JP2000258904A - Negative chemically amplified photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. which decreases imprinting phenomenon due to the reflected light from an exposure stage while maintaining good sensitivity when the compsn. is exposed to light, and to obtain an excellent resist pattern with little dimensional changes by incorporating a specified compd. SOLUTION: This compsn. contains an alkali-soluble resin, a compd. which produces an acid by irradiation with active rays, a crosslinking agent which crosslinks with the produced acid, and a compd. expressed by the formula. The compd. expressed by the formula acts as an absorbent of reflected light. In the formula, each of R1 to R10 is same as or different from others and is a hydrogen atom, hydroxy group, 1-5C, preferably 1-4C alkyl group, 1-5C, preferably 1-4C alkoxy group, or 1-5C, preferably 1-3C alkoxycarbonyl group, and each of R11 to R16 is same as or different from others and is a hydrogen atom or 1-5C, preferably 1-3C alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a negative-type chemically amplified photosensitive composition, and more particularly to a negative-type chemically amplified photosensitive composition suitable for forming a negative-type resist pattern layer on a transparent film substrate. .

[0002]

2. Description of the Related Art In the manufacture of semiconductor integrated circuits or liquid crystal display elements, a photosensitive composition (hereinafter, also referred to as a resist) film applied to a substrate is generally irradiated with active rays (exposure). Development is performed to form a predetermined resist pattern. Regardless of whether the resist is a positive type or a negative type, at the time of exposure, the influence of light reflected from a base substrate, which is a substrate to be etched, is more or less. If it is not a transparent substrate, this effect depends on the reflectance of the underlying substrate, and the greater the reflectance, the greater the effect,
For example, undesired results such as dimensional fluctuation due to halation, deterioration of the obtained resist shape, and in-plane variation of dimensions are brought about. In order to solve such a problem, in the case of a quinonediazide-based positive resist or a rubber-based negative resist, a dye or an ultraviolet absorber having absorption near the exposure wavelength is added to the photosensitive composition to reduce Have been proposed and put into practical use, for example, by suppressing absorption of reflected light and reducing the effects of standing waves generated by incident light and reflected light.

[0003] For example, Japanese Patent Application Laid-Open No.
In JP-A-3-136040, it is described that by adding curcumin to a quinonediazide-based positive resist composition, halation is prevented and dimensional accuracy is improved. Similarly, JP-A-1-243046 and U.S. Pat. Nos. 5,334,481 and 5,399,463 disclose curcumin analog compounds, and in any case, a quinonediazide-based positive resist contains a light-impermeable material. It describes that a good image was formed on the light reflecting substrate. Further, JP-A-63-2
No. 67941 discloses a technique in which an esterified product of curcumin and a quinonediazide compound is used as a photoactive compound of a positive photoresist composition, and an image having excellent dimensional stability is obtained.

[0004] However, the situation is slightly different from the case of an opaque substrate, particularly when the underlying substrate is a substrate on which a transparent conductive film such as ITO is formed on glass. In particular, in the case of a negative-type chemically amplified resist, since the light absorption of the resist film is small and the transparency is high as compared with the quinonediazide-based positive resist, reflection of the stage groove shape by reflected light from the exposure machine stage occurs. This reflection phenomenon is slightly observed even when the above positive resist is observed in detail. However, in the case of a chemically amplified negative resist, it is considered that the reflection phenomenon is apt to appear remarkably due to the high reactivity of the system. JP-A-64-54441 discloses that curcumin can be used as a light-absorbing dye in a reversible image forming process without any influence on negative image formation. However, the technique disclosed herein describes a composition and an image forming method capable of forming a negative image on a positive resist composed of quinonediazide / alkali-soluble resin.

[0005]

Accordingly, an object of the present invention is to provide a negative photosensitive composition formed on a transparent film such as ITO on a glass substrate, while maintaining good sensitivity. Another object of the present invention is to provide a negative chemically amplified photosensitive composition which can reduce the reflection phenomenon caused by light reflected from an exposure stage and can obtain an excellent resist pattern with small dimensional fluctuation.

