Chemical amplification resist composition

Abstract: There is described a chemical amplification resist composition which comprises squarylium compounds represented by the formula (I): wherein R¹ and R² are the same or different and represent substituted or unsubstituted aminophenyl, 9-julodidyl, Y=CH-(wherein Y represents substituted or unsubstituted heterocyclic group containing nitrogen ),or a group: (wherein Z¹ and Z² are the same or different and represent substituted or unsubstituted phenyl), photochemical acid generator and binders.

Description: The present invention relates to the use of a combination of a squarylium compound, a photochemical acid generator and a binder for a chemical amplification resist composition which is high sensitive, in particular, to from visible to near infrared rays and from which the positive and negative type resist can be obtained. A chemical amplification resist composition which can forms the pattern by producing a secondary chemical reaction with the catalytic action of an acid formed by exposure to light using a photochemical acid generator as a sensitizing agent, and thereby causing the change in the solubility in the developer is known [J. Synthetic Org. Chem., Japan, 49 , 437 (1991), SEN-I GAKKAISHI, 47 , 358 (1991)]. On the other hand, the squarylium compounds are known to be used for the resist material in the presence of an ethylenic unsaturated compound (JP-A-4-106548 JP-A-63-142346, JP-A-2-306247 ≙ EP-A-379200), the image formation system in the presence of light-unstable blocked surfactant (JP-A-60-243653), a charge generation material in the electrophotography (Dyes and Pigments, 9 , 85 (1988), JP-A-52-55643, JP-A-60-224674), the medium material for optical memory disc (JP-A-3-149263), the resin plate material for beam-condensing (JP-A-63-235370), LB (Langmuir-Brodget) membrane material (Nikkei New Material, published October, 26, 1987) and the like. Solid State Technology 34(1991), 53; Polym. Eng. Sci. (USA) 29(1989), 856; EP-A-452263 and IBM Technical Disclosure Bulletin 33/2 (1990), 272 relate to chemical amplification type resists sensitive in the UV region. The main object of the invention is to provide a chemical amplification resist composition which is high sensitive, in particular, to from visible to near infrared rays and from which the positive and negative type resist can be obtained. This object has been achieved by providing a use of a combination of a squarylium compound represented by the formula (I): wherein R 1 and R 2 are the same or different and represent substituted or unsubstituted aminophenyl, 9-julolidyl, Y=CH- (wherein Y is substituted or unsubstituted heterocyclic group containing nitrogen ), or a group represented by the formula: (wherein Z 1 and Z 2 are the same or different and represent substituted or unsubstituted phenyl), a photochemical acid generator and a binder for a chemical amplification resist composition. The invention relates further to certain chemical amplification resist compositions as described in claims 12 to 16. As the heterocyclic group containing nitrogen in the formula (I), there are indolin-2-ylidene, benz[e]indolin-2-ylidene, 2-benzothiazolinylidene, naphtho[2,1-d]thiazol-2(3H)-ylidene, naphtho[1,2-d]thiazol-2(1H)-ylidene, 1,4-dihydroquinolin-4-ylidene, 1, 2-dihydroquinolin-2-ylidene, 2, 3-dihydro-1 H-imidazo[4,5-b]quinoxalin-2-ylidene, 2-benzoselenazolinylidene and the like. Aminophenyl, phenyl, 9-julolidyl and heterocyclic groups containing nitrogen are optionally substituted with the same or different one to three substituents. As the substituent, there are alkyl, alkoxy, aryl, aralkyl, halogen, nitro, hydroxy, amino and the like. As the alkyl group, there is the alkyl having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl and the like. As the alkoxy group, there is the alkoxy having 1 to 6 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and the like. As the aryl group, there is the aryl having 6 to 10 carbon atoms, for example, phenyl, naphthyl and the like. As the aralkyl, there is the aralkyl having 7 to 10 carbon atoms, for example, benzyl, phenylethyl, phenylpropyl and the like. As the halogen, there are fluorine, chlorine, bromine and iodine. The squaryliums [compounds (I)] are the known compounds (see, for example, JP-A-63-142346 and JP-A-2-306247) and the novel compounds. Those compounds are prepared, for example, by the following method. Preparation 1 R 1 H( or R 1 H 2 + ·X - )+R 2 H (or R 2 H 2 + .X - )+ squaric acid → compound (I) wherein R 1 and R 2 are as defined above, X represents chlorine, bromine, iodine or a group: This reaction is carried out by reacting R 1 H (or R 1 H 2 + .X - ), the