Photosensitive composition

专利摘要:
The present invention provides a photosensitive composition useful as a photoresist containing a resin composition and a photosensitive material, wherein, as the resin composition, two or more resin mixtures having a refractive index difference of 0.03 or more, or alkali-soluble resins are used as the resin component of the resin composition. The present invention relates to a photosensitive composition using a mixture of a resin that functions as a dissolution inhibitor of a photosensitive composition, such as an acrylic polymer, a methacrylic polymer, and a styrene polymer, as a resin additive. It is preferable that the dissolution rate with respect to 2.38 weight% of tetramethylammonium hydroxide of the photosensitive composition is 5000 kPa / min or less. By using these resin compositions, the photosensitive composition which can reduce the usage-amount of a quinonediazide photosensitive agent and satisfy | fills both the characteristic of high sensitivity and high residual film simultaneously is obtained.
公开号:KR20010112227A
申请号:KR1020017007045
申请日:2000-10-04
公开日:2001-12-20
发明作者:다카하시슈이치
申请人:데머 얀, 당코 제니아 떼.；클라리언트 인터내셔널 리미티드；
IPC主号:

专利说明:

Photosensitive composition
[2] BACKGROUND ART Photolithography techniques have conventionally been used to form or fabricate microelements in a wide range of fields, such as semiconductor integrated circuits such as LSIs, and manufacturing of FPDs and circuit boards such as thermal heads. . In this photolithography technique, in order to form a resist pattern, the positive type or negative type photosensitive composition containing a resin component and the photosensitive substance is used. Among these photosensitive compositions, as a positive photosensitive composition, the composition containing alkali-soluble resin and the quinonediazide compound as a photosensitive substance is used widely. This composition is, for example, "a novolak resin / quinonediazide compound", JP 54-23570 A (US Pat. No. 3,666,473 specification) JP 56-30850 A (Patent No. 4,115,128), Unexamined-Japanese-Patent No. 55-73045, Unexamined-Japanese-Patent No. 61-205933, and many other documents have described various compositions.
[3] The compositions containing these novolak resins and quinonediazide compounds have been researched and developed on both sides of novolak resins and photosensitive materials. In view of the novolak resin, it is of course possible to develop a new resin and to obtain a photosensitive composition having excellent properties by improving physical properties and the like of a conventionally known resin. For example, JP-A-60-140235 and JP-A-H1-105243 provide a specific molecular weight distribution to the novolak resin, and also JP-A-60-140235. Japanese Patent Application Laid-Open No. 60-97347, Japanese Patent Laid-Open No. 60-189739, and Japanese Patent No. 2590342 provide a photosensitive composition having excellent characteristics by using a novolak resin from which low molecular weight components have been fractionated. Is disclosed. Moreover, as a negative photosensitive composition, what combined the novolak resin, the alkoxy methylation melamine as a crosslinking agent, and the halogenated triazine as an acid generator (Japanese Unexamined-Japanese-Patent No. 5-303196) etc. are mentioned. Photosensitive compositions having various compositions have been developed so far, and as a result of the improvement of the properties of these photosensitive compositions, many photosensitive compositions have been put to practical use.
[4] However, the degree of integration of semiconductor devices is increasing year by year, and in the production thereof, pattern processing of line widths of submicrons or less is required, and the conventional technology cannot sufficiently cope. In addition, in the manufacture of display surfaces such as LCDs, mother glass has been enlarged in size. As the mother glass substrate is enlarged, the following problem arises when using the conventional photosensitive composition as a resist material.
[5] That is, the problem of the resist sensitivity according to the enlargement of a mother glass is mentioned first. This is because the number of pattern exposures in the exposure apparatus increases as the size of the substrate increases, so that through-put (amount obtained per unit time) during manufacture decreases when a conventional photosensitive composition is used. For this reason, in order to improve this throughput, further high sensitivity of the resist is required.
[6] Conventionally, in order to make a resist highly sensitive, methods, such as use of a low molecular weight resin, reduction of the addition amount of a photosensitive substance, addition of a substance with a fast alkali dissolution rate, use of a highly sensitive photosensitive substance, are taken. However, among these methods, although the use of a low molecular weight resin and the method of reducing the addition amount of the photosensitive substance can be used, the heat resistance of the resist is lowered, although it is possible to improve the coating property and the line width uniformity of the resist pattern. This results in problems such as deterioration of etching resistance in manufacturing steps of semiconductor devices and the like, deterioration of developability, generation of scum, and residual film ratio. For example, when the amount of the photosensitive material is used in an amount of 20 parts by weight or less relative to 100 parts by weight of resin, which is less than the amount usually used in the past, the residual film property is very bad when only novolac resin is used as the resin component. This does not function as a resist. In this connection, the usage-amount of the conventional photosensitive substance is about 25 weight part per 100 weight part of resin components in the photosensitive composition.
[7] In order to solve this problem, the technique which uses 2 or more types of novolak resins derived from a specific phenolic compound as a novolak resin, and uses the molecular weight range specifically (JP-A-7-271024). Is a novolak resin derived from a specific phenolic compound, and a technique in which a molecular weight range and a dispersion degree thereof are specified and a polyhydroxy compound having a phenolic hydroxyl group is used. Hei) 8-184963), the technique using the photosensitive component which mixed the naphthoquinone diazide sulfonic acid ester of trihydroxy benzophenone and trihydroxy benzophenone in arbitrary fixed ratio (Unexamined-Japanese-Patent No. 8-82926) have been proposed.
[8] Moreover, when a large size glass substrate is used and the conventional photosensitive composition is applied, there arises a problem that the coating is increased or the in-plane uniformity of the pattern line width is not sufficiently obtained due to the unevenness of the resist film thickness. In order to improve the applicability | paintability of such a photosensitive composition, examination of the addition of surfactant to the photosensitive composition and the kind and quantity of surfactant added so far have been examined. Moreover, in the examination of the solvent for improving applicability | painting, using the solvent which has a specific boiling point, kinematic viscosity, and evaporation rate (Unexamined-Japanese-Patent No. 10-186637), propylene glycol, and dipropylene It has been reported to use a mixed solvent containing a solvent selected from glycol (Japanese Patent Laid-Open No. 10-186638).
