JPS62273260A - Novel photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive composition having high photosensitivity and improved lithographic characteristics and suitable for interlayer insulation film for semiconductor element, etc., by compounding a polymer having a specific structure, a triazole compound and a sensitizer having a specific absorption peak wavelength. CONSTITUTION:The objective composition can be produced by compounding (A) a polymer having a recurring unit of formula I [x is (2+n)-valent carbon cycle group of heterocyclic group; Y is (2+m)-valent carbon cycle group or heterocyclic group; Z is group of formula II, III etc., R* is group having C-C double bond; W is group capable of forming a ring by reacting with COOR* by heat-treatment; n is 1 or 2; m is 0-2] with (B) 0.1-20(wt)%, preferably 1-15% (based on the component A) triazole compound of formula IV (R1 and R2 are H, 1-4C alkyl or 1-4C alkoxy; R3 is 1-6C alkyl, 6-10C aromatic hydrocarbon group, etc.) and (C) 0.01-20%, preferably 0.05-15% (based on the component A) sensitizer having an absorption peak wavelength of 250-500nm (e.g. Michler's ketone).

Description

Detailed Description of the Invention λ Detailed Description of the Invention [Field of Industrial Application] The present invention provides a novel photosensitive composition, more specifically, a photosensitive composition that can be converted into a heat-resistant polymer compound by heat treatment. The present invention relates to a sexual composition.

Conventionally, heat-resistant polymerized metals represented by polyimide,
Taking advantage of its heat resistance and electrical properties, it is used as a structural member in fields such as electricity, automobiles, aircraft, space, and nuclear power.
Widely used for printed circuit board materials, heat-resistant insulation materials, etc.

On the other hand, photosensitive polymer compounds are widely used in applications such as paints and printing plates, and in recent years, their lithography properties have been particularly utilized for resists for creating printed circuits, resists for etching metal plates, and resists for creating semiconductor elements. It is well known that remarkable progress has been made in microfabrication materials such as silica and custo.

In recent years, polymer materials that have these two useful functions of heat resistance and photosensitivity have been actively developed, especially for use in electronic and optical materials, such as side-light insulation films and α-ray shielding films. Applications are being considered, such as surface protection films such as films and junction coat films, insulating films for semiconductor devices such as glabellar insulating films for multilayer wiring, alignment films for liquid crystal display devices, and insulating films for thin film magnetic heads [e.g. , "Functional Materials", July issue, pages 9-19 (1983) and [Photographic Science and
Engineering (Photographic 5ci)
ence sndljngineering)j pages 303-309 (1979)].

[Conventional technology]

Conventionally, in heat-resistant photosensitive compositions, active functional groups such as double bonds have been introduced into the ester side chains of polyamic acid, which is a precursor of polyimide. A composition is known in which a photosensitizer and a copolymerizable monomer are added to a reamer, and a crosslinked structure can be formed by light irradiation ('Fj Kosho 55-30
207, Japanese Patent Publication No. 55-41422). This is the basic composition of heat-resistant polymer materials for lithography, typified by so-called photosensitive polyimides.
The photosensitivity was low and insufficient for practical use. or,
As a composition that improves these drawbacks, a composition has been proposed in which a methacrylate group or an acrylate group is used as the active functional group in the side chain, and an azide compound such as p-acetamido-phenylsulfonazide is added as a photoinitiator. (Japanese Unexamined Patent Publication No. 155347/1983). However, although this composition has slightly improved photosensitivity, it is still not sufficient.

On the other hand, a photosensitive composition containing as a main component a mixture of a polyamic acid and an amine compound having an active functional group such as a double bond has been proposed (%Open Side No. 57-168942,
JP-A-54-145794, JP-A-59-160
140 Newsletter).

However, since the viscosity of this solution is extremely high, it is necessary to use a solution with a lower concentration, and it is difficult to form a thick film when using a spin coater, which is commonly used for forming films on the surface of semiconductor elements. It was difficult. or,
Since these are ionic bond types, there is a problem in that if they are left to stand after being applied and dried, they tend to crack due to moisture absorption.

