JPS62273259A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive composition having high photo-sensitivity and improved lithographic characteristics and suitable for interlayer insulation film for semiconductor element, etc., by compounding a polymer having a specific structure, an oxime 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 or 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 1-2; m is 0-2] with (B) 0.1-20(wt)%, preferably 1-15% (based on the component A) oxime compound of formula IV (R1 is H, 1-6C alkyl, NO2, etc.; R2 is 1-6C alkyl, 1-6C alkoxy, etc.; R3 is R2 or aromatic hydrocarbon group) 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] [Industrial Application Field] The present invention relates to a novel photosensitive composition, more specifically, to a photosensitive composition that can be converted into a heat-resistant polymer compound by heat treatment (This is doubled.

Conventionally, heat-resistant polymer compounds represented by polyimide are
Taking advantage of its heat resistance and durability characteristics, it is used as a structural member in fields such as electricity, automobiles, aircraft, space, and nuclear power.
Printed circuit board materials, heat-resistant insulating materials, etc. (widely used).

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

In recent years, polymer materials that have these two useful functions of heat resistance and photosensitivity have been actively developed, especially for use in magnetic materials and optical materials, such as passivation films, α-ray shielding films, Applications are being considered for surface protection films such as Jangkun Yong coating films, insulating films for semiconductor devices such as interlayer insulating films for multilayer wiring, alignment films for liquid crystal display devices, and insulating films for S films and magnetic heads [e.g. , “Functional Materials”, July issue No. 2~/Tapage (/9er
3 years) and ``Photographic Science and Engineering (Photographic 5)
Science and Engineering ) J
% See pages 303-309 (/7 years)].

[Conventional technology]

Conventionally, heat-resistant photosensitive compositions have been prepared by adding a photosensitizer or a copolymerizable polymer to a polymer in which an active functional group such as a double bond is introduced into the ester side chain of polyamic acid, which is a precursor of polyimide. A composition in which a crosslinked structure can be formed by light irradiation is known (Japanese Patent Publication No. 33-302
Publication No. 02, Special Publication! ! -g/<t22 publication). This is a basic composition of heat-resistant polymer materials for lithography, typified by so-called photosensitive polyimides, but its photosensitivity was low and ζ= was insufficient for practical use.

As a composition that improved on these drawbacks, he proposed a composition in which a methacrylate group or an acrylate group was used as the active functional group in the side chain, and an azide compound such as p-acetamido-phenylsulfonazide was added as a photoinitiator. (Japanese Unexamined Patent Publication No. 1983-163'17). 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 polyamic acid and an amine compound having an active functional group such as a double bond has been proposed (Japanese Unexamined Patent Publication No. 57-7 Otsu!992,
JP-A No. 5g-/4tj799, JP-A No. 69-/6
0/4tθ publication).

However, since the viscosity of this solution is extremely limited, it is necessary to use a solution with a lower concentration, and when using a spin coater, which is commonly used for forming films on the surface of semiconductor elements, it is difficult to form thick films. In addition, since these are ionic bond types, they have the problem of absorbing moisture (and more easily causing cracks) if left after coating and drying.

In both of these prior art methods of using the disclosed compositions, they are applied as a solution onto a substrate, and after drying,
After irradiating active light such as ultraviolet rays through a photomask, the unexposed areas are dissolved and removed using an appropriate developing solvent to form an image.
A typical process is to close the ring and simultaneously vaporize the polyamic acid side chains, crosslinked chains, initiator, etc. (forming a heat-resistant film).

[Problem to be solved by the invention J] By the way, in the conventional prior art, as the film thickness of so-called photosensitive polyimide is increased, the photosensitivity decreases extremely and the exposure time required for curing becomes longer. It was found that it has the following drawbacks:

Furthermore, we have already discovered that photosensitivity can be improved by combining a sensitizer with an oxime compound having a certain transversal position as a photoinitiator (Japanese Patent Application No. 1983-
23F! 4tj), but it is necessary to further improve the sensitivity by (-1).