[9] However, these various proposals have not simultaneously and sufficiently improved problems such as sensitivity, residual film property, resolution, pattern reproducibility, throughput improvement during manufacturing, coating property, or process dependency. Thus, the suggestion of a photosensitive composition which can simultaneously and sufficiently satisfy such problems, i.e., high sensitivity, high residual film property, high resolution, good pattern reproducibility, improvement in throughput during production, good applicability, or low process dependency It is strongly demanded. In addition, in order to reduce the cost of the photosensitive composition, it is also required to reduce the addition amount of the photosensitive material having a high unit cost, but the problem as described above occurs when the addition amount of the photosensitive material is reduced.
[10] On the other hand, it is already known that a light scattering phenomenon occurs by mixing two or more kinds of resins having different refractive indices to satisfy specific conditions. For example, JP-A-5-249319 discloses light incident in a single or multi-direction by incorporating a polymerizable monomer with polymer solid particles, monomers or liquids having different refractive indices and polymerizing them. It is introduced that waveguide can be carried out while scattering, whereby scattering and an optical transmission body can be obtained. As a typical application example using this light scattering effect, a backlight light guide plate of a liquid crystal display device (for example, JP-A-6-186560, JP-A-7-169311, etc.) can be cited. have. In Japanese Unexamined Patent Publication (Kokai) No. 8-255983, a photosensitive composition insulating material containing a light-scattering filler having a refractive index difference of 0.1 to 0.7 with a photosensitive composition is used in a negative photosensitive composition and scattered by light scattering. A method of installing a taper in a via hole is disclosed. However, this does not improve the sensitivity, developability, etc. of the photosensitive composition.
[11] Under the above circumstances, the present invention also has the same or higher sensitivity as in the prior art even when the amount of the photosensitive material added to the photosensitive composition containing the resin component and the photosensitive material is smaller than that of the conventional one, and also has a high residual film property. It is an object to provide a photosensitive composition having a compound.
[12] In addition, it is an object of the present invention to provide a photosensitive composition capable of achieving both high residual film properties and high sensitivity, and having excellent developability and a good pattern.
[13] Moreover, an object of this invention is to provide the photosensitive composition which satisfy | fills the said various characteristics and is excellent in coating | coating characteristic and the line width uniformity of a resist pattern, and low process dependency.
[14] Disclosure of the Invention
[15] MEANS TO SOLVE THE PROBLEM As a result of earnestly researching and examining, in the photosensitive composition containing resin and a photosensitive substance, the effect of a photosensitive substance can be improved by using 2 or more types of resin in which the refractive index mutually differs as 0.03 or more. In addition, it is possible to reduce the amount of photosensitive material to be used, and even when the addition amount of the photosensitive material is reduced by further containing a resin which functions as a dissolution inhibitor in the photosensitive composition containing the alkali-soluble resin and the quinonediazide photosensitive agent, the amount of the photosensitive material is not reduced. It was found that the resist pattern can be formed, and the present invention has been reached.
[16] That is, this 1st invention is a photosensitive composition containing a resin composition and a photosensitive substance WHEREIN: The said resin composition consists of 2 or more types of resin from which a refractive index differs, and the refractive index difference of these resin is 0.03 or more, It is characterized by the above-mentioned. It relates to a photosensitive composition.
[17] Moreover, this 2nd invention is a photosensitive composition containing a resin composition and a photosensitive substance WHEREIN: The said resin composition is a resin additive which functions as at least the resin component which consists of (a) alkali-soluble resin, and (b) dissolution inhibitor. And a photosensitive material having (c) a quinonediazide group.
[18] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
[19] In this 1st invention, as for a photosensitive composition, what is necessary is just to contain 1 or more sets of resin whose refractive index difference ((DELTA) n) mutually is 0.03 or more as a resin composition. At this time, this invention is not limited by the kind and number of resin to be used. As one of the resin from which the refractive index used in the resin composition of these photosensitive compositions differs, ie, a resin component, alkali-soluble resin is preferable. When alkali-soluble resin is used as a resin component of a resin composition, the resin composition of this 1st invention is a resin component which consists of (a) alkali-soluble resin, and (b) the difference in refractive index with resin of the said resin component is 0.03 or more. It consists of a resin additive which consists of resin which has a refractive index. Moreover, in this 1st invention, a novolak resin is preferable as alkali-soluble resin.
[20] In the first aspect of the present invention, as the resin composition used in the photosensitive composition, by using one or more sets of resins having a refractive index difference (Δn) of 0.03 or more, the effect of the photosensitive material is increased, and as a result, the amount of the photosensitive material used is reduced. It becomes possible, and the improvement of throughput is also possible by the high sensitivity of the photosensitive composition.
[21] However, in the above-mentioned photosensitive composition, for example, when an alkali-soluble resin is used as the resin component and a quinone diazide photosensitive agent is used as the photosensitive material, the amount of the photosensitive material added is lower than that of the conventional one, as a resin additive. Depending on resin used, the residual film property of the photosensitive composition may fall. At this time, when the resin additive functions as a dissolution inhibitor with respect to the photosensitive composition, it was recognized that such deterioration of residual film does not occur. In the case of the conventional photosensitive composition in which only novolak resin which is alkali-soluble resin is used as the resin component in the photosensitive composition, the dissolution rate of the photosensitive composition with respect to the alkaline developer is determined by the weight average molecular weight of the novolak resin and the addition of the photosensitive material. It is highly dependent on the quantity, and if the adjustment is made to achieve high sensitivity, it is accompanied with a decrease in developability and residual film property as described above, but when a resin functioning as a dissolution inhibitor is used in combination with a novolak resin as a resin additive, As a result, even if the addition amount of the photosensitive material to the novolak resin decreases, the high residual film property is maintained, and high sensitivity is also expected by the use of a small amount of the photosensitive material, and it is estimated that high sensitivity can be achieved without deterioration of the residual film property.
[22] Thus, in this 2nd invention using the resin additive which functions as a dissolution inhibitor, since the sensitivity can be improved by reducing the addition amount of the photosensitive substance, as the resin of a resin additive, the refractive index of a resin component is used. It is not necessary to necessarily use a resin having a refractive index different from 0.03 or more. However, when the refractive index of the resin of the resin additive differs from the refractive index of the resin of the resin component by 0.03 or more, since the improvement of the sensitivity of the photosensitive composition is expected by this, a more preferable result is obtained from the viewpoint of the reduction of the addition amount of the photosensitive material. . For this reason, also in 2nd invention, it is desired that the refractive index of resin of a resin additive differs from the refractive index of alkali-soluble resin by 0.03 or more.