[0006]

Means for Solving the Problems As a result of careful consideration of the above characteristics, the present inventors have solved the above object by the following constitution. That is, the present invention is as follows. (1) (A) an alkali-soluble resin, (B) a compound that generates an acid upon irradiation with actinic radiation, (C) a cross-linking agent that cross-links with the generated acid, and (D) a compound represented by the following general formula (I). A negative-working chemically amplified photosensitive composition comprising:

[0007]

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(In the general formula (I), R _{1 to} R ₁₀ are
Same or different, hydrogen, a hydroxyl group, an alkoxycarbonyl group having an alkyl group of 1 to 5 carbon atoms, an alkoxy group and the carbon number of 1 to 5 carbon atoms 1-5, R ₁₁ to R
₁₆ is the same or different and is hydrogen or an alkyl group having 1 to 5 carbon atoms. (2) The negative chemically amplified photosensitive composition according to claim 1, wherein the component (B) is a compound represented by the following general formula (II).

[0009]

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(In the general formula (II), Q is bromine or chlorine, P is -C (Q) ₃ , -NH, -NHR, -N
(R) ₂ , or —OR (R is a phenyl group or a lower alkyl group having 6 or less carbon atoms), n is an integer of 1 to 3, W is a substituted or unsubstituted aromatic ring, heterocyclic ring, or a compound represented by the following general formula (II)
It is a group represented by I).

[0011]

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In the above general formula (III), Z is oxygen or sulfur, and R ₂₀ is a lower alkyl group having 6 or less carbon atoms or a phenyl group. )

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the compounds used in the negative-working chemically amplified photosensitive composition of the present invention will be described. [(A) Alkali-soluble resin] The (A) alkali-soluble resin in the present invention is a resin that is insoluble in water and soluble in an aqueous alkali solution. (A) The alkali dissolution rate of the alkali-soluble resin is 0.2
It is preferably at least 20 Å / sec, particularly preferably at least 200 Å / sec, as measured (at 23 ° C.) with a 61N aqueous solution of tetramethylammonium hydroxide (TMAH).

The alkali-soluble resin (A) used in the present invention includes, for example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogen Polyhydroxystyrene,
Halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, part o- to the hydroxyl group of polyhydroxystyrene
Alkylated compounds (e.g., 5 to 30 mol% of o- (1-methoxy) ethylated compound, o- (1-ethoxy) ethylated compound;
o-2-tetrahydropyranylated product, o- (t-butoxycarbonyl) methylated product, etc.) or o-acylated product (for example, 5 to 30 mol% of o-acetylated product, o-
(T-butoxy) carbonylated compound), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxy group-containing methacrylic resin and derivatives thereof. However, the present invention is not limited to these.

Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, and a part of polyhydroxystyrene. -Alkylated or o-acylated products, styrene-hydroxystyrene copolymers, and α-methylstyrene-hydroxystyrene copolymers. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

Examples of the predetermined monomer include cresols such as phenol, m-cresol, p-cresol, o-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3- Xylenols such as xylenol, m-ethylphenol, p-
Ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5
Alkylphenols such as trimethylphenol, p
-Methoxyphenol, m-methoxyphenol, 3,
Alkoxyphenols such as 5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol p-butoxyphenol; Methyl-4-
Bisalkylphenols such as isopropylphenol, m-chlorophenol, p-chlorophenol, o
A hydroxyaromatic compound such as chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, naphthol alone or 2
More than one kind can be mixed and used, but it is not limited to these.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-
Phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, mp chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-
Methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, P-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde and their acetal compounds such as chloroacetaldehyde diethyl acetal can be used. Among them, it is preferable to use formaldehyde. These aldehydes can be used alone or in combination of two or more. Hydrochloric acid, sulfuric acid, acetic acid, oxalic acid and the like can be used as the acidic catalyst.

