Photosensitive composite, method for preparing it and use thereof

Abstract: The photosensitive composite of the present invention is obtained by including a nonsubstitutional or substitutional benzyl radical in the phenol side chain of polyvinylphenol. The photosensitive composites have not only excellent heat resistivity, RIE resistivity, and resolving power but also have a wide tolerance for the variations in the development temperature and developer concentration at the time of development. Therefore, it is possible to obtain resist patterns with fine structure. A method of fabricating a sub­ strate using such a resist pattern is also disclosed.

Description: The present invention relates to photosensitive composites useful for the formation of fine resist patterns, and more particularly, to photosensitive composites of positive or negative-type which show a wide tolerance for alkaline development conditions when applied to lithographic technique or the like. Photosensitive resins are being used wideiy in many fields of planar processes including the manufacture of semiconductors. However, the resist patterns are becoming increasingly fine in their structure in order to increase the density of the electronic devices, accompanying diversification in functions and sophistication of these devices. In addition, resistance to heat and resistance to reactive ion etching (RIE), which is being employed widely in recent times as a method of etching, of resist patterns are being required. As substances that can meet these requirements, there have been proposed in the past photosensitive composites that are formed by mixing photosensitive compounds with resins that consist of homopolymers or copolymers of vinylphenol group (reference: Japanese Patent No. 56-29261). However, there was a problem that when use is made of such prior-art photosensitive composites, resist patterns obtained by fixing after exposure have a very narrow tolerance to the development conditions in developing, although their resolving power is admittediy high. Namely, severe restrictions are imposed on the development temperature, the developer concentration, and others, and the pattern profile deteriorates rapidly if the temperature, concentration, and so on deviate from the respective predetermined values. Because of this, in order to obtain fine resist patterns, it is necessary to hold the changes in the developer concentration at small values by setting the developer concentration at a low level, which was a considerable inconvenience in practice. Accordingly, the object of the present invention is to provide photosensitive composites which have not only excellent heat resistivity, RIE resistivity, and resolving power, but also have an ample tolerance to alkaline development conditions of resist patterns, and hence, are useful to the formation of fine resist patterns. As a result of a concentrated effort to achieve the above object, the applicants of the present invention were abie to obtain knowledge that by the introduction of a nonsubstitutional or substitutional benzyl radical to the phenol side chain of polyvinylphenol, the alkaline solubility of resist at the time of development after exposure can be reduced, and hence, widens the tolerance to the alkaline development conditions. In addition, due to the presence of the phenol side chain of polyvinylphenol and the phenyl radical in the nonsubstitutional or substitutional benzyl radical, heat resistivity and RIE resistivity can be improved, which led to the completion of the present invention. Namely, a photosensitive composites of the present invention comprises a photosensitive compounds and a resin which contains polymers that include a structural unit as shown by the following formula: and a structural unit as shown by the following formula: These and additional objects, features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description on which, by way of example, only the preferred embodiments of this invention are illustrated. The photosensitive composites of the present invention are used as the photoresist in the photographic techniques such as the printing method and the bleaching out color process. The photographic techniques consists ordinarily of the resist process in which after spreading an appropriate resist material over a silicon single crystal wafer or the like, a desired resist pattern is formed by irradiating the resist material with ultraviolet rays, electron beams, or the like, and the etching process in which the wafer which is the base film is fabricated by the use of the resist pattern formed. The photosensitive composites of the present invention are used as the resist material in this method. Now, the resist process is a process in which a difference in the alkaline solubility is generated in the exposed portion and the unexposed portion to a beam irradiation, and a predetermined resist pattern is obtained by dissoling the exposed or unexposed portion with an alkaline developer. Here, the resolving power, sensitivity, and the like of the resist pattern obtained are determined eventually by the quality of the development process. Therefore, the control of the duration of development, temperature of development, concentration of the developer, and the like during the development process become extremely