JPH07271037A - Positive ionization-sensitive radioactive resin composition - Google Patents

Abstract

PURPOSE:To reduce the contraction of film, to obtain a good resist profile, high resolution and a wide process latitude by incorporating at least one kind among alkali-soluble resin, a photo-acid generator and a specified compd. into the composition. CONSTITUTION:At least one kind among alkali-soluble resin, photo-acid generator and a compd. shown by formula I or II is incorporated into the composition. In the formulas I and II, each of R1 to R41 can be the same or different and is hydrogen atom, -X-Ra1 or -CN-OD0. In this case, the compd. shown by the formula I or II is obtained, for example, by allowing a polyhydroxy compd. as the compd. shown by the formula I or II where D0-D12=H to react with di-tert-butyl dicarbonate. Further, the three-component photosensitive composition consists essentially of a dissolution inhibitor, an alkali-soluble resin and a photo- acid generator.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an ultraviolet ray containing an alkali-soluble resin, a photoacid generator and a specific acid-decomposable alkali dissolution inhibitor (hereinafter, simply referred to as "dissolution inhibitor") compound, Deep UV, X-ray, electron beam, molecular beam, γ-ray,
The present invention relates to a positive-type ionizing radiation-sensitive resin composition that is sensitive to radiation such as synchrotron radiation, and more specifically to a positive-type ionizing radiation-sensitive resin composition having excellent stability, high sensitivity, and good resolving power. It is about things.
The ionizing radiation-sensitive resin composition according to the present invention is applied to a semiconductor wafer, or a substrate such as glass, ceramics, metal or the like by a spin coating method, a roller coating method or the like, for example, 0.3 to 30.
It is applied to a thickness of μm. After that, it is heated and dried, and a circuit pattern or the like is printed through an exposure mask by ultraviolet irradiation or the like and developed to obtain an image. Further, by etching this image as a mask, the substrate can be patterned. Typical fields of application are semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, lithographic printing plates, and other photo-ablation processes.

[0002]

2. Description of the Related Art As a positive photoresist composition,
Generally, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, as "novolac type phenolic resin / naphthoquinonediazide-substituted compound" in US Pat. No. 3,666,473, US Pat. No. 4,115,128 and US Pat. No. 4,173,470, etc.,
As the most typical composition, "Novolak resin consisting of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazide sulfonate" is an example of Thompson "Introduction to Microlithography" (LFThompson "Intr.
oduction to Microlithography ") (ACS Publishing, N
o. 219, p112-121). In such a positive photoresist composition basically consisting of a novolac resin and a quinonediazide compound, the novolak resin imparts high resistance to plasma etching, and the naphthoquinonediazide compound acts as a dissolution inhibitor. When naphthoquinonediazide is irradiated with light, naphthoquinone diazide forms a carboxylic acid and loses its ability to inhibit dissolution, thus increasing the alkali solubility of the novolak resin.

From this point of view, many positive photoresists containing novolac resin and naphthoquinonediazide type photosensitive material have been developed and put into practical use from the viewpoint of 0.8 μm.
We have achieved sufficient results in line width processing up to about 2 μm. However, the degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSI, it has become necessary to process ultrafine patterns having line widths of half micron or less. In order to achieve this required resolving power, the wavelength of the exposure apparatus used for photolithography has become shorter and shorter, and now far-ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) are being studied. ing. When a conventional resist composed of novolak and naphthoquinonediazide compound is used for pattern formation of lithography using far ultraviolet light or excimer laser light, light is strong in the far ultraviolet region of novolak and naphthoquinonediazide, and light reaches the bottom of the resist. It is hard to reach, and only a pattern with low sensitivity and taper can be obtained.

One of means for solving such a problem is
U.S. Pat.No.410,201, U.S. Pat.No.873,914, JP-A-59
-45439 and the like are chemically amplified resist compositions. A chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as far-ultraviolet light, and the acid-catalyzed reaction dissolves the active radiation irradiation area and non-irradiation area in the developing solution. It is a pattern-forming material that changes properties and forms a pattern on a substrate.

As such an example, a combination of a compound capable of generating an acid by photolysis with an acetal or O, N-acetal compound (JP-A-48-89003), or a combination of an orthoester or amide acetal compound ( JP-A-51-120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1).
No. 33429), a combination with an enol ether compound (JP-A-55-12995), and a combination with an N-acyliminocarbonate compound (JP-A-55-126236).
No.), a polymer having an orthoester group in the main chain (JP-A-56-17345), a combination with a tertiary alkyl ester compound (JP-A-60-3625),
Combination with silyl ester compound (JP-A-60-102)
47) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-121446).
Etc. can be mentioned. These have a quantum yield of 1 in principle, unlike the mechanism of action of conventional resists using a diazoketone or azide compound as a photosensitizer whose quantum yield does not exceed 1.
It shows high sensitivity because it exceeds.

Similarly, a system which is stable at room temperature over time but decomposes by heating in the presence of an acid to solubilize with an alkali is disclosed in, for example, JP-A-59-45439 and JP-A-60-3625. JP-A-62-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, Polym.Eng.Sce., 23, 101
2 (1983); ACS.Sym.242, 11 (1984); Semicond
uctor World 1987, November issue, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988), etc.
Mention may be made of systems of secondary or primary carbon (eg t-butyl, 2-cyclohexenyl) in combination with ester or carbonate compounds. These systems also have high sensitivity and, compared to the naphthoquinone diazide / novolak resin system, Deep-UV
Since the absorption in the region is small, it can be an effective system for shortening the wavelength of the light source.

The positive type chemically amplified resist is composed of an alkali-soluble resin, a compound which generates an acid upon exposure to radiation (photo-acid generator) and an alkali dissolution inhibitor compound.
Component system (European Patent No. 249,139, Japanese Patent Laid-Open No. 2-248953, etc.)
And a photoacid generator and a resin having a group that becomes alkali-soluble upon reaction with an acid (US Pat. No. 4,491,62).
No. 8, JP-A-59-45439, etc.).

A conventional chemically amplified resist (US Pat. No. 41
0,201, U.S. Patent No. 873,914, U.S. Patent No. 4,101,323
No., etc.) is insufficient in dissolution inhibiting property, so that the film loss is large and the resist profile is significantly deteriorated. Also,
Since the thermal stability is also poor, there is a problem that the resist film shrinks due to baking after exposure. In addition, the line width may change depending on the time from exposure to development, the atmosphere, etc.
However, there is a problem that the shape is deteriorated and the stability is poor, and neither has reached the practical level. However, the three-component system is a promising system because it has a wide range of selection of raw materials, and the development of an acid-decomposable alkali dissolution inhibitor compound having excellent dissolution inhibiting properties used in this system has been desired.

[0009]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to reduce the film shrinkage due to baking after exposure, to have a good resist shape profile, high resolution and a wide process latitude, and to perform from exposure to baking. It is an object of the present invention to provide a positive type ionizing radiation sensitive resin composition which has little performance deterioration due to time and atmosphere and has good performance stability.

[0010]

Means for Solving the Problems As a result of intensive investigations by the present inventors, taking into consideration the above-mentioned various characteristics, the object of the present invention is to find out that an alkali-soluble resin, a photo-acid generator and a general formula [A1] or [A1]. It has been found that the positive type ionizing radiation sensitive resin composition is characterized by containing at least one compound represented by B1].

[0011]

[Chemical 4]

R _{1 to} R ₄₁ : which may be the same or different and represent a hydrogen atom or --X--Ra ₁ , --CN, --OD ₀ , one of which is on the same benzene ring is of the general formula (A
It may be a group represented by ₁₂ ). Two of the same benzene ring may be bonded to each other to form a ring.

[0013]

[Chemical 5]

X _{1 to} X ₁₀ : single bond, carbonyl group, sulfide group, sulfonyl group or --C (R _b1 ).
Represents (R _b2 )-. However, X ₃ and X ₄ may be an alkylene group having 2 to 8 carbon atoms. X: single bond, -O-, -S-, -CO-, -OCO
_{-, - N (Ra 1)} CO- or -N (Ra ₂₎ - represents a. Ra ₁ : an alkyl group having 1 to 10 carbon atoms, an alkylene group,
It represents a cycloalkyl group, a haloalkyl group, an aryl group, an alkylaryl group or an aralkyl group. Ra _2: a hydrogen atom or represents a ra _1. R _b1 and R _b2 : each represents a hydrogen atom, a methyl group, an ethyl group or a haloalkyl group having 1 to 4 carbon atoms. R _b1 and R
_b2 may combine with each other to form an alicyclic hydrocarbon residue. When m = 0, at least one of R _b1 and R _b2 represents a group represented by formula (A ₁₂ ). D _{0 to} D ₁₂ : represent hydrogen atoms or D _inh, and at least two in the same molecule are not hydrogen atoms. Further, the following bond may be formed together with -OD ₀ group or -N (Ra ₂ ) (Ra ₁ ).

[0015]

[Chemical 6]

D _inh : represents a group represented by -Xi-Ri. Xi: single bond, -C (R _b1 ) (R _b2 )-, -C (R _b1 ).
(R _b2 ) O-, -CO-, -CS-, -COO-, -C
OS-, -C ( _Rb1 ) ( _Rb2 ) CO-, -C ( _Rb1 )
It represents (R _b2 ) COO-, -C (R _b1 ) (ORi)-or -CON (R _b1 )-. Ri: hydrogen atom, alkyl group having 1 to 20 carbon atoms, alkenyl group, cycloalkyl group having 3 to 20 carbon atoms, 6 carbon atoms
To 20 aryl groups, cumyl groups, adamantanetyl groups,
It represents a —Si (ZiR _b3 ) (ZiR _b4 ) (ZiR _b5 ) group, a tetrahydropyranyl group, a pyranyl group or a 1,3-dithiaindan-2-yl group. R _b3 , R _b4 , and R _b5 : each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, or an aryl group having 6 to 20 carbon atoms. Zi: represents a single bond or -O-. i, j, k, m, n ₁ , n ₂ , w, y: 0 or 1 respectively.

The present invention will be described in detail below.