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.

[Failure to solve the problem]

As a result, a polymer with a specific structure as an essential component,
Oxime compounds and absorption peak wavelengths of 250~! θ0
It was discovered that a composition containing a sensitizer in the range of nm is suitable for the purpose, and based on this knowledge, the present invention was completed.

That is, the present invention provides (a) the general formula fi+ [wherein X is a (2+n)-valent carbocyclic group or heterocyclic group, and Y is Lz
+m) A valent carbocyclic group or a heterocyclic group R* is a group having a carbon-Fujie bond, W is -COOR* by heat treatment
A group capable of forming a ring by reacting with the carbonyl group of A polymer having a repeating unit (hereinafter referred to as component (a)) and (b) an oxime compound represented by the general formula 2) [in the formula, R1 is a hydrogen atom, or an alkyl group with a carbon number of 1 to 2], or a carbon Alcokyne group or nitro group with a number of carbon atoms / to B, R2 is an alkyl group with a carbon number of / to B, father is carbon @ /
an alkoxy group having from 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, R3 an alkyl group having 1 to 1 carbon atoms, or an alkyl group having the following system a/to 2, or an aromatic hydrocarbon group having a carbon number of 1 to 10; or an alkokyne group having 6 to /θ carbon atoms] and (/→ The present invention provides a photosensitive composition comprising as an essential component a sensitizer having an absorption peak wavelength of 250 to t 00 nm. .

The polymer used as the component (a) of the composition of the present invention (2) has a repeating unit represented by the general formula (1) above, and X in the formula is a trivalent or nonavalent carbocyclic group. Or a polycyclic group, such as X, for example, a fused polycyclic aromatic ring such as a benyne ring, a naphthalene ring, an anthracene ring, a polycyclic group such as pyridine or thiophene,
and general formula (1+) person! X2 is CH or CF] and the like. Of these, carbon number 6
~/g aromatic hydrocarbon group and Xl is ÷CH2+.

OO (l is 0 or /), -〇-1-8-1-〇-F3 In addition, the expression %formula%) Those shown are preferred.

In the self-written general formula (1), Y in + is a carbocyclic or heterocyclic group with a valence of 3 or 3, such as naphthalene, anthracene, etc. ~/Any divalent aromatic hydrocarbon ring, pyridine, imidazole, etc., and a polycyclic group having the formula Y s Y 4 CH, CH.

(Y in the formula is H, CH,, (CH,), CH1OCH
3, C0OH, halogen atom or 5O3H, Y! is +C
Hr% (where p is O or /), -8O2
-1 CH.

Ys and HiY4 HaH, CH3, C, H,, OCH,,
2. Ge, atom.

C0OH, So, H or No2, Ys and Ys&i H
, CN, halogen atom, CH3, OCH,,5o3H
or OH), and the like. Among these, there are divalent carboxylic boron rings having 70 to 9 carbon atoms, Y2 is ÷CH2+p (where p is θ or /), -C
-1-so, -1-〇- or -8-, and Ys and Y
A group represented by the formula (1s) in which 4 is a dihydrogen atom is preferred, and a group represented by the formula is more preferred.

By heat treatment, W in the general formula (1) (2) becomes -C
It is a group that can react with the carbonyl group of "0OR" to form a ring, and is particularly preferred as such.

Furthermore, R* in the general formula (1) is a group having a carbon-silicon bond, and as such,
For example, -R"-CH=CH, (us) [wherein R' is a hydrogen atom or a methyl group, R" is an alkylene group having 7 to 3 carbon atoms, and n is/or]. It will be done.

As an example of (L), -C)42-0-C-CH=CH.

0.

As an example of (12), As an example of (ls), As an example of (14).

As an example of (IIs), -CH, -CH=CH2 -CH, -C1-1, -OH=CH.

As an example of (n@), As an example of (fly), HOCH.

Examples include.

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

The oxime compound used as a component of the composition of the present invention is represented by the above general formula (2).