[23] In addition, in this invention, when "resin which functions as a dissolution inhibitor" is added simultaneously with resin of a resin component in the photosensitive composition, the dissolution rate with respect to the developing solution of the photosensitive composition film | membrane of an unexposed part is suppressed compared with the case of no addition. It says resin that can be done.
[24] As resin which functions as such a dissolution inhibitor, when added to the photosensitive composition, it is preferable that the dissolution rate with respect to the 2.38 weight% tetramethylammonium hydroxide aqueous solution of the photosensitive composition after addition is 5000 kPa / min or less.
[25] And each resin used by the photosensitive composition of this invention needs to be melt | dissolved in the same solvent, even if there is a difference in solubility.
[26] In addition, the reason why the effect of the photosensitive substance in a photosensitive composition can be improved by using resin from which 2 or more types of refractive index differs is considered to be due to the following, although it is not clear enough yet. However, this invention is not limited by this.
[27] That is, in this invention, the photosensitive composition containing resin in which 2 or more types of refractive index differs is apply | coated and a photoresist film is formed. According to the inventors, even when a thin film is prepared from a solution in which two or more kinds of resins having different refractive indices are dissolved in a solvent, the formed thin film becomes a microscopic nonuniform structure, and light scattering occurs due to light irradiation. . This phenomenon can be confirmed by irradiating a laser beam to a resin solution. For example, even when irradiating a laser beam to each single composition solution of novolak resin or polymethyl methacrylate resin, the laser beam proceeds without scattering, but is different from the novolak resin, for example, polymethyl meta When a laser beam is irradiated to the resin solution which melt | dissolved the methacrylate simultaneously with a novolak resin, light-scattering phenomenon can be confirmed in an incident part.
[28] It is considered that two or more kinds of resins having different refractive indices are dissolved in a solvent to form a solution, and a thin film is formed by applying the same, and the micro-uniform structure is attributable to the difference in solubility in solvents of the respective resins. That is, after application of the resin solution, the solvent evaporates from the coating film at the time of baking, but at this time, the resin is precipitated from a resin having a low solubility in the solvent to become a solid, and a resin having a high solubility is then precipitated, resulting in a micro-uniform structure. It is believed that conditions causing light scattering are established.
[29] When light is irradiated on the thin film formed from the photosensitive composition containing two or more kinds of resins having different refractive indices as described above, light scattering occurs in the thin film due to the above factors, and light incident on the thin film repeats scattering and there is no light scattering. Compared with the case where light enters into the thin film produced using the conventional photosensitive composition, its optical path length becomes very long, and it is considered that the utilization efficiency of irradiation light becomes especially high. Thus, the conventional photosensitive composition has a poor utilization efficiency of the irradiation light due to loss to the outside of the photosensitive resin film due to reflection of the irradiation light, and the photosensitive composition of the present invention has a light scattering effect, so that the propagation distance of the incident light is increased. It is considered that the utilization efficiency becomes extremely high, the effect on the photosensitive material is greatly improved, and high sensitivity is expected.
[30] Hereinafter, the resin component, the resin additive, and other components of the photosensitive composition of the present invention will be described in more detail.
[31] Resin component
[32] As resin of the resin component of the resin composition in the photosensitive composition of this invention, any of what is conventionally used as a resin component in the photosensitive composition can be used. Among the resin components used in these conventional photosensitive compositions, alkali-soluble resins are preferable as the resin component of the present invention.
[33] The alkali-soluble resin used in the photosensitive composition of the present invention may be any alkali-soluble resin used in a conventionally known photosensitive composition, and is not particularly limited, but a novolak resin is preferable.
[34] The novolak resin which can be preferably used in the present invention can be obtained by condensation polymerization of various phenols alone or a mixture of plural kinds thereof with one or more aldehydes such as formalin.
[35] Examples of the phenols used to produce the novolak resins include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol and 2,5-dimethylphenol. , 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2 , 4,5-trimethylphenol, methylenebisphenol, methylenebis p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, o-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3- Diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol and the like, and these may be used alone or as a mixture of two or more thereof.
[36] Moreover, as formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. are mentioned besides formalin, These can be used individually or as a mixture of 2 or more types.
[37] And the preferable weight average molecular weight of the novolak resin used by the photosensitive composition of this invention is 2,000-50,000 in conversion of polystyrene, More preferably, it is 3,000-30,000, More preferably, it is 3,000-15,000.
[38] Resin additives
[39] As resin of the resin additive of the resin composition which comprises the photosensitive composition of this invention, any resin may be used as long as it is resin which functions as a resin and / or a dissolution inhibitor whose refractive index difference with resin of resin component is 0.03 or more. As resin which has such a characteristic, polyacrylic acid ester, polymethacrylic acid ester, polystyrene derivative, polyvinyl benzoate, polyvinyl phenyl acetate, polyvinyl acetate, polyvinyl chlor acetate, poly acrylonitrile, poly (alpha) -methylacrylo Nitrile, polyvinylphthalimide and acrylic acid ester, methacrylic acid ester, styrene derivative, vinyl benzoate, vinyl phenyl acetate, vinyl acetate, vinyl chlor acetate, acrylonitrile, α-methyl acrylonitrile, N-vinyl phthalate Copolymers obtained from two or more monomers selected from mead, N-vinylimidazole, N-vinylcarbazole, 2-vinylquinoline, vinylcyclohexane, vinylnaphthalene, vinylpyridine, N-vinylpyrrolidone and the like Can be.