equivalent moles of R 2 H (or R 2 H 2 + ·X - ) and the equivalent moles of squaric acid and, if necessary, from equivalent to 2 times moles of a basic compound at 90 to 110 °C for 1 to 24 hours in a solvent. As the solvent, an alcoholic solvent is used sole or in admixture with benzene or toluene (alcohol is not less than 50%). Alternatively, acetic acid is used as a solvent. As the basic compound, there are triethylamine, quinoline, pyridine and the like. The solvent is distilled off from the reaction mixture or the product is filtered to give a compound (I). Preparation 2 wherein R 1 , R 2 and X are as defined above, R 0 represents chlorine or OR 3 (wherein R 3 represents alkyl having 1 to 4 carbon atoms). As the alkyl having 1 to 4 carbon atoms, there are methyl, ethyl, propyl, butyl and the like. A compound (III) is prepared by reacting R 1 H (or R 1 H 2 + ·X - ) and the equivalent moles of a compound (II) and, if necessary, the equivalent moles of a basic compound or metallic sodium at 10 to 35 °C for 5 minutes to 5 hours in a solvent. As the basic compound, those described above can be used. As the solvent, there are chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, diisopropyl ether, tetrahydrofuran, toluene, benzene, dimethylformamide, dimethyl sulfoxide, methanol, ethanol, propanol, butanol and the like. The compound (III) is isolated by distilling the solvent off or filtering the product. A compound (IV) is prepared by reacting a compound (III) at 90 to 110 °C for 1 to 24 hours in a 50 to 90 (wt.%) aqueous solution of acetic acid. The compound (IV) is isolated as described above. A compound (I) is prepared by reacting a compound (IV) and the equivalent moles of R 2 H (or R 2 H 2 + ·X - ) and, if necessary, the equivalent moles of a basic compound at 90 to 110 °C for 1 to 24 hours in a solvent. As the basic compound, the above compounds can be used. As the solvent, an alcoholic solvent is used sole or in admixture with benzene or toluene (alcoholic solvent is not less than 50%). The compound (I) is isolated as described above. And the compound (I) can be further purified by recrystallization, forced precipitation, column chromatography and the like. Then, the representative compounds (I) are shown in Table 1. As the photochemical acid generator, there are s-triazine compounds substituted with at least one trihalomethyl groups [such as 2,4,6-tris(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-1-naphthalenyl)-4.6-bis(trichloromethyl)-s-triazine and the like], iron-arene complexes [such as a salt of PF 6 ⊖ of (η 6 -isopropylbenzene) (η 5 -cyclopentadienyl)iron (II) and the like], onium salts {such as diaryliodonium salts [8-anilinenaphthalen-1-sulfonic acid diphenyliodonium salts and the like], triarylsulfonium. salts, triarylselenonium salts, dialkylphenacylsulfonium salts, dialkyl-4-hydroxyphenylsulfonium salts, iodonium salts and the like}, aryldiazonium salts, diazoketones, nitrobenzyl esters [such as 9,10-diethoxyanthracen-2-sulfonic acid-p-nitrobenzyl esters] and the like], sulfonic acid esters [such as α-hydroxymethylbenzoinsulfonic acid ester, N-hydroxyimidosulfonate and the like], silanol-aluminium complexes and the like. Among them, s-triazine compounds substituted with at least one trihalomethyl groups are preferable and they can be obtained, for example, according to the method described in JP-A-2-306247. As the binder, there are homopolymers or copolymers of monomers selected from acrylic acid or ester thereof, methacrylic acid or ester thereof, (anhydrous) maleic acid or ester thereof, acrylonitrile, styrene, α-alkylstyrene, α-acetoxystyrene, hydroxystyrene, α-alkylhydroxystyrene, α-acetoxyhydroxystyrene, or the substituted compounds obtained by protecting the hydroxy groups of the above compounds with a protecting group easily hydrolyzable by acid treatment, or cyclic analogues thereof, vinyl acetate, vinyl chloride, vinylidene chloride, butadiene, crotonic acid, itaconic acid, N-substituted maleimide, vinyl benzoate, or copolymer of the above esters, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyethylene terephtalate, acetyl cellulose, methyl cellulose, ethyl cellulose, polyvinyl butyrate, chlorinated polyolefine, polyalkylene, polyaldehyde, polycarbonate, epoxy resin, cresol novolak resin, melamine resin, alkyd resin, modified polyvinyl alcohol, and block or graft copolymer or modified polymer by combination of them. For improving the plasma-resistance upon development, an substituent containing silicone may be introduced in the binder before or after exposure to light. The proportion of the compound (I) is 1 to 60 parts by weight (referred to as "part" hereinafter) relative to 