The weight average molecular weight of the novolak resin thus obtained is preferably in the range of about 1,000 to 20,000. If it is less than 1,000, the film thickness of the resist film in the exposed area after development is large, and the sensitivity is low. On the other hand, if the average molecular weight exceeds 20,000, the solubility in the developer decreases, so the dissolution rate of the unexposed area becomes slow,
Long-term development is required. This is not preferable for improving the throughput. In addition, a resist residue sometimes remains in an unexposed portion, and this may cause an etching residue in a subsequent etching, which causes a defect. Therefore, it is important to select a novolak resin having a suitable molecular weight. Particularly preferred molecular weights are in the range of 2,000 to 10,000. The weight average molecular weight was measured by GPC (gel permeation chromatography).
It is a polystyrene conversion value. These (A) alkali-soluble resins can be used as a mixture of two or more kinds so as to obtain a predetermined dissolution rate. The alkali-soluble resin is used in an amount of 5% by weight to 60% based on the total amount of the composition including the solvent.
It can be dissolved well in the range of weight%. In actual use, the solution viscosity or the resin concentration varies depending on the desired coating film thickness. In order to obtain a good resist film, it is preferably in the range of about 5% by weight to 40% by weight.

[(B) Compound that generates an acid upon irradiation with actinic radiation (hereinafter also referred to as “(B) photoacid generator”)] (B) As the photoacid generator, photoinitiation of cationic photopolymerization Some are used as agents, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or microresists. These generate an acid upon irradiation with light having a wavelength of about 200 to 800 nm.Examples of such compounds include onium salts, quinonediazide compounds, and organic halides, and these may be used alone or in appropriate combination. it can.

More specifically, the onium salts include, for example, diazonium salts, phosphonium salts and sulfonium salts having fluoroborate anion, trifluoromethanesulfonate anion, paratoluenesulfonate anion and paranitrotoluenesulfonate anion as counterions. it can.

As the quinonediazide compound, naphthoquinonediazide sulfonyl chloride and salts of naphthoquinonediazidesulfonic acid can be preferably used. Organic halide means a compound that forms hydrohalic acid, for example, US Pat.
No. 6,489,377777 and West German Patent Publication No. 2243621. More specifically, see, for example, US Pat.
, Tetra (bromomethyl) methane, tetrabromoethylene, 1,2,2
3,4-tetrabromoethane, trichloroethoxyethanol, p-iodophenol, p-bromophenol, p-iodobiphenyl, 2,6-dibromophenol, 1-bromo-2-naphthol, p-bromoaniline, hexachloro-p -Xylene, trichloroacetanilide, p-bromodimethylaniline, tetrachlorotetrahydronaphthalene, a, a'-dibromoxylene,
a, a, a, a'-Tetrabromoxylene, hexabromoethane, 1-chloroanthraquinone, ω, ω, ω-tribromoquinalidine, hexabromocyclohexane, 9
-Bromofluorene, bis (penta) chlorocyclopentadiphenyl, polyvinylidene chloride and 2,4
6, -Trichlorophenoxyethyl vinyl ether, hexabromoethane, a, a, a-trichloroacetophenone, tribromotrichloroethane and halomethyl-s-triazines described in U.S. Pat. No. 3,779,778 can be mentioned. In particular, halomethyl-s-
Triazines such as 2,4-bis (trichloromethyl) -6-methyl-s-triazine and 2,4,6-tris (trichloromethyl) -s-triazine are preferred.
More preferred organic halides include vinylhalomethyl-s disclosed in U.S. Patent No. 3,987,037.
-A compound substituted with a triazine. This vinylhalomethyl-s-triazine compound is a photodegradable triazine having at least one trihalomethyl group and at least one group conjugated to a triazine ring with an ethylenically unsaturated bond, and is shown below. General formula (I
I).

[0022]

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(In the general formula (II), Q is bromine or chlorine;
Is _{-C (Q) 3, -NH 2} , -HR, ( representative of where R is phenyl or 6 below lower alkyl group having a carbon) -N (R) _2, or -OR, to n is not 1 3, W Is an aromatic ring,
It represents a heterocyclic ring or a group represented by the following general formula (III). )

[0024]

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(In the general formula (III), Z represents oxygen or sulfur, and R ₂₀ represents a lower alkyl group or a phenyl group.) In the general formula (II), an aromatic ring or a heterocyclic ring represented by W May be further substituted. Examples of the substituent include chlorine, bromine, phenyl, lower alcohol having 6 or less carbon atoms, nitro, phenoxy, alkoxy,
Acetoxy, acetyl, amino, and alkylamino can be mentioned. The above compounds can be used alone or in combination of two or more.