The method of using the compositions disclosed in these prior art techniques is to apply the compositions as a solution onto a substrate, dry it, irradiate it with active light such as ultraviolet rays through a photomask, and then remove the unexposed areas with a suitable developing solvent. A heat-resistant film is formed by dissolving and removing the polyamic acid, forming an image, then performing high-temperature treatment to close the imide ring, etc., and at the same time vaporizing the polyamic acid side chains, crosslinking chains, initiator, etc. A typical example of this is the process of instigation.

[Problem that the invention seeks to solve]

By the way, it has been found that in the conventional prior art, as the film thickness of the so-called photosensitive polyimide is increased, the photosensitivity decreases extremely and the exposure time required for curing becomes longer. .

However, we have already found that photosensitivity can be improved by combining an oxime compound with a certain structure with a sensitizer as a photoinitiator (Japanese Patent Application No. 1983-1999).
No. 238,545), but it is necessary to further improve the sensitivity.

In view of these circumstances, the inventors of the present invention have developed a material with high photosensitivity.
We have conducted intensive research to provide a heat-resistant photosensitive composition that has high photosensitivity, especially when used in thick films.

[Ninth way to solve the problem]

As a result, a polymer with a specific structure as an essential component,
Oxime compound and absorption peak wavelength of 250-50Q
It was discovered that a composition containing a sensitizer in the range of nm is suitable for the purpose, and based on this finding, the present invention was completed.

That is, the present invention provides (a) general formula (1) [wherein X is a (2+n)-valent carbocyclic group or heterocyclic group, Y is (z+
m) a valent carbocyclic group or heterocyclic group R* is a group having a carbon-carbon double bond, W is a group capable of reacting with the carzenyl group of -000R* to form a ring by heat treatment; fI is 1 or 2, m is 0.1 or 2, and C00R* and 2 are in an ortho- or peri-position relationship with each other] (hereinafter referred to as component (A)) ) and (b) a triazole compound represented by the general formula (2) [wherein R1+ R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, R
s represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aromatic hydrocarbon having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms; ) A photosensitive composition containing as an essential component a sensitizer having an absorption peak wavelength of 250 to 500 nm.

In the composition of the present invention, the polymer used as component (a) has a repeating unit represented by the above general formula (1), where X is a trivalent or tetravalent carbocyclic group or a heterocyclic group. A formula group, and the more rigid is 0 or 1, and X8 is OH or cps]. Among these, carbon number 6-14
aromatic hydrocarbon group, Xl is +CHz+t (l is 0 or 1), -a-, -S-, -O- or OF.

is -0- (the group represented by I is preferably Fs Furthermore, the expression %formula%) Those shown are preferred.

YFi2.3 or a tetravalent carbocyclic group or a heterocyclic group in the general formula (1), such as a divalent group having 10 to 18 carbon atoms derived from naphthalene, anthracene, etc. aromatic hydrocarbon ring, pyridine,
Heterocyclic groups derived from imidazole etc. and the formula y, Y4 n OHs OHs [Yl in the formula is] l , OH,, (CH,), OH,
ooHs+ 0OOHI halogen atom or 80. H,Y
, is +OH + (hole, p FiO or 1),
-80 goose-1OH.

Oh.

Ys and Y4 are H, OH3, O Hgt 0OHs +
Halogen atom, 000H, So, H or No, Ys
and y is H, ON, halogen atom, OHM, 0OH
3+ 5OsH or OH]. Among these, divalent aromatic hydrocarbon rings having 10 to 14 carbon atoms, Y2 is 1,000 OH +i) (where p is O or 1), -0-1-SO, -1-〇- or -S- and Ys and Y4 are both hydrogen atoms, formula (I,)
A group represented by the formula is preferred, and a group represented by the formula is more preferred.

W in the general formula (1) can be changed by heat treatment to -0O
A group capable of forming a ring by reacting with the carzenyl group of OR*, and -O-NH is particularly suitable as such a group. Further, n is preferably 2.

Furthermore, B* in the general formula (1) is a group having a carbon-carbon double bond, and as such,
For example, -R#-cH=aH, (Its) [wherein R' is a hydrogen atom or a methyl group, R' is an alkylene group having 1 to 3 carbon atoms, and n is 1 or 2]. It will be done.