In the formula, R is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a nitro group, preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. group, nito-o group, etc. In the formula, R2 is an alkyl group having 1 to 2 carbon atoms, or an alkoxy group having 6 to 6 carbon atoms, or 6 to 6 carbon atoms.
aryloxy group, preferably methyl group, ethyl group, n-propyl group, 1so-propyl group, n-
Butyl group, 1so-butyl group, tert-butyl group, metquine group, ethquine group, n-propoxy group, 1so-propoxy group, n-butoxy group, 1so-butoxy group, t
Examples include ert-fu)oxy group, phenyloxy group, and tonloxy group. In the formula, R3 is an alkyl group having 1 to 1 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an aromatic hydrocarbon having 6 to θ carbon atoms, or an aryloxy group having 1 to 10 carbon atoms, preferably , ethyl group, rhopropyl group, 1so-propyl group, n-butyl group, 1so-butyl group, tert-butyl group, methoxy group, ethoxy group, n-propoquine group, 1so-propoxy group, n-butoxy group, 1so -butoxy group, tert
-Butquin group, phenyl group, tosyl group, phenyloxy group, tonluoxy group, etc. Examples of Okinmu compounds include, but are not limited to these. Note that these may be used alone or in combination.

The +11 sensitizer used as component (c) in the composition of the present invention has an absorption peak wavelength of 230 to j00 nm.
is a methyl group or an ethyl group; R3 is a hydrogen atom or a methyl group; R4 is an aromatic hydrocarbon having 6 to 10 carbon atoms; R5 is a methyl group, an ethyl group, or /θ aromatic hydrocarbon, R6, R, is a hydrogen atom, an aliphatic group, a substituted aliphatic group, a group consisting of an aromatic hydrocarbon having 2 to 10 carbon atoms, and at least one of R6 and R7 is It is a group that is not a hydrogen atom, and examples thereof include R6 as a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, and m and n as θ and/or co].

Examples of sensitizers include Michler's ketone, lysate'-bis-(diethylamino)-benzophenone, λ,! -bis(ri'-diethylaminobenzal)-cyclopentanone, 2,6-bis-(4t'-diethylaminobenzal)-cyclohegysane, 6-pis(g'-dimethylaminobenzal)-termethyl-cyclohexanone ,
ko, Otsu-bis(ri'-diethylaminobenzal)-coumethyl-cyclohequinanone, g, x'-bis-(dimethylamino)-chalcone, 4t, Hiro'-bis-(diethylamino)-chalcone, goudimethylaminone annamylidene indanone, gauge methylaminobenzylidene indanone, 2-(4tl-dimethylaminophenylvinylene)-benzothiazole, 2-(a'-dimethylaminophenylvinylene)-isonaphthothiazole, /, 3-
His-(4t'-dimethylaminobenzal)-acetone, 7.3-bis-(terdiethylaminobenzal)-
Acetone, 3,3'-carbonyl-bis-(7-dinithylaminocoumarin), 7-diethylamino-3-pensoylcoumarin, 7-dinithylaminogumethylcoumarin, N-phenyl-jetanolamine, N-p −)! I
Examples include, but are not limited to, sil-ethylamine. Note that these may be used alone or in combination. Preferably (VI+) or I
A sensitizer having the structure s) and a sensitizer having the structure (vIs) are used in combination.

A compound having a carbon-carbon double bond can 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,
These include 2-ethylhexyl acrylate, 2-hydroquine ethyl acrylate, N-vinyl-2-pyrrolidone, carpitol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, /.

6-Hexitine diol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolmethane Tetraacrylate, tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, methylene bisacrylamide,
Examples include N-methylol acrylamide and those obtained by changing the above acrylate or acrylamide to methacrylate or methacrylamide, and preferred among these are compounds having two or more carbon-carbon double bonds.

Furthermore: By adding a mercaptan compound to the composition of the present invention, the photosensitivity can be further improved.