The amount of the photoacid generator (B) in the composition of the present invention is 0.001 to 5% by weight, preferably 0.01 to 5% by weight, based on the total weight of the composition of the present invention including the solvent. ~ 3
% By weight. If the addition amount is small, the sensitivity becomes low, and a decrease in the crosslink density in the exposed area results in an unfavorable result that the amount of loss of the resist film obtained after development becomes large. In addition, when added in a large amount exceeding an appropriate amount, it is not preferable because it does not completely dissolve, or recrystallizes and precipitates in a solution during storage, or an effect corresponding to the added amount cannot be obtained.

[(C) Compound Crosslinkable by Acid] Compound (C) crosslinkable by acid (hereinafter referred to as “(C) acid crosslinker” or “(C) crosslinker” as appropriate) blended in the composition of the present invention.
) Is a three-dimensional cross-linking reaction or a polymerization reaction caused by both the action of the alkali-soluble resin (A) and the action of the acid generated from the component (B) by light irradiation and the action of heating in the presence of the acid. To lower the solubility of the (A) alkali-soluble resin in an aqueous alkali solution.
Examples of such a (C) crosslinking agent include (i) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, and (ii) an epoxy compound.

The crosslinking agent (C) will be described in detail below. (I) As a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, European Patent Publication (hereinafter referred to as “EP-A”) No. 0,133,216 , West German Patent No. 3,63
No. 4,671, No. 3,711,264, monomer and oligomer-melamine-formaldehyde condensate and urea-formaldehyde condensate, alkoxy disclosed in EP-A 0,212,482 Substituted compounds include benzoguanamine-formaldehyde condensates. More preferred examples include, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups, or N-acyloxymethyl groups, among which N-alkoxymethyl derivatives are particularly preferred. .

(Ii) Examples of the epoxy compound include monomer, dimer, oligomer, and polymer epoxy compounds containing one or more epoxy groups. For example, a reaction product of bisphenol A with epichlorohydrin, a reaction product of a low molecular weight phenol-formaldehyde resin with epichlorohydrin and the like can be mentioned. Other examples include epoxy resins described and used in U.S. Pat. No. 4,026,705 and British Patent No. 1,539,192.

In the composition of the present invention, these (C) acid crosslinking agents are used in an amount of 0.001% by weight of (A) the alkali-soluble resin.
It is used in the range of 1 to 30% by weight, more preferably 0.05 to 10% by weight. (C) When the amount of the acid cross-linking agent is small, the sensitivity is low and the cross-linking density does not increase, so that the film loss in the exposed area after development is large, and a good resist image cannot be obtained. On the other hand, if the addition amount is too large, the crosslinking density becomes high, which makes it impossible to perform a good peeling treatment in the step of peeling the resist after processing the substrate, which is not preferable.

[(D) Compound represented by the above general formula (I)] (D) Compound represented by the above general formula (I)
"(D) compound") acts as a reflected light absorber, and when the negative chemically amplified photosensitive composition of the present invention is used, particularly when a transparent substrate is used, the exposure light is reduced. It has a function of reducing reflection of the groove shape of the stage, which is transmitted by the substrate and generated by reflected light from the stage of the exposure apparatus. In the general formula (I), R _{1 to} R ₁₀ are the same or different and each have a hydrogen, a hydroxyl group and a carbon number of 1 to 5, preferably 1 to 5.
And 4 alkyl groups, for example, a methyl group, an ethyl group, and a butyl group. Moreover, carbon number is 1-5 preferably 1
~ 4 alkoxy groups, such as methoxy, ethoxy,
Butoxy groups and the like can be mentioned. Examples of the alkoxycarbonyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms include an acetoxyl group and a propionyloxy group. R _{11 to} R ₁₆ are the same or different and are hydrogen and an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.

