Heat-resistant negative photoresist composition, photosensitive substrate, and process for forming negative pattern

Abstract: A heat-resistant negative photoresist composition comprising a resin component having a structural unit represented by formula (I): wherein the arrows, R₁ and R₂ are the same as defined hereinbefore, and a compound which becomes basic upon irradiation with actinic rays, represented by formula (II): wherein R₃ to R₆ and X₁ to X₄ are the same as defined hereinbefore, a photosensitive substrate obtained by coating a substrate with the heat-resistant composition, and a process for forming a negative pattern using the heat-resistant negative photoresist composition.

Description: The present invention relates to a heat-resistant negative photoresist composition, a photosensitive substrate, and a process for forming a negative pattern. Photosensitive polyimides or precursors thereof which have been in common practical use because of their heat resistance are mostly of a negative-working type which becomes less soluble in developing solutions upon irradiation with actinic rays to form a desired relief image on various substrates. Many kinds of heat-resistant photoresists and applications thereof have been proposed which photoresists employ such a negative photosensitive polyimide or precursor thereof and leave actinic ray-irradiated areas on substrates. Examples of these proposals include: (1) a method of incorporating a methacryloyl group into a polyimide precursor through an ester bond or ionic bond (e.g., JP-A-54-145794, and JP-A-56-38038); (2) soluble polyimides containing a photopolymerizable olefin (JP-A-59-108031, JP-A-59-220730, JP-A-59-232122, JP-A-60-6729, JP-A-60-72925, and JP-A-61-57620); and (3) self-sensitizing polyimides having a benzophenone skeleton and containing an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (e.g., JP-A-59-219330 and JP-A-59-231533). However, the conventional negative photoresists described above are insufficient regarding the resolving power. Further, in some applications the use thereof leads to low yields of products. Illustratively stated, the photoresists obtained by method (1) above are disadvantageous in that the ester bond-type ones are difficult to synthesize, while the ionic bond-type ones have a problem concerning dimensional stability because they not only shrink upon heat cure for imidization but decrease in thickness during development, so that a residual film thickness thereof after development and heat cure is about 50% of the initial thickness. Photoresists (2) and (3) above are disadvantageous in that they are unable to flexibly cope with various kinds of property requirements and are not suitable for use as a multipurpose photoresist, since polymers usable therein are limited in skeletal structure and, hence, films finally obtained therefrom have limited properties. On the other hand, a photosensitive material comprising a polyimide precursor and N-methylolacrylamide incorporated therein has been proposed (Polymer Preprint Japan, 39 (8), 2397 (1990)). This composition, however, is disadvantageous, for example, in that it has poor dimensional stability because the residual film thickness is 50% as in the above-described case, and in that the pre-baking thereof requires much time. EP-A-502400 which is a prior art document according to Article 54(3) for the contracting states BE,DE,FR and GB regarding those parts of the present application which are based on the priority document of July 7, 1992, discloses a heat-resistant photoresist composition comprising a resin component of formula (I) and a compound which becomes basic upon irradiation with actinic rays, which can be 2,6-dimethyl-3,5-dicyano-4-(2'-nitrophenyl)-1,4-dihydropyridine or 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine. One object of the present invention is to provide a heat-resistant negative photoresist composition comprising a polyimide precursor and showing good sensitivity and resolving power in which composition the polyimide precursor as a resin imparting the heat resistance required of a resist material is not so limited in structure and which is adaptable to practical production processes, thereby overcoming problems of the conventional negative photoresists. Another object of the present invention is to provide a photosensitive substrate obtained using the above heat-resistant negative photoresist composition. Still another object of the present invention is to provide a process for forming a negative pattern. As a result of intensive studies on the above-described negative photoresist compositions, the present inventors have found that a negative photoresist composition with which the above objects are attainable can be obtained by incorporating a specific compound which becomes basic upon irradiation with actinic rays into a resin component comprising a polyimide precursor. The present invention has been completed based on this