[40] Among these resins, as the resin of the resin additive of the present invention, a copolymer obtained from polyacrylic acid ester, polymethacrylic acid ester, polystyrene derivative and two or more monomers selected from acrylic acid ester, methacrylic acid ester and styrene derivative is preferable. . In addition, when these resins also contain repeating units having a carboxyl group or a carboxylic anhydride group as repeating units, suppressing alkali insoluble addition dissolution of polymers composed of repeating units formed from acrylic esters, methacrylic esters, styrene derivatives, and the like. In addition to improving the solubility of the photosensitive composition in the alkali-soluble addition development consisting of repeating units having a carboxyl group or a carboxylic acid anhydride group, the solubility of the photosensitive composition by the resin additive is improved. We can plan. For this reason, the copolymer formed from the at least 1 sort (s) chosen from said monomer, ie, acrylic ester, methacrylic ester, and styrene derivative, and the organic acid monomer which has a carboxyl group or a carboxylic anhydride group is also preferable as resin of the resin additive of this invention. .
[41] The following are mentioned as an example of the polyacrylic acid ester, polymethacrylic acid ester, and polystyrene derivative which can be used suitably as resin of a resin additive in this invention.
[42] Polyacrylic acid ester:
[43] Polymethyl acrylate, polyethyl acrylate, poly n-propyl acrylate, poly n-butyl acrylate, poly n-hexyl acrylate. Polyisopropyl acrylate, polyisobutyl acrylate, poly t-butyl acrylate, polycyclohexyl acrylate, polybenzyl acrylate, poly-2-chlorethyl acrylate, polymethyl-α-chloracrylate, polyphenyl α-bromoacrylate and the like.
[44] Polymethacrylic acid ester:
[45] Polymethyl methacrylate, polyethyl methacrylate, poly n-propyl methacrylate, poly n-butyl methacrylate, poly n-hexyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, Poly t-butyl methacrylate, polycyclohexyl methacrylate, polybenzyl methacrylate, polyphenyl methacrylate, poly 1-phenylethyl methacrylate, poly 2-phenylethyl methacrylate, polyfurfuryl methacrylate Latex, polydiphenylmethyl methacrylate, polypentachlorphenyl methacrylate, polynaphthyl methacrylate and the like.
[46] Polystyrene Derivatives:
[47] Poly 4-fluorostyrene, poly 2,5-difluorostyrene, poly 2,4-difluorostyrene, poly p-isopropylstyrene, polystyrene, poly o-chlorstyrene, poly 4-acetylstyrene, poly 4 -Benzoylstyrene, poly 4-bromostyrene, poly 4-butoxycarbonylstyrene, poly 4-butoxymethylstyrene, poly 4-butylstyrene, poly 4-ethylstyrene, poly 4-hexyl styrene, poly 4-meth Methoxy styrene, poly 4-methylstyrene, poly 2,4-dimethylstyrene, poly 2,5-dimethylstyrene, poly 2,4,5-trimethylstyrene, poly 4-phenylstyrene, poly 4-propoxystyrene, polyamino Styrene and so on.
[48] It is also preferred to prepare copolymers obtained from two or more monomers selected from acrylic acid esters, methacrylic acid esters and styrene derivatives or copolymers obtained from organic acid monomers having at least one of these monomers and a carboxyl group or carboxylic anhydride group. As a monomer which can be used easily, the monomer used in order to manufacture the polymer illustrated as said polyacrylic acid ester, polymethacrylic acid ester, and polystyrene derivative about an acrylic acid ester, methacrylic acid ester, and a styrene derivative is mentioned. . Moreover, the following are mentioned as a preferable thing as an organic acid monomer which has a carboxyl group or a carboxylic anhydride group.
[49] Organic acid monomers having carboxyl groups or carboxylic anhydride groups:
[50] Acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, 2-acryloylhydrogenphthalate, 2-acryloyloxypropylhydrogenphthalate and the like.
[51] The copolymer having the acid component preferably used in the present invention in the repeating unit usually includes one or more monomers selected from the above acrylic acid esters, methacrylic acid esters or styrene derivatives and one or more monomers selected from the above organic acid monomers. It can manufacture by copolymerizing by the method of. Among these copolymers, acrylic copolymers include copolymers of at least one monomer selected from acrylic acid esters and methacrylic acid esters with at least one organic acid monomer selected from organic acid monomers, and from the acrylic acid esters and methacrylic acid esters. Copolymers of two selected monomers with one or more organic acid monomers selected from the above organic acid monomers are preferred. Furthermore, methyl methacrylate, one or more methacrylic acid esters except methyl methacrylate, acrylic acid and More preferred are copolymers composed of one or more selected from methacrylic acid.
[52] Furthermore, polyacrylic acid ester resin, polymethacrylic acid ester resin, consisting of a copolymer obtained from at least one monomer selected from acrylic acid esters, methacrylic acid esters, styrene derivatives and organic acid monomers having a carboxyl group or a carboxylic anhydride group Or when the acid value of polystyrene resin is 1-80 mgKOH / g, favorable applicability | paintability of a photosensitive composition is obtained and it is preferable. In addition, by using a resin having an acid value of 1 to 80 mg KOH / g as the resin of the resin additive, it was found that the process dependency of the resist pattern was small and excellent line width uniformity was obtained. The acid value of such polyacrylic acid ester resin, polymethacrylic acid ester resin, or polystyrene resin is more preferably 2 to 30 mg KOH / g.
[53] 0.1-10.0 weight part is preferable with respect to 100 weight part of other monomer components, and, as for the usage-amount of the organic acid monomer in the case of using an organic acid monomer as a copolymerization component of a copolymer, 0.5-3.0 weight part is more preferable.
[54] In addition, the copolymer containing the said acid component is not limited to what was obtained by copolymerizing the monomer corresponded to the repeating unit which comprises a copolymer as mentioned above, For example, acrylic acid ester and methacrylic acid ester 1 or more types It is sufficient to manufacture by arbitrary methods, such as the method of introduce | transducing an acid component in a polymer, such as hydrolyzing the polymer superposed | polymerized using this as a polymerization component.
[55] The preferable weight average molecular weight of resin of these resin additives is 2,000-80,000 in polystyrene conversion. And when the said resin contains less than 50 mol% of styrene monomer units, such as a polyacrylic-ester type or polymethacrylic-ester type resin, the polystyrene conversion weight average molecular weight of this resin has more preferable 5,000-40,000, More preferably, it is 7,000-20,000. In addition, when the resin of the resin additive is a styrene resin containing 50 mol% or more of styrene monomer units such as polystyrene derivatives, the weight average molecular weight is more preferably 3,000 to 25,000, and more preferably 5,000 to 20,000.
