Photosensitive polymer composition

Abstract: A photosensitive polymer composition comprising, in admixture, a polymer predominantly comprising a recurring unit of the formula ( I ): wherein X is a tri- or tetravalent organic group, Y is a divalent organic group, and n is equal to 1 or 2 and a compound having a urea bond of the formula ( II ): wherein R¹ is a group having a functional group capable of forming a dimer or polymer upon exposure to radiation, R² and R³ are independently a hydrogen atom or a monovalent organic group is shelf stable and applicable as relatively thick coatings having sufficient photosensitivity to form semiconductor element surface protective films.

Description: This invention relates to photosensitive polymer compositions e.g. suitable for forming resin coatings useful as semiconductor element surface protective films, semiconductor element insulating films, liquid crystal element orienting films, multi-layer printed circuit board insulating films and the like. BACKGROUND In recent years, polyimide resin materials have been used as protective films on semiconductor elements such as transistors, IC's and LSI's as well as for interlayer insulating films between multi-layer wirings. The polyimide resin materials utilized for such purposes are subject to the fine working steps, e.g. forming through-holes and the like, always required in the manufacture of semiconductor elements. For the purpose of making the fine working process more effective, attempts were made to develop polyimide resin materials which could also be used as photosensitive heat-resistant material. There were proposed several materials including (1) a composition comprising a polyamic acid and a bichromate (JP-B-17374/1974), (2) a composition comprising a compound obtained by introducing a photosensitive group into the carboxyl group of a polyamic acid through ester linkage (JP-B-30207/1980), (3) a composition comprising a compound obtained by reacting a polyamic acid with an epoxy-containing compound having a photosensitive group (JP-A-45746/1980), and (4) a composition comprising a polyamic acid and an amine compound having a photosensitive group (JP-B-145794/1979). Composition (1) has a very short pot life and forms polyimide films having residual chromium ions therein. Composition (2) forms polyimide films having residual chloride ions therein, because a dehydrochlorination reaction is used to introduce the photosensitive group. Therefore films of compositions (1) and (2) suffer from an impurity problem. In composition (3), a photosensitive group can be introduced into the base compound through ester linkage without contaminating it with an ionic impurity, but at a very low rate of introduction which leads to low sensitivity in practical applications. Composition (4) is advantageous in that no ionic impurities are introduced and a sufficient amount of photosensitive group can be introduced, but has some disadvantages. In a prebaking step of volatilizing the solvent from a photosensitive polymeric solution before exposure, the photosensitive component can be partially volatilized off. A problem also arises in forming thick films. As the solvent volatilizes off in the prebaking step, the photosensitive component becomes a poor solvent for the polyamic acid, causing whitening of the resulting films and difficulty in subsequent steps. Earlier EP-A-453237, which is in Article 54(3) relation with the present case by virtue of earlier claimed priority dates, discloses photosensitive polyimide-forming compositions combining an ordinary polyimide precursor, and a photopolymerisable monomer or oligomer which is preferably (meth)acrylic; cited preferred components are polyester, epoxy, urethane and silicon acrylates. JP-A-1/105241 describes a photosensitive composition containing a polyimide precursor and a polymerisable unsaturated compound which may be an ester compound e.g. alkyl or brominated alkyl acrylates and diacrylates. The general problem addressed herein is to provide novel photosensitive polymer compositions and methods of making them. A preferred novel composition is substantially free of ionic impurity, stable on shelf storage and can form heat-curable, relatively thick polyimide resin films of good quality and having a high and stable degree of photosensitivity. We have found that by blending a polyimide precursor polymer predominantly comprising recurring units of the general formula ( I ) with a photosensitive compound of the general formula (II), we can make a photosensitive polymer composition which is fully stable on shelf storage, has good photosensitivity, sensitivity stability and thick-film-forming ability, and is curable e.g. to polyimide resin films of quality suitable as semiconductor element surface protective films. Formula ( I ): In the formula, X is a tri- or tetravalent organic group, Y is a divalent organic group, and n is 1 or 2. Formula ( II ): R 1 is a functional group capable of forming a dimer or polymer upon exposure to radiation, and R 2 and R 3 are selected independently