof include n-butylbenzaldehyde, m-n-butylbenzaldehyde, pn-butylbenzaldehyde and furfural.

Of these aldehydes (c), formaldehyde is particularly preferable. These aldehydes (c) can be used alone or in combination of two or more.

When formaldehyde is used as the aldehyde (c), examples of the formaldehyde source include formalin, trioxane, 1,3-dioxolane, paraformaldehyde, methyl hemiformal, ethyl hemiformal, propyl hemiformal, butyl hemiformal, Examples thereof include phenyl hemiformal. Of these, formalin and butyl hemiformal are particularly preferable. These formaldehyde generating sources can be used alone or in admixture of two or more.

In the polycondensation reaction, the amount of all aldehydes used is based on 1 mol of all phenols used.
It is preferably 0.7 to 3 mol.

In the polycondensation reaction, an acidic catalyst such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, oxalic acid or acetic acid is usually used. The amount of these acidic catalysts used is usually 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mol per 1 mol of the total amount of all phenols.

In the polycondensation reaction, water is usually used as the reaction medium. However, when the phenols used do not dissolve in the aqueous solution in which the aldehydes are dissolved and become heterogeneous from the initial stage of the reaction, a hydrophilic solvent can be further added to use as a uniform reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol and propylene glycol; diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-
Ethers such as diethoxyethane; cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 parts by weight per 100 parts by weight of the reaction raw material.

As the polycondensation reaction method, phenols,
It is possible to employ a method in which the aldehydes and the acidic catalyst are charged in a reactor at the same time to carry out the reaction, and further a method in which the reaction is carried out while gradually adding these to the reactor.

The reaction temperature of the polycondensation reaction can be appropriately adjusted depending on the reactivity of the reaction raw materials, and is usually 10
~ 200 ° C.

After completion of the polycondensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium and the like existing in the reaction system, generally, the temperature of the reaction system is raised to 130 ° C to 230 ° C. The volatile matter is distilled off under reduced pressure, for example, under a pressure of about 20 to 50 mmHg, and the produced resin (A) is recovered.

The resin (A) used in the present invention has a standard polystyrene equivalent weight average molecular weight (hereinafter referred to as "Mw") of usually 3,000 to 20,000, preferably 4,000 to 15,000. is there. When the Mw is in the above range, it becomes easy to uniformly coat the positive radiation-sensitive resin composition of the present invention on the substrate, and the developability, sensitivity and heat resistance are further improved.

Particularly when a high molecular weight resin (A) is desired, the resin (A) obtained by the polycondensation reaction is
After dissolving in a good solvent such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dioxane, methanol, ethyl acetate, add and mix poor solvent such as water, n-hexane, n-heptane, toluene, xylene. The separated high molecular weight resin (A) can be obtained by separating the deposited novolak resin from the solution layer.

In the positive-type radiation-sensitive resin composition of the present invention, the resin (A) may be used alone or as a mixture of two or more kinds of resins (A) having different composition ratios or different molecular weights.

Quinonediazide Compound The positive-working radiation-sensitive resin composition of the present invention contains a quinonediazide compound as a radiation-sensitive component. Examples of the quinonediazide compound include a quinonediazidesulfonic acid ester of a phenol compound (hereinafter referred to as "photosensitizer (B)"), for example, a quinonediazidesulfonic acid ester of a phenol compound having a benzene ring number of about 2 to 5.