The compound represented by the general formula [A1] or [B1] of the present invention is described by J. Frechet et al. [POLYMER vol.
August, p995 (1983)] and the like, for example, in the presence of a basic catalyst, a compound represented by the general formula [A1] or [B1] having a polyhydroxy compound of D _{0 to} D ₁₂ = H and a di-hydroxy compound. ter
It can be obtained by reacting t-butyl dicarbonate.

The three-component positive photosensitive composition of the present invention comprises
Basically, it consists of a dissolution inhibitor, an alkali-soluble resin and a photo-acid generator. The dissolution inhibitor has the function of suppressing the solubility of the alkali-soluble resin in alkali, deprotecting the acid-decomposable group by the acid generated upon exposure, and conversely promoting the solubility in alkali. JP-A-63-27,829 and JP-A-3-198,059 disclose dissolution inhibitors having naphthalene, biphenyl and diphenylcycloalkane as a skeletal compound, but film shrinkage after baking, profile, resolution and performance stability Is not enough.

The main component of the dissolution inhibitor of the present invention is selected from the compounds represented by the above general formula [A1] or [B1]. These compounds have a group capable of decomposing with an acid in the structure. A compound having at least 2 and having at least 11, preferably at least 12 and more preferably at least 13 bond atoms excluding the acid-decomposable group at the position where the distance between the acid-decomposable groups is the longest. Is. The number of acid-decomposable groups contained in one molecule of these compounds is preferably 2 to 20, more preferably 3 to 15, and particularly preferably 3 to 10. The number of acid-decomposable groups in one molecule is 2
If it is less than the number, sufficient dissolution inhibiting properties cannot be obtained. When the number of acid-decomposable groups in one molecule exceeds 20, the amount of acid-decomposable groups required to release the dissolution suppressing effect in the exposed area is too large, and sufficient dissolution discrimination is achieved. Can't get Further, when a volatile component is generated by the decomposition reaction of the acid-decomposable group, if the number of acid-decomposable groups in one molecule is too large, the film shrinkage of the exposed portion after PEB (post-exposure bake) becomes large, which is preferable. Absent. Further, in D _{0 to} D ₁₂ of the compound represented by the general formula [A1] or [B1], when the unprotection ratio is defined as α = H / (H + D _inh ), the resist performance stability, the resist From the viewpoint of shape and high sensitivity, α
Is preferably 0.1 to 0.8, more preferably 0.2 to
0.7 is preferred. Particularly, a compound having α of 0.3 to 0.6 is preferable. If α is too small, stability of resist performance, resist shape, sensitivity and the like are deteriorated, and further, deterioration of performance due to time from exposure to baking and atmosphere is increased.
On the other hand, if it is too large, the dissolution inhibiting ability deteriorates and the resolution decreases. Also, the preferable upper limit of the number of bond atoms is 50,
More preferably, it is 40.

In the present invention, when the dissolution inhibiting compound has three or more acid-decomposable groups, preferably four or more, even when it has two acid-decomposable groups, the acid-decomposable groups have each other. When it is separated by a certain distance or more, the dissolution inhibiting property for the alkali-soluble resin is remarkably improved. The distance between acid-decomposable groups in the present invention is indicated by the number of via bond atoms excluding acid-decomposable groups. For example, in the following compounds (a) and (b), the distance between the acid-decomposable groups is 4 bonding atoms each, and in compound (c) the bonding atom 12
It is an individual.

[0022]

[Chemical 7]

The dissolution inhibiting compound of the present invention may have a plurality of acid decomposable groups on one benzene ring, but preferably one acid decomposable group on one benzene ring. Compounds composed of a skeleton having are preferred. Further, the dissolution inhibiting compound of the present invention has a molecular weight of 3,000 or less,
Preferably 500 to 3,000, more preferably 700
~ 2,500.

In the compound represented by the general formula [A1] or [B1], R ^{1 to} R ⁴ ₁ may be the same or different and may be a hydrogen atom or -X-Ra ₁ , -CN,-. Representing OD ₀ , one on the same benzene ring may be a group represented by the general formula (A ₁₂ ), and two on the same benzene ring may be bonded to each other to form a ring. Although it may be formed, a hydrogen atom, —X—Ra ₁ , or —OD ₀ is preferable from the viewpoint of dissolution inhibiting ability, performance stability, production suitability, etc., and particularly, a hydrogen atom, —X—Ra ₁ (ring May be formed).

X _{1 to} X ₁₀ are a single bond, a carbonyl group, a sulfide group, a sulfonyl group or --C (R _b1 ).
(R _b2 )-, and X ₃ and X ₄ may be an alkylene group having 2 to 8 carbon atoms, but from the viewpoint of resist shape, production suitability and the like, a single bond, a sulfide group or —C (R _b1 )
(R _b2 ) _-is preferable, particularly a single bond and —C (R _b1 ).
(R _b2 ) _-is preferable.

X is a single bond, --O--, --S--, --CO--,
-OCO-, -N (Ra ₁ ) CO-, and -N (Ra ₂ )-are shown, but in view of dissolution inhibiting ability, performance stability, production suitability, etc., a single bond, -O-, -S-, -CO-, -OCO-,
-N (Ra ₂₎ - are preferred, a single bond, -O- is preferable.

Ra ₁ represents an alkyl group having 1 to 10 carbon atoms, an alkylene group, a cycloalkyl group, a haloalkyl group, an aryl group, an alkylaryl group or an aralkyl group. From the viewpoint of production suitability and the like, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms are preferable,
Particularly, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, and a phenyl group are preferable. Ra ₂ represents a hydrogen atom or Ra ₁ .

R _b1 and R _b2 each represent a hydrogen atom, a methyl group, an ethyl group or a haloalkyl group having 1 to 4 carbon atoms,
R _b1 and R _b2 may combine with each other to form an alicyclic hydrocarbon residue, and when m = 0, at least one of R _b1 and R _b2 is represented by the general formula (A ₁₂ ). The group represents a hydrogen atom, a methyl group, a haloalkyl group having 1 to 2 carbon atoms, and an alicyclic hydrocarbon residue having R _b1 and R _b2 bonded to each other, from the viewpoints of sensitivity, performance stability, production suitability, and the like. Are preferred, and in particular, a hydrogen atom, a methyl group, a trifluoromethyl group and C, respectively.
A 1,1-cyclohexylene group in which (R _b1 ) and R _b2 are bonded is preferable.

D₀~ D₁₂Is a hydrogen atom or D_inhThe table
However, at least two in the same molecule are not hydrogen atoms.
Preferably, from the viewpoint of dissolution suppression efficiency, D₁, D₃, D_Five,
D₆, D ₁₂Is D_inhIs. D_inhIs represented by -Xi-Ri
Represents a group₀The base is -N (Ra₂) (Ra ₁)When
Together, the following bonds may be formed.

[0030]

[Chemical 8]

Xi is a single bond, -C (R_b1) (R_b2)-,
-C (R_b1) (R_b2) O-, -CO-, -COO-,-
CS-, -COS-, -C (R_b1) (R_b2) CO-,-
C (R_b1) (R_b2) COO-, -C (R_b1) (ORi)
-, -CON (R_b1)-, Ri is a hydrogen atom or carbon
Number 1 to 20 alkyl group, alkenyl group, carbon number 3 to 2
A cycloalkyl group having 0, an aryl group having 6 to 20 carbon atoms,
Cumyl group, adamantantyl group, -Si (ZiR_b3)
(ZiR_b4) (ZiR_b5) Group, tetrahydropyranyl
Group, pyranyl group, 1,3-dithiaindan-2-yl group
Represents sensitivity, dissolution inhibiting ability, performance stability, manufacturing suitability, etc.
From the viewpoint of, Xi is a single bond, -C (R_b1) (R _b2) O
-, -CO-, -COO-, -C (R_b1) (R_b2) CO
-, -C (R_b1) (R_b2) COO-, -CON (R_b1)
-, Ri is an alkyl group having 1 to 10 carbon atoms, an allyl group,
C3-C10 cycloalkyl group, C6-C10
Aryl group, cumyl group, adamantane group, -Si
(ZiR_b3) (ZiR_b4) (ZiR_b5) Group, tetrahydr
A lopyranyl group is preferred, and Xi is a single bond, -C
OO-, -C (R_b1) (R_b2) CO-, -C (R_b1)
(R_b2) COO-, Ri is alkyl having 3 to 6 carbon atoms
Group, cycloalkyl group having 3 to 6 carbon atoms, phenyl group,
Silyl group, toluyl group, cumenyl group, naphthyl group, kumi
Group, adamantane group, -Si (ZiR_b3) (Zi
R_b4) (ZiR_b5) Groups, tetrahydropyranyl groups are preferred
Good

R_b3, R_b4, R_b5Is 1 to 2 carbon atoms
0 alkyl group, cycloalkyl group, alkenyl group, charcoal
Represents an aryl group having a prime number of 6 to 20, Zi is a single bond or-
Represents O-, but sensitivity, dissolution inhibiting ability, resist shape, manufacturing
R from the viewpoint of suitability_b3, R _b4, R_b5Is the number of carbon
1-8 alkyl group, cycloalkyl having 3-6 carbon atoms
Groups, alkenyl groups and aryl groups having 6 to 10 carbon atoms are preferred.
Specifically, especially, an alkyl group having 1 to 4 carbon atoms and charcoal, respectively.
Cycloalkyl group, allyl group, phenyl having 5 to 6 primes
Group, xylyl group, toluyl group, cumenyl group, naphthyl group
Is preferred.