important. It means then that discovery of resist materials which permits the formation of patterns with high accuracy desired under lax control conditions will be very welcome. On the other hand, for the etching process, the reactive ion etching (RIE) method which enables finer fabrication is in wide use in recent years, as mentioned earlier. The resist materials of the present invention will also be used in the RIE method. Accordingly, these photosensitive composites have to possess an excellent resistivity to RIE. In addition, the resist material is heated to an extremely high temperature in the RIE process so that it has to be a substance which will not generate deformation at high temperatures. Otherwise, the accuracy of the resist pattern will be deteriorated quickly by such a deformation. Moreover, the photosensitive composites has to have in general a satisfactory adhesivity to a substrate or the like for which an eventual pattern formation is desired. The photosensitive composites of the present invention that satisfy these requirements consist of photosensitive compounds and resins that contain polymers that include a structural unit shown by the following formula: and a structural unit shown by the following formula: In these photosensitive composites, nonsubstitutional or substitutional benzyl radical is introduced to the phenol side chain, so that their acidity is lowered, alkaline solubility of the resist, at the time of development after exposure, is reduced, and hence, tolerance to the alkaline development conditions can be increased. It should be noted here that the number average molecular weight of the resin is desirable to be of order of 10³ to 10⁵. In addition, the ideal content of a polymer that contains structural units shown by the formula (I) and (II) in the resin, is 10 to 100% by weight. Moreover, the groups R₁, R₂, R₃, ..., R₄, and R₅ in the formula (I) may be identical or may be different, and each represents hydrogen atom, halogen atom, alkyl radical, carboxyl radical, alkylcarbonyl radical, alkoxycarbonyl radical, alkoxy radical, acyloxy radical, allyl radical, aryl radical, hydroxy radical, halogenoalkyl radical, cyanoalkyl radical, or alkoxyalkyl radical. In addition, R₆ represents hydrogen atom, alkyl radical, allyl radical, aryl radical, alkylcarbonyl radical, allylcarbonyl radical, or quinonediazidosulphonyl radical. As mentioned earlier, a photosensitive composites of the present invention consists of a resin that contains a polymer that includes the formula (I) and (II) as the structural units, as a first indispensable constituent, and a photosensitive composites as a second indispensable constituent. The resin which is the first indispensable constituent necessarily contains a polymer which contains in the molecule as the components a structural unit shown by the formula (I) and a structural unit shown by the formula (II). The form in which these units are contained is under no special restrictions, and can take, for example, modes as will be enumerated in the following. (a) A copolymer that consists only of the structural unit shown by the formula (I) and the structural unit shown by the formula (II). More precisely, it is a copolymer that has a structure, for example, given by (b) A coplymer that contains, in an identical molecule, a plurality of structural units (I) in which at least one set of the substitutional groups R₁ to R₅ is different from the rest. More precisely, it is a copolymer that has, for example, the following structure (where at least one of the pairs R₁ and R₁₁; R₂ and R₁₂; ...; R₅ and R₁₅ has mutually different substitutional groups): (c) A mixture of a plurality of copolymers each of which consists of the structural unit shown by the formula (I) and the structural unit shown by the formula (II) in which at least one of the set of the substitutional groups R₁ to R₅ and is different from the rest. More specifically, it is a mixture, for example, of a copolymer with the structure and a copolymer that has the structure (where R₁ and R₁₁; R₂ and R₁₂; ...; R₅ and R₁₅ are pairs of substitutional groups in which at least one pair has different groups. (d) A mixtures of one kind of copolymer consisting only of the structural unit shown by formula (I) and the structural unit shown by formula (II), or a plurality of the coplymers of the above kind in which at least one set of the substitutional groups R₁ to R₅ is different from the rest, and a copolymer consisting of molecules which have one or a plurality of structural units in which at least one set of the substitutional groups R₁ to R₅ in the formulas (I) is different from the rest. More specifically, it is a mixture, for example, of a copolymer that has the structure and a copolymer that has the structure (where at least one pair of R₁₁ and R₂₁; R₁₂ and R₂₂; ...; R₁₅ and R₂₅ has mutually different substitutional groups). (e) A mixture of a plurality of copolymers that contain in the same molecule a plurality of structural units in which at least one set of the substitutional groups R₁ to R₅ in the formulars (I) is different from the others. More specifically, it is a mixture, for example, of a copolymer that has a structure (where at least one pair of R₁ and R₁₁; ...; R₅ and R₁₅ has mutually different substitutional groups) and a copolymer which has a