JPH05323608A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant photosensitive compsn. having high photosensitivity when exposed to g-line by incorporating a polymer having a specified structure, oxime compd. and styryl compd. CONSTITUTION:This photosensitive compsn. contains a polymer having a repeating unit expressed by formula I, oxime compd. expressed by formula II, and a compd. containing a styryl group expressed by formula III. In formula I, X is a (2+n)-valent carbocyclic group or heterocyclic group, Y is a (2+ m)-valent carbocyclic group or heterocyclic group, Z is expressed by formulae IV-VI, R0 is a group having a carbon-carbon double bond, W is a group which can react with a carbonyl group -COOR0 by heat treatment to form a ring, (n) is 1 or 2,(m) is 0, 1, or 2, and COOR0 and Z are in ortho- or peri-releation to each other. In formula II, R1-R3 are hydrogen atoms, etc., R4 is an aromatic alkyl groups of 6-10 carbon number, etc., and R5 is an alkoxy group of 1-6 carbon number, etc. In formula III, Q is a group containing a carbocyclic group, etc., and R6 and R7 are hydrogen atoms, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition, and more particularly to a photosensitive composition which can be converted into a heat resistant polymer compound by heat treatment and can be used for a g-line stepper.

[0002]

2. Description of the Related Art In recent years, polymer materials obtained by imparting photosensitivity to polyimide, which is a heat-resistant polymer, have been actively developed, especially for electronic materials and optical materials. For example, passivation films and α-ray shielding films. Applications such as surface protective films such as junction coat films, insulating films for semiconductor elements such as interlayer insulating films for multilayer wiring, alignment films for liquid crystal displays, and insulating films for thin film magnetic heads are being studied [eg,
"Functional Materials" July issue, pages 9 to 19 (1983),
"Photographic Science and Engineering" pages 303-309 (1979) and "Polyfile" February issue pages 19-21 (19)
1990)]].

Conventionally, as a heat-resistant photosensitive composition, for example, a polymer in which an active functional group such as a double bond is introduced into an ester side chain of an acid of polyamide, which is a precursor of polyimide, is added to a photosensitizer or a copolymer. There is known a composition in which a crosslinkable structure is formed by irradiation with light, which contains a volatile monomer (see JP-B-55-30207 and JP-B-55-41422). This is a basic composition of a heat-resistant polymer for lithography represented by a so-called photosensitive polyimide, but it has low photosensitivity and is insufficient for practical use.

On the other hand, a photosensitive composition containing a mixture of a polyamic acid and an amine compound having an active functional group such as a double bond as a main component has been proposed (JP-A-57-1689).
42, JP-A-54-145794, and JP-A-59-160140), but these are difficult to handle because their solution viscosity is extremely high, and they are ionic bond type. In addition, if left after coating and drying, there is a problem that cracks are likely to occur due to moisture absorption.

[0005]

In the conventional photosensitive composition, the g-line stepper, which is the most widely used exposure machine in the current LSI manufacturing process, and other types of exposure machines using g-line. It has been found that when exposed using, the photosensitivity is not sufficient, the exposure time required for curing becomes long, and there are drawbacks from the effective use of an expensive exposure machine and the throughput of the product.

In view of such circumstances, the present inventors have conducted extensive studies to provide a heat-resistant photosensitive composition having high photosensitivity when exposed to g-rays.

[0007]

As a result, a polymer having a specific structure as an essential component, an oxime compound, and
It has been found that a composition containing a styryl compound can meet this purpose, and the present invention has been completed based on this finding. That is, the present invention provides (a) the general formula (1)

[0008]

[Chemical 7]

[Wherein X is a (2 + n) -valent carbocyclic group or heterocyclic group, Y is a (2 + m) -valent carbocyclic group or heterocyclic group, and Z is

[0010]

[Chemical 8]

Or

[0012]

[Chemical 9]

Or

[0014]

[Chemical 10]

R ₀ is a group having a carbon-carbon double bond, W
Is a group capable of reacting with the carbonyl group of —COOR ₀ to form a ring by heat treatment, n is 1 or 2, m is 0, 1 or 2, and COOR ₀ and Z are in the ortho or peri position. A polymer having a repeating unit represented by the following formula (hereinafter referred to as "component (a)") (b) General formula (2)