Specific examples of the above compound (D) are shown below. However, the present invention is not limited to this specific example. 1.7-Phase- (3-methoxy-4 human peroxyphenyl) -1.6-heptadiene-3.5-dione 1.7-Phase- (3-methoxy-4-acetoxyphenyl) -1.6-heptadiene-3.5-dione 1- (3-methoxy- 4-humanperoxyphenyl) -7- (3-methoxy-4-acetoxyphenyl) -1.6
-Heptadiene-3.5-dione 1.7-bis- (3-methyl-4-hydroxypropyl) -1.6-heptadiene-3.5-dione 1.7-diethyl- (3-methyl-4-acetoxyphenyl) -1.6-heptadiene-3.5-dione 1- (3-methyl-4-human peroxyphenyl) -7- (3-methyl-4-acetoxyphenyl) -1.6-heptadiene-3.5-dione 1.7-bis- (3-ethoxy-4-human peroxyphenyl) -1.6- Heptacien-3.5-dione 1.7-bis- (3-ethoxy-4-acetoxyphenyl) -1.6-heptadiene-3.5-dione 1- (3-ethoxy-4-human-hydroxyphenyl) -7- (3-ethoxy-4-acetoxy) (Phenyl) -1.6
-Heptadiene-3.5-dione 1.7-Phase- (3-ethyl-4-hydroxypropyl) -1.6-heptadiene-3.5-dione 1.7-His- (3-ethyl-4-acetoxyphenyl) -1.6-heptadiene-3.5 diion 1 -(3-ethyl-4-humanperoxyphenyl) -7- (3-ethyl-4-acetoxyphenyl) -1.6-heptadiene-3.5-dione 1.7-bis- (3-methoxy-4-fluorodionyloxyphenyl) -1.6- Heftasien-3.
5-dione 1.7-bis- (3-ethoxy-4-fluorophenyloxyphenyl) -1.6-heptadiene-3.
5-dione 1.7-bis- (3-methoxy-4 human peroxyphenyl) -1.2.6.7-tetramethyl-1.6-heptadiene-3.5-dione 1.7-bis- (3-methoxy-4-acetoxyphenyl) -1.2.6.7- Tetramethyl-1.6-heptadiene-3.5-dione 1- (3-methoxy-4-humanperoxyphenyl) -7- (3-methoxy-4-acetoxyphenyl) -1.
2.6.7-Tetramethyl-1.6-heptadiene-3.5-dione 1.7-bis- (3-ethoxy-4-humanhydroxyphenyl) -1.2.6.7-tetramethyl-1.6-
Heptacien-3.5-dione 1.7-bis- (3-methoxy-4-humanoxyphenyl) -4.4-dimethyl-1.6-heptadiene-3.5-dione 1.7-bis-93-methoxy-4-acetoxyphenyl) -4.4-dimethyl- 1.6-heptadiene-3.5-dione 1- (3-methoxy-4-humanperoxyphenyl) -7- (3-methoxy-4-acetoxyphenyl) -4.4
-Dimethyl-1.6-heptadiene-3.5-dione 1.7-bis- (3-methoxy-4-fluorodioxycarbonyl) -4.4-dimethyl-1.6-
Heptacien-3.5-dione 1.7-bis- (3-ethoxy-4-humanhydroxyphenyl) -4.4-dimethyl-1.6-heptadiene-3.5-dione and the like.

These compounds (D) can be used alone or in combination of two or more. Also, 43
A light absorbing agent having a maximum absorption value around 6 nm can be used in combination. Examples of such light absorbers include, for example, 4- (4-nitrophenylazo) resorcinol, 4- (2-thiazolylazo) resorcinol,
JP-A-63-303344, JP-A-62-295
And compounds described in JP-A No. 044, JP-A-63-159839, JP-A-63-274945 and the like. In addition, a yellow dye having a maximum absorption around 350 to 450 nm, such as a chalcone compound (benzalacetophenoneoxy derivative or the like), can also be used in combination.

The amount of the compound (D) in the composition of the present invention is 0.005 to the total amount of the solution of the photosensitive composition.
% To 5% by weight, preferably 0.05% to 2% by weight. If the added amount is less than 0.005% by weight, the expected effect is hardly obtained. On the other hand, if the added amount is more than 5% by weight or more, it does not completely dissolve in the solution, or is coated in the solution or on the substrate. Undesired results such as precipitation on the substrate and a significant decrease in sensitivity. The compound (D) used in the present invention has good solubility in a solvent,
Within the appropriate amount range, it is possible to stably dissolve over time.