sturcture (where at least one pair of R₂₁ and R₃₁; ...; R₂₅ and R₃₅ has mutually different substitutional groups) (f) A copolymer which is formed by a strructural unit that consists of formula (I) and formula (II); and a structural unit that consists of at least one kind of vinyl chain or vinylidene chain such as acrylic acid, metacrylic acid, acrylic acid ester, metacrylic acid ester, or vinylalkyl ether (for instance, vinylmethyl ether), or esther chain that includes melamine, benzoguanidine, or the like. (g) A mixture obtained by mixing a copolymer described in (a) or (b) above and a copolymer described in (f). (h) A mixture obtained by mixing a plurality of copolymers described in (f) above. (i) A mixture obtained by mixing a copolymer described in (a) or (b); and a homopolymer which contains as its structural unit, other than a structural unit consisting of formula (I) and at least one of styrenes such as α-methylstyrene, styrene, and 4-chhlorostyrene, vinyl chain or vinylidene chain such as acrylic acid, metacrylic acid, acrylic acid ester, metacrylic acid ester, or vinylalkyl ether (for instance, vinylmethyl ether), or ester chain which includes melamine, benzoguanidine, or the like. (j) A mixture obtained by mixing a copolymer described in (f) above; and a homopolymer which has at least one of the following constituents as the structural unit or a copolymer which has at least two kinds of the following constituents as the structural units, the constituents in question being, other than a structural unit consisting of formula (I), styrenes such as α-methylstyrene, styrene, and 4-chlorostyrene, vinyl chain or vinyliden chain such as acrylic acid, metacrylic acid, acrylic acid ester, metacrylic acid ester, or vinylalkyl ether (for instance, vinylmethyl ether), or ester chain which includes melamine, benzoguanidine, and the like. It should be noted that whichever of the above modes is to be adopted, the rate that the copolymers, which consists of a structural unit shown by formula (I) and a structural unit shown by formula (II), occupy in the resin has to be set at 10 to 100% by weight. This is because if the rate is less than 10% by weight, there will arise such problems as the RIE resistivity becomes poor and the control of the alkaline solubility becomes difficult (in other words, if an acidic group such as acrylic acid is introduced in excess, then resin obtined becomes excessively soluble, whereas if the amount of alkaline insoluble group such as styrene is increased, resin obtained becomes excessively insoluble). Further, it is necessary to set the number average molecular weight of the components of resin that contains these polymers, in the range of 10³ to 10⁵. In particular, it is desirable to choose it in the range of 2,000 to 60,000 because of a more conspicuous tolerance to alkaline development, compared with the case of polyvinylphenol that was disclosed in the past. If the number average molecular weight is less than 10³, adhesivity of the resist becomes poor and the tolerance to alkaline development is also deteriorated. On the other hand, if it exceeds 10⁵, exposure sensitivity and the resolving power during development become poor and the tolerance to alkaline development is also deteriorated. Further, in the case of a copolymer which consists of a structural unit shown by formula (I) and a structural unit shown by formula (II), let the number of the structural unit shown by formula (I) to be k, and the number of the structural unit shown by formula (II) to be ℓ; it is desirable to set approximately 0.1 ≦ k/(k+ℓ) ≦ 0.5 . If the ratio k/(k+ℓ) is less than 0.1 the resistivity to RIE is deterirated, whereas if it exceeds 0.5 the tolerance to the alkaline development conditions becomes narrow. The polymers in the photosensitive composite can be obtained by adding styrene to polyvinylphenol with parasulfonic acid as a catalyst. For the photosensitive compound which represents the second indispensable component of the photosensitive composite of the present invention, use may be made of a photosensitive compound of positive or negative type. As examples of such photosensitive compound, one may mention, for instance, p-quinonediazides such as β-napththylamide of p-benzoquinone diazidosulfonic acid, p-iminoquinonediazides as disclosed in the specifications of British Patents No. 723382 and No. 942404, organic solvent soluble condensation products of diazonium salts and formaldehyde, aromatic diazonium salts such as the cocondensation products of p-diazodiphenylamine salts and 4,4-bis-methoxymethyldiphenyl ether with formaldehyde, and copolymerization products of other aromatic products and formaldehyde as disclosed in the specification of British Patent No. 1110017 and the specification of French Patent No. 2022413, and aromatic azides such as azido compounds as disclosed in the specification of British Patent No. 745886. However, an organic halogen compound such as bromoform can be used if in the mixing withh polyvinylphenol, use is made of low molecular weight diazonium, diazosulfonates of aromatic and complex ring type amines, quinonediazides, diazo radical, azido radicals, high molecular weight products that contain other photosensitive groups, or polyethylene oxides. Further, as the photosensitive compound particularly useful is