The specific acid-decomposable group represented by -Xi-Ri is preferably acid-decomposable efficiency, dissolution inhibiting ability,
From the viewpoint of developability, suitability for production, etc., a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, a tertiary alkyl ester group, It is a tertiary alkyl carbonate group or the like.
More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

When D ₁ , D ₃ , D ₅ , D ₆ and D ₁₂ are D _inh , the dissolution inhibiting efficiency of the acid-decomposable alkali dissolution inhibitor of the present invention is remarkably improved, and from exposure to baking. The performance deterioration due to time and atmosphere is reduced, which is preferable. In the compound represented by the general formula [A1] or [B1], R
_{Among 1 to} R ₄₁ , the case where two or more of those on the same benzene ring are bonded to each other to form at least one ring structure is preferable because the hydrophobicity of the dissolution inhibitor and the dissolution inhibition ability are excellent. . The ring structure is preferably a cycloalkyl ring or an aromatic ring, and particularly, the ring structure has 4 to 4 carbon atoms.
The case of 10 cycloalkyl rings is preferable. i,
j, k, m, n ₁ , n ₂ , w and y each represent 0 or 1, but i, n ₁ and w are from the viewpoints of developability, performance stability, dissolution inhibiting ability, production suitability and the like. 0, m, n ₂ and y are preferably 1, and i, j, n ₁ and w are 0, m,
n ₂ and y are preferably 1.

The following compounds can be exemplified as specific examples of the dissolution inhibitor of the present invention, but the present invention is not limited thereto. Here, D represents the same group as D _{0 to} D ₁₂ .

[0036]

[Chemical 9]

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

[0051]

[Chemical formula 24]

[0052]

[Chemical 25]

[0053]

[Chemical formula 26]

[0054]

[Chemical 27]

[0055]

[Chemical 28]

[0056]

[Chemical 29]

[0057]

[Chemical 30]

[0058]

[Chemical 31]

[0059]

[Chemical 32]

Examples of the alkali-soluble resin used in the present invention include novolac resin, acetone-pyrogallol resin, acetone-resole resin, polyhydroxystyrene (poly (p-hydroxystyrene), poly (m-hydroxystyrene) and poly ( o-hydroxystyrene)), 3
Hydroxystyrene copolymer containing at least one hydroxystyrene monomer selected from among p-, m-, and o-hydroxystyrene monomers, halogen- or alkyl-substituted polyhydroxystyrene or polyhydroxystyrene copolymer, maleimide Copolymer, N
-Hydroxyphenylmaleimide copolymer, maleic anhydride copolymer, carboxyl group, sulfonyl group, lactone group, phosphonic acid group or phenolic hydroxyl group-containing resin, the main chain and side chains are decomposed by the action of acid, alkali Examples thereof include, but are not limited to, resins having a group that becomes soluble, and derivatives thereof, and partial hydrides thereof, or partial O-alkylated products or O-acylated products thereof. . Particularly preferred alkali-soluble resins are novolac resins, polyhydroxystyrene, copolymers containing hydroxystyrene and halogen- or alkyl-substituted polyhydroxystyrene or polyhydroxystyrene copolymers, decomposed into the main chain and side chains by the action of acid. And an alkali-soluble resin having a group that becomes alkali-soluble, as well as a partial hydride, a partial O-alkyl compound, or an O-acyl compound of the above resin.

The novolac resin is obtained by addition-condensing aldehydes in the presence of an acidic catalyst, with a predetermined monomer as a main component.

As the predetermined monomer, phenol, m
-Cresol, p-cresol, o-cresol and other cresols, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol and other xylenols, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-
Alkoxyphenols such as methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxyphenol, 2-methyl-4-isopropylphenol. Bisalkylphenols such as m-chlorophenol, p-
Hydroxy aromatic compounds such as chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol and naphthol, or JP-A-2-248954, JP-A-3-200252, 3-200254, JP-A-200254. 4-1650, JP-A-4-12356,
JP4-211257A, JP4-251849A, EP 0,35
The polyhydroxy aromatic compounds described in US Pat. No. 8,871, US Pat. No. 5,130,225 and the like can be used alone or in combination of two or more, but are not limited thereto.

The aldehydes include, for example, formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde. , O-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and acetals thereof such as chloroacetaldehyde diethyl acetal can be used, and of these, formaldehyde is preferably used. These aldehydes are
They may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or the like can be used.

Action of acid on main chain and side chain used in the present invention
Decomposition with an acid in a resin having a group
Preferred groups that can be used are chain acetal and ON.
-Acetal, silyl ether bond and the acid-decomposable acetic acid
OD of Lucari dissolution inhibiting compound _inhIs the same as. Minutes with acid
As the base resin when the solvable group is bonded as a side chain
Is an alkenyl having a —OH or —COOH group in its side chain.
Re-soluble resins are preferred, for example, novolac resins and
Cetone-pyrogallol resin, acetone-resole resin,
Polyhydroxystyrene, hydroxystyrene copolymerization
Body, halogen- or alkyl-substituted polyhydroxys
Tylene or polyhydroxystyrene copolymer, male
Imide copolymer, N-hydroxyphenylmaleimide copolymer
Polymer, maleic anhydride copolymer, carboxyl group, sulfur
Rufonyl group, lactone group, phosphonic acid group or phenol
Resins containing a hydroxyl group and their derivatives, and
Partial hydrides of the resins mentioned in 1.
Fluoride or O-acyl compound can be mentioned.
The alkali dissolution rate of these base resins is 0.261N
Tramethylammonium hydroxide (TMA
H) measured (23 ° C) and 10A / sec or more is preferable
Good More preferably 100 A / sec or more, particularly preferably
Is 200 A / sec or more (A is Angstrom
Mu). The content of the acid-decomposable group depends on the base resin.
Alkali-soluble group contained (for example, -OH group or -COO
It is preferable that the H group) remains at 50 mol% or more. Further
Preferably 70 mol%, particularly preferably 80 mol% or more
It remains. The remaining amount of alkali-soluble groups is
If it is less than 50 mol%, the sensitivity is reduced, the film is shrunk, and the film is adhered to the substrate
Defects and properties depending on time and atmosphere from exposure to baking
It is not preferable because of deterioration of performance.

The weight average molecular weight of the alkali-soluble resin used in the present invention is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed area after development is large, and if it exceeds 30,000, the developing speed becomes low and the sensitivity and resolution are insufficient. Particularly preferred is the range of 2,000 to 20,000. here,
The weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

In the present invention, the general formula [A1] or [B
1] and the alkali-soluble resin are used in an amount of 3 to 100 parts by weight, preferably 5 to 100 parts by weight of the compound represented by the general formula [A1] or [B1]. 60 parts by weight. If the use ratio is less than 3 parts by weight, the residual film rate is significantly reduced,
If it exceeds the weight part, the sensitivity of the resist is lowered and the resolution is also deteriorated. In addition, heat resistance and dry etching resistance decrease.

The photo-acid generator used in the present invention is used as a photo-initiator for photo-cationic polymerization, a photo-initiator for photo-radical polymerization, a photo-decoloring agent for dyes, a photo-discoloring agent, or a micro resist. Known compounds that generate an acid upon irradiation with ionizing radiation and mixtures thereof can be appropriately selected and used. For example SISchlesinger, Photo
gr.Sci.Eng., 18,387 (1974), TSBal etal, Polymer, 21,
423 (1980) etc., diazonium salt, U.S. Pat.
No. 9,055, No. 4,069,056, No. Re 27,992, Japanese Patent Application No. 3-14
Ammonium salts described in No. 0,140, DC Necker et al, M
acromolecules, 17,2468 (1984), CSWen et al, Teh, Pro
c.Conf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, phosphonium salts described in 4,069,056, JVCrivello et al, Macromorecules, 10 (6), 130
7 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201,
JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, JVCrivello et al, Polymer J. 17,73 (198
5), JVCrivello et al. J. Org. Chem., 43, 3055 (1978),
WRWatt et al, J. Polymer Sci., Polymer Chem. Ed., 22,1
789 (1984), JVCrivello et al, Polymer Bull., 14,279
(1985), JVCrivello et al, Macromorecules, 14 (5), 114
1 (1981), JVCrivello et al, J. Polymer Sci., Polymer C
hem.Ed., 17,2877 (1979), European Patent 370,693, and 3,9.
02,114, 233,567, 297,443, 297,442, U.S. Pat.Nos. 4,933,377, 4,760,013, 4,734,444
No., No. 2,833,827, No. 4,734,444, No. 4,760,013,
Dokoku Patent Nos. 2,904,626, 3,604,580 and 3,604,581
No. 295,421, 3,924,299, JP-A-64-26550,
JP 2-6503 A, JP 4-11626 A, JP 2-199177 A
Sulfonium salts described in JP-A 2-6503, J.
V.Crivello et al, Macromorecules, 10 (6), 1307 (1977),
JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed.,
17,1047 (1979) and other selenonium salts, CSWen eta
l, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct (198
8) Onium salts such as arsonium salts described in

US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605
JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63-70243
No., organic halogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), TP
Gilletal, Inorg.Chem., 19,3007 (1980), D.Astruc, Acc.C
hem.Res., 19 (12), 377 (1896), JP-A-2-61445, JP-A-4-136941, JP-A-4-219755, JP-A-4-367865,
JP-A-4-338757, JP-A-5-197150, JP-A-5-303196
No. 5-313370, No. 5-341522, No. 5-28
1729, organic metal / organic halides described in JP-A-6-3824, S. Hayase et al, J. Polymer Sci., 25, 753 (198
7), E. Reichmanis et al, J. Pholymer Sci., Polymer Chem.
Ed., 23, 1 (1985), QQZhu et al., J. Photochem., 36, 85, 39,
317 (1987), B. Amit et al, Tetrahedron Lett., (24) 2205 (1
973), DHR Barton et al, J. Chem Soc., 3571 (1965), PM
Collins et al, J. Chem. SoC., Perkin I, 1695 (1975), M. Rud
instein et al, Tetrahedron Lett., (17), 1445 (1975), J.
W. Walker et al. J. Am. Chem. Soc., 110, 7170 (1988), SCBus
man etal, J. Imaging Technol., 11 (4), 191 (1985), HMHo
ulihan et al, Macormolecules, 21,2001 (1988), PMColli
ns etal, J.Chem.Soc., Chem.Commun., 532 (1972), S.Hayas
e etal, Macromolecules, 18, 1799 (1985), E. Reichmanis e
tal, J.Electrochem.Soc., Solid State Sci.Technol., 13
0 (6), FMHoulihan et al, Macromolcules, 21, 2001 (198
8), European Patent Nos. 0290,750, 046,083, 156,535
No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,71
0, 4,181, 531, JP-A-60-198538, JP-A-53-13
3022, etc., a photoacid generator having a 0-nitrobenzyl type protecting group, a compound, as described in US Pat. No. 5,204,217, which undergoes photolysis to generate a carboxylic acid,