finding. The present invention provides a heat-resistant negative photoresist composition comprising a resin component having a structural unit represented by formula (I): wherein the COOH groups should always take the ortho-positions or adjacent positions with respect to the -CONH- linkages, R 1 represents a tetravalent aromatic or aliphatic hydrocarbon residue, and R 2 represents a divalent aromatic or aliphatic hydrocarbon residue, and a compound which becomes basic upon irradiation with actinic rays, represented by formula (II) or formula (III): wherein R 3 and R 4 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 5 and R 6 each is an alkyl group having 1 to 4 carbon atoms, and X 1 to X 4 each is one member selected from the group consisting of a hydrogen atom, a fluorine atom, a nitro group, a methoxy group, a dialkylamino group, an amino group, a cyano group and a fluoroalkyl group. The present invention further provides a neat-resistant negative photoresist composition comprising a resin component having a structural unit represented by formula (I): wherein the COOH groups should always take the ortho-positions or adjacent positions with respect to the -CONH- linkages, R 1 represents a tetravalent aromatic or aliphatic hydrocarbon residue, and R 2 represents a divalent aromatic or aliphatic hydrocarbon residue; a compound which becomes basic upon irradiation with actinic rays, represented by formula (II'): wherein R 3 and R 4 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 5 and R 6 each is one member selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an anilino group, a toluidino group, a benzyloxy group, an amino group and a dialkylamino group, and X 1 to X 4 each is one member selected from the group consisting of a hydrogen atom, a fluorine atom, a nitro group, a methoxy group, a dialkylamino group, an amino group, a cyano group and a fluoroalkyl group; and a dissolution accelerator represented by formula (IV): wherein R 7 and R 8 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 9 and R 10 each is one member selected from the group consisting of a hydrogen atom, a cyano group, an acetyl group, an amide group and a group of the formula COR 11 , wherein R 11 is one member selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an anilino group, a toluidino group and a benzyloxy group, and X 5 is one member selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group and a phenyl group. The present invention also provides a photosensitive substrate obtained by coating a surface of a substrate with either of the above heat-resistant negative photoresist compositions. The present invention still further provides a process for forming a negative pattern which comprises coating a photosensitive liquid on a substrate, said photosensitive liquid being prepared by dissolving the heat-resistant negative photoresist composition of the invention in an organic solvent, drying the resulting coating to form a film on the substrate, irradiating the resulting film with actinic rays through a photomask, heat-treating the irradiated film, and removing unexposed areas of the film by development with a basic development solution. The resin component used in the heat-resistant negative photoresist composition of the present invention functions as a skeletal substance for resist formation. This component is a polyimide precursor having a structural unit represented by the formula (I) described above. Examples of R 1 in the structural unit represented by the formula (I) include tetravalent aromatic or aliphatic hydrocarbon residues having a skeleton such as benzene, naphthalene, perylene, diphenyl, diphenyl ether, diphenyl sulfone, diphenylpropane, diphenylhexafluoropropane, benzophenone, butane, or cyclobutane. However, R 1 is not limited to those residues. preferred examples of R 1 are tetravalent residues having a skeleton of benzene, diphenyl, or benzophenone. If required and necessary, the groups of R 1 in the resin component can comprise at least two kinds of such residues. Examples of R 2 include divalent aromatic or aliphatic hydrocarbon residues having a skeleton such as diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfoxide, diphenyl sulfone, biphenyl, pyridine, or benzene. However, R 2 is not limited to those residues. Preferred examples of R 2 are divalent residues having a skeleton of diphenyl ether, diphenyl sulfone, or benzene. If required and necessary, the groups of R 2 in the resin component can comprise at least two kinds of such residues. The resin component having such a structural unit can be obtained by, for example, reacting substantially equimolar amounts of an aromatic or aliphatic tetracarboxylic dianhydride containing R 1 in the molecule thereof and an aromatic or aliphatic diamine containing R 2 in the molecule thereof in an organic solvent such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide or hexamethylphosphoramide. The first heat-resistant