100 parts of photochemical acid generator, and the amount of the binder is 2 to 100 parts, preferably 5 to 50 parts, relative to one part of the photochemical acid generator. In particular, when the negative type resist is prepared by the thermal cross-linking reaction in the presence of an acid, a cross linking agent may be contained therein. As the cross linking agent, there are amino compounds having as a functional group at least two alkoxymethyl group, methylol group, acetoxymethyl group and the like such as melamine derivative [hexamethoxymethylated melamine (manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 300 series (1) )and the like], benzoquanamine derivative [methyl/ethyl mixed alkylated benzoguanamine resin (manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 1100 series (2) )and the like], glycoluril derivative [tetramethylolglycoluril (manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 1100 series (3)) and the like], at least disubstituted aromatic compounds having, as a functional group, alkoxymethyl group, methylol group, acetoxymethyl group and the like such as 1,3,5-trihydroxymethylbenzene, 1,3,5-triacetoxymethylbenzene, 1,2,4,5-tetraacetoxymethylbenzene and the like. These cross linking agents can be synthesized according to the method described in Polym. Mater. Sci. Eng., 64 , 241 (1991). The amount of the cross linking agent is 0.1 to 100 parts, preferably 0.2 to 50 parts, relative to one part of the photochemical acid generator. Further, solvent (such as ethyl cellosolve and the like), dissolution inhibiting agent (such as silyl ether and the like), plasticizer (such as dioctyl phthalate and the like), sensitivity improving agent (such as tertiary amine and the like), dark reaction inhibitor, colorant composed of organic or inorganic dye or pigment and the like may be contained therein depending upon the use of the chemically amplifying resist. The chemical amplification resist composition of the present invention is prepared, for example, by mixing the compound (I), the photochemical acid generator and the binder and, if necessary, cross linking agent and the like. Further, a photosensitive material having the high sensitivity to, in particular, from visible to near infrared rays can be obtained by coating a solution of the chemical amplification resist composition of the present invention dissolved in a solvent (such as ethyl cellosolve and the like) on the aluminium plate having the treated surface, silicon wafer, glass plate and the like and drying. As the light source for from visible to near infrared rays, the source for the rays which can be absorbed by the compound (I) such as mercury lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, light-emitting diode, laser rays and the like can be used. The temperature at heat-treating following the light irradiation is not higher than the melting point (decomposition point) of a photosensitive material obtained at room temperature, most preferably 50 to 120 °C. Upon development for final image formation, the wet development using a solvent (for example, dilute aqueous alkaline solution and the like) and dry etching using heating, plasma, accelerated ion and the like can be used depending upon the composition of the photosensitive material. The following Examples and Reference Examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof. Example 1 100 Parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co. Ltd., Resin M], 40 parts of hexamethoxymethylated melamine [manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 301], 8 parts of 2,4,6-tris(chloromethyl)-s-triazine and 1 part of the compound 1 were dissolved in 900 ml of ethyl cellosolve to give a solution of a chemical amplification resist composition. This solution was coated on the aluminium plate which had been treated by graining and anodic oxidation using a spin-coater and dried using a warm air drier to give the dry-state thickness of 1 µm. A step tablet having the optical density step of 0.15 was piled on the resulting photosensitive sample, and the rays (I 0 =80.5 µJ/cm 2 ·s) having the wavelength around 630 nm were irradiated from 3 KW ultra-high pressure mercury lamp through a heat rays absorbing filter HA-30 (manufactured by HOYA Corporation), a colored glass filter R-61 and an interference filter [both filters are manufactured by Toshiba Glass Co., Ltd.]