M.TUNOOKA et al, Polymer Preprints Japa
n, 35 (8), G.Berner et al, J.Rad.Curing, 13 (4), WJMijs
et al, Coating Technol., 55 (697), 45 (1983), Akzo, H. Adac
hietal, Polymer Preprints, Japan, 37 (3), European Patent 0,1
99,672, 845,15, 044,115, 0101122,
383,343, 537,879, 571,330, U.S. Pat.No. 4,6
18,564, 4,371,605, 4,431,774, JP 64-1
8143, JP2-245756, JP3-223864, JP3-223865, JP3-245756, JP4-314055,
Japanese Patent Laid-Open No. 5-197149, Japanese Patent Publication No. 5-70814, Japanese Patent Application No. 3-140109
Compounds that generate sulfonic acid by photolysis as described in No.
JP 61-166544, JP 2-71270, JP 5-210239
Disulfone compounds described in JP-A-3-71139, JP-A-4-210960, JP-A-4-217249, JP-B-3-5739,
Japanese Patent Publication No. 3-6495, U.S. Patent Nos. 4,735,885 and 4,808,512
No. 4,902,784, 5,039,596, 5,171,656,
5,182,185, 5,158,855, 5,256,517, European Patents 378,068, 417,556, 417,557, 440,3
Examples thereof include diazo compounds described in No. 75, No. 552,548 and German Patent No. 4,014,649.

Further, 1,2-naphthoquinonediazide-5, which is a known aromatic or aliphatic polyhydroxy compound, is used.
(And / or -4-) sulfonic acid ester compound, for example, Japanese Patent Publication No. 56-2333, Japanese Patent Publication No. 62-3411, Japanese Patent Publication No. 3293
JP-B 3-42656, JP-A-58-150948, JP-A-60-1
54249, JP60-134235, JP62-10646, JP62-153950, JP60-146234, JP62-178562.
JP, 63-113451, 64-76047, 1-1
47538, JP 1-189644, JP 1-309052, JP 2-19846, JP 2-84650, JP 2-72363, JP 2-103543, JP 2-285351. No. 2-296248
JP-A-2-296249, JP-A-3-48251, JP-A-3-482
49, JP-A-3-119358, JP-A-3-144454, JP-A-3-
185447, Japanese Patent Laid-Open No. 4-1652, Japanese Patent Laid-Open No. 4-60548, Japanese Patent Laid-Open No. 5
-158234, JP-A-5224410, JP-A-5-303198, JP-A-5297580, JP-A-5-323597, and Japanese Patent Application No. 5-251781.
Japanese Patent Application No. 5-251780, Japanese Patent Application No.5-233537, U.S. Patent No.
4,797,345, 4,957,846, 4,992,356, 5,15
1,340, 5,178,986, European Patent Nos. 530,148, 57
The compound described in 3,056 etc. can be mentioned.

Further, European Patent Nos. 342,494 and 342,495.
No. 64-35433, No. 2-18564, No. 4-199
A compound containing both an acid-decomposable group and a photoacid-generating group as described in JP-A-152-152, JP-A-4-355760 and JP-A-5-181264 may be used.

Further, a group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer, such as ME Woodhouse et al., J. Am. Chem. Soc., 1
04,5586 (1982), SPPappas et al, J. Imaging Sci., 30
(5), 218 (1986), S. Kondo et al, Makromol. Chem., Rapid C.
ommun., 9,625 (1988), Y.Yamada et al, Makromol.Chem., 1
52,153,163 (1972), JVCrivello et al, J. PolymerSci.,
Polymer Chem. Ed., 17,3845 (1979), U.S. Pat.No. 3,849,1
37, Dokoku Patent No. 3914407, JP-A-63-26653, JP-A-5
5-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-14602
The compounds described in No. 9 and the like can be used.

Further, VNR Villai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712 and the like which generate an acid by light can also be used.

Among the compounds which decompose when exposed to actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (XI
I) or an oxazole derivative represented by the general formula (XI
S-triazine derivative represented by II).

[0075]

[Chemical 33]

In the formula, R ¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group or —CY 3. Y represents a chlorine atom or a bromine atom. The following compounds can be specifically mentioned, but the compounds are not limited thereto.

[0077]

[Chemical 34]

[0078]

[Chemical 35]

[0079]

[Chemical 36]

(2) An iodonium salt represented by the following general formula (XIV) or a sulfonium salt represented by the general formula (XV).

[0081]

[Chemical 37]

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group and a halogen atom.

R ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and a substituted derivative thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for the aryl group, and an alkyl group for the alkyl group. An alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

Z ^- represents a counter anion, for example B
_{^{F 4 -, AsF 6 -,}} PF 6 -, SbF 6 -, SiF 6 -, ClO
_{^{4 -, CF 3 SO 3 -}} , BPh 4 -, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion,
Examples thereof include anthraquinone sulfonate anion and sulfonate group-containing dyes, but are not limited thereto.

Two of R ³ , R ⁴ and R ⁵ and A
r ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0087]

[Chemical 38]

[0088]

[Chemical Formula 39]

[0089]

[Chemical 40]

[0090]

[Chemical 41]

[0091]

[Chemical 42]

[0092]

[Chemical 43]

[0093]

[Chemical 44]

[0094]

[Chemical formula 45]

[0095]

[Chemical formula 46]

[0096]

[Chemical 47]

[0097]

[Chemical 48]

[0098]

[Chemical 49]

The onium salts represented by the general formulas (XIV) and (XV) are known, and for example, JWKnapczyk eta.
l, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok et al., J.
Org.Chem., 35,2532, (1970), E.Goethas et al, Bull.So
c.Chem.Belg., 73,546, (1964), HMLeicester, J.Ame.Ch
em.Soc., 51,3587 (1929), JVCrivello et al, J.Polym.C
hem. Ed., 18, 2677 (1980), US Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

(3) A disulfone derivative represented by the following general formula (XVI) or an iminosulfonate derivative represented by the general formula (XVII).

[0101]

[Chemical 50]

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenyl group, or arylene group. Specific examples include the compounds shown below, but the invention is not limited thereto.

[0103]

[Chemical 51]

[0104]

[Chemical 52]

[0105]

[Chemical 53]

[0106]

[Chemical 54]

[0107]

[Chemical 55]

The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.01 to 100 based on the total weight of the ionizing radiation-sensitive resin composition (excluding the coating solvent). It is used in the range of wt%, preferably 0.1 to 50 wt%. If the amount of the photo-acid generator is less than 0.01% by weight, it is difficult to obtain a sufficient pattern forming ability, and if it exceeds 100% by weight, the sensitivity and pattern shape are deteriorated and the developability is also deteriorated. These photo-acid generators may be used alone or in combination of two or more.

If necessary, the ionizing radiation-sensitive resin composition of the present invention further comprises a dissolution inhibitor, a dissolution accelerator, an acid crosslinking agent, and
Adhesion aids, light absorbers, storage stabilizers, plasticizers, surfactants,
Various compounding agents such as photosensitizers can be added.

Examples of the dissolution inhibitor include, for example, European Patent No. 47.
5,903, 558,272, 541,112, 535,653,
249,139, 520,654, U.S. Pat.No. 4,250,247,
5,015,554, 5,204,216, 5,210,003, 5,20
0,529, 5,081,001, German Patent 4,143,081,
4,207,263, acid-decomposable low molecular weight dissolution inhibiting compounds described in 4,005,212 and the like, or, for example, European Patent No. 472,290.
No. 553,737, U.S. Pat.Nos. 5,258,257, 5,120,63
No. 3, No. 4,931,379, No. 4,912,018, No. 4,962,171,
Resins described in JP-A-62-229242, JP-A-63-36240 and the like can be mentioned.

The dissolution accelerator which may be used in the ionizing radiation-sensitive resin composition of the present invention is added in order to accelerate and control the alkali solubility. As such a dissolution accelerator, a benzene ring or Examples include phenolic compounds or heterocyclic compounds having about 2 to 6 heterocycles. For example, 2,3,4-trihydroxybenzophenone, 2,
3,4,4′-tetrahydroxybenzophenone, bisphenol A, tris (4-hydroxyphenyl) methane, 1,1-bis (hydroxyphenyl) cyclohexane or JP-A-2-248954, JP-A-3-200252, Kohei
3-200254, JP 4-1650, JP 4-12356, JP 4-211257, JP 4-251849, European Patent No. 0,358,87
1, polyhydroxy aromatic compounds described in U.S. Pat. No. 5,130,225, etc., methylbenzotriazole, indazole, quinazoline described in JP-B-48-12242, etc.
56-19619 and the like hydantoin, sulphimide benzoate, urasol, barbituric acid, alloxan, maleimide and other heterocyclic compounds described in JP-A-61-219951, JP-A-52- Nicotinic acid, picric acid, coumaric acid described in 40125 etc. and polyhydric alcohols such as triethylene glycol described in JP-A-57-201229 etc., alone or in combination of two or more kinds. Can be used.
These dissolution accelerators are usually used in a proportion of 50% by weight or less, preferably 30% by weight or less, based on the resin.

A light absorber may be added to the ionizing radiation-sensitive resin composition of the present invention for the purpose of preventing halation from the substrate and enhancing the visibility when applied to a transparent substrate. Examples of light absorbers include industrial dye technology and market (CMC Publishing)
And compounds described in the Handbook of Dyes (Organic Synthetic Chemistry Association), etc.,
For example, C.I. I. Disperse Yellow-1, 3, 4,
5,7,8,13,23,31,49,50,51,5
4,56,60,64,66,68,79,82,8
8, 90, 93, 102, 114, 124, C.I. I. Disperse Orange 1, 5, 13, 25, 29, 30,
31, 44, 57, 72, 73, C.I. I. Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 5
4, 58, 65, 72, 73, 88, 117, 137,
143, 199, 210, C.I. I. Disperse Bioet 43, C.I. I. Disperse Bull-96, C.I.
I. Optical brightener 112, 135, 163, C.I. I. Solvent Yellow-14, 16, 33, 56, C.I. I. Solvent Orange 2,45, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 49, C.I. I.
Pigment Green 10, C.I. I. Pigment Brown 2 and the like can be preferably used.