negative photoresist composition according to the present invention is characterized in that the resin component having a structural unit represented by the formula (I) contains a photosensitive compound represented by the formulae (II) or (III) described above. That is, the composition contains a photosensitive compound represented by any of the formulae (II) and (III) and becoming basic upon irradiation with actinic rays. This photosensitive compound may be incorporated in combination with a conventional sensitizer if required and necessary. The amount of the photosensitive compound of the formula (II) or (III) added is from 5 to 50 parts by weight, preferably from 10 to 40 parts by weight, per 100 parts by weight of the resin component having a structural unit represented by the formula (I). If the amount of the photosensitive compound added is too small, dissolution inhibition ability of the exposed areas deteriorates and, hence, poor solubility contrast is apt to result. If the amount thereof is too large, the composition may show poor stability during storage in solution state to develop a solid precipitate, which not only adversely affects pattern-forming properties but also leads to a considerable decrease in film thickness upon heat treatment after the formation of a negative pattern, resulting in poor mechanical strength. In the present invention, the compound of the formula (II) or (III) is presumed to function as follows. When irradiated with actinic rays, the compound undergoes intramolecular rearrangement to change its structure to a structure containing a pyridine skeleton and to become basic. Thereafter, a chemical reaction proceeds upon subsequent heat treatment to cause some interaction either between the resulting basic compound and the resin component having a structural unit represented by the formula (I) or within the basic compound. As a result, the resulting composition has reduced alkali solubility and hence can form a good negative pattern. Preferred examples of the compound of the formulae (II) and (III) include 2,6-dimethyl-3,5-dicyano-4-(2'-nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine. The compound represented by-the formula (II) or (III) can be obtained by, for example, reacting a substituted benzaldehyde with 2 mol of aminocrotonitrile per mol of the benzaldehyde in glacial acetic acid with refluxing, or reacting a substituted benzaldehyde with 2 mol of acetylacetone and 1 mol of ammonia per mol of the benzaldehyde in methanol. Alternatively, the desired compound can be obtained by the conventional method for synthesizing 1,4-dihydropyridine derivatives (e.g., J. Chem. Soc ., 1931 , 1835, 1931). The second heat-resistant negative photoresist composition according to the present invention is characterized in that a dissolution accelerator represented by the formula (IV) described above is further added to the composition comprising the resin component having a structural unit represented by the formula (I) and the photosensitive compound represented by the formula (II'). The dissolution accelerator of the formula (IV) which is contained in the composition is not activated at all by irradiation with actinic rays. It, however, has the effect of accelerating the rate of dissolution of unexposed areas during development, to thereby improve the developing rate and make the composition practically useful. Preferred examples of the compound of the formula (IV) include 2,6-dimethyl-3,5-dicyano-4-methyl-1,4-dihydropyridine and 2,6-dimethyl-3,5-dicyano-1,4-dihydropyridine. The amount of the compound of the formula (IV) added as a dissolution accelerator is from 5 to 50 parts by weight, preferably from 5 to 15 parts by weight, per 100 parts by weight of the resin component having a structural unit represented by the formula (I). If the amount of the dissolution accelerator added is too small, acceleration of the dissolution of the resin component in unexposed areas is not expected in development. Too large amounts thereof are undesirable in that a considerable decrease in film thickness may result from the final heat cure or that dissolution inhibition ability of exposed areas may deteriorate. Preferred amounts and examples and the function of the compounds represented by formula (II') correspond to those of formulae (II) and (III). One example of the process for forming an image using the heat-resistant negative photoresist composition of the present invention is described below. First, the resin component represented by the formula (I) is dissolved in an organic solvent such as those described hereinabove, together with either the compound of the formula (II) or (III) or the compounds of the formulae (II') and (IV), to prepare a photosensitive liquid. This photosensitive liquid is then applied on a substrate at a dry thickness of from 1 to 30 µm, preferably from 10 to 20 µm. The resulting coating film is dried (e.g., at 80°C for 10 minutes) and then exposed to light