As an example of (■1), -OH, -0-0-OH= OH錞OCHx -OH冨-OH* O0-0H=OHt (As an example of (■), as an example of (■3), As an example of (■4), As an example of (IIs), OHt -OH= OHM -OH heat - 0H1-OH=OH! As an example of (■-), As an example of (■te), Examples include.

Among these, photosensitivity, storage stability, etc.
preferable.

The triazole compound used as component (b) in the composition of the present invention is represented by the general formula (2).

T1. .

In the formula, R1+ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkohexyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group, a methyl group, a methoxy group, or an ethoxy group. There are many examples. In the formula, R3 has 1 carbon number
In the alkyl group having 1 to 6 carbon atoms, y is an alkoxy group having 1 to 6 carbon atoms, an aromatic hydrocarbon having 6 to 10 carbon atoms, or an aryloxy group having 62 to 10 carbon atoms, preferably ethyl, n-propyl group, 1ao -propyl group, n
-butyl group, 1so-butyl group, terl-butyl group, methoxy group, ethoxy group, n-propoxy group, 1s
o-propoxy group, n-butoxy group, 130-butoxy group% tert-butoxy group, phenyl group, tosyl group, phenyloxy group, tosyloxy group, etc.
Examples include, but are not limited to, υ.

Note that these may be used alone or in combination.

The sensitizer used as component (iii) in the composition of the present invention has an absorption wavelength of 250 to 500n+n, and examples of such a sensitizer include: [wherein R1+ Rt is a methyl group, or ethyl group, R
3 is a hydrogen atom or a methyl group, R4 is an aromatic hydrocarbon having 6 to 10 carbon atoms, R3 is a methyl group, an ethyl group, or an aromatic hydrocarbon having 6 to 10 carbon atoms% R
6, Rt is a group consisting of a hydrogen atom, an aliphatic group, a substituted aliphatic group, or an aromatic hydrocarbon having 6 to 10 carbon atoms;
), R411'L7 is a group other than a hydrogen atom, 38 is a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, m and n are 0.1 or 2], and the like.

Examples of sensitizers include Michler's ketone, 4°4'-his-(diethylamino)-hensiphenone, 2, s
t% Su(4'-diethylaminobenzal)-cyclointanone, 2.6-bis(4'-diethylaminobenzal)-cyclohexanone, 2.6-♂su(4'-dimethylaminobenzal)-4-methylsu(4'-dimethylaminobenzal)-cyclointanone pa hexanone, 2,6-bis(4'-diethylamino-4-)-
4-Methyl-cyclohexanone, 4.4'-pis-(dimethylamino)-chalcone, 4.4'-bis-(diethylamine)-chalcone, 4-dimethylaminocinnamylidene indanone, 4-・cumylaminobenzylidene Indanone, 2-(4'-dimethylaminophenylvinylene)-benzothiazole, 2-(4'--)methylaminophenylvinylene)-isonaphthothiazole, 1.3
-bis-(4'-dimethylaminobenzal)-a7ton, 1,3-bis-(4'--7ethylaminobenzal)-a7ton, 3°3'-carzenylupisu(7 -Dinithylamino coumarin), 7-J) ethylamino-3
-benzoylcoumarin, 7-danitylamino-4-methylcoumarin, N-phenyl-jetanolamine, N-
Examples include, but are not limited to, p-tolyl-diethylamine. Note that these may be used alone or in combination. Preferably, a sensitizer having the structure (■1) to (■s) and a sensitizer having the structure (■.) are used in combination.

A compound having a carbon-carbon dibond may be added to the composition of the present invention, if necessary.

This compound having a carbon-carbon double bond is a compound that facilitates the photopolymerization reaction when added,
Such compounds include 2-ethylhex'7 acrylate, 2-hydroxyethyl acrylate, N-vinyl-2-pyrrolidone, carpitol acrylate, tetrahydrofurfuryl acrylate, isomylnylacrylate, and 1°6-hexanediol diol acrylate. Acrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, diintererythritol hexaacrylate, tetramethylolmethanetetraacrylate, tetraethylene glycol Examples include diacrylate, nonaethylene glycol diacrylate, methylene bisacrylamide, N-methylolacrylamide, and those obtained by changing the above acrylate or acrylamide P to methacrylate or methacrylamide. Among these, two are preferred. It is a compound having the above carbon-carbon double bond.