Furthermore, the photosensitive composition of the present invention can be obtained by adding a spectral sensitizer as described below and sensitizing it to a longer wavelength region than far ultraviolet where the photo-acid generator used does not have absorption. Sensitivity can be imparted to the i or g line. Examples of suitable spectral sensitizers include benzophenone,
p, p'-tetramethyldiaminobenzophenone, p,
p'-tetraethylethylaminobenzophenone, 2-
Chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline,
N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,
9-benzanthrone, dibenzalacetone, 1,2-
Naphthoquinone, 3,3'-carbonyl-bis (5,7-
Dimethoxycarbonylcoumarin), 9,10-phenanthrenequinone, camphor-quinone, thiomihira-ketone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 2,4-diethyl. Thioxanthone, 2,
4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, coronene and the like, but not limited thereto.

An acid crosslinking agent is added to the positive-type ionizing radiation-sensitive resin composition of the present invention for the purpose of adjusting sensitivity, improving heat resistance, improving dry etching resistance, etc. within a range that does not affect positive image formation. Good. Examples of the cross-linking agent include JP-A-59
-113435, JP-A-60-263143, JP-A-62-164045,
JP-A-3-75652, JP-A-5-45879, JP-A5-224420 and the like, melamine-modified compounds, benzoguanamine, aldehyde-modified compounds such as glycolurils, JP-A-1-
No. 293338, epoxy compounds described in JP-A-3-125543, JP-A-3-185449, aldehyde compounds described in JP-A-4-143761, JP-A-3-107162, JP-B-523429, etc. The polymerizable group-containing compound described in U.S. Pat. No. 5,019,481
German Patent No. 4,038,711, Japanese Patent Laid-Open No. 5-45878, Japanese Patent Laid-Open No.
Methylol derivative compounds described in No. 5-134412, etc.
1-49932, Resole resin compounds described in British Patent No. 2,082,339, etc., oxazoline or oxazine compounds described in JP-A No. 5-281715, JP-A No. 2-154266, JP-A No. 2-17
Compounds containing silanol groups described in JP-A No. 3647, JP-A-63-1
And the azide compounds described in No. 91142 and the like. These cross-linking agents are added in an amount of 0.0001 to the alkali-soluble resin.
It is used in a proportion of 10 to 10% by weight, preferably 0.001 to 5% by weight.

The ionizing radiation sensitive resin composition of the present invention comprises
Many proposals have been made so far in order to improve the so-called "delay effect" in which the line width changes depending on the time from exposure to development and the atmosphere, and the pattern shape deteriorates, resulting in poor stability. Additives can be applied arbitrarily. Examples of the storage stabilizer for improving the delay effect include, for example, JP-A-63-149640, JP-A-3-241354, and JP-A-5-232706.
Basic compounds described in JP-A-5-249683 and JP-A-6-11835, and inclusion compounds described in JP-A-5-165219 and JP-A-5173333, or JP-A-63- 149639, JP 4
-248554 etc. are mentioned.

Further, if necessary, a photobase generator, a thermal base generator, etc. may be added. Examples thereof include compounds such as benzoylcyclohexyl carbamate and triphenyl methanol described in JP-A-4-16040, and thermal base generators described in JP-A-5-158242.

The ionizing radiation sensitive resin composition of the present invention comprises
An adhesion aid may be added to improve the adhesion between the substrate and the resist. For example, JP-A-51-52002, JP-A-51-52002
53-39115 and the like methyldiphenylchlorosilane,
Silane compounds such as dimethylvinylethoxysilane, hexamethyldisilazane, 3-aminopropyltriethoxysilane, benzotriazolcarboxylic acids described in JP-A-62-262043, urea compounds described in JP-A-2-84654, etc. , Thiourea compounds, arylamine compounds and the like. These adhesion aids are usually used in a proportion of 10% by weight or less, preferably 5% by weight or less, based on the alkali-soluble resin.

The ionizing radiation sensitive resin composition of the present invention comprises
A surfactant can be added for the purpose of improving the coatability. Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene nonylphenyl ether, and other polyoxyethylene ethers and polyoxyethylene polyether. Oxypropylene block copolymer
, Sorbitan monostearate, sorbitan fatty acid esters such as sorbitan trioleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan trioleate, etc. Polyoxyethylene sorbitan fatty acid esters, F-top EF301, EF3
03, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Fluoride FC430, FC431 (Sumitomo 3M Co., Ltd.)
Made), Asahi Guard AG710, Surflon S-38
2, SC101, SC102, SC103, SC106
(Asahi Glass Co., Ltd.) and other fluorochemical surfactants, organosiloxane polymer-KP341 (Shin-Etsu Chemical Co., Ltd.)
Manufactured), acrylic acid-based or methacrylic acid-based (co) polymerized polymer No. 75, no. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. The blending amount of these surfactants is 10% by weight of the alkali-soluble resin in the composition of the present invention.
It is usually 2 parts by weight or less, preferably 1 part by weight or less, based on 0 parts by weight.

The ionizing radiation sensitive resin composition of the present invention can be used by dissolving it in a solvent capable of dissolving the above components and coating it on a support. As the solvent used here,
For example, methyl ethyl ketone, methyl amyl ketone, 4
-Methoxy-4-methyl-2-pentanone, cyclopentanone, cyclohexanone and other ketones, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and other alcohol ethers, n-propyl alcohol -Le, iso-
Butyl alcohol, n-butyl alcohol, cyclohexyl alcohol, diacetone alcohol and other alcohols, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers, methyl cellosolve acetate, ethyl cellosolve acetate, Methyl methoxypropionate, propyl formate, propyl acetate, butyl acetate, amyl acetate, isoamyl acetate, diethyl carbonate, ethylene carbonate, methyl propionate, methyl lactate,
Ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methoxyethyl propionate, methoxymethyl propionate, ethoxyethyl propionate, α
-Methyl hydroxyisobutyrate, ethyl hydroxyacetate,
Esters such as ethyl ethoxyacetate, methyl 2-hydroxy-3-methylbutanoate, ethyl pyruvate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate And other propylene glycols, halogenated hydrocarbons such as 1,1,2-trichloroethylene and the like, aromatic hydrocarbons such as toluene, xylene and anisole, and further dimethylacetamide, N-methylpyrrolidone and dimethyl Examples thereof include high boiling point solvents such as formamide, dimethyl sulfoxide, and benzyl ethyl ether. These solvents may be used alone or as a mixture of a plurality of solvents.

Appropriate application of a spinner, coater or the like on a substrate (eg, silicon / silicon dioxide coating, glass substrate, ITO substrate) such as used in the production of precision integrated circuit devices, with the above ionizing radiation-sensitive resin composition. After applying by the method,
A good resist pattern can be obtained by exposing through a predetermined mask, baking, and developing.

The developer of the ionizing radiation-sensitive resin composition of the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, ethylamine,
Primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetra Aqueous solutions of quaternary ammonium salts such as methylammonium hydroxide, tetraethylammonium hydroxide and choline, and alkalis such as cyclic amines such as pyrrole and piperidine can be used. The alkali concentration of these alkaline aqueous solutions is
0.001-1N is preferable. More preferably 0.01
˜0.5 N, particularly preferably 0.05 to 0.3 N. Further, an appropriate amount of alcohols and surfactants may be added to the above aqueous solution of alkalis for use. Hereinafter, the present invention will be described in more detail with reference to Examples, but the content of the present invention is not limited thereto.

[0122]

【Example】

Synthesis Example 1 Synthesis of Dissolution Inhibitor (2A) Using a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 6-hydroxy-5,7-bis (hydroxymethyl) -1,2,3 , 4-Tetrahydronaphthalene 62.5 g (0.3 mol) and o-cresol 194.
7 g (1.8 mol) was dissolved in 250 ml of methanol, and 9.1 g of 36% hydrochloric acid was added. Then, the mixture was reacted under heating under reflux for 7 hours. The reaction mixture was poured into 4 l of water, the precipitate was washed with water, and then hexane / dichloromethane (2 /
Stirred in 1) to remove unreacted raw materials. Ethanol /
54 g of a white solid was obtained by recrystallization from water.
According to NMR, this is 6-hydroxy-5,7-bis (3'-methyl-4'-hydroxybenzyl) -1,
It was confirmed to be 2,3,4-tetrahydronaphthalene. 6-hydroxy-5,7-bis (3'-methyl-
9.71 g (0.025 mol) of 4'-hydroxybenzyl) -1,2,3,4-tetrahydronaphthalene was dissolved in 200 ml of dimethylacetamide, and 3.5 g (0.025 mol) of potassium carbonate and t of bromoacetic acid were added thereto.
-Butyl 9.75 g (0.05 mol) was added. Then, it stirred at 120 degreeC for 5 hours. The reaction mixture was poured into 2 liters of ion-exchanged water, neutralized with acetic acid, and then extracted with ethyl acetate. The ethyl acetate extract was concentrated and subjected to column chromatography (filler: silica gel, developing solution:
It was purified with ethyl acetate / hexane = 1/5). Column eluate was concentrated to dryness, dissolution inhibitor (2A) (D is H or _{-CH 2 -COOC (CH 3) 3} ) was obtained 12.3 g. When analyzed by high performance liquid chromatography (HPLC), the diester form was 59% and the triester form was 2%.
It was 4%.

Synthesis Example 2 Synthesis of Dissolution Inhibitor (2B) 6-Hydroxy-5,7-bis (3′-methyl-4′-)
Hydroxybenzyl) -1,2,3,4-tetrahydronaphthalene 6-hydroxy-5 instead of 9.71 g
7-bis (3'-methyl-4'-hydroxybenzyl)
-1,2,3,4-tetrahydronaphthalene 6.60
g, potassium carbonate 6.9 g (0.05 mol), except that the dissolution inhibitor (2B) was prepared in the same manner as in Synthesis Example (1).
(D is H or _{-CH 2 -COOC (CH 3) 3} ) 1
7.1 g was obtained. Analysis by HPLC revealed that the diester form was 10% and the triester form was 85%.