o-naphthoquinonediazidosulfonic acid, o-quinonediazides such as aromatic esters or amides of o-naphthoquinonediazidocarbonic acid. In the photosensitive composites of the present invention, the mixing ratio of resin and photosensitive compound varies depending upon the kind of resin and photosensitive compound used, and their combination. However, generally speaking, it is desirable to use 0.1 to 50% by weight of the photosensitive compound in the photosensitive composite. This is because if the ratio is less than 0.1% by weight, sensitivity to exposure is extremely poor whereas if it exceeds 50% by weight, adhesivity of resist becomes very unsatisfactory. Next, an example of using the photosensitive composite of the present invention as a resist material in the photographic techniques of the printing method or the bleaching out color process will be described concretely. As a support member (substrate) on which is to be formed a resist layer by the use of a photosensitive composite, one may choose it from general materials such as plastic, metallic foil, or metallic plate. Now, in preparing a plate for printing, for example, one needs to spread a solution in an organic solvent of a photosensitive compound of the present invention, on a support material which is rotating. As organic solvent for this purpose, it is desirable to use such ketone-based solvents as cyclohexanone, acetone, methylethylketone, methylisobutylketone, cellosolve-based solvents such as methylcellosolve, methylcellosolve acetate, and ethylcellosolve acetate, or ester-based solvents such as acetic ester, acetic butyl, and acetic isoamyl, or a mixture of some of these solvents. A printing plate prepared in the above manner is exposed to a mercury lamp or the like, and then is developed with an aqueous solution of an alkali. The alkaline solution used for the development may be anything if it can dissolve the exposed portion in the case of positive type, and the unexposed portion in the case of negative type, and has an extremely low dissolution speed for the remaining portion. One may mention such as tetraalkylammonium aqueous solution like tetramethylammonium aqueous solution and inorganic alkaline aqueous solution such as pottasium hydroxide, sodium hydroxide, and the like. Then, using the pattern formed in the above process as the mask, the support material is etched. Of the two types of etching, namely, wet etching and dry etching, dry etching is preferred for the case of forming fine patterns with line width less than 3 µm. As a gas for dry etching, CF₄, C₂F₆, CCl₄, Bℓ₃, Cℓ₂, HCl, H₂, or the like is used, as combined if needed. The unexposed portion that remains on the substrate after etching, is removed from the top of the above material by means of a remover such as J-100 (manufactured by Nagase Chemical Industries, Inc.), oxygen gas plasma, or the like. In this way a desired fine pattern can be formed on the support member. As described in the foregoing, the photosensitive composite of the present invention has not only excellent heat resistivity, RIE resistivity, and resolving power, but also has a wide tolerance width for alkaline development conditions, for instance, variations in concentration and temperature during development, so that it is possible to form a fine resist pattern with ease by using it. In the following, the present invention will be described in detail by examining embodiments and a comparative example. However, the embodiments should be construed for the sake of mere explanation, and should by no means be understood to limit the present invention. Example 1 Styrene and polyvinylphenol (number average molecular weight: 7,000) were brought to reaction in a molar ratio of 2 : 10 to obtain a copolymer as shown by the following formula: Then, a resin was prepared by introducing benzoyl radical in place of hydrogen atom of the hydroxyl radical in phenol, by supplying benzoyl in a molar ratio of 1 : 10 for the copolymer. After that, 20 parts by weight of a photosensitive compound shown by the following formula: is mixed for 80 parts by weight of the resin to obtain a photosensitive composite. On the other hand, after heating a silicon wafer in hot plate at 150°C for one hour, the wafer was cooled down to the room temperature, and was left in an atmosphere of hexamethyldisilazane (HMDS) for 3 minutes before it was taken out. Then, a cyclohexanone solution of the photosensitive composite was spread over the silicon wafer with a spinner, dried in hot plate at 90°C for 5 minutes, and there was formed a photoresist of thickness of 1.5 µm. Following that, the photoresist was exposed to a stepper that uses monochromatic radiation of 436 nm, developed for 20 seconds in a 3.0% aqueous solution of tetramethylammoniumhydroxide (TMAH) at 21°C, to form a resist pattern. Here, with the initial film thickness of 1.5 µm maintained, lines and spaces (L/S) of 1.0 µm each were resolved. Result of observation with scanning electron microscope confirmed that there was obtained a resist pattern whose cross section has a steep profile. When a photoresist which is irradiated by a stepper in a manner similar to the above, was developed for 20 seconds in a 3.2% aqueous solution of TMAH at 21°C, there was obtained a resist pattern which has a profile approximately similar to the above. As a result of repeated