. Subsequently, the heat-treating was carried out in an oven at 100 °C for 5 minutes, the development was carried out using an aqueous solution containing 2 wt% sodium metasilicate, the ink was applied using the ink PI-2 for PS form plate development [manufactured by Fujiphoto Film Co., Ltd.], and the necessary energy for curing was calculated from the curing step number with the ink applied to give the high sensitivity of 0.7 mJ/cm 2 . Example 2 The sensitivity of 1.4 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that one part of the compound 4 and heat treating conditions (90 °C, 10 minutes) were used in place of one part of the compound 1 and the heat treating conditions (100 °C, 5 minutes). Example 3 The very high sensitivity of 0.24 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that the heat treating conditions (90 °C, 10 minutes) were used in place of (100 °C, 5 minutes). Example 4 The sensitivity of 3.4 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that 8 parts of PF 6 ⊖ salt of (η 6 -isopropylbenzene) (η 5 -cyclopentadienyl) iron (II) was used in place of 8 parts of 2,4,6-tris(trichloromethyl)-s-triazine. Example 5 The sensitivity of 4 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that one part of the compound 3 and the heat treating conditions (90 °C, 10 minutes) were used in place of one part of the compound 1 and heat treating conditions (100 °C, 5 minutes). Example 6 The sensitivity of 4.5 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that one part of the compound 2 and heat treating conditions (90 °C, 10 minutes) were used in place of one part of the compound 1 and heat treating conditions (100 °C, 5 minutes). Example 7 The sensitivity of 5 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that 100 parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co., Ltd., PHS MARUKA LYNCUR H3F], one part of the compound 6 obtained in Reference Example 1 and the heat treating conditions (90 °C, 10 minutes) were used in place of 100 parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co., Ltd., Resin M], one part of the compound 1 and the heat treating conditions (100 °C, 5 minutes), and the rays (I 0 =2.46 mJ/cm 2 ·s) having the wavelength around 600 to 800 nm were irradiated without using an interference filter KL-63 [manufactured by Toshiba Glass Co., Ltd.]. Example 8 The sensitivity of 5 mJ/cm 2 was obtained according to the same manner as that in Example 7 except that one part of the compound 7 obtained in Reference Example 2 was used in place of one part of the compound 6 obtained in Reference Example 1. Example 9 The sensitivity of 18 mJ/cm 2 was obtained according to the same manner as that in Example 7 except that one part of the compound 5 was used in place of one part of the compound 6 obtained in Reference Example 1. Example 10 The sensitivity of 0.9 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that 100 parts of polymethacrylic acid ester polymer and the heat treating conditions (90 °C, 6 minutes) were used in place of 100 parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co., Ltd., Resin M] and the heat treating conditions (100 °C, 5 minutes). Example 11 A photosensitive sample having the dry-state thickness of 1 µm was obtained by spin-coating on the glass having the treated surface a solution of a chemical amplification resist composition prepared according to the same manner as that in Example 1 except that 100 parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co., Ltd., PHS MARUKA LYNCUR H3F] and 40 parts of hexamethoxymethylated melamine [manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 300] were used in place of 100 parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co., Ltd., Resin M] and 40 parts of hexamethoxymethylated melamine [manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 301], and drying. The He-Ne laser rays were split into two light flux using a beam splitter and the two light flux were introduced in the photosensitive sample from the same plane at the angle Θ=74 °. After exposure to light, the photosensitive sample was heat-treated in an oven at 90 °C for 15 minutes, subsequently developed with an aqueous solution containing 2 wt% sodium metasilicate, washed with water and dried to give the bright surface hologram. Example 12 The sensitivity of 0.7 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that 100 parts of metacresol novolak resin (m/p=6/4) and the heat treating conditions (90°C, 10 minutes) were used in place of 100 parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co., Ltd., Resin M] and the heat treating conditions (100 °C, 5 minutes). Example 13 The sensitivity of 6 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that 100 parts of styrene-maleic acid monoisobutyl copolymer and the heat treating conditions (90 °C, 1 minute) were used in place of 100 parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co., Ltd., Resin M] and the heat treating conditions (100 °C, 5 minutes). Example 