[0016]

[Chemical 11]

[Wherein R ₁ , R ₂ and R ₃ are hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms or nitro groups, and R ₄ is 6 to 1 carbon atoms]
0 aromatic acyl group, 1 to 6 carbon aliphatic acyl group, 1 to 6 carbon alkoxycarbonyl group, 6 to 10 carbon aromatic sulfonyl group, or 1 to 6 carbon aliphatic sulfonyl group group, R ₅ is an alkoxy group having 1 to 6 carbon atoms, aromatic groups having 6 to 10 carbon atoms, or an oxime compound represented by showing the aryloxy group of 6 to 10 carbon] (hereinafter the component (ii) And (c) general formula (3)

[0018]

[Chemical formula 12]

[Wherein Q is a carbocyclic group, a heterocyclic group,
Or a group containing a carbonyl group, and R ₆ and R ₇ represent a hydrogen atom, a methyl group or an ethyl group], and a photosensitive composition containing a compound containing a styryl group (hereinafter referred to as compound (c)) Is provided. The polymer used as the component (a) in the composition of the present invention has a repeating unit represented by the general formula (1), wherein X is a trivalent or tetravalent carbocyclic or heterocyclic compound. A cyclic group, such as X is, for example, a condensed polycyclic aromatic group such as a benzene ring, a naphthalene ring or an anthracene ring, a heterocyclic group such as pyridine or thiophene, and a compound represented by the general formula (I-1 )

[0020]

[Chemical 13]

And the like. Among these, aromatic hydrocarbon groups having 6 to 14 carbon atoms,

[0022]

[Chemical 14]

Those represented by are preferred. Y in the general formula (1) is a divalent, trivalent or tetravalent carbocyclic group or a heterocyclic group, and examples of such a group include C10 to C1 derived from naphthalene, anthracene and the like.
8 aromatic hydrocarbon rings, pyridine, and

[0024]

[Chemical 15]

[0025]

[Chemical 16]

Those represented by are preferred. Further, as Y in the general formula (1),

[0027]

[Chemical 17]

And the like. General formula in these Y

[0029]

[Chemical 18]

[0030]

[Chemical 19]

The group represented by is preferable in terms of photosensitivity. W in the general formula (1) is -COO by heat treatment.
A group capable of reacting with the carbonyl group of R ₀ to form a ring, and as such a group, especially —NH ₂ ,

[0032]

[Chemical 20]

Is preferred. Further, n is preferably 2. Further, R ₀ in the general formula (1) is a group having a carbon-carbon double bond, and examples of such a group include, for example, II-1.

[0034]

[Chemical 21]

II-2

[0036]

[Chemical formula 22]

II-3

[0038]

[Chemical formula 23]

II-4

[0040]

[Chemical formula 24]

II-5

[0042]

[Chemical 25]

II-6

[0044]

[Chemical formula 26]

II-7

[0046]

[Chemical 27]

[Wherein R'is a hydrogen atom or a methyl group,
R ″ is an alkylene group having 1 to 3 carbon atoms, R ″ ″ is a methyl group or an ethyl group, r is 1 or 2], etc. Examples of II-1 are:

[0048]

[Chemical 28]

As an example of II-2,

[0050]

[Chemical 29]

As an example of II-3,

[0052]

[Chemical 30]

As an example of II-4,

[0054]

[Chemical 31]

As an example of II-5,

[0056]

[Chemical 32]

As an example of II-6,

[0058]

[Chemical 33]

As an example of II-7,

[0060]

[Chemical 34]

And the like. Of these, light sensitivity,
And because of storage stability, etc.