Examples of such a photosensitizer (B) include 2,3,4-trihydroxybenzophenone, 2,4,6-
Trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 3,4'-tetrahydroxybenzophenone, 3'-methoxy-2,3,4,
4'-tetrahydroxybenzophenone, 2,2 ', 4,4'
-Tetrahydroxybenzophenone, 2,2 ', 3,4,4'
-Pentahydroxybenzophenone, 2,2'3,4,6 '
-Pentahydroxybenzophenone, 2,3,3 ', 4,
4 ', 5'-hexahydroxybenzophenone, 2,3'4,
1,2-naphthoquinonediazide-4-sulfonic acid ester of (poly) hydroxyphenyl aryl ketone such as 4 ′, 5 ′, 6-hexahydroxybenzophenone or 2-
Naphthoquinonediazide-5-sulfonic acid esters;

1,2,4-Trimethyl-2 ', 4', 7-trihydroxy-2-phenylflavan, 2,4,4'-trimethyl-2 ', 4', 5 ', 6,7-penta Hydroxy-2-
Mention may be made of 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of polyhydroxyphenylflavan such as phenylflavan.

Furthermore, 1,2-naphthoquinonediazide-4 of phenol compounds represented by the following formulas (2) to (9) is used.
-Sulfonic acid esters or 1,2-naphthoquinonediazide-5-sulfonic acid esters may be mentioned.

[0052]

[Chemical 3]

(In the formula (2), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and when a plurality of R ¹ are present, they may be the same or different, and R ² is A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, p, q,
r, x, y and z are each an integer of 0 to 3, provided that p and q are not 0 at the same time, and p + x ≦
5, q + y ≦ 5 and r + z ≦ 5 are satisfied. )

[0054]

[Chemical 4]

(In the formula (3), R ³ represents an alkyl group having 1 to 6 carbon atoms, and when a plurality of R ³ are present, they may be the same or different, and R ⁴ and R ⁵ may be the same or different from each other, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, p, q, x
And y are each an integer of 0 to 3, provided that p and q
And cannot be 0 at the same time, and p + x ≦ 5 and q +
It satisfies y ≦ 5. )

[0056]

Embedded image

(In the formula (4), R ⁶ represents an alkyl group having 1 to 6 carbon atoms, and when a plurality of R ⁶ are present, they may be the same or different from each other, such as p, q, x and y are each an integer of 0 to 3, provided that p and q do not become 0 at the same time, and p + x ≦ 5 and q + y ≦ 5 are satisfied.)

[0058]

[Chemical 6]

(In the formula (5), R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and when a plurality of R ^7's are present, they may be the same or different, and p, q, r, x, y, and z are each an integer of 0 to 3, provided that p, q, and r do not become 0 at the same time, and p + x ≦ 5, q +
It satisfies y ≦ 4 and r + z ≦ 5. )

[0060]

[Chemical 7]

[0061] (In the formula (6), R ⁸ represents an alkyl group having 1 to 6 carbon atoms, if R ⁸ there are a plurality or different and be identical to one another, R ¹⁰ to R ^13's may be the same or different from each other and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, p, q, r,
x, y and z are each an integer of 0 to 3, provided that
p, q, and r never become 0 at the same time, and p + x ≦
5, q + y ≦ 4 and r + z ≦ 5 are satisfied. )

[0062]

Embedded image

(In the formula (7), R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms, and when a plurality of R ¹⁴ are present, they may be the same or different, and R ^{15 to} R ^{15 19} may be the same or different from each other, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, p, q, r,
x, y and z are each an integer of 0 to 3, provided that
p, q, and r never become 0 at the same time, and p + x ≦
5, q + y ≦ 5 and r + z ≦ 5 are satisfied. )

[0064]

[Chemical 9]

(In the formula (8), R ^{20 to} R ²² may be the same as or different from each other, and are an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms or a carbon number. 7-1
8 is an aralkyl group, and when a plurality of R ^{20 to} R ²² groups are present, the plurality of groups may be the same or different, and R ^{23 to} R ²⁶ are R ²⁷ , which may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and R ²⁷ To R ^{29, which} may be the same as or different from each other, each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a, b and c are each an integer of 1 to 3, x, y and z. Are integers of 0 to 3, respectively, a + x ≦ 5, b
+ Y ≦ 5 and c + z ≦ 5 are satisfied)

[0066]

[Chemical 10]

(In the formula (9), R ^{30 to} R ^{39, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an alkoxy group or a hydroxyl group, and R ^{30 to} R ³⁴ and R ^{30 In} each combination of ^{35 to} R ³⁹ , at least one is a hydroxyl group, and R ⁴⁰ is a hydrogen atom, an alkyl group or an aryl group.)