14 The sensitivity of 43 mJ/cm 2 was obtained according to the same manner as that in Example 7 except that 42 parts of hexamethoxymethylated melamine [manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 300], 9 parts of 8-anilinenaphthalen-1-sulfonic acid diphenyliodonium salt, one part of the compound 1 and the heat treating conditions (90 °C, 6 minutes) were used in place of 40 parts of hexamethoxymethylated melamine [manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 301], 8 parts of 2,4,6-tris(trichloromethyl)-s-triazine, one part of the compound 6 obtained in Reference Example 1 and the heat treating conditions (90 °C, 10 minutes). Example 15 The sensitivity of 3 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that 8 parts of 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine and the heat treating conditions (90 °C, 12 minutes) were used in place of 8 parts of 2,4,6-tris(trichloromethyl)-s-triazine and the heat treating conditions (100 °C, 5 minutes). Example 16 100 Parts of alkali-insoluble polyimide containing fluorine in which the hydroxy group is protected with tetrahydropyranyl group, 8.4 parts of 2,4,6-tris(trichloromethyl)-s-triazine and 0.9 parts of the compound 1 were dissolved in 900 ml of ethyl cellosolve to give a solution of chemical amplification resist composition. This solution was coated on the aluminium plate treated with graining and anodic oxidation using a spin-coater, and dried using a warm air drier to give the dry-state thickness of 1 µm. A step tablet having the optical density step of 0.15 was piled on the resulting photosensitive sample, and the rays having the wavelength around 610 nm were irradiated from 3KW ultra-high pressure mercury lamp through a heat rays absorbing filter HA-30 (manufactured by HOYA Corporation) and a colored glass filter R-61 [manufactured by Toshiba Glass Co., Ltd.]. The photosensitive sample was subsequently heat-treated in an oven at 120 °C for 15 minutes, and developed with DN3C developer for PS form plate [manufactured by Fujiphoto Film Co., Ltd.], upon which the irradiated parts were dissolved to give a positive image. Example 17 The sensitivity of 2.0 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that 100 parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co., Ltd., PHS MARUKA LYNCUR H3F], 40.8 parts of hexamethoxymethylated melamine [manufactured by K&K], 7.6 parts of 2,4,6-tris(trichloromethyl)-s-triazine, 1.02 parts of the compound 6 obtained in Reference Example 1, the rays (I 0 =162 µJ/cm 2 ·s) having the wavelength around 780 nm obtained by irradiating from 3KW ultra-high pressure mercury lamp and passing through KL-78 [manufactured by Toshiba Glass Co., Ltd.] and the heat treating conditions (90 °C, 10 minutes) were used in place of 100 parts of poly-p-hydroxystyrene [manufactured by Maruzen Petrochemical Co., Ltd., Resin M], 40 parts of hexamethoxymethylated melamine [manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 301], 8 parts of 2,4,6-tris(trichloromethyl)-s-triazine, one part of the compound 1, the rays (I 0 =80.5 µJ/cm 2 ·s) having the wavelength around 630 nm obtained by irradiating from 3 KW ultra-high pressure mercury lamp and passing through a heat rays absorbing filter HA-30 (manufactured by HOYA Corporation), a colored glass filter R-61 and an interference filter KL-63 [both filters are manufactured by Toshiba Glass Co., Ltd.]. Example 18 The sensitivity of 1.36 mJ/cm 2 was obtained according to the same manner as that in Example 17 except that 1.25 parts of the compound 7 obtained in Reference Example 2 and the heat treating conditions (90 °C, 11 minutes) were used in place of 1.02 parts of the compound 6 obtained in Reference Example 1 and the heat treating conditions (90 °C, 10 minutes). Example 19 The sensitivity of 3.1 mJ/cm 2 was obtained according to the same manner as that in Example 17 except that 1.1 parts of the compound 8 obtained in Reference Example 3 and the heat treating conditions (90 °C, 13 minutes) were used in place of 1.02 parts of the compound 6 obtained in Reference Example 1 and the heat treating conditions (90 °C, 10 minutes). Example 20 The sensitivity of 3.4 mJ/cm 2 was obtained according to the same manner as that in Example 1 except that 100 parts of poly-p-hydroxystyrene (manufactured by Maruzen Petrochemical Co., Ltd., PHS MARUKA LYNCUR H3F), 48 parts of hexamethoxymethylated melamine (manufactured by K&K), 1.1 parts of the compound 9 obtained in Reference Example 4 and the heat treating conditions (90 °C, 8 minutes) were used in place of 100 parts of poly-p-hydroxystyrene (manufactured by Maruzen Petrochemical Co., Ltd., Resin M), 40 parts of hexamethoxymethylated