through an ordinary photomask. Post-exposure baking is then conducted (e.g., at a temperature of 150-200°C, preferably at 170°C or higher for 10 minutes), followed by developing treatment in which the unirradiated areas are removed e.g. by an immersion or spraying method. The developing solution used in the developing treatment is a basic solution preferably capable of completely dissolving and removing the unirradiated areas of the exposed film within a suitable period of time. Examples of such developing solutions include aqueous alkaline solutions of inorganic bases such as sodium hydroxide or potassium hydroxide and aqueous alkaline solutions of organic bases such as propylamine, butylamine, monoethanolamine, tetramethylammonium hydroxide, or choline. Those bases can be used alone or in combination of two or more thereof. The aqueous alkaline solution can contain an organic solvent such as an alcohol, or various kinds of surfactants, if required and necessary. After development, the resulting film is washed with a rinsing liquid to form a resin image having the desired negative pattern. The image-bearing film thus obtained is finally subjected to a high-temperature heat treatment (about 200 to 450°C) to allow the polyimide precursor to undergo dehydration cyclization and imidization, thereby obtaining an image-bearing polyimide resist having heat resistance. The present invention will be explained in more detail by reference to the following examples, but the invention is not construed as being limited thereto. EXAMPLE 1 Biphenyltetracarboxylic dianhydride was reacted with an almost equimolar amount of p-phenylenediamine at room temperature for 24 hours in dimethylacetamide at a monomer concentration of 20% by weight, thereby obtaining a solution of a polyimide precursor having a structural unit represented by the formula (I). To 100 parts by weight, on a solid basis, of the thus-obtained polyimide precursor solution was added 30 parts by weight of the compound represented by the formula (II) wherein R 3 and R 4 each was methyl group and X 1 , X 2 , X 3 , and X 4 each was hydrogen atom (hereinafter referred to as "o-NCN"). The compound added was uniformly dissolved in the solution. This solution was applied on a silicon wafer with a spin coater at 2,200 rpm for 20 seconds, and predried on an 80°C hot plate for 10 minutes to form a film having a dry thickness of about 18 µm. The film was then exposed through a glass mask to a 436 nm actinic ray emitted by a 250W superhigh-pressure mercury lamp placed at a distance of 30 cm from the film and which had been filtered through a glass filter, for 3 minutes by means of vacuum contact exposure. After the exposure, the resulting film was heated at 185°C for 10 minutes, developed for 4 minutes with a developing solution composed of 3 wt% aqueous tetramethylammonium hydroxide solution and methyl alcohol (2/1 by volume), and then rinsed with water. As a result, a negative pattern was obtained in which only the irradiated areas remained distinctly on the substrate. This pattern was subjected to high-temperature heating (400°C for 2 hours) for imidization. As a result, the percentage of the residual film thickness to the initial film thickness was about 75%. The polyimide film finally obtained was of a brown color and showed various properties which were well on practical levels. EXAMPLE 2 A negative pattern was formed in the same manner as in Example 1 except that the organic solvent used for polyimide precursor synthesis was changed from dimethylacetamide to N-methyl-2-pyrrolidone. Although the predrying required a temperature of 100°C, the pattern obtained had good properties as in Example 1. EXAMPLE 3 A negative pattern was formed in the same manner as in Example 1 except that in place of o-NCN, the compound represented by the formula (II) wherein R 3 and R 4 each was methyl group, X 1 , X 3 , and X 4 each was hydrogen atom, and X 2 was nitro group (hereinafter referred to as "2,4-NCN") was used in the same amount. The pattern thus obtained had good properties as in Example 1. COMPARATIVE EXAMPLE 1 A pattern was formed in the same manner as in Example 1 except that in place of o-NCN, the compound represented by the formula (II) wherein R 3 and R 4 each was methyl group, X 1 , X 3 , and X 4 each was hydrogen atom, X 2 was nitro group, and the cyano group at each of the 3- and 5-positions in the 1,4-dihydropyridine ring had been replaced by -COOCH 3 (hereinafter referred to as "2,4-NE") was used in the same amount, and that the post-exposure heating was conducted at 165°C for 10 minutes. However, the pattern thus obtained was a positive pattern in which the unirradiated areas remained on the substrate. EXAMPLE 4 A negative pattern was formed in the same manner as in Example 1 except that in place of o-NCN, the compound represented by the formula (III) wherein R 3 , R 4 , R 5 , and R 6 each was methyl group and X 1 , X 2 , X 3 , and X 4 each was hydrogen