As the solvent used in the negative-working chemically amplified photosensitive composition of the present invention, those capable of dissolving the above-mentioned components and forming a uniform coating film on the support substrate are used. . For example, cyclohexanone, cyclopentanone, γ-butyrolactone, methyl ethyl ketone, ketones such as methyl amyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol such as ethylene glycol monoethyl ether acetate, and Those acetates,
Propylene glycol such as propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether propionate and their acetates, or propionates, acetates such as ethyl acetate, methyl acetate, butyl acetate, and methyl lactate And lactate esters such as ethyl lactate, and so-called polar solvents such as N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide and N-methyl-2-pyrrolidone. These solvents may be used as a mixture of two or more of them in order to improve coating characteristics. If necessary, a poor solvent may be mixed and used in an appropriate amount to improve the coating properties as long as the solubility is not impaired. The solvent can be used so that the concentration (solid content) of the negative chemically amplified photosensitive composition is 5 to 40% by weight.

[Other Additives] In the negative type chemically amplified photosensitive composition of the present invention, in order to promote the dissolution rate of unexposed portions, adjust the sensitivity, or improve other image characteristics,
A low molecular aromatic polyhydroxy compound can be contained. As an example of such a polyhydroxy compound, a compound called a dissolution promoter used in a quinonediazide-novolak positive resist can be applied as it is. However, in the case of the negative-working chemically amplified photosensitive composition of the present invention, such a compound has the effect of promoting the dissolution of unexposed portions, the effect of reducing sensitivity, and the effect of promoting film reduction of exposed portions. Have both. Therefore, when applying such a compound, it is necessary to give due consideration to such points, to select an appropriate compound, and to design a formulation having a balanced performance.

Further, the photosensitive composition of the present invention may contain a plasticizer, a surfactant, an adhesion aid and the like, if necessary. Stearic acid as a plasticizer,
Acetal resins, phenoxy resins, alkyd resins, epoxy resins and the like are listed.

In order to improve the coating performance and the in-plane uniformity of the film thickness, and to improve the developability, the wettability of the developer of the present invention is increased. A surfactant can be added to the hydrophilic composition. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene acrylyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenyl ether, etc. Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan trioleate, etc. Sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmi Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, and those with more specific trade names , F-top EF301 manufactured by Shin-Akita Chemical Co., Ltd.
303, 352, Megafac F171, 173 manufactured by Dainippon Ink and Florad FC-430, 431 manufactured by Sumitomo 3M Limited Surflon S manufactured by Asahi Glass Co., Ltd.
-382, SC-101, 102, 103, 104, 1
Fluorosurfactants such as 05 and 106, Shin-Etsu Chemical Co., Ltd.
Silicone surfactant such as KP-341 manufactured by Kyoeisha Yushi Kogyo Co., Ltd., or acrylic or methacrylic acid (co) polymerized polyflow No. 75, 95 and the like can be mentioned as examples. The amount of these surfactants to be added is generally 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content in the composition. These surfactants may be used alone or in combination of two or more.

Further, an adhesion improver (also referred to as an adhesion aid) can be appropriately added to the photosensitive composition of the present invention in order to improve the adhesion during wet etching of the underlying substrate. Examples of such compounds are disclosed in
Heterocyclic mercaptan-containing compounds described in JP-A-3-702, imidazole derivatives described in JP-A-56-36648, heterocyclic thiol compounds described in JP-A-60-2945, JP-A-58-149042 Benzoxazolinone compounds described in JP-A-63-21
Examples thereof include urea and thiourea compounds described in JP-A-8946, and organic phosphoric acid compounds described in JP-A-5-181281. These are used by adding about 0.01 to 5% by weight, preferably about 0.1 to 2% by weight, based on the total amount of the photosensitive composition. They can be used alone or in combination of two or more.