from H, CH 3 , CH 2 CH 3 , phenyl and functional groups as for R 1 . In our work, we have found that in embodiments using a compound having a urea linkage, of formula ( II ), as a photosensitive component and blending a polyimide precursor of formula ( I ) with the compound of formula ( II ), a photosensitive group may be introduced without developing or introducing an ionic impurity. Since the compound of formula ( II ) did not evaporate off during preheating of the composition applied to substrates, films are obtainable without whitening so that the films may remain sensitive, that is, when subject to exposure. In addition, the photo-sensitive. polymer embodiments experienced a minimal viscosity variation during a long term of storage. The compositions also had acceptable photosensitivity, pattern retention after heat treatment, and thick-film-forming ability, and cured to coatings having good heat resistance, electrical and mechanical properties. Therefore, the present invention provides a photo-sensitive polymer composition comprising in admixture, a Polyimide precursor polymer predominantly comprising recurring units of formula ( I ) with a compound having a urea linkage, of formula ( II ). DETAILED DESCRIPTION The first component of the photosensitive polymer composition of the present invention is a polyimide precursor having recurring units of the following general formula ( I ): wherein X is a tri- or tetravalent organic group, Y is a divalent organic group, and n is 1 or 2. In (I), X is effectively an acid anhydride residue, and thus derived from, for example, aryl, di- or polyaryl anhydrides such as: trimellitic anhydride where X is pyromellitic dianhydride where X is benzophenonetetracarboxylic dianhydride where X is 3,3',4,4'-biphenyltetracarboxylic dianhydride where X is 2,2-bis(3,4'-benzenedicarboxylic anhydride)perfluoropropane where X is bis(3,4'-dicarboxyphenyl)dimethylsilane dianhydride where X is and 1,3-bis(3,4-dicarboxyphenyl-1,1,3,3,-tetramethyl disiloxane dianhydride where X is It will be understood that X may be any one of the above-mentioned acid anhydride residues or a mixture of two or more. Y is a divalent organic group, regarded as derived from a diamine H 2 N-Y-NH 2 . Y may be a divalent organic group containing an aromatic ring, siloxane linkage, silethylene linkage or silphenylene linkage. Illustrative examples of the 'source' diamine include aromatic ring-containing diamines having 6 to 20 carbon atoms, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(m-aminophenylsulfonyl)benzene, 1,4-bis(p-aminophenylsulfonyl)benzene, 1,4-bis(m-aminophenylthioether)benzene, 1,4-bis(p-aminophenylthioether)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-methyl4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-chloro-4-(4-amino-phenoxy)phenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-methyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dimethyl-4-(4-aminophenoxy)-phenyl]ethane, bis[4-(4-aminophenoxy)phenyl]methane, bis[3-methyl-4-(4-aminophenoxy)phenyl]methane, bis[3-chloro-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]perfluoropropane and diamines and polyamines having an amino or amide group as a nuclearly substituting group and silicon diamines as shown below. It will be understood that Y may be any one of the above-mentioned diamine residues or a mixture of two or more. The second component of the composition is a compound having a urea linkage, of the following general formula ( II ): In formula ( II ), R 1 is a group having a functional group capable of forming a dimer or polymer upon exposure to radiation. Examples of the group represented by R 1 are given below. CH 2 =CH-, CH 2 =CH-CH 2 -, In formula ( II ), R 2 and R 3 are selected independently from H, -CH 3 , -CH 2 CH 3 , and groups as previously exemplified for R 1 . Illustrative examples of the compound of formula ( II ) are given below. These compounds may be used alone or in admixture of two or more. The compound of formula ( II ) may be blended in any desired amount, preferably of about 0.2 to 1.5 molar equivalents, more preferably about 0.4 to 1.2 molar equivalents relative to the carboxyl group (-COOH group) in the polymer of formula ( I ). Compositions containing less than 0.2 molar equivalents of compound ( II ) on this basis would have low photosensitivity whereas more than 1.5 molar equivalents of compound ( II ) is sometimes undesirable because of a substantial film thickness reduction during final heat treatment. Preferably, the composition of the present invention contains a sensitizer having photosensitization effect on the photosensitive group the compound of formula ( II ) has or a polymerization initiator capable of initiating polymerization of the compound of formula ( II ). Examples of the sensitizer and initiator include benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-1-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, diacetyl, benzyl, benzyldimethylketal, benzyldiethylketal, diphenyldisulfide, anthracene, 2-nitrofluorene, dibenzalacetone, 