Furthermore, by adding a mercaptan compound to the composition of the present invention, photosensitivity can be further improved. Examples of mercaptan compounds include, for example, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-IH-tetrazole, 2-mercaptothiacine, 2-mercapto-4-
Phenylthiazole, 2-amino-5-mercapto-1
゜3.4-thiazole, 2-mercaptoimidazole,
2-mercapto-5-methyl-1,3,4-thiadiazole, 5-mercapto-1-methyl-IH-tetrazole, 2,4.6-drimercabuto 3-triazine, 2
-dibutylamino-4,6-dimercabuto-s-triazine, 2,5-dimethylcapto-1,3,4-thiadiazole, 5-mercapto-1°3.4-thiadiazole, 1-ethyl-5-mercapto-1, 2,3,4-tetrazole, 2-mercapto-6-nitrothiazole, 2
-mercapto-4-zoxazole, 4-7enyl-2-
Examples include mercaptothiazole, mercaptopyridine, 2-mercaptoquinoline, l-methyl-2-mercaptoimidazole, 2-mercapto-β-naphthothiazole, and the like.

Furthermore, a functional dialkoxysilane compound can be added to the composition of the present invention, or a base material can be precoated therewith, if necessary. This dialkoxysilane compound is a compound that improves the adhesion of the interface between the heat-resistant polymer film of the composition of the present invention and the base material Si and inorganic insulating film, and examples thereof include, for example. , γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)r-aminopropyldimethoxysilane, γ-glycidoxy7propylmethyldimethoxysilane, r-mercaptopropylmethyldimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperi dinopropylsilane, jetoxy-3-glycyP
Examples thereof include xizolobylmethylsilane, N-(3-jethoxymethylcrylprobyl)succinimir, and the like.

The usage and effects of these dialkoxysilane compounds are described in detail in, for example, Japanese Patent Application No. 38242/1983. Furthermore, a polymerization inhibitor may be added to improve the storage stability of the solution of the composition of the present invention. Examples of the polymerization inhibitor include tert, hydroquinone, N-nitron diphenylamine, p-1crt-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, and the like. However, it is not limited to these.

There is no particular restriction on the content of the triazole compound in the (oral) component in the present invention, but preferably (a)
It is desirable to contain it in a range of 0.1 to 20% by weight, more preferably 1 to 15% by weight, based on the component polymer. If the content is low, the photosensitivity will not be sufficient, and if the content is too high, the film properties after heat treatment will deteriorate.

In addition, the content ratio of the sensitizer as component (c) in the present invention is 0.01 to 20% by weight 2 to the polymer of component 0.
, preferably in a range of 05 to 15% by weight. When the content is small, the photosensitivity is insufficient, and when the content is too large, the photosensitivity decreases.

The amount of the compound having a carbon-carbon double bond is (a)
The amount of the lehemerkabutan compound added is preferably 2.0% by weight or less based on the component polymer, preferably 10% by weight or less based on the component (a) polymer, and more preferably SX amount% or less. It is. In addition, when the functional dialkoxysilane compound is added and used, the amount added is O,OS to iol amount%, based on the polymer of component (a),
Preferably it is 0.1 to 4% by weight.

Further, the polymerization inhibitor has a content of 5% to the polymer of component (a)
It is used in an amount of not more than 0.5% by weight, preferably not more than 0.5% by weight.

The polymer used as component (a) in the composition of the present invention can be obtained, for example, by polycondensation or polyaddition of a compound represented by the general formula and a compound represented by the general formula. Examples of zl in the above general formula [phase] and Shiteha, -COOH (IIIt), -Cool (L)
, -Neo(IIIs) -NH (L), OH(
IIIg) is l), and the corresponding general formula (a)
The abbreviation is shown within 0. Also, as examples of Z in the general formula ω, -oocl(■t), -000H(Mz
).

-NOO (Ms), NHZ (■4), and the corresponding abbreviations of the general formula ω are shown within 0. Oh,
X, R, Y and W have the same meanings as above.

By polycondensation or polyaddition reaction between the compound represented by the general formula (1) and the compound represented by the general formula (1), Sea Z! and Z
The bond chain 2 is formed by reacting with l-.