As a phenol compound capable of forming a particularly preferred quinonediazide sulfonic acid ester, the following formula (2
-1) to (8-1)

[0069]

[Chemical 11]

Examples thereof include phenol compounds represented by:

Furthermore, quinonediazide compounds described in JP-A-1-144446 and JP-A-1-156738 can also be used. These photosensitizers (B) can be used alone or in admixture of two or more.

In the positive-type radiation-sensitive resin composition of the present invention, the amount of the photosensitizer (B) is usually 3 to 100 parts by weight, preferably 5 to 5 parts by weight, relative to 100 parts by weight of the resin (A).
It is 0 part by weight, and particularly, the total amount of quinonediazidesulfonyl groups in the composition is usually 5 to 35% by weight, preferably 10 to 30% by weight in terms of solid content.

Additives The positive-working radiation-sensitive resin composition of the present invention may further contain various compounding agents such as a dissolution accelerator, a sensitizer, and a surfactant, if necessary. .

The dissolution accelerator is a compound used for the purpose of promoting the alkali solubility of the resin (A).
Preferable examples thereof include a phenol compound having a benzene ring number of about 2 to 6, and specifically, a low molecular weight phenol compound represented by the above formulas (2) to (9). You can

For example, the following formulas (2-2) and (9-1)

[0076]

[Chemical 12]

The compound represented by is a typical example thereof.

The dissolution accelerator may be used alone or in admixture of two or more, and the blending amount thereof is the resin (A).
It is usually 50 parts by weight or less, preferably 5 to 30 parts by weight, per 100 parts by weight.

The sensitizer has a function of improving the sensitivity of the composition to radiation. As an example, 2H-pyrido- [3,2-b] -1,4-oxazine-3- (4H) -ones, 10H-pyrido- [3,2-
b] -1,4-benzothiazines, urazoles, hydantoins, parbituric acids, glycine anhydrides, 1
-Hydroxybenzotriazoles, alloxans, maleimides, etc. can be mentioned. These sensitizers can be used alone or in admixture of two or more, and the compounding amount thereof is usually 50 parts by weight or less per 100 parts by weight of the resin (A).

The above-mentioned surfactant has a function of improving the coatability and developability of the positive-type radiation-sensitive resin composition of the present invention, and examples thereof include polyoxyethylene lauryl ether and polyoxyethylene lauryl ether. Nonionic surfactants such as oxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate; EFTOP EF122A, EF122B, EF351, EF3
52, EF601, EF801, EF802 (trade name, made by Mitsubishi Metals); Megafax F142D, F144D,
F171, F172, F173, F177, F179A (trade name, manufactured by Dainippon Ink); Fluorard FC176, F
C430, FC431 (trade name, made by Sumitomo 3M);
Asahi Guard AG710, Surflon S-381, S
-382, SC-101, SC-102, SC-103, S
C-104, SC-105, SC-106 (trade name, manufactured by Asahi Glass); KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); acrylic acid-based or methacrylic acid-based (co) polymer polyflow No. 75, No. 90. , No.95, S, Floren A
C202, AC300, AC303, AC326F, AC9
03, AC1190 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo KK); Hyonic PE40, PE90, PE100,
PE120, Modicol L, X, Dapro S-65, Perenol F40, Color Sparse 188A (trade name, manufactured by San Nopco); Emazole O-15R, O-3
0 (F), S-20 (trade name, made by Kao); ZONYE
FSN, FSN-100, FSO, FSO-100 (trade name, manufactured by DuPont); DS-401, DS-403, DS-
406, DS-451 (trade name, made by Daikin); Futgent 250, 251, PEF-203, PFE-80
0B, NBX-15 (trade name, manufactured by Neos) and the like.