[0062]

[Chemical 35]

And the like are preferred. The oxime compound used as the component (b) in the composition of the present invention is represented by the general formula (2). In the formula, R ₁ , R ₂ , R
₃ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a nitro group,
Preferred are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a nitro group and the like. R _{4 in the} formula
Is an aromatic acyl group having 7 to 11 carbon atoms, an aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an aromatic sulfonyl group having 6 to 10 carbon atoms, or 1 carbon atom To 6 aliphatic sulfonyl groups, preferably a benzoyl group, toluoyl group, acetyl group, propionyl group, ethoxycarbonyl group, benzenesulfonyl group, tolylsulfonyl group, methanesulfonyl group, ethanesulfonyl group and the like. R in the formula
₅ is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, preferably an ethyl group, Examples thereof include a butyl group, a methoxy group, an ethoxy group, a phenyl group, a tolyl group, and a phenoxy group. As an example of the component (b),

[0064]

[Chemical 36]

[0065]

[Chemical 37]

[0066]

[Chemical 38]

[0067]

[Chemical Formula 39]

[0068]

[Chemical 40]

[0069]

[Chemical 41]

[0070]

[Chemical 42]

Examples include, but are not limited to: These may be used alone or in combination of two or more. The compound containing a styryl group used as the component (c) in the composition of the present invention is represented by the general formula (3). R ₆ and R ₇ in the formula are hydrogen atoms,
It is a methyl group or an ethyl group. Q in the formula is a carbocyclic group, a heterocyclic group, or a group containing a carbonyl group such as an aromatic acyl group, and examples thereof include a benzene ring, a naphthalene ring, and an anthracene ring. A fused polycyclic aromatic group, a heterocyclic group derived from pyridine, and III-1

[0072]

[Chemical 43]

[Wherein Q ₁ is -O-, -S- or (CH
₃ ) ₂ C, Ar ₃ is a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms], and III-2

[0074]

[Chemical 44]

Examples include a group represented by [R ₈ and R ₉ in the formula are a hydrogen atom, a methyl group or an ethyl group]. Of these, the groups represented by III-1 and III-2 are preferable, and the group represented by III-1 is particularly preferable.
These may be used alone or in combination of two or more.
If necessary, a compound having a carbon-carbon double bond can be added to the composition of the present invention. The compound having a carbon-carbon double bond is a compound that facilitates a photopolymerization reaction by adding it, and examples thereof include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and N-. Vinyl-2-pyrrolidone, carbitol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate,
Tetramethylol methane tetraacrylate, tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, methylenebisacrylamide, N
-Methylol acrylamide and those obtained by replacing the above acrylate or acrylamide with methacrylate or methacrylamide, and the like are preferable, and among these, a compound having two or more carbon-carbon double bonds is preferable.

Further, by adding an aromatic amine compound to the composition of the present invention, the photosensitivity to a g-line stepper exposure machine can be improved. Examples of aromatic amine compounds include 4-dimethylamino-acetophenone, 4-morpholinoacetophenone, 4-dimethylamino-benzophenone, 4-morpholino-benzophenone, N-phenyl-diethanolamine, Np-tolyl-diethanolamine, Np-tolyl-diethylamine etc. are mentioned.

Further, the photosensitivity can be further improved by adding a mercaptan compound to the composition of the present invention. Examples of mercaptan compounds include, for example:
2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1H
-Tetrazole, 2-mercaptothiazole, 2-mercapto-4-phenylthiazole, 2-amino-5-mercapto-1,3,4-thiazole, 2-mercaptoimidazole, 2-mercapto-5-methyl-1,3,3. Four
-Thiadiazole, 5-mercapto-1-methyl-1H
-Tetrazole, 2,4,6-trimercapto-S-triazine, 2-dibutylamino-4,6-dimercapto-S-triazine, 2,5-dimercapto-1,3,4
-Thiadiazole, 5-mercapto-1,3,4-thiadiazole, 1-ethyl-5-mercapto-1,2,
3,4-tetrazole, 2-mercapto-6-nitrothiazole, 2-mercaptopentazoxazole, 4-phenyl-2-mercaptothiazole, mercaptopyridine, 2-mercaptoquinoline, 1-methyl-2-mercaptoimidazole, 2- Examples thereof include mercapto-β-naphthothiazole.

If desired, a functional silane compound may be added to the composition of the present invention, or a substrate may be pre-coated for use. This silane compound is a compound that improves the adhesiveness at the interface between the heat-resistant polymer film of the composition of the present invention and the substrate Si and the inorganic insulating film, and examples of these compounds include γ -Aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide Etc. For the usage and effects of these silane compounds, see, for example, JP-A-61-1
It is described in detail in 198634. Further, in order to improve the storage stability of the solution of the composition of the present invention, a polymerization inhibitor may be added. As this polymerization inhibitor,
For example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2,6-di-ter.
Examples thereof include t-butyl-p-methylphenol,
It is not limited to these.