In this case, a preferable combination of Zl and Z, generated 2
Table 1 summarizes the types of and the ring structure groups formed when the obtained polymer is heat-treated.

Table 1 [Notes] *1 Ring structure engineering M: imito ring QD: quinazolinedione ring OD = oxazinedione ring 0) The polymer of the component can also be produced by the method shown below. That is, a product obtained by reacting a compound represented by the general formula (% formula %) [X in the formula has the same meaning as above] with a compound represented by the general formula (■3) or (■4) The carzexyl group of the compound can be converted into an epoxy compound represented by the general formula [R* in the formula has the same meaning as above], or an amine compound represented by the general formula, or a quaternary ammonium compound represented by the general formula. The polymer is obtained by reacting with a salt.

Note that these reactions are described, for example, in JP-A-56-32524.
It is described in Japanese Patent Application No. 59-49339.

The compound represented by the above general formula (■1) can be obtained, for example, by ring-opening the acid anhydride represented by the general formula (ms) O with R*OH (1'L* has the same meaning as above). It will be done. The acid anhydride (■-
), for example, pyromellitic anhydride, 3.3'.

4.4'-benzophenonetetracarzenic dianhydride,
3.3',4.4'-cyphenyl ethertetracarzenic acid dianhydride, 3.3',4.4'-diphenyltetracarzenic acid dihydride, 3,3',4,4 '-Diphenylsulfonetetracarnoic dianhydride, 2,3,6
．． 7-S7talentetracarzenic anhydride, thiophene-2゜3.4.5-tetracarzenic anhydride, 2.2-
Examples include bis-(3,4-biscarxyphenyl)zolonocene anhydride, and alcohol R*OH includes 2
Examples include -hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyzologyl acrylate, allyl alcohol, and ethylene glycol monoallyl ether.

When these acid anhydrides (■-) are reacted with alcohol R*OH, the reaction is accelerated by adding pyridine, dimethylaminopyridine, etc.

The combination of numbers 1 and 1' in Table 1 above is one example of a preferred embodiment, and the diamine represented by the general formula (4) used in this combination is, for example, 4,4'-diaminodiphenyl ether. , 4.4'
-diaminopiphenyl, 2,4'-diaminotoluene,
4.4'--)amine (nzophenone, 414/,
7 aminodiphenyl sulfone, phenylindane diamine, 4,4'-diaminodiphenylmethane p-)unilene diamine, m-phenylene diamine, 1.5--)
Aminonaphthalene, 3,3'-dimethoxy-4,4'-
Diaminopiphenyl, 3,3'-dimethyl-4,4'-
Diaminopiphenyl, O-toluidine sulfone, 2.2
-Bis(4-aminephenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfone, bis(
4-aminophenoxyphenyl)sulfur, x, <-
Bis(4-aminophenoxy)benzene, 1.3-bis(4-aminophenoxy)benzene, 3.4'-diaminodiphenyl ether, 9.9-bis(4-aminophenyl)anthracene-(10), 9.9 -bis(4-aminophenyl)fluorene, 3.3'-diaminodiphenylsulfone, 4.4'-di(3-aminophenoxy)diphenylsulfone, 4.4'-)aminopenzanilyr, 3.4'- Diaminodiphenyl ether, 4.4
'-(1,3-phenylenebis(1-methylethyl IJ
7")], 4.4'-[1,4-7
-methylethylidene) ), 414' (111-7
22 dilene propylidene) bis(m-toluidine)
, 4,4'-CP-phenylene diisopropylidene) bis(m-toluidine), and the like.

Among these combinations, the reaction between the compound represented by the general formula (■1) and the compound represented by the general formula (■4) is performed using a CalI diimide) 11 type dehydration condensation agent, such as dicyclohexyl calzediimide P. It can be done using

Furthermore, the compound represented by the general formula (mx) is represented by the general formula (mx).
(2) It can be obtained by reacting the half ester shown in 1) with thionyl chloride, phosphorus pentachloride, etc.

For the methods of these reactions, see, for example, Japanese Patent Application No. 1986-1.
No. 93737, Patent Application No. 1983-9918, Patent Application No. 1983-
It is described in detail in No. 238545, etc.