melamine (manufactured by MITSUI-CYANAMID, LTD., CYMEL ® 301), one part of the compound 1 and the heat treating conditions (100 °C, 5 minutes). Example 21 The sensitivity of 1.9 mJ/cm 2 was obtained according to the same manner as that in Example 20 except that 1.1 parts of the compound 10 having the following structure was used in place of 1.1 parts of the compound 9 obtained in Reference Example 4. The compound 10 is known (see, for example, JP-A-2-306247). Example 22 The sensitivity of 4.9 mJ/cm 2 was obtained according to the same manner as that in Example 20 except that 40 parts of hexamethoxymethylated melamine (manufactured by K&K), 1.0 part of the compound 11, the rays (I 0 =2.55 mJ/cm 2 ·s) having the wavelength of not less than 660 nm obtained by irradiating from 3KW ultra-high pressure mercury lamp and passing through a heat rays absorbing filter HA-30 (manufactured by HOYA Corporation) and a colored glass filter R-66 (manufactured by Toshiba Glass Co., Ltd.) and the heat treating conditions (90 °C, 18 minutes) were used in place of 48 parts of hexamethoxymethylated melamine (manufactured by K&K), 1.1 parts of the compound 9, the rays (I 0 =80.5 µJ/cm 2 ·s) having the wavelength around 630 nm obtained by irradiating from 3KW ultra-high pressure mercury lamp and passing through a heat rays absorbing filter HA-30 (manufactured by HOYA Corporation), a colored glass filter R-61 and an interference filter KL-63 (both filters are manufactured by Toshiba Glass Co., Ltd.) and the heat treating conditions (90 °C, 8 minutes). Example 23 The sensitivity of 3.3 mJ/cm 2 was obtained according to the same manner as that in Example 20 except that 40 parts of hexamethoxymethylated melamine (manufactured by K&K), 1.0 part of the compound 12, the rays (I 0 =112 µJ/cm 2 ·s) having the wavelength around 680 nm obtained by irradiating from 3KW ultra-high pressure mercury lamp and passing through a heat rays absorbing filter HA-30 (manufactured by HOYA Corporation), a colored glass filter R-66 and an interference filter KL-68 (both filters are manufactured by Toshiba Glass Co., Ltd.) and the heat treating conditions (90 °C, 5 minutes) were used in place of 48 parts of hexamethoxymethylated melamine (manufactured by K&K), 1.1 parts of the compound 9, the rays (I 0 =80.5 µJ/cm 2 ·s ) having the wavelength around 630 nm obtained by irradiating from 3 KW ultra-high pressure mercury lamp and passing through a heat rays absorbing filter HA-30 (manufactured by HOYA Corporation), a colored glass filter R-61 and an interference filter KL-63 (both filters are manufactured by Toshiba Glass Co., Ltd.) and the heat treating conditions (90 °C, 8 minutes). The compound 12 having the following structure is known (see, for example, JP-A-3-149263). Reference Example 1 15 ml of dichloromethane was added to 0.3 g of 3,4-dichloro-3-cyclobuten-1,2-dione [Tetrahedron Lett. No. 10, P.781 (1970)], and 0.54 g of 1,1-bis(p-dimethylaminophenyl)ethylene was added thereto to stir at room temperature. After 1 hour, the dichloromethane was distilled off from the reaction mixture using a rotary evaporator. 7.6 ml of acetic acid and 10 ml of water were added to the residue and the mixture was heated on an oil bath at 100 °C. After heating for 1 hour, the acetic acid and water were distilled off using a rotary evaporator. 20 ml of n-butanol and 20 ml of benzene as well as 1.05 g of 1,3-di-n-hexyl-2-methylimidazo[4,5-b]quinoxalinium tosylate and 0.27 g of quinoline were added to the residue and the mixture was heated for 2 hours. Thereafter, the mixture was concentrated using a rotary evaporator, and purified by column chromatography to give 0.45 g of a compound 6. The melting point and the results of elementary analysis are as follows. Melting point: 147 °C (dec.) Elementary analysis Calc'd (%) C 75.83, H 7.52, N 12.06 Found (%) C 76.13, H 7.54, N 12.26 Reference Example 2 A mixture of 1.98 g of 3,4-diisopropoxy-3-cyclobuten-1,2-dione, 2.99 g of N-ethyllepidinium iodide and 20 ml of isopropanol was stirred at room temperature, 0.23 g of sodium was added thereto and the mixture was stirred for 4 hours. The insolubles were filtered, the filtrate was concentrated, and the residue was purified by column chromatography. 30 ml of acetic acid and 10 ml of water were added to this purified material, and the mixture was heated at 95 °C for 1.5 hours. After completion of the reaction, the volatile portion was concentrated and dried. 