[56] In addition, resin which consists of these homopolymers or copolymers may be used independently as a resin additive, and may use 2 or more types together.
[57] About a part of thing illustrated as resin of the said resin additive, the outline refractive index is shown below. In this regard, the refractive index of the novolak resin preferably used as the resin component is 1.64. In addition, the refractive index is the refractive index in 436 nm in all.
[58] Having a refractive index of less than 1.50
[59] Polymethyl methacrylate, polyethyl methacrylate, poly n-propyl methacrylate, poly n-butyl methacrylate, poly n-hexyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, Poly t-butyl methacrylate, polymethyl acrylate, polyethyl acrylate, poly n-butyl acrylate, polyvinyl acetate and the like.
[60] Having a refractive index of 1.50 to 1.60
[61] Polycyclohexyl methacrylate, polybenzyl methacrylate, polyphenyl methacrylate, poly 1-phenylethyl methacrylate, poly 2-phenylethyl methacrylate, polyfurfuryl methacrylate, polybenzyl acrylate, poly -2-chloroethyl acrylate, polyvinyl benzoate, polyvinylphenyl acetate, polyvinyl chloracetate, polyacrylonitrile, polyα-methyl acrylonitrile, polymethylα-chloracrylate, poly p-fluorostyrene , Poly o, p-difluorostyrene, poly p-isopropylstyrene, polystyrene, polydiphenylmethyl methacrylate and the like.
[62] Refractive index greater than 1.6
[63] Polyphenyl alpha-bromoacrylate, polynaphthyl methacrylate, polyvinyl phthalimide, poly o-chlorostyrene, polypentachlorphenyl methacrylate, and the like.
[64] As resin used together with novolak resin as these resin additives, polymethyl methacrylate, polyethyl methacrylate, poly n-propyl methacrylate, poly n-butyl methacrylate, poly n-hexyl methacrylate, Styrene, such as polymer of methacrylic acid ester, such as polyisopropyl methacrylate, polyisobutyl methacrylate, poly t-butyl methacrylate, polydiphenylmethyl methacrylate, polypentachlorphenyl methacrylate, polystyrene, etc. Particularly preferred are copolymers obtained by using polymers of derivatives or monomers used to prepare these polymers as at least one of the copolymerization components.
[65] In addition, since the use ratio of the resin additive with respect to a resin component differs according to the kind of resin of the resin component to be used specifically, and the resin of the resin additive, it is difficult to specify a range generally preferable, for example, For example, when the resin is a combination of a novolak resin which is an alkali-soluble resin and a styrene derivative in a resin additive resin such as a homopolymer or copolymer of methacrylic acid ester, that is, a resin having a composition of styrene-based monomer units of less than 50 mol%, It is preferable that it is 1-20 weight part with respect to 100 weight part of novolak resin which is alkali-soluble resin, or, as for content of an additive, it is more preferable that it is 1-15 weight part. In the case where the resin additive is a styrene resin having a styrene monomer unit composition of 50 mol% or more, the use ratio thereof is preferably 0.5 to 5.0 parts by weight based on 100 parts by weight of the novolak resin that is an alkali-soluble resin. Preferably it is 1.0-3.0 weight part.
[66] Resin components other than resin components and resin additives
[67] In the resin composition used for the photosensitive composition of this invention, in order to balance the dissolution inhibiting effect of a photosensitive composition and the improvement of solubility, it has a carboxyl group or a carboxylic anhydride group other than the resin component which consists of said alkali-soluble resin, and the said resin additive. The polymer containing 50 mol% or more of repeating units may also be contained. It is preferable that it is 0.1-10.0 weight part with respect to 100 weight part of resin additives, and, as for the usage ratio with respect to the homopolymer of such an organic acid monomer or the copolymer whose monomer is a main component, it is more preferable that it is 0.5-3.0 weight part. Do. In addition, resin components other than this resin component and a resin additive are 1-20 weight part, More preferably, it is 1-10 weight part, or 2-5 weight amount with respect to 100 weight part of novolak resins with the total amount with a resin additive. It is preferable to use a weight part.
[68] The following are mentioned as a polymer containing 50 mol% or more of repeating units which have a carboxyl group or a carboxylic anhydride group preferably used in this invention.
[69] Polymers containing at least 50 mol% of organic acid monomers:
[70] Polyacrylic acid, polymethacrylic acid, polyitaconic acid, polymaleic anhydride, poly-2-acryloyl hydrogenphthalate, poly-2-acryloyloxypropyl hydrogenphthalate and monomers used to prepare these polymers A copolymer prepared by using 50 mol% or more of the monomer component.
[71] In addition, as a resin composition in the photosensitive composition of this invention, when the peak integral value of 7.2-5.6 ppm of the ¹ H-NMR spectrum of the heavy acetone solution of a resin composition is A, and the peak integral value of 1.3-0.95 ppm is B, B It is preferable that the value X of / A is 0.01 to 0.13.
[72] In the present invention, the peak integration value A in the range of 7.2 to 5.6 ppm and the peak integration value B in the range of 1.3 to 0.95 ppm of the ¹ H-NMR spectrum of the heavy acetone solution of the resin composition are in the method described below. The peak integrals A and B of the respective spectral ranges are obtained from the NMR spectrum of the resin composition measured by the above formula, and X = B / A is calculated using this value.
[73] That is, first, the alkali-soluble resin is dissolved in propylene glycol monomethyl ether acetate, and this solution is applied onto the substrate by rotation coating to form a thin film. The thin film was dissolved in heavy acetone to prepare an NMR spectral measurement sample, and ¹ H-NMR spectral measurement was performed using this sample. From the obtained chart, the peak integral value in the range of 7.2 to 5.6 ppm was calculated and A was obtained. Then, the peak integral value in the range of 1.3 to 0.95 ppm excluding the propylene glycol monomethyl ether acetate solvent peak is calculated to be B, and the value X of B / A is calculated.
[74] Photosensitive material
[75] As the photosensitive material used in the photosensitive composition of the present invention, any one can be used as long as it is conventionally used as a photosensitive material of a photosensitive composition composed of a resin component and a photosensitive material.