The triazole compound used as component (b) in the present invention can be produced by reacting an N-hydroxybenzo)+77 sol derivative with a carinyl halide. A method for producing N-hydroxybenzotriazole derivatives is described by Ohemisehe Berichte.
Berichte) No. 103, pp. 788-798 (
(1970).

The composition of the present invention is used by dissolving it in a solvent that can dissolve all the components in the composition and coating it on a predetermined substrate. At this time, in order to improve the adhesion to the substrate, the dialkoxysilane compound may be pre-coated on the substrate.

The solvent is preferably a polar solvent, such as dimethylformamide, N-methylpyrrolidone, dimethylacetamide r1 diglyme, inbutyl acetate, or cyclopentanone, which does not have an excessively high boiling point. Furthermore, solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, and esters can be added to the extent that the components are not precipitated.

The method for coating the substrate on the substrate is such that the solution obtained as described above is filtered, and then coated on the substrate using an EVA spin coater, a Nono coater, a spray P coater, a curtain coater, a screen printing method, etc. A method of coating, a method of dipping the substrate in the solution, a method of spraying the solution onto the substrate, etc. can be used.

As the substrate, heat-resistant materials such as metallic glass, silicon semiconductors, metal oxide insulators, and silicon nitride are preferable, and when heat treatment is not performed, materials such as copper-clad glass eix laminates can be used.

Next, the coating film obtained in this way is air-dried, heat-dried,
After drying using a combination of vacuum drying and the like, exposure is usually performed through a photomask. At this time, the active light used includes, for example, ultraviolet rays, X-rays, electron beams, etc. Among these, ultraviolet rays are preferable, and the light source thereof is as follows:
Examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps. Among these light sources, ultra-high pressure mercury lamps are preferred. Further, it is preferable that the exposure is performed under a nitrogen atmosphere.

After exposing in this way, in order to remove the unexposed area,
Development is performed using a dipping method, a spray method, etc. The present solution used for this removal is preferably one that can completely dissolve and remove the unexposed film within an appropriate time, such as N-methylpyrrolidone, N-7 cetyl-2-pyrrolidone, N-7,
N-dimethylformamide p, N,N-dimethylacetamide r1 dimethyl sulfoxide, hexamethylphosphoric triamide, N-benzyl-2-pyrrolidone,
An aprotic polar solvent such as γ-butyrolactone may be used alone, or as a second component,
For example, ethanol, isoprono-alcohol, toluene, xylin natono-aromatic hydrocarbon compound,
Ketones such as methyl ethyl ketone and methyl indithyl ketone; esters such as ethyl acetate and methyl propionate;
A mixture of solvents such as ethers such as tetrahydrofuran and dioxane may be used. Furthermore, it is preferable to rinse with a solvent such as that shown as the second component immediately after development.

The image obtained in this way has an image density of 150 to 450 after drying.
By heating in the temperature range of .degree. C., it is converted into a heat-resistant polymer compound having an imi-P ring, an inoindroquinazolinedione ring, an oxazinedione ring, a quinazolinedione ring, and the like.

〔Effect of the invention〕

The compositions of the present invention have many advantages over compositions disclosed in the prior art. The advantages of this include, first, that high photosensitivity was achieved;
The lithography properties, which are considered important as photoresist properties, have also been significantly improved. These results show that the composition of the present invention has ideal properties as a photoresist, such as exhibiting high resolution at low exposure doses. Furthermore, the composition has the advantage of long-term storage stability and no undesirable gelation or cracking during coating drying.

When the composition of the present invention is used as a glabella insulating film or a surface protective film for semiconductor devices, the process can be further shortened and microfabrication can be facilitated by reflecting the above-mentioned characteristics. It exhibits characteristics such as being able to form a thick layer.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples in any way. Table 2 shows the names of the polymers, triazole compounds, sensitizers, compounds having carbon-carbon double bonds (monomers), mercaptan compounds, functional dialkoxysilane compounds, and polymerization inhibitors used in the examples. .

The following margin (2) triazole compound (3) sensitizer absorption peak wavelength was measured using a Nomarian C!ARY 219 spectrophotometer (Varian C! ARY 219 spec).
trophotometer) using ethanol as a solvent.