Examples of mercaptan compounds include, for example, λ-mercaptobenzimidazole, 2-)lucafthohenzothiazole, /-phenyl-! -mercapto/H-tetrazole, 2-mercaptothiazole, λ-mercapto-phenylthiazole, -monoamino! -Mercapto-
/.

3. Tertiazole, Komelkabutoimidazole, λ
-Mercapto, one methyl-7,3,'! teradiazole, j-mercapto-/-methyl-/H-tetrazole 1.2,4t, 4-) dimercapto-S-triazine, 2-dibutylamino-q, ot-dimercapto-3-
Triazine, ko! -dimethylcapto-7゜3.4t-
Thiadiazole, j-mercapto-/, 3.4, monothiadiazole, /-ethyl-termercapto-7,2,3
, 41-tetrazole, Komelkabuto-nitrothiazole, 2-merkabutopenzoquinazole, daphenyl-λ-mercaptothiazole, mercaptopyridine, λ-mercaptoquinoline, /-methyl-2-mercaptoimidazole, λ-mercapto β-naphthothiazole Examples include.

Furthermore, the composition of the present invention (2) can be used by adding a functional dialkoxysilane compound as necessary or by precoating it on the substrate. This dialkoxysilane compound improves the heat resistance of the composition of the present invention Polymer membrane and base material Si
and compounds that improve the adhesion of the interface with the inorganic insulating film, examples of which include r-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyldimethoquine, Silane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercabutobrobylmethyldimethoxysilane, diftquine-3-
Mercabutpropyl methyl, 3-methacryloxypropyldimethoxymethyl, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-
Examples include piperidinoprobylsilane, jetoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylbropyl)succinimide, and the like.

How to use and effects of these dialkoxysilane compounds (
Regarding the second, for example, patent application No. 1 (=detailed number is given).In order to improve the storage stability of the solution of the composition of the present invention, a polymerization inhibitor can also be added. Examples of the polymerization inhibitor include hydroquinone, N-nitron diphenylamine, ptcrt-
Examples include, but are not limited to, butylcatechol, phenothiazine, N-phenylnaphthylamine, 6-tert-butyl-p-methylphenol, and the like.

The content ratio of the oxime compound in the component (i) of the present invention is not particularly limited, but it is preferably 0. / ~ 20 Evk Chi, further (= preferably, / ~ / It is desirable to contain it at the axis of Yuto Roki. If the content is small, the photosensitivity is insufficient, and if the content is too much acid. In this case, the film properties after heat treatment deteriorate.

Regarding the content ratio of the sensitizer as component (c) in the present invention, the content ratio of the sensitizer as component (c) is 0. θ/~20 weight, preferably 0.0j~/! It is desirable to contain it in an amount of t% by weight. When the content is small, the photosensitivity is insufficient, and when the content is too large, the opposite is true (= photosensitivity decreases).

The amount of the compound having a carbon-carbon double bond is (a)
It is desirable that the fat θ weight is t% or less based on the component polymer. The amount of the mercaptan compound added is preferably 70 times or less, more preferably 2 times or less, relative to the polymer of component (a).

In addition, when the functional dialkoxysilane compound is added and used, the amount added is O,OS to 0%, preferably 0.7 to 0%, relative to the polymer of component (a). It is 壬.

Also, the polymerization inhibitor is against the polymer of component (a)!
Below the weight factor, preferably θ,! It is used by adding less than 1% of mold.

The polymer used as component (a) in the composition of the present invention includes, for example, a compound represented by the general formula and a compound represented by the general formula Z, -y -Z,
It can be obtained by polycondensation or polyaddition (=) with the compound represented by (ff).
), NC0(Is), NHL(j4), OH(
Is), and the corresponding abbreviations of general formula (1) are shown within 0. Father, general formula (■) (- Examples of Z goose include -COCI (IVs), -COOH (IV
s), NC0(Ih), and Nkb(Na), each of which is represented by the abbreviation of the corresponding general formula (ff).