experiments of similar kinds, it was found that resist patterns with steep cross sectional profile can be obtined for variations in the range of 25°C±5°C for the developer temperature and for variations in the range of 3.0%±0.2% for the developer concentration. Resist patterns that are obtained in this manner have sufficient resistivity to heat, with absolutely no flow even for a baking at 140°C, in the case of L/S of 10 µm. In addition, the resistivity to RIE was found to be improved by about 30% compared with the prior-art resist patterns. Here, the resistivity to RIE is determined by measuring the film thickness before and after giving RIE. Example 2 An experiment was carried out similarly to Example 1, except for the use of 1,2-naphthoxydiazido-5-sulfonic acid ester (average esterification factor of 2.0) of 2,3,4-trihydroxybenzophenone as the photosensitive compound. A resist pattern was obtained by developing for 60 seconds at 21°C using a 2.2% aqueous solution of TMAH as the developer. Analogous to Example 1, there was obtined a resist pattern with a steep cross sectional profile even if the developer temperature is varied in the range of 25°C±5°C and the concentration is varied in the range of 2.2%±0.2%. In addition, heat resistivity and RIE resistivity obtained were similar to the results in Example 1. Example 3 Esterification was carried out for the copolymer shown by the formula (III) as used in Example 1 by causing to react with 1,2-naphthoquinonediazido-5-sulfonic acid chloride of molar ratio of 0.3, to obtain a resin by the introduction of in place of the hydrogen atom in the hydroxyl radical of phenol. As a result of carrying out an experiment similar to Example 1 without utilizing a photosensitive compound, due to the fact that the resin possesses photosensitivity of its own, it was confirmed that the resin has excellent properties analogous to that of Example 1. Example 4 By bringing styrene into reaction with polyvinylphenol (number average molecular weight : 9,000) in a molar ratio of 3 : 10 the copolymer which is shown by the following formula was obtained: then, methyl radical was added to the copolymer in the molar ratio of 3 : 10 to introduce methy radical in place of hydrogen atom in the hydroxyl radical of phenol, and a resin was obtined. Using the resin, a photosensitive composite was obtained in a manner similar to Example 1. Experiments similar to Example 1 confirmed that the composite has excellent properties similar to the composite of Example 1. Example 5 A resin consisting of a copolymer shown by the following formula: was obtained by bringing styrene and polyvinylphenol (number average molecular weight : 6,000) into reaction in the molar ratio of 2 : 10. A photosensitive composite was obtained by mixing 30 parts by weight of the photosensitive compound shown by the following formula: for 100 parts by weight of the resin produced,where A in the avove formula represents On the other hand, a silicon wafer was heated in hot plate at 150°C for one hour, and after cooling it down to the room temperature, it was left standing for 3 minutes in an atmosphere of hexamethyldisilazane (HMDS) before it was taken out. Next, a solution of the photosensitive composite was spread over the silicon wafer with spinner, dried in hot plate for 2 minutes at 90°C, and a photoresist of thickness 1.5 µm was formed. Then, a resist pattern was formed by exposing the photoresist to monochromatic radiation of 436 nm by means of a stepper, and by developing for 45 seconds with a 2.38% aqueous solution of tetramethylammonium hyeroxide (TMAH) at 25°C. As a result, lines and spaces of 0.7 µm were resolved while maintaining the initial film thickness of 1.5 µm. In addition, it was confirmed by an observation of scanning electron microscope that there was formed a resist pattern whose cross section shows a steep profile. Further, when a photoresist which was similarly exposed by the use of a stepper, was developed for 30 seconds with a 2.5% aqueous solution of TMAH at 25°C, there was obtained a resist pattern that possesses an approximately same profile as above. As a result of repetition of these experiments, it was found that resist patterns with steep sectional profile can be obtained even if the developer temperature is varied in the range of 25°C±5°C and the concentration is varied in the range of 2.3%±0.2%. Further, it was confirmed that resist patterns obtained in this manner have sufficient resistivity to heat with absolutely no flow even for a baking of 5 minutes at 140°C in the case of lines and spaces of 10 µm. Moreover, the resistivity to RIE was found to be improved by about 50% compared with the existing resist patterns. Comparative Example A solution of photosensitive composite was prepared by mixing, in 80 g of cyclohexanone 20 g of polyvinylphenol of number average molecular weight 10,000 and 4 g of a photosensitive compound, 4-azido-4′-methoxy-α-cyanostilbene. Following that, tests similar to those of Example 1 showed that development had to be given for 30 seconds with a 0.76% aqueous solution of TMAH at 25°C. Moreover, it was found that development could not proceed unless under strict conditions compared with the case of the present invention with respect to the temperature control as well as to the adjustment of the concentration of TMAH.