atom (hereinafter referred to as "o-NA") was used in the same amount. The pattern thus obtained had good properties as in Example 1. EXAMPLE 5 A negative pattern was formed in the same manner as in Example 4 except that the organic solvent used for polyimide precursor synthesis was changed from dimethylacetamide to N-methyl-2-pyrrolidone. Although the predrying required a temperature of 100°C, the pattern obtained had good properties as in Example 4. EXAMPLE 6 A negative pattern was formed in the same manner as in Example 4 except that in place of o-NA, the compound represented by the formula (III) wherein R 3 , R 4 , R 5 , and R 6 each was methyl group, X 1 , X 3 , and X 4 each was hydrogen atom, and X 2 was nitro group (hereinafter referred to as "2,4-NA") was used in the same amount. The pattern thus obtained had good properties as in Example 4. EXAMPLE 7 To 100 parts by weight, on a solid basis, of the polyimide precursor solution obtained in Example 1 were added 20 parts by weight of the compound represented by the formula (II') wherein R 3 and R 4 each was methyl group, X 1 , X 2 , X 3 , and X 4 each was hydrogen atom, and R 5 and R 6 each was methyl group (compound "o-NA", see also Example 4) and 10 parts by weight of the compound represented by the formula (IV) wherein X 5 was methyl group, R 7 and R 8 each was methyl group, and R 9 and R 10 each was cyano group (hereinafter referred to as "CH 3 -CN"). The compounds added were uniformly dissolved in the solution. A negative pattern was then formed in the same manner as in Example 1 except that the solution obtained above was used. This pattern was subjected to high-temperature heating (400°C for 2 hours) for imidization. As a result, the percentage of the residual film thickness to the initial film thickness was about 75%. The developing rate was as high as about 1.5 to 2 times that in Example 1. The polyimide film finally obtained was of a brown color and showed various properties which were well on practical levels. EXAMPLE 8 A negative pattern was formed in the same manner as in Example 7 except that in place of compound "o-NA" used in Example 7, the compound represented by the formula (II') wherein R 3 and R 4 each was methyl group, X 1 , X 3 , and X 4 each was hydrogen atom, X 2 was nitro group, and R 5 and R 6 each was a methoxy group ("2,4-NE" as in the Comparative Example) was used in the same amount. The pattern thus obtained had good properties as in Example 7. EXAMPLE 9 A negative pattern was formed in the same manner as in Example 7 except that in place of compound "o-NA", the compound represented by the formula (II) wherein R 3 and R 4 each was methyl group, X 1 , X 3 , and X 4 each was hydrogen atom, X 2 was nitro group, and R 5 and R 6 each was methyl group ("2,4-NA" as in Example 6) was used in the same amount, and that the post-heating was conducted at 200°C for 10 minutes. The pattern thus obtained had good properties as in Example 7. EXAMPLE 10 A negative pattern was formed in the same manner as in Example 7 except that the post-heating was conducted at 130°C for 10 minutes and then at 200°C for 10 minutes. This pattern was subjected to high-temperature heating at 360°C for 2 hours for imidization. The polyimide film thus obtained was superior in mechanical strength to that obtained in Example 7. EXAMPLE 11 A negative pattern was formed in the same manner as in Example 7 except that the pre-baking was conducted at 90°C for 30 minutes. This pattern was subjected to high-temperature heating for imidization in the same manner as in Example 10. The polyimide film thus obtained was superior in mechanical strength to that obtained in Example 7. As described above, when the heat-resistant negative photoresist composition of the present invention is irradiated with actinic rays having a wavelength which is a major absorption wavelength for the specific photosensitive compound contained in the composition, the alkali solubility of the irradiated areas is reduced and a large difference in the rate of dissolution in an alkaline developing solution results between the irradiated areas and the unirradiated areas. Thus, the photoresist composition shows high sensitivity and high resolving power and can form a practically usable negative pattern. Further, by the combined use of a specific dissolution accelerator, development for pattern formation can be conducted within a practical period of time. Moreover, a desired pattern can be formed from the composition of the present invention at low cost by conducting relatively simple procedures, and products of high quality can be provided. A further advantage of the composition is that since the final product obtained through high-temperature heat treatment has excellent thermal resistance and electrical and mechanical properties, it can be advantageously used in the semiconductor industry as a material for forming a protective or insulating film for solid elements or circuit substrates.