Note that X, R, Y and W have the same meanings as above.

Compounds represented by the above general formula (厘) and general formula (IV)
Polycondensation or polyaddition reaction with the compound represented by (: from -
Z1 and Z2- react to form a bond chain Z. In this case, the preferable combination of zl and Z2, the type of 2 produced, and the ring structure groups produced when the obtained polymer is heat-treated are summarized in Table 7 (=.

Table / Notes *1 Ring structure IM, imide ring QD: quinazolinedione ring OD nioxazinedione ring The polymer of component (a) can also be produced by the method shown below. That is, the compound represented by the general formula % formula % (7) [X in the formula has the same meaning as above] is converted into the compound represented by the general formula (IV3) or (■4)
The carboxyl group of the product obtained by reacting with the compound represented by the formula is 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, for example. or by reacting with a quaternary ammonium salt represented by the general formula; 2, the polymer is obtained.

Note that these reactions are described, for example, in JP-A-56-3252q.
It is described in Japanese Patent Application No. 9-9339.

The compound represented by the general formula (L) can be obtained, for example, by ring-opening with fp1 anhydride R"OH (R" has the same meaning as above) represented by the general formula (I6). The acid anhydride (sodium 6
), for example, pyromellitic anhydride, 3°3',
4t, '1. '-benzophenone tetracarboxylic dianhydride, 3. r, <t, <c-diphenyl ether detracarboxylic dianhydride, 3,324t, <t'-diphenyl tetracal, j? 1jl22water3.3','1
．． 41'-diphenylsulfone tetracarboxylic dianhydride, 2,3. t,7-naphthalenetetracarboxylic anhydride, thiophene-2,3,'l.

! -Tetracarboxylic anhydride, λ,! -Bis-(3゜q
-biscarboquinphenyl)propane anhydride, etc., and examples of the alcohol R*OH include 2-hydroxylethyl methacrylate, λ-hydroxyethyl acrylate, co-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, aryal alcohol and hyethylene Examples include glycol monoallyl ether.

When reacting these acid anhydrides (6) with alcohol R*OH, adding pyridine, dimethylaminopyridine, etc. (secondarily, the reaction is accelerated).

The combinations of numbers / and /' in Table 1 above are seven examples of preferred embodiments, and the diamines represented by the general formula (■4) used in these combinations include, for example, g,4t'-diaminodiphenyl ether , Shimadadiaminobiphenyl, g'-diaminotoluene, g
, g'-diaminobenzophenone, Ri.

q'-diaminodiphenylsulfone, phenylindane diamine, 4t, 4t'-diaminodiphenylmethane,
p-phenylenediamine, m-phenylenediamine, /
,! -diaminonaphthalene, 3.3'-9methoxy-g
, g'-diaminobiphenyl, 3,31-dimethyl-¥
, 'l'-diaminobiphenyl, o -toluidine sulfone, co, corbis (couaminophenoquinphenyl)
Propane, bis(4t-aminophenoxyphenyl)sulfone, bis(kuaminophenoquinphenyl)sulfide, /, coubis(4t-aminophenoxy)benzene, /, 3-bis(kuaminophenoquine)benzene,
3. Ri'-diaminodiphenyl ether, De, Davis (quaminophenyl) anthracene (10), Ri,
Tervis(guaminophenyl)fluorene, 3.3'
-diaminodiphenylsulfone, g,darzi(3-aminophenoxy)diphenylsulfone, g,g'-diaminobenzanilide, 3. ￥'-diaminodiphenyl ether, g, g' -(/, 3-phenylene bis(/-
methylethylidene)),g,ttt'-(/,<
t-phenylenebis(/-methylethylidene)], 41
, 4t'-(m-phenylenediisopropylidene)bis(m-toluidine), g,g'-(p-phenylenediisopropylidene)bis(m-toluidine), and the like.

Among this combination, the reaction between the compound represented by the general formula (11) and the compound represented by the general formula (■4) can be carried out using a carbodiimide-type dehydration condensation agent, for example, dicyclohequinyl lupodiimide. .