(4) Nanatsumer (5) Mercaptan compound (6) Functional dialkoxysilane compound (7) Polymerization inhibitor Examples 1 to 20 shown in Table 3? The additives shown in the table are 7 tons for 100 parts by weight of rif-1. i parts were added and dissolved in 120 parts of N-methylpyrrolidone. Spin this solution onto a silicon wafer) (700 rpm x 75ec) L, 70
A uniform coating film was obtained by drying for 6 hours in °C air.

Next, under a nitrogen atmosphere, gray scale (KodakPho)
tographic 5tep Tablet, A
2) through an ultra-high pressure water lamp (8m W/cm”
) for 5 minutes. The wafer was left at 23° C. for 30 minutes, developed with a mixed solution of equal amounts of γ-butyrolactone and xylene using a spray developer, rinsed with xylene, and dried. Sensitivity was calculated as the number of stages from the curing state of each step of the gray scale. (The higher the number of steps, the higher the sensitivity; increasing the number of steps by one means that the exposure amount is lower by V]-.) The obtained results are shown in the same table.

Comparative Examples 1 to 5 Experiments were conducted on the compositions in Table 4, which are the same as Examples 1 to 20, and the results shown in the table were obtained.

Comparative Examples 6-11 Experiments were conducted on the compositions in Table 5 in the same manner as in Examples 1-20 using other photopolymerization initiators instead of the oxime compound of the present invention, and the results are shown in the table. I got it.

Examples 21 to 23 1 ton (o, s mol) of diaminodiphenyl ether was dissolved in 880 f of N-methylpyrroli, and 109 t (0,5 mol) of pyromellitic dianhydride was added.
By reacting at 0 to 60°C for 3 hours, 2
A polymer solution of 8 poise was obtained. (This polymer solution is expressed as p-a) To 100 parts by weight of this polymer solution, the additives shown in Table 6 are added in parts by weight and dissolved. This solution was applied onto a silicon wafer using a spin code (500 rpm).
Xlosec) L was dried at 70° C. for 1 hour to obtain a uniform coating film. Further, on this coating film, the solution was applied with a spin cord and dried four times to obtain a coating film. Next, grayscale (Kodakphotography) was performed under a nitrogen atmosphere.
! The wafer was exposed to ultra-high pressure mercury lamp (8 mW/m'') for 5 minutes through a 9tep Tablot A2). After the wafer was left at 23°C for 30 minutes, it was exposed to N-methylpyrrolidone (2 parts) using a spray developer. The film was developed with a mixed solution of and methanol (1 part), rinsed with methanol, and dried.The curing sensitivity is shown as the number of stages.The obtained results are shown in Table 6.

Margin Reference Example 1 An example of a method for producing a triazole compound (abbreviation 2-3) having the following structure is shown below as a method for producing a triazole compound used in the present invention.

N-hi)' o #shihe7zotriazole 13.5
F (0,1 mol)totriethylamine 11.1 F
(0.11 mol) dissolved in 7 tons of 400d, 10
Benzoyl chloride 15.46 t (0,
11 mol) was added dropwise. After the dropwise addition, stirring was continued for 1 hour at room temperature. After the reaction is completed, the reaction solution is passed through the mouth, and the oral solution is evaporated to dryness. The obtained triazole compound is recrystallized from ethanol. The yield is 16? (yield 67%).

Claims (1)

[Claims] (1) (A) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, X is a (2+n)-valent carbocyclic group or heterocyclic group, Y is a (2+m)-valent carbon Cyclic group or heterocyclic group, Z has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc.
A group that can react with the carbonyl group of ^* to form a ring, n is 1 or 2, m is 0, 1 or 2, and COOR^*
and Z are in an ortho- or peri-position relationship with each other], and (b) a polymer having a repeating unit represented by the general formula (
2) Triazole compound ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) [In the formula, R_1 and R_2 are hydrogen atoms, or alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms. , R_3 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 6 to 10 carbon atoms
an aromatic hydrocarbon or an aryloxy group having 6 to 10 carbon atoms], and (c) a sensitizer having an absorption peak wavelength of 250 to 500 nm.