Claims: A photosensitive composite comprising: (a) a resin which comprises a polymer that comprises (i) a structural unit as shown by the following formula: , wherein R₁, R₂, R₃, R₄, and R₅ may be identical or may be different, each representing hydrogen atom, halogen atom, alkyl radical, carboxyl radical, alkylcarbonyl radical, alkoxycarbonyl radical, alkoxy radical, acyloxy radical, allyl radical, aryl radical, hydroxy radical, halogenoalkyl radical, cyanoalkyl radical, or alkoxyalkyl radical, and R₆ represents hydrogen atom, alkyl radical, allyl radical, aryl radical, alkylcarbonyl radical, allylcarbonyl radical, or quinoneazidosulfonyl radical, and (ii) a structural unit as shown by the following formula: and (b) a photosensitive compound. The photosensitive composite of claim 1 wherein said resin comprises a copolymer which consist of the structural unit shown by the formula (I) and the structural unit shown by the formula (II). The photosensitive composite of claim 1 wherein said resin comprises a copolymer consists of (a) a plurality of structural units shown by the formula (I) in which at least one set of the substitutional groups R₁ to R₅ is different from the rest, and (b) a structural unit shown by the formula (II). The photosensitive composite of claim 1 wherein said resin comprises a mixture of plural kinds of mutually different copolymers as described in claim 2, in which at least one set of the substitutional groups R₁ to R₅ included in the copolymers differs from the rest. The photosensitive composite of claim 1 wherein said resin comprises a mixture of a copolymer as described in claim 2, and a copolymer which consist of a structural unit shown by the formula (I), a structural unit shown by the formula (II) and a structural unit selected from the group consisting of vinyl chain, vinylidene chanin and ester chain. The photosensitive composite of claim 1 wherein said resin comprises a mixture of plural kinds of mutually different copolymers each of which consists of a structural unit shown by the formula (I), structural unit shown by the formula (II), and a structural unit selected from the group consisting of vinyl chain, vinyliden chain and ester chain. The photosensitive composite of claim 1 wherein the number average molecular weight of said resin is 10³ to 10⁵. The photosensitive composite of claim 7 wherein the number average molecular weight of said resin is 2,000 to 60,000. The photosensitive composite of claim 7 wherein the content in said resin of a polymer which comprises structural units shown by the formula (I) and the formula (II), is 10 to 100% by weight. The photosensitive composite of claim 9 wherein the content of said photosensitive compound in the photosensitive composite is 0.1 to 50% by weight. The photosensitive composite of claim 9 wherein if the number of structural unit shown by the formula (I) is k, and the number of structural unit shown by the formula (II) is ℓ, these numbers satisfy the condition 0.1 ≦ k/(k+ℓ) ≦ 0.5 . The photosensitive composite of claim 9 wherein said photosensitive compound is (a) a condensation product, which is soluble in organic solvent, between a p-quinonediazide, p-iminoquinonediazide, or diazonium salt and formaldehyde, (b) a copolymerization product between an aromatic diazonium salt or an aromatic product and formaldehyde, (c) an aromatic azide, or (d) an organic halogen compound. The photosensitive composite of claim 9 wherein said photosensitive compound is (a) an aromatic ester of o-naphthoquinonediazidosulfonic acid or o-naphthoquinonediazidocarbonic acid, or (b) o-quinonediazide such as amide. The photosensitive composite of claim 9 wherein said photosensitive compound comprises a compound shown by where A in the above formula is represented by The photosensitive composite of claim 14 wherein said resin comprises a copolymer shown by the following formula and the mixing ratio of the resin and the photosensitive compound is 30 parts by weight of the photosensitive compound for 100 parts by weight of the resin. A method of producing the photosensitive composite of claim 9 comprising the steps of: (a) obtaining a copolymer shown by the formula by bringing styrene and polyvinylphenol into