Synthesis Example 3 Synthesis of Dissolution Inhibitor (3A) Using a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 40.4 g of 2,6-bis (hydroxymethyl) -p-cresol was obtained. 176 g of 2,5-xylenol was dissolved in 170 ml of methanol, and 7.3 g of 36% hydrochloric acid was used.
Was added. Then, the mixture was reacted under heating under reflux for 12 hours. After pouring the reaction mixture into 3.5 l of water and washing the precipitate with water,
Further stirring in hexane / dichloromethane (2/1),
Unreacted raw material was removed. By recrystallizing with ethanol / water, 41 g of a white solid was obtained. It was confirmed by NMR that this was 2,6-bis (2 ', 5'-dimethyl-4'-hydroxybenzyl) -p-cresol. 2,6-bis (2 ', 5'-dimethyl-4'-hydroxybenzyl) obtained using a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping device.
-P-Cresol 7.34 g was added to methylacetamide 20.
It was dissolved in 0 ml and 5.2 g of potassium carbonate (0.0
38 mol) and t-butyl bromoacetate 7.22 g
(0.037 mol) was added. The subsequent treatment was performed in the same manner as in Synthesis Example 1 to obtain 10.5 g of the dissolution inhibitor (3A) (D is H or —CH ₂ —COOC (CH ₃ ) ₃ ). When analyzed by HPLC, the diester form was 61
%, The triester form was 35%.

Synthesis Example 4 Synthesis of Dissolution Inhibitor (3B) 2,6-bis (2 ', 5'-dimethyl-4'-hydroxybenzyl) -p-cresol Instead of 7.34 g of 2,6-bis ( An acid-decomposable dissolution inhibitor (3) was prepared in the same manner as in Synthesis Example (3) except that 4.91 g of 2 ', 5'-dimethyl-4'-hydroxybenzyl) -p-cresol was used.
B) 8.9 g was obtained. Analysis by HPLC revealed that the diester form was 18% and the triester form was 77%.

Synthesis Example 5 Synthesis of dissolution inhibitor (139A) Using a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 50.5 g of 2,6-bis (hydroxymethyl) -p-cresol was added. 194.7 g of o-cresol was dissolved in 200 ml of methanol, and 9.1 g of 36% hydrochloric acid was added. Then, the mixture was reacted under heating under reflux for 7 hours. The reaction mixture was poured into 4 l of water, the precipitate was washed with water, and then stirred in hexane / dichloromethane (2/1) to remove unreacted raw materials. By recrystallizing with ethanol / water, 54 g of a white solid was obtained. By NMR, this is 2,
6-bis (3'-methyl-4'-hydroxybenzyl)
It was confirmed to be -p-cresol. Obtained 2,
6-bis (3'-methyl-4'-hydroxybenzyl)
-P-cresol 34.9 g, potassium hydroxide 5.7 g
Was dissolved in 300 ml of methanol / water (4/6), 37
% Formalin 81 g was added. After that, 2 at 40 ℃
The reaction was carried out for 4 hours. The reaction mixture was diluted with 500 ml of water and then neutralized with acetic acid. The precipitated pale yellow solid was filtered and washed with water to obtain 35 g of 2,6-bis (3'-methyl-4'-hydroxy-5'-hydroxymethylbenzyl) -p-cresol. 20.5 g of this 2,6-bis (3'-methyl-4'-hydroxy-5'-hydroxymethylbenzyl) -p-cresol was treated with phenol 56.5.
g and 200 ml of methanol were added, and 36% hydrochloric acid 3 was added.
g was added and the mixture was heated to reflux for 7 hours. Then, the mixture was poured into 3 l of water, and the precipitated light brown solid was purified by column chromatography (filler: silica gel, eluent: hexane / ethyl acetate = 3/1). 12 g of white solid was obtained, NM
The structure was confirmed by R. White solid obtained by the above method 14.
02 g was dissolved in 400 ml of tetrahydrofuran (THF). 8.4 g (0.075 mol) of potassium tert-butoxide was added to this solution under a nitrogen atmosphere, and after stirring at room temperature for 10 minutes, 16.6 g (0.076 mol) of di-tert-butyl dicarbonate was added. At room temperature,
The reaction was carried out for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The subsequent treatment was carried out in the same manner as in Synthesis Example (1) to obtain a dissolution inhibitor (139A). Analysis by HPLC revealed that the diester form was 25% and the triester form was 40%.

Synthesis Examples (6 to 20) The dissolution inhibitors shown in Table 1 were synthesized in the same manner as in Synthesis Examples 1 to 5.

Table 1: Acid-decomposable alkali dissolution inhibitors ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Synthesis Example Dissolution inhibition Skeleton Acid-decomposable diester body Triester body Tetraester body Agent number Number Group type (%) (%) (%) ───────────────────── ───────────────── 1 2A 2 tBuE 59 24 2 2B 2 tBuE 10 85 3 3A 3 tBuE 61 35 35 4 3B 3 tBuE 18 77 5 5 139A 139 tBOC 25 B 78 78 t 10 80 7 78B2 78 THP 18 69 8 8 126B 126 tBOC 20 70 9 80A 80 tBOC 60 30 10 80B 80 tBuE 15 65 65 ━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━ ━━━━━━━━

Continuation of Table 1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Synthesis example Dissolution suppression Skeleton Acid decomposability Hydrogen in D Atomic% Agent number Number Group (preparation ratio during reaction) ──────────────────────────────── 11 140A 141 tBuE 40 12 161A 161 tBOC 50 13 179A 179 tBuE 60 14 180A 180 THP 66.7 15 223A 223 tBOC 35 16 16 236A 236 tBuE 30 CbuE 30 C 17 17 249A 249 tBu 3CuE 30 247A ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0130]

[Chemical 56]

The production examples of the alkali-soluble resin according to the present invention are shown below.

Synthesis Example (11) Synthesis of novolac resin (a) m-cresol 50 g, p-cresol 50 g, 37%
Formalin aqueous solution 45.5 g and oxalic acid dihydrate 0.0
Charge 5 g into a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, raise the temperature to 100 ° C. with stirring,
The reaction was carried out for 10 hours. After the reaction, the mixture was cooled to room temperature, the reflux condenser was removed, and the pressure was reduced to 25 mmHg. Then gradually 1
The temperature is raised to 60 ° C to remove water and unreacted monomers, and
3 g of novolak resin (a) was obtained. When analyzed by GPC, the Mw was 6540 and the dispersity was 7.4.

Synthesis Example (12) Synthesis of Novolac Resin (b) 44 g of the novolak resin (a) was taken and dissolved in 400 ml of MEK, then 1600 ml of cyclohexane was added and heated to 60 ° C. with stirring. This solution was allowed to stand at room temperature for 16 hours to obtain a precipitate.
The precipitate was collected, filtered and dried in a vacuum oven at 50 ° C. to obtain about 15 g of novolak resin (b). This is GP
When analyzed by C, the Mw was 8720 and the dispersity was 4.3.

Synthesis Example (13) Synthesis of novolac resin (c) m-cresol 456.6 g, p-cresol 295.
8 g and 404.35 g of a 37% aqueous formalin solution were charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and stirred while heating in an oil bath at 110 ° C. When the internal temperature reached 90 ° C, 1.03 g of oxalic acid dihydrate was added. Then, the reaction was continued under reflux for 15 hours, the temperature of the oil bath was further raised to 200 ° C., and water and unreacted monomers were removed under reduced pressure except for the reflux condenser to obtain 565 g of novolac resin (c). When analyzed by GPC, Mw
Was 8860 and the dispersity was 7.7.

Synthesis Example (14) Synthesis of novolak resin (d) 44 g of the novolak resin (c) was taken and dissolved in 280 ml of acetone and 175 ml of toluene, and then 18
0 ml of hexane was added, and the mixture was heated to 40 ° C with stirring. This solution was allowed to stand at room temperature for 16 hours to obtain a precipitate. The precipitate was collected, filtered, and dried in a vacuum oven at 50 ° C. to obtain about 15 g of novolak resin (d). When this is analyzed by GPC, Mw is 11400,
The dispersity was 3.9.

Synthesis Example (15) Synthesis of novolac resin (e) In a three-necked flask having an inner volume of 500 ml equipped with a stirrer and a reflux condenser, 50 g of m-cresol and 25 parts of p-cresol were prepared.
g, 2,5-xylenol 28 g, formalin (37
% Aqueous solution), and stirred well while heating in an oil bath at 110 ° C., 0.15 g of oxalic acid was added, and the mixture was heated and stirred for 15 hours. Then raise the temperature to 200 ° C and gradually increase
The pressure was reduced to 2 mmHg and distillation was carried out for 2 hours to remove unreacted monomers, water, formaldehyde, oxalic acid and the like. The temperature was lowered to room temperature to obtain 81 g of novolak resin (e). When this was analyzed by GPC, the Mw was 4400 and the dispersity was 6.5.

Synthesis Example (16) Synthesis of novolak resin (f) 20 g of novolak resin (e) was dissolved in 60 g of methanol. To this, 30 g of distilled water was gradually added with stirring to precipitate the resin component. The upper layer separated into two layers was removed by decanting. Then, 30 g of methanol was added to and dissolved in this, and 40 g of distilled water was gradually added again with stirring to precipitate the resin component. The separated upper layer was removed by decanting and the recovered resin component was heated to 40 ° C. in a vacuum dryer and
After drying for 4 hours, 7 g of novolak resin (f) was obtained. GP
When analyzed by C, the Mw is 9860 and the dispersity is 2.8.
It was 0.

Synthesis Example (17) Synthesis of novolak resin (g) Methylenebis-p-cresol 14.4 g, o-cresol 2.2 g, 2,3-dimethylphenol 70.2
g, 2,3,5-trimethylphenol 27.2 g,
9.77 g of 2,6-dimethylphenol was mixed with 50 g of diethylene glycol monomethyl ether and charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. Then, 37% formalin aqueous solution 85.2
g, and stirred with heating in an oil bath at 110 ° C. When the internal temperature reached 90 ° C, 6.2 g of oxalic acid dihydrate was added. Then, the temperature of the oil bath is kept at 130 ° C for 18 hours to continue the reaction, and then the reflux condenser is removed to 200 ° C.
It was distilled under reduced pressure to remove unreacted monomers. The obtained novolak resin had an Mw of 3530 and a dispersity of 2.25.