[Method of Using the Composition of the Present Invention] The photosensitive composition of the present invention can be used for a substrate used for manufacturing a semiconductor device or a liquid crystal display device, for example, a silicon oxide film, a silicon nitride film, polysilicon, molybdenum, or tantalum. , Tantalum oxide, chromium, chromium oxide, aluminum, ITO and the like. When using the photosensitive composition of the present invention,
Hexamethyldisilazane processing (HMDS processing) generally performed for a positive resist is not performed. Spinner coating is performed at a rotation speed such that a predetermined film thickness (generally, about 0.7 to 2 μm) is obtained, and drying is performed using a hot plate to minimize temperature variations. Thereafter, exposure is performed with a ghi mixed line, a gh mixed line, or a single g-line through a predetermined reticle to form a latent image. The optical system used at this time is a stepper, projection aligner,
Alternatively, it is a contact aligner or the like. Appropriate equipment will be used according to the purpose. After the formation of the latent image, heat treatment is performed at a predetermined temperature (110 ° C. to 150 ° C.).

The negative-working chemically amplified photosensitive composition of the present invention is subjected to a heat treatment in the presence of an acid generated by exposure, whereby a crosslinking reaction proceeds between the crosslinking agent and the novolak resin to form a three-dimensional network. A structure is formed and the molecular weight increases. As a result, it is based on the principle that solubility in an alkali developing solution is reduced in an exposed portion, and a predetermined resist pattern can be obtained. The heat treatment performed at this time is PEB
(Post Exposure Bake).

After the PEB processing is performed, the developing processing is subsequently performed. An organic alkali aqueous solution composed of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH) or an inorganic alkali aqueous solution such as caustic soda or caustic potassium is used for the developer. In the case of a TMAH system, the developer concentration is 1 to 2.6% by weight, particularly 2.38%. In the case of an inorganic alkali, it is generally about 0.4 to 1.2% by weight, and especially about 0.5 to 0.7%. In the developer, alcohols, surfactants and the like can be appropriately added and used.

After the development is completed, post-baking is performed at a predetermined temperature to perform an etching process. The etching includes dry etching and wet etching, and either method is applicable. In the case of manufacturing liquid crystal display elements, especially IT
In the case of an O substrate, wet etching is generally used. Thus, a predetermined pattern can be transferred to the substrate through the etching process.

[0044]

(Liquid preparation)

 A resist solution having the following composition was prepared. Component (A): cresol novolak resin 22.48 g (m / p / phenol = 57/38/5, average molecular weight = about 5500) Component (B): photoacid generator (the following structure) 0.93 g

[0045]

Embedded image

Component (C): 2.25 g of hexamethoxymethylated melamine (monomer content = about 70%, average molecular weight = about 500) Component (D): (any of the following compounds) 0.34 g 1.7 -Phase- (3-methoxy-4-humanperoxyphenyl) -1.6-heptadiene-3.5-dione (Example 1) 1-7-Phase- (3-methoxy-4-acetoxyphenyl) -1.6-heptadiene-3.5-dione (Example 2) 1.7-Phase- (3-ethoxy-4-humanoxyphenyl) -1.6-heptadiene-3.5-dione (Example 3) 1.7-Phase- (3-ethoxy-4-acetoxyphenyl) -1.6-heptadiene -3.5-dione (Example 4) 1.7-bis- (3-methoxy-4-humanperoxyphenyl) -1.2.6.7-tetramethyl-1.6-heptadiene-3.5-dione (Example 5) 1.7-bis- (3 -Methoxy-4-fluorophenyloxyphenyl) -1.6-heptasi Ene-3,5-dione (Example 6)

74.0 of each solvent (propylene glycol monoethyl ether acetate (PGMEA))
g, and filtered using a membrane filter having a pore size of 0.2 μm to obtain coating solutions of Examples 1 to 6. The coating liquid of Comparative Example 1 was prepared in the same manner as in Example 1 except that the component (D) was not added.

Example 7 A coating solution was prepared in the same manner as in Example 1 except that 0.2 g of Sudan Orange G () was added as another dye to the solution of the formulation of Example 1.