reaction in the molar ratio of 2 : 10; (b) preparing a resin by introducing benzyl radical to the copolymer in the molar ratio of 1 : 10 to introduce the benzoyl radical in place of the hydrogen atom in the hydroxyl radical of phenol; and (c) mixing 20 parts by weight of a photosensitive compound shown by and 80 parts by weight of the resin obtained. A method of producing the photosensitive composite of claim 9 comprising the steps of: (a) obtaining a copolymer shown by the formula by bringing styrene and polyvinylphenol into reaction in the molar ratio of 2 : 10; (b) preparing a resin by supplying benzoyl radical to the copolymer in the molar ratio of 1 : 10 to introduce the benzoyl radical in place of hydrogen atom in the hydroxyl radical of phenol; and (c) mixing the resin with 1,2-naphthoxydiazido-5-sulfonic acid ester (average esterification factor of 2.0) of 2,3,4-trihydroxybenzophenone as a photosensitive compound. A method of producing the photosensitive composite of claim 9 comprising the steps of: (a) obtaining a copolymer shown by the formula by bringing styrene and polyvinylphenol into reaction in the molar ratio of 2 : 10; and (b) introducing in place of the hydrogen atom in the hydroxyl radical of phenol, by carrying out esterification in which 1,2-naphthoquinonediazido-5-sulfonic acid chloride and the copolymer are brought into reaction in the molar ratio of 3 : 10. A method of producing the photosensitive composite of claim 9 comprising the steps of: (a) obtaining a copolymer shown by the formula by bringing styrene and polyvinylphenol into reaction in the molar ratio of 3 : 10; (b) introducing the methyl radical in place of the hydrogen atom in the hydroxyl radical of phenol by supplying methyl radical to the copolymer in the molar ratio of 3 : 10; and (c) mixing 20 parts by weight of a photosensitive compound shown by to 80 parts by weight of the resin. A method of forming a resist pattern on the surface of a substrate by the use of the photosensitive composite of claim 1 comprising the steps of: (a) dissolving the photosensitive composite in an organic solvent; (b) spreading the photosensitive composite on the surface of the substrate; (c) creating a difference in the solubility to an alkaline aqueous solution between the exposed portion and the unexposed portion by irradiating the surface of the substrate with either one of light or electron beam to form a predetermined pattern; and (d) dissolving either one of the exposed portion or unexposed portion by developing the surface of the substrate with an alkali. The method of forming a resist pattern of claim 20 wherein the photosensitive compound included in the photosensitive composite is of positive type so that the exposed portion is dissolved in said alkaline development. The method of forming a resist pattern of claim 20 wherein the photosensitive compound included in the photosensitive composite is of negative type so that the unexposed portion is dissolved in said alkaline development. The method of forming a resist pattern of claim 20 wherein said organic solvent is (i) a ketone-based solvent such as cyclohexanone, acetone, methylethylketone, and methylisobutylketone, (ii) a cellosolve-based solvent such as methylcellosolve, methylcellosolve acetate, and ethylcellosolve acetate, or (iii) ester-based solvent such as acetic acid ethyl, acetic acid butyl, and acetic acid isoamyl, (iv) or a mixture of these solvents. The method of forming a resist pattern of claim 20 wherein said alkaline solution for the alkaline development comprises an aqueous solution of tetraalkylammonium or an aqueous solution of an inorganic alkali. A method of fabricating a substrate by the use of a resist pattern formed on the surface of the substrate according to the method described in claim 20 comprising the steps of: (a) etching the substrate using said resist pattern as the mask; and (b) removing the resist material that remains on the substrate.

Inventors: HAYASE SHUZI, HORIGUCHI RUMIKO, ONISHI YASUNOBU G- TOMIOKASEAS, HAYASE, SHUZI, HORIGUCHI, RUMIKO, ONISHI, YASUNOBU G-508 TOMIOKASEASIDE-CORPO
Applicants: TOSHIBA KK, KABUSHIKI KAISHA TOSHIBA
Application year: 1987
Main classification: G03F7
IPC codes: G03F7, G03C1