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

These reaction methods (for example, Japanese Patent Application No. 1983)
-/ri No. 3737, Tokugan Sho-otsu 0-99//, Toku-gan Shoj
Tar23♂tag! Details are given in the issue.

The method for producing the oxime compound used as the component in the present invention is to first nitronize /, 3-propanedione-/, 3-disubstituted product.

2. Synthesize 3-propanetrione-/3-disubstituted-2-oxime. This synthesis method is used to create Organic Synsense Collective Volume■,! 73~! ／≦
Page or organic synth.

It is described in Sys Collective Volume U, pages 363-3≦G, etc. Furthermore, the oxime compound of the present invention can be produced by reacting the obtained oxime compound with a carbonyl halide.

The composition of the present invention is used by dissolving all the components in a solvent (dissolved in a solvent) and coating it on a predetermined substrate. It is also possible to use a dialkoxysilane compound as a base (nib record).

The solvent is preferably a polar solvent, such as one having a not too high boiling point, such as dimethylformamide, N-methylpyrrolidone, dimethylacetamide, diglyme, isobutyl acetate, or cyclopentanone. Furthermore, solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, and esters can be added to the extent that the components are not precipitated.

The solution obtained as described above is filtered through a filter, and then coated on the substrate (= usually) using a spin coater, bar coater, flake coater, curtain coater, screen printing method, etc. A method in which the substrate is immersed in the solution, a method in which the solution is sprayed onto the substrate, etc. can be used.

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

Next (2) After the coating film thus obtained is dried by a combination of air drying, heat drying, vacuum drying, etc., it is exposed to light through a photomask. At this time, the active light used is, for example, ultraviolet rays, rays, electron beams, etc. Among these, ultraviolet rays are preferable, and examples of the light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, etc. Among these light sources, ultra-high-pressure mercury lamps are the most preferred. Further, it is preferable that the exposure is carried out 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 developer to be used for this removal is preferably one that can completely dissolve and remove the end-chain optical film within an appropriate time, such as N-methylpyrrolidone, N-acetyl-copyrrolidone, N-acetylpyrrolidone,
, N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hequinamethylphosphoric triamine F, N-pendyl-cobyroliton, γ-
Aprotic polar solvents such as butyrolactone may be used alone, or they may be combined with alcohols such as ethanol and isopropanol, aromatic hydrocarbon compounds such as toluene and xylene, methyl ethyl ketone, and methyl isobutyl. Ketones such as ketones,
A mixture of solvents such as esters such as ethyl acetate and methyl propionate, and ethers such as tetrahydrofuran and dioquinane may be used. Furthermore, immediately after development, the above-mentioned;
It is preferred to rinse with a solvent such as those indicated as components.

After drying, the image obtained in this way has an image density of 750 to 950
By heating in the temperature range of °C, a heat-resistant polymer compound having an imide ring, an isoindoroquinazolinedione ring, an oquinazinedione ring, a quinazolinedione ring, etc. is converted.

〔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 regarded as highly important properties of photoresists, 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 an interlayer insulating film or a surface protective film for semiconductor devices, the above-mentioned characteristics will result in shorter processes, easier microfabrication, and a smoother layer. It exhibits characteristics such as being able to form .

〔Example〕

The present invention will be explained in more detail from the following (=, Example (2), but the present invention is not limited in any way by these Examples (-). Sensitizers, compounds with carbon-carbon double bonds (
Table 2 shows the names of the polymerization inhibitors, mercaptan compounds, functional dialcoquine silane compounds, and polymerization inhibitors.

(2) Oxime compound (4) Seven-layer compound (5) Mercaptan compound (6) Functional dialkoxysilane compound (71 Polymerization inhibitor examples/~2θ Additives were added to 100 parts by weight of the polymer shown in Table 3. Add the parts by weight shown in the same table, and dissolve N-methyl pyrrolidone (=dissolved) in the /2θ weighted part.The solution was placed on a silicon cube with a spin cord (700 rpm x 7 gM) and dried in air at 70°C for 6 hours. A uniform coating film was obtained.