The proportion of the oxime compound as the component (b) in the present invention is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 1 to 20% by weight based on the polymer of the component (a). It is desirable to contain it in the range of 15% by weight. When the content is low, the photosensitivity is not sufficient, and when the content is too high, the film characteristics after heat treatment are deteriorated.

The content ratio of the styryl compound of the component (c) in the present invention is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the polymer of the component (a). It is desirable to include it. When the content is low, the photosensitivity is not sufficient, and when the content is too high, the photosensitivity is decreased. The amount of the compound having a carbon-carbon double bond added is 20 with respect to the polymer of the component (a).
Weight% or less is desirable. The amount of the aromatic amine compound added is preferably 10% by weight or less, more preferably 5% by weight or less, based on the polymer of the component (a). The amount of the mercaptan compound added is preferably 10% by weight or less, more preferably 5% by weight, based on the polymer of the component (a).
It is less than or equal to weight%. When the functional silane compound is added and used, its addition amount is 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the polymer of the component (a). The polymerization inhibitor is used in an amount of 5% by weight or less, preferably 0.5% by weight or less, based on the polymer of the component (a).

The polymer used as the component (a) in the composition of the present invention is, for example, one represented by the general formula IV:

[0082]

[Chemical 45]

And a compound of the general formula V

[0084]

[Chemical 46]

It can be obtained by polycondensation or polyaddition with the compound represented by: Z in the general formula (IV)
Examples of ₁ include -COOH (IV-1), -COCl
(IV-2), - NCO (IV-3), - NH 2 (IV
-4) and -OH (IV-5), and the corresponding abbreviations of general formula (IV) are shown in parentheses. Further, as an example of Z ₂ in the general formula (V), —COCl (V−
1), -COOH (V-2), -NCO (V-3),-
There is NH ₂ (V-4), and the corresponding abbreviations of general formula (V) are shown in parentheses. Incidentally, X, R, X and W have the same meaning as described above.

By the polycondensation or polyaddition reaction between the compound represented by the general formula (IV) and the compound represented by the general formula (V), -Z ₁ and Z _2- are reacted to form a bonding chain Z. To be done. Table 1 collectively shows preferable combinations of Z ₁ and Z _{2 in} this case, types of Z to be formed, and ring structure names to be formed when the obtained polymer is heat-treated.

[0087]

[Table 1]

The polymer of component (a) can also be produced by the following method. That is, the general formula

[0089]

[Chemical 47]

Carboxyl of a product obtained by reacting a compound represented by the formula [wherein X has the same meaning as described above] with a compound represented by the general formula (V-3) or (V-4). A group represented by the general formula (VI)

[0091]

[Chemical 48]

[0092] Epoxy compound [R ₀ in the formulas have the same meanings as defined above] represented by or, for example, the general formula (VI
I)

[0093]

[Chemical 49]

An amine compound represented by: or a general formula (VIII)

[0095]

[Chemical 50]

The polymer is obtained by reacting with a quaternary ammonium salt represented by: For these reactions, known methods are used, for example, Japanese Patent Laid-Open No.
6-32524 and JP-A-60-194444. The compound represented by the general formula (IV-1) is, for example, the general formula (IV-6).

[0097]

[Chemical 51]

It is obtained by ring-opening the acid anhydride represented by the formula: R ₀ OH (R ₀ has the same meaning as described above). Examples of the acid anhydride (IV-6) include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid. Acid dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride, 3,3', 4
4'-diphenylsulfone tetracarboxylic acid dianhydride,
2,3,6,7-naphthalene tetracarboxylic acid anhydride,
Thiophene-2,3,4,5-tetracarboxylic anhydride, 2,2-bis (3,4-biscarboxyphenyl)
Examples of the alcohol R ₀ OH include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, allyl alcohol and ethylene glycol monoallyl ether. Can be mentioned.