[76] In the photosensitive composition of the present invention, when alkali-soluble resin is used as the resin component of the resin composition, a photosensitive material having a quinonediazide group is preferable as the photosensitive material.
[77] In the present invention, as the photosensitive material having a quinonediazide group used as the photosensitive material, any one of conventionally known photosensitive materials having a quinonediazide group can be used, but 1,2-naphthoquinonediazide-4- Quinonediazidesulfonic acid halides such as naphthoquinonediazidesulfonic acid halides or benzoquinonediazidesulfonic acid chlorides such as sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and these acid halides It is preferably obtained by reacting a low molecular compound or a high molecular compound having a functional group capable of condensation reaction with. Although a hydroxyl group, an amino group, etc. are mentioned as a functional group which can be condensed with an acid halide here, especially a hydroxyl group is preferable.
[78] As a low molecular weight compound containing the said hydroxyl group, for example, hydroquinone, resorcin, 2, 4- dihydroxy benzophenone, 2, 3, 4- trihydroxy benzophenone, 2, 4, 6-tri Hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2 And 2 ', 3,4,6'-pentahydroxybenzophenone. On the other hand, examples of the polymer compound containing a hydroxyl group include novolak resins, polyhydroxystyrenes, and the like.
[79] The photosensitive material containing these quinone diazide groups is, in view of using a small amount of the photosensitive material, in the present invention, when the resin of the resin additive consists of a resin having a styrene monomer unit composition of less than 50 mol%, the alkali in the photosensitive composition It is preferable to use 1-20 weight part with respect to 100 weight part of soluble resin. In this case, when resin which functions as a dissolution inhibitor is used as a resin additive, the photosensitive material containing a quinonediazide group is 1 with respect to 100 weight part of alkali-soluble resin in a photosensitive composition from a coating property of a photosensitive composition. It is more preferable that it is 18 weight part. In addition, when a resin with a styrene monomer unit composition of 50 mol% or more is used as the resin additive, that is, when a styrene resin is used, the content of the photosensitive material containing quinonediazide is alkali-soluble resin 100 in the photosensitive resin composition. 10-30 weight part is preferable with respect to a weight part, More preferably, it is 15-25 weight part. If it is less than 10 parts by weight, the residual film ratio tends to be lowered, and if it is more than 30 parts by weight, it ends in a low degree, which is a problem in practical use.
[80] additive
[81] In the present invention, the photosensitive resin composition can contain a low molecular compound having a phenolic hydroxyl group represented by the following general formula (I).
[82]
[83] In the above formula,
[84] R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently H, C ₁ to C ₄ alkyl group, C ₁ to C ₄ alkoxyl group, cyclohexyl group, or a chemical formula Is a group of
[85] R ₈ is H, a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ alkoxyl group or a cyclohexyl group,
[86] m and n are each 0, 1 or 2,
[87] a, b, c, d, e, f, g and h are integers of 0 or 1 to 5 satisfying a + b ≦ 5, c + d ≦ 5, e + f ≦ 5, g + h ≦ 5 ego,
[88] i is 0, 1 or 2.
[89] The low molecular weight compound having a phenolic hydroxyl group represented by the formula (I) is suitably used as the photosensitive composition of the present invention as a dissolution accelerator to adjust the dissolution rate of the photosensitive composition or to improve or adjust the sensitivity of the photosensitive composition. Can be.
[90] As a low molecular weight compound which has a phenolic hydroxyl group represented by the said Formula (I), o-cresol, m-cresol, p-cresol, 2, 4- xylenol, 2, 5- xylenol, 2, 6- xylene Knoll, Bisphenol A, B, C, E, F and G, 4,4 ', 4 "-methylidinetrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methyl Phenol, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4', 4 "-ethylidinetrisphenol, 4 -[Bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4,4 '-[(2-hydroxyphenyl) methylene] bis [2,3-dimethylphenol], 4,4'-[ (3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[ (2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 '-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[ (3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy Ci-6-methylphenyl) methyl] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4, 4 '-[(2-hydroxyphenyl) methylene] bis [3-methylphenol], 4,4', 4 "-(3-methyl-1-propaneyl-3-iridine) trisphenol, 4,4 ', 4', 4 '"-(1,4-phenylenedimethylidine) tetrakisphenol, 2,4,6-tris" (3,5-dimethyl-4-hydroxyphenyl) methyl] -1,3 -Benzenediol, 2,4,6-tris "(3.5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4.4 '-[1- [4- [1- [4-hydroxy -3,5-bis [(hydroxy-3-methylphenyl) methyl] phenyl] -1-methylethyl] phenyl] ethylidene] bis [2,6-bis (hydroxy-3-methylphenyl) methylphenol and the like The low molecular weight compound having these phenolic hydroxyl groups is usually used in an amount of 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the novolak resin.
[91] Moreover, dye, an adhesion | attachment adjuvant, surfactant, etc. can be mix | blended with the photosensitive composition of this invention as needed. Examples of the dye include methyl violet, crystal violet, marachite green, and the like. Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinylmethyl ether, t-butyl novolac, and epoxysilane. , Epoxy polymers, silanes, and the like, and examples of the surfactant include nonionic surfactants such as polyglycols and derivatives thereof such as polypropylene glycol or polyoxyethylene lauryl ether, fluorine-containing surfactants such as Floroid (brand name, product made by Sumitomo 3M), megapek (brand name, product made by Dainippon Ink & Chemicals Co., Ltd.), sulfon (brand name, product made by Asahi Glass Co., Ltd.) or an organic siloxane surfactant, for example, KP341 (brand name, Shin-Etsuga Kaku High School).
[92] solvent
[93] As a solvent which melt | dissolves the resin component of a resin composition contained in the photosensitive composition of this invention, a resin additive, a photosensitive substance, another additive, etc., ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Propylene glycol monoalkyl ethers such as glycol monomethyl ether acetate, ethylene glycol monoalkyl ether acetates of ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Propylene glycol monoalkyl ether acetates of monoethyl ether acetate, methyl lactate, lactic acid esters of ethyl lactate, aromatic hydrocarbons such as toluene, xylene, methyl ethyl ketone, 2-heptanone, cyclohexanone Ketones such as these, amides such as N, N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyl lactone. These solvents can be used individually or in mixture of 2 or more types.