Synthesis Example (18) Synthesis of novolak resin (h) p-cresol 8.1 g, o-cresol 6.6 g,
2,3-Dimethylphenol 119.1 g, 2,3,5
-Trimethylphenol 40.8 g and 2,6-dimethylphenol 11 g were mixed with 73.5 g of diethylene glycol monomethyl ether and charged into a three-neck flask equipped with a stirrer, a reflux condenser and a thermometer. Then
Add 133.8 g of 37% formalin aqueous solution, 110
The mixture was stirred with heating in an oil bath at ℃. When the internal temperature reached 90 ° C, 9.3 g of oxalic acid dihydrate was added. After that, the temperature of the oil bath was kept at 130 ° C. for 18 hours to continue the reaction, and then the reflux condenser was removed, followed by vacuum distillation at 200 ° C. to remove unreacted monomers. The obtained novolak resin had an Mw of 3830 and a dispersity of 2.36.

Synthesis Example (19) Synthesis of Polyhydroxystyrene Resin (a) (1) To 17.6 g of p-tert-butoxystyrene was added a catalytic amount of 2,2′-azobisisobutyronitrile, and toluene was added. Polymerization reaction was carried out at 80 ° C. for 6 hours in a solvent under a nitrogen atmosphere. After cooling the reaction solution, it was poured into methanol for crystallization, and the precipitated crystal was collected by filtration, washed with methanol and dried under reduced pressure to obtain 15.5 g of poly (p-tert-butoxystyrene) white powder. Weight average molecular weight is 12,40
It was 0.

(2) 15.0 g of this poly (p-tert-butoxystyrene) was dissolved in 1,4-dioxane,
10 ml of concentrated hydrochloric acid was added, and the mixture was stirred and refluxed for 3.5 hours. After cooling, the reaction solution was poured into water for crystallization, and the precipitated crystal was collected by filtration.
It was washed with water and dried under reduced pressure to obtain 7 g of white powder of poly (p-hydroxystyrene). The weight average molecular weight was 8,500.

Synthesis Example (20) Preparation of Polyhydroxystyrene Resin (b) The stirring reflux time of Synthesis Example (19) (2) was 3.5 hours to 2.5 hours.
9 g of white powder of poly (p-tert-butoxystyrene-p-hydroxystyrene) was obtained in the same manner as in Synthesis Example (19) (1) and (2) except that the time was changed. The resulting unit ratio of p-tert-butoxystyrene unit and p- hydroxystyrene unit of the polymer 1 by ¹ H-NMR measurement: 3, weight average molecular weight was 9,800.

Synthesis Example (21) Preparation of Polyhydroxystyrene Resin (c) Synthesis Example (19) (1) 17.6 g of p-tert-butoxystyrene m-hydroxystyrene 15.8 g, polymerization conditions of 80 ℃, 6 g of white powder of poly (m-hydroxystyrene) was obtained in the same manner as in Synthesis Example (19) (1) except that the temperature was changed from 6 hours to 100 ° C. for 7 hours. The weight average molecular weight was 8,500.

Synthesis Example (22) Preparation of Polyhydroxystyrene Resin (d) 17.6 g of p-tert-butoxystyrene of Synthesis Example (19) (1) was added to p-tert-butoxystyrene 8.8.
g, m-tert-butoxystyrene A white powder of poly (p-hydroxystyrene-m-hydroxystyrene) was prepared in the same manner as in Synthesis Example (19) (1) and (2) except that the mixture was replaced with 8.8 g of m-tert-butoxystyrene. 8 g was obtained. P- of the obtained polymer
Unit ratio of hydroxystyrene units and m- hydroxystyrene units is 1 by ¹ H-NMR measurement: 1,
The weight average molecular weight was 15,000.

Synthesis Example (23) Preparation of polyhydroxystyrene resin (e) Hydrogenated polyhydroxystyrene (Mulllinker PHM-
50 g of C (manufactured by Maruzen Petrochemical Co., Ltd .; weight average molecular weight: 5,200, hydrogenation rate: 10 to 20 mol%)) is added to 1 part of ethyl lactate.
It was dissolved in 50 g, then 150 g of n-hexane was added, and the mixture was shaken well and left to stand to separate an n-hexane layer (upper layer) and an ethyl lactate layer (lower layer). Remove the upper layer,
To the remaining lower layer, 150 g of n-hexane was added, and the same operation was repeated twice. The resulting ethyl lactate layer is 2
It was poured into liters of ion-exchanged water for crystallization, and the precipitated crystals were collected by filtration, washed with pure water and dried under reduced pressure to obtain purified hydrogenated polyhydroxystyrene.

Synthesis Example (24) Preparation of Polyhydroxystyrene Resin (f) Poly (p-hydroxystyrene) (weight average molecular weight 9,
600 g) was dissolved in 100 ml of dimethoxyethane, then 3,4-dihydro-2H-pyran 12.6.
g and 0.5 ml of sulfuric acid were added, and the mixture was stirred at 30 to 40 ° C. for 15 hours. After the reaction, the reaction solution was concentrated under reduced pressure, the residue was neutralized with sodium carbonate, poured into water and crystallized, and the precipitated crystal was collected by filtration, washed with water and dried under reduced pressure to give poly (p-tetrahydropyranyloxystyrene- 11.0 g of white powder of p-hydroxystyrene) was obtained. The unit ratio of p-tetrahydropyranyloxystyrene unit and p-hydroxystyrene unit of the obtained polymer was 3: 7 by ¹ H-NMR measurement, and the weight average molecular weight was 11,000.

Examples 1 to 32, Comparative Examples 6 to 8 Resists were prepared using the compounds of the present invention shown in the above synthesis examples. The prescription at that time is shown in Table 2.

Comparative Examples 1 and 2, t-butoxycarbonyloxystyrene polymer and t-butoxycarbonyloxy-α-methylstyrene polymer were synthesized according to the method described in US Pat. No. 4,491,628 to prepare a two-component positive type composition. A resist was prepared.
The prescription at that time is shown in Table 2.

Comparative Examples 3,4,5 The compound di-t-butyl terephthalate, 4-t-butoxy-p-, described in EP 249,139.
A three-component positive resist was prepared using biphenyl, t-butyl-2-naphthyl carbonate as a dissolution inhibitor.
The prescription at that time is shown in Table 2.

Table 2: Formulation of ionizing radiation sensitive resin composition ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━ Actual resin Dissolving acid-decomposable dissolution inhibitor Photo-acid generating agent ─────── Acceleration ─────────────────── Example Class (g) Agent * (g ) I (g) II (g) Type (g) ───────────────────────────────────── 1 Novolac 1.37 None 2A 0.475 PAG 0.057 Resin (a) 4-5 2 〃 〃 〃 3A 〃 〃 〃 〃 〃 〃 〃 〃 4 〃 〃 〃 5 〃 4 〃 5 〃 5 〃 5 〃 6 〃 〃 〃 126B 〃 〃 〃 7 〃 〃 〃 80B 〃 〃 〃 5 〃 〃 〃 〃 Resin (e) 9 〃 〃 〃 11 〃 〃 〃 236A 〃 PAG 〃 5-13 12 〃 〃 〃 249A 〃 PAG 〃 6-15 13 Novolac 〃 〃 2B 0 .333 140A 0.143 PAG 〃 Resin (c) 6-2 14 〃 〃 〃 3B 0.238 78B2 0.238 PAG 〃 4-5 15 〃 〃 〃 126B 0.380 180A 0.095 〃 〃 16 Nohorak 1.27 0.242 2B 0.525 Nob 0.025 〃 0.242 〃 〃 〃 〃 Resin (d) 18 Novolac 1.16 0.348 〃 〃 〃 〃 Resin (f) 19 Novolac 1.27 0.242 〃 〃 〃 〃 〃 0.3 1.37 None 78B 0.475 PAG 0.057 Styrene tree 4-3 Fat (a) 22 Holycht 〃 〃 〃 0.475 〃 〃 Styrene resin and fat (b) 23 Holycht 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 24 〃 〃 〃 24 〃 〃 Styrene tree 4-4 fat (a / e = 50/50) 25 porridge 〃 〃 〃 0.475 〃 〃 styrene resin and fat (c) 26 〃 179A 0.380 PAG 〃 styrene resin 4-5 fat (f) 28 porcelain 1.37 〃 78B 0.333 140B 0.143 〃 〃 styrene resin (a) 29 novolac resin (b) 〃 〃 〃 〃 〃 styrene a) = 70/30 30 〃 1.37 〃 3C 0.475 PAG 0.057 4-4 31 〃 〃 〃 139C 〃 〃 〃 32 〃 〃 〃 78C 〃 〃 〃 ━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━ * 1- [α-methyl-α- (4'-human alkoxyphenyl) ethyl] -4- [α ', α'-virus
(4 "-Hydroxyphenyl) ethyl] benzene

Table 2: Formulation of ionizing radiation sensitive resin composition ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━ Ratio Resin dissolution Acid decomposable dissolution inhibitor Photo acid generator Comparison ─────── Acceleration ──────────── ────── Example Class (g) Agent * (g ) I (g) II (g) type (g) ───────────────────────────────────── 1 TBOCS 1.73 PAG4-3 0.173 2 TBAMS 〃 〃 〃 3 Novolak tree 1.30 DTBTP 0.56 〃 0.043 Fat (a) 4 〃 〃 TBPBP 〃 〃 5 〃 ━━━━〃 ━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━

The abbreviations used in Table 2 have the following meanings.