When the acid anhydride (IV-6) is reacted with the alcohol R ₀ OH, the reaction is accelerated by adding pyridine, dimethylaminopyridine or the like. The combination of numbers 1 and 1'in Table 1 above is an example of a preferred embodiment, and the diamine represented by the general formula (V-4) used in this combination is
For example, 4,4'-diaminodiphenyl ether, 4,
4'-diaminobiphenyl, 2,4-diaminotoluene, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, phenylindanediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, m- Phenylenediamine, 1,5-diaminonaphthalene, 3,3'-dimethoxy-4,4'-
Diaminobiphenyl 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone, 2,2-
Bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4
-Aminophenoxyphenyl) sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 3,4'-diaminodiphenyl ether, 9,9-bis (4-amino) Phenyl) anthracene- (10), 9,9-bis (4-aminophenyl) fluorene, 3,3'-diaminodiphenyl sulfone, 4,4'-di- (3-aminophenoxy) diphenyl sulfone, 4,4 ' -Diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,
4 '-(m-phenylenediisopropylidene) bis (m
-Toluidine), 4,4 '-(p-phenylenediisopropylidene) bis (m-toluidine) and the like.

Of these combinations, the general formula (IV-
The reaction of the compound represented by 1) with the compound represented by the general formula (V-4) can be carried out using a carbodiimide type dehydration condensation agent, for example, dicyclohexylcarbodiimide. The compound represented by the general formula (IV-2) can be obtained by reacting the half ester represented by the general formula (IV-1) with thionyl chloride or phosphorus pentachloride.

Known methods are used for these reactions, and they are described in detail in, for example, JP-A-61-207022 and JP-A-61-118423. The method for producing the oxime compound used as the component (b) in the present invention is described in JP-A-62-201859, JP-A-62-286961, JP-A-63-10612 and JP-A-63-125510. Can be performed by the method described in.

The composition of the present invention is used by dissolving it in a solvent capable of dissolving all components in the composition and coating it on a predetermined substrate. At this time, in order to improve the adhesion to the substrate, the silane compound may be precoated on the substrate and used. The solvent is preferably a polar solvent such as dimethylformamide, N-methylpyrrolidone, dimethylacetamide, diglyme, isobutyl acetate or cyclopentanone, which does not have too high a boiling point. further,
Solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, esters, etc. can be added within a range in which components are not precipitated. As a method of coating on a substrate, after the solution obtained as described above is filtered with a filter, for example, a spin coater, a per coater, a blade coater,
It is possible to use a method of coating the substrate with a curtain coater, a screen printing method or the like, a method of immersing the substrate in the solution, a method of spraying the solution on the substrate, or the like.

As the substrate, for example, a heat resistant material such as metal, glass, silicon semiconductor, compound semiconductor, metal oxide insulator, silicon nitride is preferable, and when heat treatment is not carried out, material such as copper clad glass epoxy laminated plate is used. Can be used. Next, the coating film thus obtained is dried by a combination of air drying, heat drying, vacuum drying, etc., and then exposed through a normal photomask. On this occasion,
A g-line stepper exposure machine is used as the exposure machine.
The g-line stepper is a device for extracting and exposing only the g-line (wavelength 436 nm) of the bright lines of the ultra-high pressure mercury lamp used as a light source. Further, the exposure is preferably performed in a nitrogen atmosphere.

After exposure in this way, development is carried out by a dipping method, a spray method or the like in order to remove the non-irradiated portion. The developer used at this time is preferably one that can completely dissolve and remove the unexposed film within an appropriate time,
For example, N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, N-benzyl-2-pyrrolidone, γ-ptyrolactone, etc. The aprotic polar solvent may be used alone or as the second component thereof, for example, alcohols such as ethanol and isopropanol, aromatic hydrocarbon compounds such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone. , Ethyl acetate, ester such as methyl propionate, and solvent such as ether such as tetrahydrofuran and dioxane may be mixed and used. Furthermore, it is preferable to rinse with a solvent as shown as the second component immediately after development.

The image thus obtained was dried and then 1
By heating in the temperature range of 50 to 450 ° C., it is converted into a heat resistant polymer compound having an imide ring, an isoindoloquinazolinedione ring, an oxazinedione ring, a quinazolinedione ring, or the like.