Next, under a nitrogen atmosphere, gray scale (KodakPho)
rographie 5tep Tablet, A,
2) and was exposed to an ultra-high pressure mercury lamp (f mW) for 5 minutes. After the wafer was left at 23° C. for 3 portions, it was developed with a mixture of equal amounts of r-butyrolactone and xylene using a spray developing machine, 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 stages, the higher the sensitivity. When the number of stages increases by seven stages, it means that the exposure device JΣ is lower.) The obtained results are shown in the same table.

Comparative example 7~! Experiments were conducted on the compositions shown in the table in the same manner as in Examples 7 to 20, and the results shown in the table were obtained.

Comparative Example B~ // Instead of the oxime compound of the present invention, other photopolymerization initiators were used in the same manner as in Examples 7 to 2o. An experiment was conducted on the composition of 1, and the results shown in the table were obtained.

Examples 2/~23 Diaminodiphenyl ether/θOf (o, r mol)
Dissolve in hemethylpyrrolidone♂♂θ2 to obtain pyromellitic dianhydride/09? (0.3 mol) and 5
By reacting at 0 to 60°C for 3 hours, a copoise polymer solution was obtained at 0°C.

(This polymer solution will be referred to as P-B.) To this polymer solution/θ0* parts, add the additives shown in S6 and dissolve them. This solution was applied onto a silicone cube (JOORPM X/θ crown) and dried at 70° C. for 7 hours to obtain a uniform coating film. Furthermore, on this coating film, the solution was applied with a spin code and drying was repeated nine times to obtain a coating film.Next (=
, Grayscale # (Kodak Ph
otographic 5tepTablet A 2
) through an ultra-high pressure mercury lamp (J'm expletive)! exposed for minutes. After leaving this wafer at 23°C for 3 parts,
Using a spray developing device, the film was developed with a mixed solution of N-methylpyrrolidone (2 parts) and methanol (7 parts), rinsed with methanol, and dried. Cure sensitivity is expressed as number of stages. The obtained results are shown in Table B.

(The following is a blank space) Reference Example/ As a method for manufacturing an oxime compound used in the present invention, an example of a method for manufacturing an oxime compound (abbreviation 2-3) having the following structural formula is shown.

(1) Production method of oxime i Benzoyl acetate ethyl ester/92? (1 mol) is dissolved in acetic acid g00- and ethanolic θ-, and an aqueous solution of sodium nitrite/t (/, 2 mol)/water/4tO2 is added dropwise over 3 hours. After the addition was completed, the mixture was stirred at room temperature overnight. To this reaction solution, add water ♂00- while stirring,
The precipitated crystals are passed through the mouth and washed with water. The obtained crystals are dried under vacuum. Is the yield 2/2? (Yield: 9≦%).

(2) Production method of oxime compound Oxime compound @66.3? (0.3 mol) and triethylamine j J,4tf (0.3 d mol) are dissolved in acetone/2t, and ethyl chloroformate J 9 f (0.36 mol) is added dropwise at 70° C. or lower. After the dropwise addition, stirring was continued for 7 hours at room temperature. After the reaction is completed, the reaction solution is passed through the mouth and the solution is evaporated to dryness. The obtained oxime compound is recrystallized from ethanol. The yield is /79? (Yield: O/O).

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 is -C-NH-, -NH-C-NH-, or ▲ has a numerical formula, chemical formula, table, etc. ▼, R^* is a group having a carbon-carbon di straight bond, W is a group that can react with the carbonyl group of -COOR^* to form a ring by heat treatment, 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). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) [R_1 in the formula 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, R_2 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, and R_3 is an alkyl group having 1 to 6 carbon atoms.
an alkyl group, or an alkoxy group having 1 to 6 carbon atoms,
or an aromatic hydrocarbon having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms; sexual composition.