(Image formation)
Spin coating on a 100 mm square 7059 glass substrate on which a 0A ITO film is formed, and heat-treating for 90 seconds on an adsorption hot plate maintained at 90 ° C.
A resist film was formed to have a thickness of μm. The thus formed resist film was exposed through a reticle having a predetermined pattern. The exposure machine used was Can
on Inc. contact aligner PLA-501F was used. An ultra-high pressure mercury lamp was used as a light source, an i-ray cut filter was attached, and exposure was performed with a gh-ray mixed line. The exposure stage used was not subjected to any special anti-reflection treatment. The point where the 20 μm line and space pattern dimension becomes 1: 1 is defined as the optimum exposure amount (Eopt). Based on this exposure amount, 8 points while increasing the exposure amount by 20 mj.
Exposure was performed in stages.

Then, paddle development was performed at room temperature (23 to 25 ° C.) for 90 seconds using a 2.45% TMAH aqueous solution as a developing solution. After the development, the film was washed with running ion-exchanged water for 30 seconds, and subsequently, water was removed by blowing nitrogen.

(Evaluation of Reflection) A sodium lamp was irradiated from the back surface of the glass substrate which had been subjected to the development processing, and it was confirmed with naked eyes whether reflection of the stage groove pattern due to reflection of the exposure stage was observed. This confirmation is difficult to observe with a yellow lamp in a normal clean room, and is easy to observe with a sodium lamp or the like. In this way, each sample is checked, and it can be confirmed that the sample to which the compound is added has an effect as compared with the sample without the component (D). The reflection is observed not as a change in the profile of the resist pattern but as a slight increase in size.

The sensitivity was evaluated by the following method. For the sensitivity evaluation, a 4-inch bare silicon wafer was used for convenience. Using an Optline wedge mask manufactured by Optline, 150 m in terms of h-line using the same exposure machine as described above.
j. After the exposure, development washing was performed as described above. For a 20 μm line and space pattern, the dimensions were measured for each exposure dose, the measurement points were plotted to obtain an approximate expression, and the optimum exposure dose Eopt was calculated from this.
I asked. Table 1 shows the results.

[0053]

[Table 1]

As shown in Table 1, by adding the component (D) to the composition of the present invention, reflection due to reflection from the stage can be reduced. The sensitivity is about 20% to 50% lower than Eopt of the additive-free product. In Example 7, by combining with other dyes,
It has been found that the effect of preventing reflection is increasing, and it is also effective to use a mixture of two or more types.

[0055]

The negative-working chemically amplified photosensitive composition of the present invention, when applied to a transparent substrate, reduces reflection due to light reflected from an exposure stage without causing a significant decrease in sensitivity. A good pattern with small dimensional fluctuation can be obtained.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Shinya Kato 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fuji Film Orin Co., Ltd. F term (for reference) 2H025 AA01 AA02 AA03 AA04 AB16 AB20 AC01 AD01 BE00 BE08 CB17 CB29 CB52 CC13 CC17 CC20

Claims (2)

[Claims] 1. An alkali-soluble resin (A), a compound that generates an acid upon irradiation with actinic radiation, (C) a crosslinking agent that crosslinks with the generated acid, and (D) a compound represented by the following general formula (I): Negative-working chemically amplified photosensitive composition comprising a compound to be prepared. Embedded image (In the general formula (I), R _{1 to} R ₁₀ are the same or different and each is hydrogen, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. R _{11 to} R ₁₆ are the same or different and are hydrogen and an alkyl group having 1 to 5 carbon atoms.) 2. The negative-working chemically amplified photosensitive composition according to claim 1, wherein the component (B) is a compound represented by the following general formula (II). Embedded image (In the general formula (II), Q is bromine or chlorine, and P is-
C (Q) ₃ , -NH, -NHR, -N (R) ₂ , or-
OR (R is a phenyl group or a lower alkyl group having 6 or less carbon atoms), n is an integer of 1 to 3, W is a substituted or unsubstituted aromatic or heterocyclic ring or a group represented by the following general formula (III). . Embedded image In formula (III), Z is oxygen or sulfur, R ₂₀
Is a lower alkyl group having 6 or less carbon atoms or a phenyl group. )