These surfactants can be used alone or in admixture of two or more, and the compounding amount is usually as an active ingredient of the surfactant per 100 parts by weight of the solid content of the composition. It is 2 parts by weight or less.

Further, in the positive-type radiation-sensitive resin composition of the present invention, by blending a dye or a pigment, the latent image in the exposed area can be visualized and the effect of halation during exposure can be reduced, and the adhesion can be improved. By incorporating an auxiliary agent, the adhesion of the composition to the substrate can be improved. Further, other additives such as a storage stabilizer and an antifoaming agent can be added.

Solvent When forming a resist pattern using the positive-type radiation-sensitive resin composition of the present invention, for example, a solid is used together with the resin (A) and the photosensitizer (B) and, if necessary, various additives. It is prepared as a composition solution by dissolving it in a solvent so that the partial concentration becomes 20 to 40% by weight, and filtering it with a filter having a pore size of about 0.2 μm.

Examples of the solvent used for preparing the composition solution include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether. Ethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2
-Methyl hydroxy-3-methylbutanoate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate Etc. can be mentioned.
These solvents may be used alone or in admixture of two or more.

Further, as the solvent, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and benzylethyl are used. Ether, dihexyl ether, acetonylacetone, isophorone, caproic acid,
One high boiling solvent such as caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate. The above can be added.

The positive-type radiation-sensitive resin composition of the present invention prepared as a resist pattern forming composition solution is coated with, for example, a silicon wafer or aluminum by a coating method such as spin coating, cast coating, or roll coating. A radiation-sensitive resin composition layer is formed by coating on a substrate such as a wafer, exposed through a predetermined mask pattern, and developed with a developing solution to form a resist pattern. As the radiation used at this time,
In particular, ultraviolet rays such as i-rays are preferably used, but various radiations such as g-rays, far ultraviolet rays, and electron rays can be selected and used according to the characteristics of the composition.

In the present invention, the composition solution is applied onto a substrate, prebaked and exposed, and then 70 to 140.
The effect of the present invention can be further improved by performing a heat treatment (hereinafter referred to as "post-exposure baking") at a temperature of ° C and then performing development.

Examples of the developer used in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n. -Propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline,
Pyrrole, piperidine, 1,8-diazabicyclo- [5,
4,0] -7-Undecene, 1,5-diazabicyclo-
The concentration of the alkaline compound such as [4,3,0] -5-nonene is usually 1 to 10% by weight, preferably 2 to 5% by weight.
An alkaline aqueous solution dissolved so that
Further, an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol and a surfactant can be added to the developer. When a developer containing such an alkaline aqueous solution is used, it is generally washed with water after development.

[0089]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless it exceeds the gist of the invention. Here, measurement of Mw and evaluation of each resist were performed by the following methods.

Mw: GPC column (G2 manufactured by Tosoh Corporation)
000H _XL 2 pcs, G3000H _XL 1 pcs, G4000
H _{XL (} 1 piece), the flow rate was 1.0 ml / min, the elution solvent was tetrahydrofuran, and the column temperature was 40 ° C. The analysis conditions were gel permeation chromatography using monodisperse polystyrene as a standard.

Sensitivity: NSR-2005 manufactured by Nikon Corporation
Using an i9C reduction projection exposure machine (numerical aperture of lens: 0.57), the exposure time was changed, and exposure was performed with i-line having a wavelength of 365 nm, followed by post-exposure baking for 1 minute on a hot plate kept at 110 ° C. Then, it was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds, washed with water, and dried to form a positive resist pattern on the wafer. At that time, the line width is 0.3
5 μm line and space pattern (1L1
The exposure time (hereinafter referred to as "optimum exposure time") for forming S) in a width of 1: 1 was defined as the sensitivity.