Claims: Claims for the following Contracting States : CH, LI, NL A heat-resistant negative photoresist composition comprising a resin component having a structural unit represented by formula (I): wherein the COOH groups should always take the ortho-positions or adjacent positions with respect to the -CONH- linkages, R 1 represents a tetravalent aromatic or aliphatic hydrocarbon residue, and R 2 represents a divalent aromatic or aliphatic hydrocarbon residue; and a compound which becomes basic upon irradiation with actinic rays, represented by formula (II) or formula (III): wherein R 3 and R 4 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 5 and R 6 each is an alkyl group having 1 to 4 carbon atoms, and X 1 to X 4 each is one member selected from the group consisting of a hydrogen atom, a fluorine atom, a nitro group, a methoxy group, a dialkylamino group, an amino group, a cyano group and a fluoroalkyl group. The heat-resistant negative photoresist composition of claim 1, wherein R 1 in the structural unit represented by the formula (I) is a tetravalent aromatic or aliphatic hydrocarbon residue having a skeleton of benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenyl sulfone, diphenylpropane, diphenylhexafluoropropane, benzophenone, butane or cyclobutane. The heat-resistant negative photoresist composition of claim 1, wherein R 2 in the structural unit represented by the formula (I) is a divalent aromatic or aliphatic hydrocarbon residue having a skeleton of diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfone, biphenyl, pyridine or benzene. The heat-resistant negative photoresist composition of claim 1, wherein the resin component is obtained by reacting an aromatic or aliphatic tetracarboxylic dianhydride containing R 1 in the molecule thereof and an aromatic or aliphatic diamine containing R 2 in the molecule thereof in substantially equimolar amounts in an organic solvent. The heat-resistant negative photoresist composition of claim 1, wherein the compound of the formula (II) or (III) is used in an amount of from 5 to 50 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 5, wherein the amount of the compound of the formula (II) or (III) is from 10 to 40 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 1, wherein the compound of the formula (III) is 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine. A heat-resistant negative photoresist composition comprising a resin component having a structural unit represented by formula (I): wherein the COOH groups should always take the ortho-positions or adjacent positions with respect to the -CONH- linkages, R 1 represents a tetravalent aromatic or aliphatic hydrocarbon residue, and R 2 represents a divalent aromatic or aliphatic hydrocarbon residue; a compound which becomes basic upon irradiation with actinic rays, represented by formula (II'): wherein R 3 and R 4 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 5 and R 6 each is one member selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an anilino group, a toluidino group, a benzyloxy group, an amino group and a dialkylamino group, and X 1 to X 4 each is one member selected from the group consisting of a hydrogen atom, a fluorine atom, a nitro group, a methoxy group, a dialkylamino group, an amino group, a cyano group and a fluoroalkyl group; and a dissolution accelerator represented by formula (IV): wherein R 7 and R 8 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 9 and R 10 each is one member selected from the group consisting of a hydrogen atom, a cyano group, an acetyl group, an amide group and a group of the formula COR 11 , wherein R 11 is one member selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an anilino group, a toluidino group and a benzyloxy group, and X 5 is one member selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group and a phenyl group. The heat-resistant negative photoresist of claim 8, wherein R 1 in the structural unit represented by the formula (I) is a tetravalent aromatic or aliphatic hydrocarbon residue having a skeleton of benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenyl sulfone, diphenylpropane, diphenylhexafluoropropane, benzophenone, butane or cyclobutane. The heat-resistant negative photoresist composition of claim 8, wherein R 2 in the structural unit represented by the formula (I) is a divalent aromatic or aliphatic hydrocarbon residue having a skeleton of diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfone, biphenyl, pyridine or benzene. The heat-resistant negative photoresist composition of claim 8, wherein the resin