[94] In addition, in this invention, the dissolution rate with respect to the 2.38 weight% aqueous solution of the tetramethylammonium hydroxide of a photosensitive composition is measured and calculated as follows.
[95] (Measurement and calculation method of the dissolution rate of the photosensitive composition)
[96] The photosensitive composition was spun on a silicon wafer and baked on a hot plate at 100 ° C. for 90 seconds to form a photoresist film about 1.5 μm thick. At this time, the film thickness d ₁ (Å) of the photoresist was measured, and a test pattern provided with various line widths in which the line and space widths were 1: 1 by a g-line stepper (FX-604F) manufactured by Nikon Corporation. After exposing, it develops at 23 degreeC and 60 second in 2.38 weight% aqueous solution of tetramethylammonium hydroxide. After the development, the film thickness d ₂ (kV) of the resist is again measured, and the film thickness difference d ₁ -d ₂ before and after the development is taken as the dissolution rate (µs / min) of the photosensitive composition.
[1] INDUSTRIAL APPLICABILITY The present invention is suitably used as a photoresist material or the like in the production of a photosensitive composition comprising a resin composition and a photosensitive material, more specifically a semiconductor device such as LSI, a flat panel display (FPD) such as a liquid crystal display (LCD), and the like. It relates to a photosensitive composition that can be.
[97] 1 is a ¹ H-NMR spectral chart of a resin composition, measured using a mixed resin film of novolak resin: acrylic polymer = 100: 10 as a sample.
[98] FIG. 2 is a ¹ H-NMR spectrum chart of a photosensitive composition measured using a resist film formed from a photosensitive composition prepared using a mixed resin of novolak resin: acrylic polymer = 100: 10 as the resin composition.
[99] Best Mode for Carrying Out the Invention
[100] Although an Example, a comparative example, and a synthesis example demonstrate this invention further more concretely below, the aspect of this invention is not limited by these examples. In addition, in the following examples, description of a "molecular weight" or a "weight average molecular weight" shows the polystyrene conversion weight average molecular weight unless there is particular notice.
[101] Synthesis Example
[102] Synthesis Example 1
[103] In a 2000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introduction tube, 900 g of propylene glycol monomethyl ether acetate, 189 g of methyl methacrylate, 81 g of t-butyl methacrylate, 30 g of acrylic acid, and 6 g of azobisdimethylvaleronitrile And 4.5 g of azobismethylbutyronitrile were added and stirred, and the temperature was raised while blowing in nitrogen, followed by polymerization at 85 ° C. for 8 hours to obtain an acrylic copolymer having a weight average molecular weight of 15,000 and an acid value of 80 mg KOH / g.
[104] Synthesis Example 2
[105] In a 2000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introduction tube, 900 g of propylene glycol monomethyl ether acetate, 207.9 g of methyl methacrylate, 89.1 g of t-butyl methacrylate, 3 g of acrylic acid, and azobisdimethylvalero 6 g of nitriles and 4.5 g of azobismethylbutyronitrile were added and stirred, and the temperature was raised while blowing in nitrogen, followed by polymerization at 85 ° C for 8 hours to obtain an acrylic copolymer having a weight average molecular weight of 13,000 and an acid value of 8 mg KOH / g.
[106] Synthesis Example 3
[107] In a 2000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introduction tube, 900 g of propylene glycol monomethyl ether acetate, 207.9 g of methyl methacrylate, 89.1 g of n-butyl methacrylate, 3 g of acrylic acid, and azobisdimethylvalero 6 g of nitrile and 4.5 g of azobismethylbutyronitrile were added and stirred, and the temperature was raised while blowing in nitrogen, followed by polymerization at 85 ° C. for 8 hours to obtain an acrylic copolymer having a weight average molecular weight of 13,000 and an acid value of 8 mg KOH / g.
[108] Synthesis Example 4
[109] In a 2000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introduction tube, 900 g of propylene glycol monomethyl ether acetate, 207.9 g of methyl methacrylate, 89.1 g of cyclohexyl methacrylate, 3 g of acrylic acid, and azobisdimethylvaleronitrile 6 g and 4.5 g of azobismethylbutyronitrile were added and stirred, and the temperature was raised while blowing in nitrogen, followed by polymerization at 85 ° C. for 8 hours to obtain an acrylic copolymer having a weight average molecular weight of 12,000 and an acid value of 8 mg KOH / g.
[110] Synthesis Example 5
[111] In a 2000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube, 900 g of propylene glycol monomethyl ether acetate, 210 g of methyl methacrylate, 90 g of t-butyl methacrylate, 0.3 g of acrylic acid, azobisdimethylvaleronitrile 6 g and 4.5 g of azobismethylbutyronitrile were added and stirred, and the temperature was raised while blowing in nitrogen, followed by polymerization at 85 ° C. for 8 hours to obtain an acrylic copolymer having a weight average molecular weight of 13,000 and an acid value of 1 mg KOH / g.
[112] Synthesis Example 6
[113] In a 2000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introduction tube, 900 g of propylene glycol monomethyl ether acetate, 210 g of methyl methacrylate, 90 g of t-butyl methacrylate, 6 g of azobisdimethylvaleronitrile, azobis 4.5 g of methyl butyronitrile is added and stirred, the temperature is raised while blowing in nitrogen, polymerization is carried out at 85 ° C. for 8 hours to obtain an acrylic copolymer having a weight average molecular weight of 13,000 and an acid value of 0.3 mg KOH / g.
[114] (Examples and Comparative Examples)
[115] Example 1
[116] Reaction of 2,3,4.4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride as a photosensitive material with respect to 100 parts by weight of a novolak resin (refractive index of 1.64 at 436 nm) 15 parts by weight of esterified material, 5 parts by weight of polymethyl methacrylate (PMMA, refractive index 1.48 at 436 nm), which is a resin different from the novolak resin with a refractive index of 0.03 or more, and also functions as a dissolution inhibitor, is added to the novolak resin. In order to dissolve in propylene glycol monomethyl ether acetate and to prevent radial wrinkles and so-called striations occurring on the resist film during rotation coating, 300 ppm of a fluorine-based surfactant and fluoride-472 (manufactured by Sumitomo 3M) were added. After stirring, the mixture was filtered with a 0.2 μm filter to prepare the photosensitive composition of the present invention. The composition was spun onto a 4 inch silicon wafer and baked on a hot plate at 100 ° C. for 90 seconds to obtain a 1.5 μm thick resist film. The resist film was exposed to a test pattern equipped with various line widths having a line and space width of 1: 1 using a g-line stepper (DSW6400) manufactured by GCA, and then, 23 ° C. and 60 seconds in a 2.20% by weight aqueous solution of tetramethylammonium hydroxide. Develop. After development, the film thickness is measured again, and the residual film ratio is measured from the following equation.