1-nitropyrene, 1,8-dinitropyrene, 1,2-naphthoquinone, 1,4-naphthoquinone, 1,2-benzanthraquinone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentanone, 2,6-(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, 4-dimethylaminocinnamylideneindanone, 4-dimethylaminopendylideneindanone, 2-(4'-dimethylaminophenylvinylene)-benzothiazole, 2-(4'-dimethylaminophenylvinylene)-isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 7-diethylamino-3-benzoylcoumarine, 7-diethylamino-4-methylcoumarine, N-phenyl-diethanol amine, N-p-tolyldiethylamine, 2,6-di(p-azidobenzal)-4-methylcyclohexanone, 2,6-di(p-azidobenzal)cyclohexanone, 4,4'-diazidochalcone, 4,4'-diazidobenzalacetone, 4,4'-diazisostilbene, 4,4'-diazidobenzophenone, 4,4'-diazidodiphenylmethane, 4,4'-diazidophenylamine. These sensitizers and initiators may be used alone or in admixture of two or more. The sensitizers or initiators are preferably blended in an amount of about 0.01 to 20% by weight, more preferably about 0.05 to 15% by weight based on the total weight of the polymer of formula ( I) and the compound of formula ( II ). Less than 0.01% by weight is insufficient to provide photosensitivity whereas more than 20% by weight would rather lower photosensitivity. For improving photosensitivity, the composition of the present invention may further contain a compound capable of photo forming a dimer or polymer as a comonomer. Examples of the photopolymerizable or photodimerizable compound include 2-ethylhexylacrylate, 2-hydroxyethylacrylate, N-vinyl-2-pyrrolidone, 2-dimethylaminoethylmethacrylate, 2-diethylaminoethylmethacrylate, N-methylbis(methacryloxyethyl)amine, carbitol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, methylenebisacrylamide, N-methylolacrylamide, and similar compounds in which acrylate or acrylamide is changed into methacrylate or methacrylamide. Preferred among these are compounds having at least two carbon-to-carbon double bonds such as ethylene glycol diacrylate, trimethylol propane triacrylate, and methylenebisacrylamide. These comonomers are preferably added in amounts of up to about 10% by weight, more preferably about 1 to 5% by weight based on the total weight of the polymer of formula ( I ) and the compound of formula ( II ). More than 10% by weight of comonomer would cause coatings to be whitened after preheating. If desired, a functional alkoxysilane compound may be added to the photosensitive polymer composition. The functional alkoxysilane compound is effective for improving the interfacial adhesion between a heat resistant polymeric coating of the polymer composition and a substrate in the form of silicon which is covered with the coating or an inorganic insulating film thereon. Examples include α-aminopropylmethyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyldimethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, etc. These functional alkoxysilane compounds are preferably added in amounts of about 0.1 to 5% by weight, more preferably about 0.5 to 3% by weight based on the total weight of the polymer of formula ( I ) and the compound of formula ( II ). For improving the shelf stability of the photosensitive polymer composition in solution form, a polymerization inhibitor is preferably added. Some illustrative examples of the inhibitor include hydroquinone, hydroquinone monomethyl ether, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2,6-ditert-butyl-p-methylphenol. The inhibitors are preferably added in amounts of up to about 5% by weight, more preferably up to about 0.5% by weight based on the total weight of the polymer of formula ( I ) and the compound of formula ( II ). In a use aspect of the invention, the photosensitive polymer composition is dissolved in a solvent in which the components are soluble, forming a coating solution which is applied to substrates or supports. The substrate may be precoated with an alkoxysilane compound as mentioned above for improving the adhesion of the coating to the substrate. The solvents used herein are often polar solvents, for example, such as dimethylformamide, N-methylpyrrolidone, dimethylacetamide, diglyme, isobutyl acetate, and cyclopentanone. Other solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, and esters may be additionally used in limited amounts as long as none of the components will precipitate. After the photosensitive polymer composition is dissolved in a solvent, the coating solution is passed through a filter and then applied to substrates. Application may be done by conventional methods, for example, by coating substrates with the coating solution by means of a spin coater, bar coater or blade coater, or screen printing, by dipping substrates in the coating solution, and by spraying the coating solution to substrates. The coatings thus applied are dried by air drying, heat drying, vacuum drying or a combination thereof, and then exposed to light typically through photomasks. Activation light rays are ultraviolet radiation, X-rays, and electron radiation, with UV being preferred. Suitable light sources include