component is obtained by reacting an aromatic or aliphatic tetracarboxylic dianhydride containing R 1 in the molecule thereof and an aromatic or aliphatic diamine containined R 2 in the molecule thereof in substantially equimolar amounts in an organic solvent. The heat-resistant negative photoresist composition of claim 8, wherein the compound of the formula (II') is used in an amount of from 5 to 50 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 12, wherein the amount of the compound of the formula (II') is from 10 to 40 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 8, wherein the compound of the formula (II') is 2,6-dimethyl-3,5-dicyano-4-(2'nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine or 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine. The heat-resistant negative photoresist composition of claim 8, wherein the dissolution accelerator is 2,6-dimethyl-3,5-dicyano-4-methyl-1,4-dihydropyridine or 2,6-dimethyl-3,5-dicyano-1,4-dihydropyridine. The heat resistant negative photoresist composition of claim 8, wherein the dissolution accelerator is used in an amount of from 5 to 50 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 16, wherein the amount of the dissolution accelerator is from 5 to 15 parts by weight per 100 parts by weight of the resin component. A photosensitive substrate obtained by coating a surface of a substrate with the heat-resistant negative photoresist composition of claim 1 or 8. A process for forming a negative pattern which comprises coating a photosensitive liquid on a substrate, said photosensitive liquid being prepared by dissolving the heat-resistant negative photoresist composition of claim 1 or 8 in an organic solvent, drying the resulting coating to form a film on the substrate, irradiating the resulting film with actinic rays through a photomask, heat-treating the irradiated film, and removing unexposed areas of the film by development with a basic development solution. The process of claim 19, wherein the heat treatment is conducted at a temperature of 170°C or higher. Claims for the following Contracting States : BE, DE, FR, GB A heat-resistant negative photoresist composition comprising a resin component having a structural unit represented by formula (I): wherein the COOH groups should always take the ortho-positions or adjacent positions with respect to the -CONH- linkages, R 1 represents a tetravalent aromatic or aliphatic hydrocarbon residue, and R 2 represents a divalent aromatic or aliphatic hydrocarbon residue; and a compound which becomes basic upon irradiation with actinic rays, represented by formula (II) or formula (III): wherein R 3 and R 4 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 5 and R 6 each is an alkyl group having 1 to 4 carbon atoms, and X 1 to X 4 each is one member selected from the group consisting of a hydrogen atom, a fluorine atom, a nitro group, a methoxy group, a dialkylamino group, an amino group, a cyano group and a fluoroalkyl group, with the proviso that 2,6-dimethyl-3,5-dicyano-4-(2'-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2'nitrophenyl)-1,4-dihydropyridine are excluded. The heat-resistant negative photoresist composition of claim 1, wherein R 1 in the structural unit represented by the formula (I) is a tetravalent aromatic or aliphatic hydrocarbon residue having a skeleton of benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenyl sulfone, diphenylpropane, diphenylhexafluoropropane, benzophenone, butane or cyclobutane. The heat-resistant negative photoresist composition of claim 1, wherein R 2 in the structural unit represented by the formula (I) is a divalent aromatic or aliphatic hydrocarbon residue having a skeleton of diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfone, biphenyl, pyridine or benzene. The heat-resistant negative photoresist composition of claim 1, wherein the resin component is obtained by reacting an aromatic or aliphatic tetracarboxylic dianhydride containing R 1 in the molecule thereof and an aromatic or aliphatic diamine containing R 2 in the molecule thereof in substantially equimolar amounts in an organic solvent. The heat-resistant negative photoresist composition of claim 1, wherein the compound of the formula (II) or (III) is used in an amount of from 5 to 50 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 5, wherein the amount of the compound of the formula (II) or (III) is from 10 to 40 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 1, wherein the compound of the formula (III) is 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine. A heat-resistant