Resolution: The dimension of the smallest resist pattern resolved when exposed for the optimum exposure time was taken as the resolution.

Focus Tolerance A line and space pattern (1L1S) having a line width of 0.35 μm was observed using a scanning electron microscope, and the resolved pattern dimension was within ± 10% of the mask design dimension. And, when the ratio of the thickness of the resist pattern after development to the thickness of the film before development (hereinafter, referred to as “residual film rate”) is 90% or more, depending on the focus swing range (focus range), Focus tolerance was evaluated. The larger the focus range, the better the focus tolerance.

Developability: The degree of scum and residual development was examined using a scanning electron microscope.

Pattern shape: A lower side dimension La and an upper side dimension Lb of a rectangular cross section of a line and space pattern (1L1S) having a line width of 0.35 μm are measured using a scanning electron microscope, and are 0.85. When ≦ Lb / La ≦ 1, the pattern shape was considered good. However, 0.85
Even if ≦ Lb / La ≦ 1, the pattern was not considered to be good when the pattern had a skirt or an inverse taper.

Heat resistance: The wafer on which the resist pattern was formed was placed in a clean oven and heated at 130 ° C. for 2 minutes, and when the pattern shape did not collapse, the heat resistance was judged to be good.

Production of Resin (A) Synthesis Example 1 m-Cresol 59.5 g (0.55 mol) 2,3-xylenol 42.8 g was placed in a flask equipped with a stirrer, a condenser and a thermometer. (0.35 mol) 3,4-xylenol 12.2 g (0.10 mol) 40% glyoxal solution 108.8 g (glyoxal 0.75 mol) Oxalic acid dihydrate 2.52 g (0.02 mol) ) Was charged, the flask was immersed in an oil bath, and polycondensation was performed for 100 minutes under stirring while refluxing the reaction solution. Furthermore, 37% by weight formaldehyde aqueous solution 40.6 g (formaldehyde 0.5 mol) dioxane 115.0 g was added and polycondensation was further performed for 2 hours. Then the temperature of the oil bath is raised to 180 ° C. and the pressure inside the flask is raised to 30
The pressure was reduced to -50 mmHg to remove volatile matter, and the molten resin (A) was cooled to room temperature and recovered. This resin was dissolved in ethyl acetate so that the resin component would be 30% by weight, 1.15 times the amount of methanol and 0.75 times the amount of water of this solution were added, and the mixture was left standing after stirring. Then, the lower layer separated into two layers was taken out, concentrated and dried to collect the resin (A). This resin (Mw = 8800)
Let it be resin (A1).

Synthesis Example 2 m-cresol 86.5 g (0.80 mol) 2,3-xylenol 12.2 g (0.10 mol) 3,4-xylenol 12.2 g (0.10 mol) 40% glyoxal solution 50.8 g (glyoxal 0.35 mol) 37 wt% aqueous formaldehyde solution 48.7 g (formaldehyde 0.60 mol) dioxane 110.0 g , Resin (A) was recovered. This resin (Mw = 8500) is referred to as resin (A2).

Synthesis Example 3 m-cresol 48.6 g (0.45 mol) 2,3-xylenol 48.9 g (0.40 mol) 2,3,5-trimethylphenol 20.4 g ( 0.15 mol) 40% glyoxal solution 72.6 g (glyoxal 0.50 mol) 37% by weight aqueous formaldehyde solution 40.6 g (formaldehyde 0.50 mol) Propylene glycol monomethyl ether 118.0 g The same operation was performed to collect the resin (A). This resin (Mw = 8400) is referred to as resin (A3).