low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, and halogen lamps, with the ultrahigh pressure mercury lamps being preferred. Light exposure favors a nitrogen atmosphere. After exposure, unexposed portions are removed by development using a dipping or spraying method. The preferred developer used herein is one capable of completely dissolving away unexposed portions within an appropriate time, typically aprotic polar solvents, for example, N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethyl-formamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, N-benzyl-2-pyrrolidone, and γ-butyrolactone, alone or in admixture with a second solvent, for example, alcohols such as ethanol and isopropanol, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and methyl propionate, and ethers such as tetrahydrofuran and dioxane. Preferably, development is immediately followed by rinsing with a solvent as exemplified above as the second solvent. The above-mentioned development leaves a relief pattern of the coating in which the polymer of formula ( I ) exists in the form of a polyimide precursor. The developed coating is then heat treated, for example, at 200 to 450°C for 10 minutes to 10 hours, obtaining a patterned and cured polyimide resin coating. The patterned polyimide resin coatings resulting from the photosensitive polymer composition of the present invention have improved heat resistance, electrical and mechanical properties. BENEFITS Within these teachings, we have been able to prepare embodiments of photosensitive polymer compositions with advantages including substantial elimination of an ionic impurity, stable shelf storage, stable sensitivity and ability to form thick films. The compositions are heat curable into polyimide resin films of quality having improved heat resistance, electrical and mechanical properties. Therefore, when applied to semiconductor elements as coatings thereon, the composition allows for creation of a fine pattern through light exposure. Therefore, the embodiments may find application as semiconductor element surface protective coatings such as junction coating films, passivation films, buffer coating films, and α-radiation shielding films; semiconductor element insulating films such as interlayer insulating films in multi-layer wiring structures; liquid crystal display element orienting films; and insulating films in multi-layer printed circuit boards. Examples of the present invention are given below by way of illustration. In the examples, all parts are by weight. Examples 1-8 & Comparative Example Photosensitive polymer solutions (Examples 1-8) were prepared by furnishing the polymer, photosensitive compound, photosensitizer, and polymerization initiator shown in Tables 1 to 3, blending them in the combination and amount shown in Table 5, and dissolving the blends in 400 parts of N-methyl-2-pyrrolidone. Another photosensitive polymer solution (Comparative Example) was prepared as above except that the compound shown in Table 4 was used instead of the photosensitive compound and blended in the combination and amount shown in Table 5. Each of these photosensitive polymer solutions was spin coated on a silicon wafer at 1,500 rpm for 12 seconds and dried at 70°C for one hour, obtaining a coating of even thickness. The coating was exposed to light in a nitrogen atmosphere for 10 seconds through a mask under a high pressure mercury lamp operating at 2 kw. After exposure, the wafer was dipped in a mixture of N-methyl-2-pyrrolidone and xylene (1/1 by volume) for development, rinsed with xylene, and then dried. The light exposure was evaluated at this point. Thereafter, the wafer was heated at 150°C for one hour and then at 350 °C for a further one hour. The heated coating was evaluated. Exposure is evaluated "Good" when the retention of the coating after development and rinsing is 80% or higher and "Poor" when the same coating retention is less than 80%. Quality of heated coating is evaluated "Good" when it is free of cracking or separation and "Poor" when cracking or separated occurs. Additionally, for evaluating shelf stability, the photosensitive polymer solutions were allowed to stand for 6 months at 5°C and measured for viscosity by means of Ostwald's viscometer before and after standing. The results are shown in Table 5. Symbol Photosensitizer or polymerization initiator S-1 Michler's ketone S-2 2,6-di(p-azidobenzal-4-methylcyclohexanone S-3 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone S-4 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone S-5 2-isopropylthioxanthone S-6 3,3'-carbonyl-bis-(7-diethylaminocoumarin) As seen from Table 5, the photosensitive polymer compositions embodying the present invention (Examples 1-8) could form relatively thick coatings having acceptable photosensitivity and pattern retention after heat treatment. The compositions in solution form were held stable as demonstrated by a viscosity change within 10% over 6-month shelf storage. The coatings were excellent in heat resistance, electrical and mechanical properties.