13 ml of n-butanol and 0.92 g of 1,3-di-n-butyl-2-methylimidazo[4,5-b]quinoxalinium chloride and 0.27 g of quinoline were added to the dried material, and the mixture was heated to reflux for 4 hours. The solvent and produced water were distilled off using a rotary evaporator. The residue was purified by column chromatography to give 0.31 g of a compound 7. The melting point and the results of elementary analysis are as follows. Melting point: 237-238 °C (dec.) Elementary analysis: Calc'd (%) C 74.84, H 6.47, N 12.83 Found (%) C 75.13, H 6.52, N 12.94 Reference Example 3 A mixture of 1.98 g of 3,4-diisopropoxy-3-cyclobuten-1,2-dione, 2.99 g of N-ethyllepidinium iodide and 20 ml of isopropanol was stirred at room temperature, 0.23 g of sodium was added thereto, and the mixture was stirred for 4 hours. The insolubles were filtered, the filtrate was concentrated, and the residue was purified by column chromatography. 30 ml of acetic acid and 10 ml of water were added to this purified material, and the mixture was heated at 90-100 °C for 1.5 hours. After completion of the reaction, the volatile portion was concentrated and dried. 0.37 g of 1,3,3-trimethyl-2-methyleneindoline, 21 ml of n-butanol and 21 ml of benzene were added to the dried material, and the mixture was heated to reflux for 5 hours. The volatile portion was concentrated, and the residue was purified by column chromatography to give 0.24 g of a compound 8 having the following structure. The melting point and the results of elementary analysis are as follows. Melting point: 260-263 °C (dec.) Elementary analysis: Calc'd (%) C 79.59, H 6.20, N 6.63 Found (%) C 79.90, H 6.15, N 6.80 Reference Example 4 20 ml of dichloromethane was added to 1.5 g of 3,4-dichloro-3-cyclobuten-1,2-dione, 1.7 g of 1,3,3-trimethyl-2-methyleneindoline was added dropwise under ice-cooling, and after 2 hours, the precipitates were filtered and dried. 35 ml of acetic acid and 50 ml of water were added to the dried material, the mixture was heated on an oil bath at 100 °C for 1 hour, and the acetic acid and water were distilled off using a rotary evaporator. 100 ml of n-butanol, 5.25 g of 1,3-di-n-hexyl-2-methylimidazo[4,5-b]quinoxalinium tosylate and 1.01 g of triethylamine were subsequently added to the residue, and the mixture was heated to reflux for 3 hours. The volatile portion was concentrated, and the residue was purified by column chromatography to give 3.57 g of a compound 9 having the following structure. The melting point and the results of elementary analysis are as follows. Melting point: 173.5-174.9 °C Elementary analysis: Calc'd (%) C 75 59, H 7.51, N 11.60 Found (%) C 73.99, H 7.47, N 11.17 Reference Example 5 0.17 g of a compound 11 having the following structure was prepared according to the same manner as that in Reference Example 3 except that 0.72 g of 1,1,2,3-tetramethyl-1H-benz[e]indolium iodide and 0.28 g of quinoline were added in place of 1 ,3,3-trimethyl-2-methyleneindoline. The melting point and the results of elementary analysis are as follows. Melting point: 266-267.6 °C (dec.) Elementary analysis: Calc'd C 81.33, H 5.97, N 5.93 Found C 81.52, H 6.06, N 5.97

Claims: Use of a combination of a squarylium compound represented by the formula (I): wherein R 1 and R 2 are the same or different and represent substituted or unsubstituted aminophenyl, 9-julolidyl, Y=CH- (wherein Y represents substituted or unsubstituted heterocyclic group containing nitrogen), or a group: (wherein Z 1 and Z 2 are the same or different and represent substituted or unsubstituted phenyl), a photochemical acid generator and a binder for a chemical amplification resist composition. Use according to claim 1, wherein the aminophenyl group, phenyl group and 9-julolidyl group are optionally substituted with the same or different one to three substituents selected from alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 10 carbon atoms, halogen, nitro, hydroxy and amino, and the heterocyclic group containing nitrogen is selected from of indolin-2-ylidene, benz[e]indolin-2-ylidene, 2-benzothiazolinylidene, naphtho[2,1-d]thiazol-2(3H)-ylidene, naphtho[1 ,2-d]thiazol-2(1H)-ylidene, 1,4-dihydroquinolin-4-ylidene, 1 ,2-dihydroquinolin-2-ylidene, 2,3-dihydro-1H-imidazo[4,5-b]quinoxalin-2-ylidene and 2-benzoselenazolinylidene, said heterocyclic group containing nitrogen being optionally substituted with the same or different one to three substituents selected from alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 10 carbon atoms, halogen, nitro, hydroxy and amino. Use according to claim 1, the squarylium compound is selected from Use according to any of claims 1 to 3, wherein the photochemical acid generator is selected from s-triazine compound substituted with at least one trihalomethyl groups, iron-arene complexes, onium salt, aryldiazonium salt, diazoketones, nitrobenzyl ester, sulfonic acid ester and silanol-aluminium complex. Use acording