negative photoresist composition comprising a resin component having a structural unit represented by formula (I): wherein the COOH groups should always take the ortho-positions or adjacent positions with respect to the -CONH- linkages, R 1 represents a tetravalent aromatic or aliphatic hydrocarbon residue, and R 2 represents a divalent aromatic or aliphatic hydrocarbon residue; a compound which becomes basic upon irradiation with actinic rays, represented by formula (II'): wherein R 3 and R 4 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 5 and R 6 each is one member selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an anilino group, a toluidino group, a benzyloxy group, an amino group and a dialkylamino group, and X 1 to X 4 each is one member selected from the group consisting of a hydrogen atom, a fluorine atom, a nitro group, a methoxy group, a dialkylamino group, an amino group, a cyano group and a fluoroalkyl group; and a dissolution accelerator represented by formula (IV) : wherein R 7 and R 8 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 9 and R 10 each is one member selected from the group consisting of a hydrogen atom, a cyano group, an acetyl group, an amide group and a group of the formula COR 11 , wherein R 11 is one member selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an anilino group, a toluidino group and a benzyloxy group, and X 5 is one member selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group and a phenyl group. The heat-resistant negative photoresist of claim 8, wherein R 1 in the structural unit represented by the formula (I) is a tetravalent aromatic or aliphatic hydrocarbon residue having a skeleton of benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenyl sulfone, diphenylpropane, diphenylhexafluoropropane, benzophenone, butane or cyclobutane. The heat-resistant negative photoresist composition of claim 8, wherein R 2 in the structural unit represented by the formula (I) is a divalent aromatic or aliphatic hydrocarbon residue having a skeleton of diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfone, biphenyl, pyridine or benzene. The heat-resistant negative photoresist composition of claim 8, wherein the resin component is obtained by reacting an aromatic or aliphatic tetracarboxylic dianhydride containing R 1 in the molecule thereof and an aromatic or aliphatic diamine containined R 2 in the molecule thereof in substantially equimolar amounts in an organic solvent. The heat-resistant negative photoresist composition of claim 8, wherein the compound of the formula (II') is used in an amount of from 5 to 50 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 12, wherein the amount of the compound of the formula (II') is from 10 to 40 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 8, wherein the compound of the formula (II') is 2,6-dimethyl-3,5-dicyano-4-(2'nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine or 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine. The heat-resistant negative photoresist composition of claim 8, wherein the dissolution accelerator is 2,6-dimethyl-3,5-dicyano-4-methyl-1,4-dihydropyridine or 2,6-dimethyl-3,5-dicyano-1,4-dihydropyridine. The heat resistant negative photoresist composition of claim 8, wherein the dissolution accelerator is used in an amount of from 5 to 50 parts by weight per 100 parts by weight of the resin component. The heat-resistant negative photoresist composition of claim 16, wherein the amount of the dissolution accelerator is from 5 to 15 parts by weight per 100 parts by weight of the resin component. A photosensitive substrate obtained by coating a surface of a substrate with the heat-resistant negative photoresist composition of claim 1 or 8. A process for forming a negative pattern which comprises coating a photosensitive liquid on a substrate, said photosensitive liquid being prepared by dissolving the heat-resistant negative photoresist composition of claim 1 or 8 in an organic solvent, drying the resulting coating to form a film on the substrate, irradiating the resulting film with actinic rays through a photomask, heat-treating the irradiated film, and removing unexposed areas of the film by development with a basic development solution. The process of claim 19, wherein the heat treatment is conducted at a temperature of 170°C or higher.

Inventors: FUJII HIROFUMI, HAYASHI SHUNICHI, OMOTE TOSHIHIKO, FUJII, HIROFUMI, HAYASHI, SHUNICHI, OMOTE, TOSHIHIKO
Applicants: NITTO DENKO CORP, NITTO DENKO CORPORATION
Application year: 1993
Main classification: G03F7
IPC codes: H01L21, G03F7, C08G73