<Polymer> TBOCS t-Butoxycarbonyloxy styrene polymer (number average molecular weight 21,6
00) TBAMS t-Butoxycarbonyloxy-α-methylstyrene polymer (Number average molecular weight 46,900) TBNC t-Butyl-2-naphthyl carbonate

<Dissolution Inhibitor> DTBTP di-t-butyl terephthalate TBPBP 4-t-butoxy-p-biphenyl TBNC t-butyl-2-naphthyl carbonate

[Preparation and Evaluation of Photosensitive Composition] Each of the materials shown in Table 1 was dissolved in 6 g of propyleneglycol monomethyl ether acetate and filtered through a 0.2 μm filter to prepare a resist solution. Add this resist solution to 30
A silicon wafer was coated with a spin coater having a rotation speed of 00 rpm and dried on a vacuum adsorption type hot plate at 120 ° C. for 60 seconds to obtain a resist film having a thickness of 1.0 μm. The wafer thus obtained was exposed, PEB, developed, rinsed and dried by the following method to form a resist pattern.

[When there is no delay between exposure and PEB] This resist film was used as a KrF excimer laser stepper (N
A0.5), and immediately heated at 90 ° C. (Examples 21 to 29, 100 ° C. in the case of the comparative example) for 60 seconds on a vacuum adsorption type hot plate to obtain 2.38% (Examples 21, 23 and 23).
In the case of 24 and 28, 1.19%) was immersed in an aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds and dried.

[When there is a delay between exposure and PEB] This resist film is applied to a KrF excimer laser stepper (N
A0.5) exposure, 6 in a standard environment clean room
After being left for 0 minutes, 60 on a vacuum adsorption type hot plate at 90 ° C (Examples 21 to 29, 100 ° C in the case of Comparative Example).
After heating for 2 seconds, 2.38% (Examples 21, 23, 2
In the case of 4,28, it was immersed in a tetramethylammonium hydroxide (TMAH) aqueous solution of 1.19%) for 60 seconds, rinsed with water for 30 seconds and dried.

The pattern thus obtained on the silicon wafer was observed with a scanning electron microscope to evaluate resist sensitivity, resolution, film shrinkage, development film reduction, profile without delay and pattern deterioration due to delay. did. The results are shown in Table 2.

Sensitivity is 0.4 μm without delay
The mask pattern was defined as the reciprocal of the exposure dose, and the relative value of the sensitivity of Comparative Example 1 was used. The film shrinkage is expressed as a percentage of the ratio of the film thickness of the exposed part before and after the exposure. Resolution is de
This represents the limiting resolution at an exposure dose that reproduces a mask pattern of 0.4 μm in the case of no lay. The reduction of the development film was expressed as a percentage of the ratio of the film thickness reduction before and after the development of the unexposed portion and the film thickness before the development. The pattern deterioration due to the delay was judged by the 0.5 μm pattern when processed by the above method. The fact that the resist profile becomes an overhang shape or a T-TOP shape in which the surfaces are connected is defined as deterioration of the profile, and the size of the deterioration is represented by (large) ×, Δ, and ○ (small). From the results shown in Table 3, the resist of the present invention shows little film shrinkage due to baking after exposure, has a good profile, high resolution, and a wide process latitude, and has little performance deterioration due to the time from exposure to baking and the atmosphere. I understand.

Table 3: Evaluation results ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Relative sensitivity Film shrinkage Development film Reduction Resolving power Due to profile delay (%) (%) (μm) Pattern deterioration ─────────────────────────────────── ── Example 1 1.4 1 1 0.26 Rectangle ○ 2 1.3 1 1 0.30 〃 ○ 3 1.3 1 1 0.25 〃 ○ 4 1.4 1 1 0.26 〃 ○ 5 1.2 1 1 0.28 〃 ○ 6 1.2 1 1 0.30 〃 ○ 7 1.2 1 1 0.26 〃 ○ 8 1.2 1 <1 0.26 〃 ○ 9 1.1 1 <1 0.28 〃 ○ 10 1.2 1 <1 0.26 〃 ○ 11 1. 3 1.5 <1 0.26 〃 ○ 12 1.3 2 <1 0.26 〃 ○ 13 1.2 1 1 0.28 〃 ○ 14 1.5 1 1 0.30 〃 ○ 15 1.5 1.5 1 1 0.28 〃 ○ 16 1.3 1 <1 0.2 8 〃 ○ 17 1.2 1 <1 0.28 〃 ○ 18 1.1 1 <1 0.26 〃 ○ 19 1.2 1 <1 0.26 〃 ○ 20 1.2 1 <1 0.26 〃 ○ 21 1.6 1.6 3 0.24 〃 ○ 22 1.5 1 1 0.28 〃 ○ 23 1.3 1 1 1 0.26 〃 ○ 24 1.6 1 2 0.24 〃 ○ 25 1.5 1 2 0.26 〃 ○ 26 1.6 1 2 0.24 〃 ○ 27 1. 4 1 1 0.26 〃 ○ 28 1.6 1 2 0.24 〃 ○ 29 1.7 1 1 0.28 〃 ○ 30 1.4 1.4 1.5 2 0.30 〃 △ 31 1.2 1.2 1 0.28 〃 △ 32 1.3 2 1 0.28 〃 △ ──────────────────────────────────── Comparative Example 1 1.0 10 4 0.35 Theta × 2 0.9 11 4 0.35 〃 × 3 1.2 4 10 0.35 〃 × 4 1.2 3 8 0.35 〃 × 5 1.2 3 9 0.35 〃 × ━━━━━━━━━━━━━━━ ━━━━ ━━━━━━━━━━━━━━━━━━

[0161]

According to the present invention, there is little film shrinkage due to baking after exposure, a good profile, a high resolution and a wide process latitude are provided, and there is little performance deterioration due to the time from exposure to baking and the atmosphere. A positive ionizing radiation sensitive resin composition having good performance stability can be obtained.

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Yasumasa Kawabe 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Shashin Film Co., Ltd.

Claims (6)

[Claims] 1. A positive-type ionizing radiation-sensitive resin composition comprising an alkali-soluble resin, a photoacid generator, and at least one compound represented by the general formula [A1] or [B1]. object. [Chemical 1] Here, R _{1 to} R ₄₁ : which may be the same or different and represent a hydrogen atom or —X—Ra ₁ , —CN, or —OD _0, and one of those on the same benzene ring is represented by the general formula (A It may be a group represented by ₁₂ ). Two of the same benzene ring may be bonded to each other to form a ring. [Chemical 2] X _{1 to} X ₁₀ : Represents a single bond, a carbonyl group, a sulfide group, a sulfonyl group or —C (R _b1 ) (R _b2 ) —.
However, X ₃ and X ₄ may be an alkylene group having 2 to 8 carbon atoms. X: single bond, -O-, -S-, -CO-, -OCO
_{-, - N (Ra 1)} CO- or -N (Ra ₂₎ - represents a. Ra ₁ : an alkyl group having 1 to 10 carbon atoms, an alkylene group,
It represents a cycloalkyl group, a haloalkyl group, an aryl group, an alkylaryl group or an aralkyl group. Ra _2: a hydrogen atom or represents a ra _1. R _b1 and R _b2 : each represents a hydrogen atom, a methyl group, an ethyl group or a haloalkyl group having 1 to 4 carbon atoms. R _b1 and R
_b2 may combine with each other to form an alicyclic hydrocarbon residue. When m = 0, at least one of R _b1 and R _b2 represents a group represented by formula (A ₁₂ ). D _{0 to} D ₁₂ : represent hydrogen atoms or D _inh, and at least two in the same molecule are not hydrogen atoms. Further, the following bond may be formed together with -OD ₀ group or -N (Ra ₂ ) (Ra ₁ ). [Chemical 3] D _inh : represents a group represented by -Xi-Ri. Xi: single bond, -C (R _b1 ) (R _b2 )-, -C (R _b1 ).
(R _b2 ) O-, -CO-, -CS-, -COO-, -C
OS-, -C ( _Rb1 ) ( _Rb2 ) CO-, -C ( _Rb1 )
It represents (R _b2 ) COO-, -C (R _b1 ) (ORi)-or -CON (R _b1 )-. Ri: hydrogen atom, alkyl group having 1 to 20 carbon atoms, alkenyl group, cycloalkyl group having 3 to 20 carbon atoms, 6 carbon atoms
To 20 aryl groups, cumyl groups, adamantanetyl groups,
It represents a —Si (ZiR _b3 ) (ZiR _b4 ) (ZiR _b5 ) group, a tetrahydropyranyl group, a pyranyl group or a 1,3-dithiaindan-2-yl group. R _b3 , R _b4 , and R _b5 : each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, or an aryl group having 6 to 20 carbon atoms. Zi: represents a single bond or -O-. i, j, k, m, n ₁ , n ₂ , w, y: 0 or 1 respectively. 2. In the compound represented by the above general formula [A1] or [B1], the unprotection ratio α defined by α = H / (H + D _inh ) is 0.2 to 0.7. And, and
The positive ionizing radiation sensitive resin composition according to claim ₁ , wherein D ₁ , D ₃ , D ₅ , D ₆ and D ₁₂ are D _inh . 3. The compound represented by the above general formula [A1] or [B1] has at least two groups capable of being decomposed by an acid in its structure, and the distance between the acid-decomposable groups. The positive ionizing radiation sensitive resin composition according to claim 1, which is a compound having 13 to 40 bond atoms excluding the acid-decomposable group at the furthest position. 4. In the compound represented by the above general formula [A1] or [B1], two or more of R _{1 to} R ₄₁ on the same benzene ring are bonded to each other to form at least 1 The positive type ionizing radiation sensitive resin composition according to claim 1, 2 or 3, which has two ring structures. 5. In the compound represented by the above general formula [A1] or [B1], m = 1, i = j = 0, and R
_b1, claim 1, wherein the non-group none of R _b2 are represented by the general formula (A _12), the positive-sensitive ionizing radiation resin composition according to claim 2 claim 3 or claim 4 object. 6. The compound represented by the general formula [A1] or [B1], wherein the group represented by -OD _inh is a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group. The positive type ionizing radiation sensitive resin according to claim 1, claim 2, claim 3, claim 4 or claim 5, wherein the positive type ionizing radiation resin is a tertiary alkyl ester group or a tertiary alkyl carbonate group. Composition.