to claim 4, wherein the photochemical acid generator is s-triazine compound substituted with at least one trihalomethyl groups. Use according to claim 5, wherein the s-triazine compound substituted with at least one trihalomethyl groups is selected from 2,4,6-tris(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine and 2-(4-methoxy-1-naphthalenyl)-4,6-bis(trichloromethyl)-s-triazine Use according to any of claims 1 to 6, wherein the iron-arene compound is a salt of PF 6 ⊖ of (η 6 -isopropylbenzene) (η 5 -cyclopentadienyl)iron (II). Use according to any of claims 1 to 7, wherein the onium salt is selected from diaryliodonium salt, triarylsulfonium salt, triarylselenonium salt, dialkylphenacylsulfonium salt, dialkyl-4-hydroxyphenylsulfonium salt and iodonium salt. Use according to any of claims 1 to 8, wherein the nitrobenzyl ester is 9,10-diethoxyanthracen-2-sulfonic acid-p-nitrobenzyl ester. Use according to any of claims 1 to 9, wherein the sulfonic acid ester is α-hydroxymethylbenzoinsulfonic acid ester and/or N-hydroxyimidosulfonate. Use according to any of claims 1 to 10, wherein the binder is a homopolymer or copolymer of monomers selected from acrylic acid or ester thereof, methacrylic acid or ester thereof, (anhydrous) maleic acid or ester thereof, acrylonitrile, styrene, α-alkylstyrene, α-acetoxystyrene, hydroxystyrene, α-alkylhydroxystyrene, a-acetoxyhydroxystyrene, or the substituted compounds obtained by protecting the hydroxy groups of the above compounds with a protecting group easily hydrolyzable by acid treatment, or cyclic analogues thereof, vinyl acetate, vinyl chloride, vinylidene chloride, butadiene, crotonic acid, itaconic acid, N-substituted maleimide, vinyl benzoate, or copolymer of the above esters, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyethylene terephtalate, acetyl cellulose, methyl cellulose, ethyl cellulose, polyvinyl butyrate, chlorinated polyolefine, polyalkylene, polyaldehyde, polycarbonate, epoxy resin, cresol novolak resin, melamine resin, alkyd resin, modified polyvinyl alcohol, and block or graft copolymer or modified polymer by combination of them. A chemical amplification resist composition comprising a squarylium compound as defined in any of claims 1 to 6, a photochemical acid generator and a binder, wherein the iron-arene compound is a salt of PF 6 ⊖ of (η 6 -isopropylbenzene) (η 5 -cyclopentadienyl)iron (II). A chemical amplification resist composition comprising a squarylium compound as defined in any of claims 1 to 6, a photochemical acid generator and a binder, wherein the onium salt is selected from diaryliodonium salt, triarylsulfonium salt, triarylselenonium salt, dialkylphenacylsulfonium salt, dialkyl-4-hydroxyphenylsulfonium salt and iodonium salt. A chemical amplification resist composition comprising a squarylium compound as defined in any of claims 1 to 6, a photochemical acid generator and a binder, wherein the nitrobenzyl ester is 9,10-diethoxyanthracen-2-sulfonic acid-p-nitrobenzyl ester. A chemical amplification resist composition comprising a squarylium compound as defined in any of claims 1 to 6, a photochemical acid generator and a binder, wherein the sulfonic acid ester is α-hydroxymethylbenzoinsulfonic acid ester and/or N-hydroxyimidosulfonate. The chemical amplification resist composition according to any of claims 12 to 15, wherein the binder is a homopolymer or copolymer of monomers selected from acrylic acid or ester thereof, methacrylic acid or ester thereof, (anhydrous) maleic acid or ester thereof, acrylonitrile, styrene, α-alkylstyrene, α-acetoxystyrene, hydroxystyrene, α-alkylhydroxystyrene, α-acetoxyhydroxystyrene, or the substituted compounds obtained by protecting the hydroxy groups of the above compounds with a protecting group easily hydrolyzable by acid treatment, or cyclic analogues thereof, vinyl acetate, vinyl chloride, vinylidene chloride, butadiene, crotonic acid, itaconic acid, N-substituted maleimide, vinyl benzoate, or copolymer of the above esters, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyethylene terephtalate, acetyl cellulose, methyl cellulose, ethyl cellulose, polyvinyl butyrate, chlorinated polyolefine, polyalkylene, polyaldehyde, polycarbonate, epoxy resin, cresol novolak resin, melamine resin, alkyd resin, modified polyvinyl alcohol, and block or graft copolymer or modified polymer by combination of them.

Inventors: ITO YUKIYOSHI, KOSEKI KENICHI, OBARA MITSUHARU, SHIMIZU IKUO, YAMAOKA TSUGUO, ITO, YUKIYOSHI, KOSEKI, KENICHI, OBARA, MITSUHARU, SHIMIZU, IKUO, YAMAOKA, TSUGUO
Applicants: KYOWA HAKKO KOGYO KK, KYOWA HAKKO KOGYO CO., LTD.
Application year: 1993
Main classification: G03F7
IPC codes: G03F7