Claims: A photosensitive polymer composition comprising, in admixture, (a) polyimide precursor polymer predominantly comprising recurring units of the formula ( I ): wherein X is a tri-or tetravalent organic group, Y is a divalent organic group, and n is 1 or 2, and (b) photosensitive compound having a urea linkage, of the formula ( II ) : wherein R 1 is a functional group capable of forming a dimer or polymer upon exposure to radiation, and R 2 and R 3 are selected independently from H, CH 3 , CH 2 CH 3 , phenyl and functional groups as for R 1 . A composition according to claim 1 wherein the compound of formula ( II ) is blended in an amount of about 0.2 to 1.5 molar equivalents relative to carboxyl groups in the polymer of formula. (I). A composition according to claim 1 or claim 2 in which in the compound of formula (II) R 1 is selected from CH 2 =CH-, CH 2 =CH-CH 2 -, A composition according to any one of the preceding claims in which in the compound of formula (II) R 2 and R 3 are selected from H, -CH 3 , -CH 2 CH 3 , and the options listed for R 1 in claim 3. A composition according to claim 1 or claim 2 in which the compound of formula (II) is selected from and mixtures thereof. A composition according to any one of the preceding claims which comprises (c) a sensitizer or polymerization initiator in an amount of from 0.01 to 20% by weight based on the total weight of the polymer of formula (I) and the compound of formula (II). A composition according to any one of the preceding claims which comprises d) further compound capable of photo-forming dimer or polymer, in an amount of up to about 10% by weight based on the total weight of the polymer of formula (I) and the compound of formula (II). A composition according to claim 7 in which the further compound (d) is selected from 2-ethylhexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, N-vinyl-2-pyrrolidone, 2-dimethylaminoethylmethacrylate, 2-diethylaminoethylmethacrylate, N-methylbis(methacryloxy-ethyl)amine, carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, methylene-bis(meth)acrylamide and N-methylol(meth)acrylamide. A composition according to any one of the preceding claims which comprises e) alkoxysilane compound. A composition according to any one of the preceding claims in which in the polymer (a) X is the residue of an aryl, diaryl or polyaryl anhydride. A composition according to claim 10 in which X is selected from and A composition according to any one of the preceding claims in which in the polymer (a) Y is the residue of a diamine H 2 N-Y-NH 2 . A composition according to any one of claims 1 to 11 in which in polymer (a) Y is a divalent organic group containing an aromatic ring, siloxane linkage, silethylene linkage or silphenylene linkage. A composition according to claim 13 in which Y is the residue of a C 6-20 diamine containing at least one aromatic ring. A method comprising the production of a composition according to any one of claims 1 to 14 by blending the ingredients thereof. Use of a composition according to any one of claims 1 to 14 as a photosensitive coating.

Inventors: KATO HIDETO, OKINOSHIMA HIROSHIGE, KATO, HIDETO, OKINOSHIMA, HIROSHIGE
Applicants: SHINETSU CHEMICAL CO, SHIN-ETSU CHEMICAL CO., LTD.
Application year: 1992
Main classification: G03F7
IPC codes: C08L79, G02F1, G03F7, C08K5, C09D179, H01L21, C08F283