Synthesis Example 4 m-cresol 70.3 g (0.65 mol) 2,3-xylenol 24.4 g (0.20 mol) 2,3,5-trimethylphenol 20.4 g ( 0.15 mol) 40% glyoxal solution 50.8 g (glyoxal 0.35 mol) p-toluenesulfonic acid monohydrate 0.95 g (0.005 mol) Propylene glycol monomethyl ether 58.0 g After charging, the flask Was immersed in an oil bath, and polycondensation was performed for 150 minutes while stirring while refluxing the reaction solution. Furthermore, 1,3-dioxolane 51.9 g (formaldehyde 0.7 mol) propylene glycol monomethyl ether 86 g water 38 g were added, and polycondensation was further performed for 100 minutes. Then, the temperature of the oil bath was raised to 180 ° C., and at the same time, the pressure inside the flask was reduced to 30 to 50 mmHg to remove volatile components, and the molten resin (A) was cooled to room temperature and recovered. This resin was dissolved in ethyl acetate so that the resin component was 35% by weight, and washing with water was repeated until the aqueous layer became neutral. Further, the resin component was diluted with ethyl acetate so as to be 30% by weight, 1.05 times amount of methanol and 0.75 times amount of water of this solution were added, and the mixture was left standing after stirring. Then, the lower layer separated into two layers was taken out, concentrated and dried to collect the resin (A). This resin (Mw = 8800)
This is a resin (A4).

Synthesis Example 5 m-cresol 81.1 g (0.75 mol) 2,3,5-trimethylphenol 34.1 g (0.25 mol) 40% glyoxal solution 36.3 g (glyoxal 25 mol) p-toluenesulfonic acid monohydrate 0.95 g (0.005 mol) dioxane 58 g was charged, and then the flask was immersed in an oil bath, and the reaction solution was refluxed and polycondensed for 120 minutes while stirring. I went. Further, 1,3-dioxolane 59.3 g (formaldehyde 0.8 mol) dioxane 115 g water 43 g was added and polycondensation was further carried out for 100 minutes. Then, the same operation as in Synthesis Example 4 was carried out to obtain the resin (A ) Was recovered.
This resin (Mw = 8200) is referred to as resin (A5).

Synthesis Example 6 A flask equipped with a stirrer, a condenser and a thermometer was charged with m-cresol 118.9 g (1.1 mol) p-cresol 97.3 g (0.9 mol) 37% by weight formaldehyde aqueous solution 142 g. After charging 0.30 g (0.0024 mol) of oxalic acid dihydrate (1.75 mol of formaldehyde), the flask was immersed in an oil bath, and polycondensation was carried out for 90 minutes under stirring while refluxing the reaction solution. went. Next, the temperature of the oil bath was raised to 180 ° C., and at the same time, the pressure inside the flask was reduced to 30 to 50 mmHg to remove volatile components, and the molten resin was recovered. This resin was dissolved in ethyl acetate such that the resin component was 30% by weight, 0.95 times the amount of methanol and 0.75 times the amount of water of this solution were added, and the mixture was left to stand after stirring. Then, the lower layer separated into two layers was taken out, concentrated and dried to collect the resin (a). This resin (Mw = 8500) is referred to as resin (a1).

Synthesis Example 7 m-cresol 48.6 g (0.45 mol) p-cresol 59.5 g (0.55 mol) 40% glyoxal solution 72.6 g (glyoxal 0.50 mol) 37% by weight formaldehyde Aqueous solution 40.6 g (formaldehyde 0.50 mol) Resin (a) was recovered in the same manner as in Synthesis Example 1 except that 108 g of propylene glycol monomethyl ether was used. This resin (Mw = 8700) is referred to as resin (a2).

Examples 1 to 5 and Comparative Examples 1 and 2 Resins (A1) to (A5), (a1) to (a2), a photosensitizer (B), and a dissolution accelerator which were synthesized in the above synthesis examples as alkali-soluble resins. The agent and the solvent were mixed to form a uniform solution, which was then filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution having the composition shown in Table 1. Here, parts are based on weight.

The types of the photosensitizer (B), the dissolution accelerator and the solvent used here are as follows.