[0106]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In addition, the names and structures of the polymers, oxime compounds, styryl compounds, compounds having a carbon-carbon double bond (monomers), aromatic amine compounds, mercaptan compounds, functional silane compounds, and polymerization inhibitors used in the examples are shown. 2 to Table 7.

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

[Table 7]

In Table 2, the structural formulas of the diamine components represented by abbreviations are as follows.

[0114]

[Chemical 52]

[0115]

Examples 1 to 23 To 100 parts by weight of the polymer shown in Table 2, the additives were added in the parts by weight shown in Tables 8 and 9, and 13
It was dissolved in 0 parts by weight of N-methylpyrrolidone. This solution was spin-coated on a silicon wafer (2000 rpm x
30 seconds) and dried in air at 70 ° C. for 90 minutes to obtain a uniform coating film. The film thickness of the coating film was about 20 μm.

Next, exposure was performed through a test pattern photomask in a nitrogen atmosphere. Canon FP for exposure
A1550M IV (The illuminance on the silicon wafer surface is 7
00 mw / cm ² ) was used. After leaving this wafer at room temperature for 1 hour, it was developed with a mixed solution of N-methylpyrrolidone / xylene = 1/1 (volume ratio) using a spray-type developing machine, rinsed with isopropyl alcohol and dried. The photosensitivity was determined from the exposure dose at which the lines and spaces of 20 μm in the test pattern were finely resolved (the smaller the exposure dose, the higher the photosensitivity). The obtained results are shown in the same table.

[0117]

[Table 8]

[0118]

[Table 9]

[0119]

[Comparative Examples 1 to 11]
An experiment was conducted on the composition of No. 1 and the results shown in the same table were obtained.

[0120]

Comparative Examples 12 to 17 Other photopolymerization initiators were used in place of the oxime compound of the present invention, experiments were conducted on the compositions in Table 11 in the same manner as in Examples 1 to 23, and the results are shown in the same table. I got the result.

[0121]

[Table 10]

[0122]

[Table 11]

[0123]

The composition of the present invention has many advantages over the compositions disclosed in the prior art. The advantage is that first, high photosensitivity was achieved for the g-line stepper exposure machine, and that the lithographic characteristics, which are important as the characteristics of the photoresist, were significantly improved. As a result of these, it can be seen that the composition of the present invention has ideal characteristics as a photoresist showing high resolution at a low exposure amount. Further, the composition has an advantage that it has extremely excellent long-term storage stability and is free from undesirable gelation, cracks, and surface film formation when the coating film is dried.

When the composition of the present invention is used for an interlayer insulating film or a surface protective film for a semiconductor element, the process is further shortened and the fine processing is facilitated by reflecting the above characteristics,
In addition, it exhibits characteristics such that a flatter layer can be formed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 79/08 LRB 9285-4J H01L 21/027

Claims (1)

[Claims] 1. (a) General formula: [Wherein X is a (2 + n) -valent carbocyclic group or heterocyclic group, Y is a (2 + m) -valent carbocyclic group or heterocyclic group,
Z is Or Or R ₀ is a group having a carbon-carbon double bond, W is a group capable of reacting with the carbonyl group of —COOR ₀ to form a ring by heat treatment, n is 1 or 2, m is 0, 1 or 2. ,
And COOR ₀ and Z are in an ortho position or a peri position with respect to each other], a polymer having a repeating unit represented by the following formula: [Wherein R ₁ , R ₂ and R ₃ are hydrogen atoms and have 1 to 6 carbon atoms]
Is an alkyl group having 1 to 6 carbon atoms, or a nitro group, R ₄ is an aromatic acyl group having 6 to 10 carbon atoms, an aliphatic acyl group having 1 to 6 carbon atoms, and 1 carbon atom.
To C6 alkoxycarbonyl groups, C6 to C1
An aromatic sulfonyl group having 0 or an aliphatic sulfonyl group having 1 to 6 carbon atoms, R ₅ represents an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or 6 to 10 carbon atoms; And an oxime compound represented by the general formula: [Wherein Q represents a carbocyclic group, a multicyclic group, or a group containing a carbonyl group, and R ₆ and R ₇ represent a hydrogen atom, a methyl group or an ethyl group]. A photosensitive composition containing a compound.