Quinonediazide compound (B1); Condensate of compound of formula (2-1) and 2 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride (B2); compound of formula (6-1) And 1,2-naphthoquinonediazide-5-sulfonyl chloride 3 mol condensate (B3); the compound of formula (7-1) and 1,2-naphthoquinonediazide-5-sulfonyl chloride condensate 2.5 mol (B4); Condensate of the compound represented by the formula (8-1) and 2.5 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride.

Dissolution accelerator (C1); compound represented by formula (2-2) (C2); compound represented by formula (9-1)

Solvent S1; ethyl 2-hydroxypropionate S2; ethyl 3-ethoxypropionate

[0109]

[Table 1]

A solution of each composition was applied on a silicon wafer using a spinner, and then prebaked for 2 minutes on a hot plate kept at 100 ° C. to a thickness of about 1.1 μm. Was formed. This resist film was exposed to i-line through a mask pattern and then baked after exposure. Then, it was developed with an alkali developing solution, washed, and dried to form a resist pattern, and the performance of each resist was evaluated based on the obtained resist pattern. Table 2 shows the evaluation results.

[0111]

[Table 2]

[0112]

The positive-type radiation-sensitive resin composition of the present invention is particularly excellent in focus acceptability, sensitivity, resolution, developability, etc., and also in heat resistance of the resulting resist and its pattern shape. It is one. Therefore, the positive-type radiation-sensitive resin composition of the present invention is extremely useful particularly as a positive-type resist for manufacturing integrated circuits, which is considered to be further integrated in the future.

Preferred embodiments relating to the positive radiation-sensitive resin composition of the present invention described in detail above will be additionally described below. 1. Use m-cresol and phenols (a) as phenol to obtain resin A by polycondensation reaction with aldehyde. 2. Use m-cresol and mixed phenols (b) as phenols for obtaining resin A by polycondensation reaction with aldehyde. 3. In the above item 2, the phenols (a) are present in an amount of 5 mol% or more in the mixed phenols (b). 4. In the above item 2, the phenols (a) are present in the mixed phenols (b) in an amount of 10 mol% or more. 5. Use aldehydes (a) as aldehydes to obtain resin A by polycondensation reaction with phenol. 6. Use mixed aldehydes (b) as aldehydes to obtain resin A by polycondensation reaction with phenol. 7. In the above 6, the mixed aldehydes (b) is a combination of aldehydes (a) and formaldehyde. 8. In 6 above, 5 mol% or more of aldehydes (a) are present in the mixed aldehydes (b). 9. In the above 6, the aldehydes (a) are present in the mixed aldehydes (b) in an amount of 10 mol% or more. 10. In the above 6, 10 to 90 mol% of the aldehyde (a) is present in the mixed aldehyde (b). 11. The proportion of m-cresol in all phenols used for obtaining resin A by polycondensation reaction with aldehyde is 5 to 95 mol%. 12. Aldehydes (a) are glyoxal, malonaldehyde, succinaldehyde or glutaraldehyde.

Claims (1)

[Claims] 1. (1) (i) m-cresol and (ii)
2,3-xylenol, 3,4-xylenol and 2,
At least one dimethyl or trimethylphenol selected from the group consisting of 3,5-trimethylphenol or this at least one dimethyl or trimethylphenol and other phenols (provided that m
-Excluding cresol) and (iii) the following formula (1) (In the formula (1), R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 10 carbon atoms. Group, substituted or unsubstituted polycycloalkylene group having 7 to 12 carbon atoms, 6 to 18 carbon atoms
Substituted or unsubstituted arylene group or having 8 to 8 carbon atoms
18 substituted or unsubstituted aralkylene groups,
Is 0 or 1. ), An alkali-soluble resin obtained by polycondensation of at least one aldehyde represented by the formula (1) or a combination of the at least one aldehyde and another aldehyde, and (2) a quinonediazite compound. Positive type radiation sensitive resin composition.