[117] Residual film ratio = [(film thickness before development-film thickness after development) / film thickness before development] × 100
[118] In addition, the amount of exposure energy in which the line-and-space of 5 µm is resolved to 1: 1 is observed as a sensitivity, and the results shown in Table 1 are obtained, respectively.
[119] Example 2, 3
[120] The amount of PMMA was carried out in the same manner as in Example 1 except that the addition amount of PMMA was as described in Table 1 with respect to 100 parts by weight of the novolak resin, and the results in Table 1 were obtained.
[121] Example 4
[122] Except for adding 10 parts by weight of poly n-butyl methacrylate (PnBMA, a refractive index of 1.47 at 436 nm) to 100 parts by weight of the novolak resin instead of PMMA, it was carried out in the same manner as in Example 1 to obtain the results in Table 1. do.
[123] Example 5
[124] The results in Table 1 were obtained in the same manner as in Example 1 except that 5 parts by weight of PMMA and PnBMA were added to 100 parts by weight of the novolak resin instead of PMMA.
[125] Example 6
[126] Except for adding 10 parts by weight of poly (methyl methacrylate-co-n-butyl methacrylate) [P (MMA-nBMA), refractive index of 1.48 at 436 nm] to 100 parts by weight of the novolak resin, The same procedure as in Example 1 was carried out to obtain the results of Table 1.
[127] Example 7
[128] Same as Example 1, except that 10 parts by weight of poly (methyl methacrylate-co-styrene) [P (MMA-St), refractive index of 1.52 at 436 nm] was added to 100 parts by weight of the novolak resin. To give the results in Table 1.
[129] Example 8
[130] The results of Table 1 were obtained in the same manner as in Example 1, except that 10 parts by weight of polydiphenylmethyl methacrylate [PDPMMA, refractive index of 1.36 at 436 nm] was added to 100 parts by weight of the novolak resin instead of PMMA. do.
[131] Example 9
[132] Except for adding 10 parts by weight of polypentachlorphenyl methacrylate [PPCPMA, refractive index of 1.36 at 436 nm] to 100 parts by weight of the novolak resin, instead of PMMA, it was carried out in the same manner as in Example 1 to obtain the results in Table 1. do.
[133] Comparative Example 1
[134] The same procedure as in Example 1 was conducted except that no PMMA was used to obtain the results of Table 1.
[135] Resin Additives Added to Novolak Resins Addition amount of a resin additive with respect to 100 weight part of novolak resins (weight part) Residual Rate (%) Sensitivity (mJ / ㎠) Example 1 PMMA 5 100 30 Example 2 PMMA 10 100 25 Example 3 PMMA 15 100 35 Example 4 PnBMA 10 100 26 Example 5 PMMA / PnBMA 5/5 100 25 Example 6 P (MMA-nBMA) 10 100 25 Example 7 P (MMA-St) 10 100 21 Example 8 PDPMMA 10 100 29 Example 9 PPCPMA 10 100 30 Comparative Example 1 - 0 100 50
[136] In addition, scum is not recognized in any of the resist patterns obtained in Examples 1 to 9, and the pattern shape is also good.
[137] Example 10
[138] The photosensitive composition adjusted in Example 1 was spin-coated on a glass substrate, and baked at 100 degreeC and a hotplate for 90 second, and the resist film of 1.2 micrometers thickness was obtained. The ultraviolet visible absorption spectrum of this resist film was measured by the ultraviolet visible spectrophotometer (Cary4E) from Varian, and after exposure with energy of 80 mJ / cm <2> by g line stepper (DSW6400) by GCA company, the ultraviolet visible absorption spectrum was measured again, From the change of absorbance before and after exposure at 436 nm which is a wavelength of g line | wire, the decomposition rate of the photosensitive substance is calculated | required by following Formula. The obtained results are shown in Table 2.
[139] Resolution = [(absorbance before exposure-absorbance after exposure) / absorbance before exposure] × 100
[140] Examples 11 and 12 and Comparative Example 2
[141] The amount of PMMA was carried out in the same manner as in Example 10 except that the addition amount of PMMA was as described in Table 2, to obtain the results in Table 2.
[142] Addition amount (part by weight) of 100 parts by weight of novolak resin of PMMA Degradation rate of photosensitive material (% @ 436nm) Example 10 5 48 Example 11 10 51 Example 12 15 46 Comparative Example 2 0 39
[143] As a resin of the resin composition used for the photosensitive composition from the results of the above Examples 1 to 12 and Comparative Examples 1 to 2, by using two or more kinds of resins having a refractive index difference of 0.03 or more, high sensitivity, developability, and excellent film resistance It was found that the composition can be obtained. In addition, it was also found that the improvement in sensitivity is attributable to improving the decomposition rate of the photosensitive material, that is, improving the effect of the photosensitive material.
[144] Example 13
[145] 100 parts by weight of a novolak resin having a weight average molecular weight of 15,000, 15 parts by weight of an esterified product of 2.3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride and a weight average In order to dissolve 4.0 parts by weight of poly t-butyl methacrylate having a molecular weight of 18,000 in propylene glycol monomethyl ether acetate and to prevent radiation wrinkles and so-called striations occurring on the resist film during rotation coating, further, a fluorine-based surfactant, 300 ppm of fluoride-472 (manufactured by Sumitomo 3M) is added and stirred, followed by filtration with a 0.2 µm filter to prepare the photosensitive composition of the present invention. The sensitivity and applicability of the composition are measured as follows. The results are shown in Table 3.
[146] (Sensitivity)
[147] The photosensitive composition was spun on a 4 inch silicon wafer and baked on a hot plate at 100 ° C. for 90 seconds to obtain a 1.5 μm thick resist film. Nikon's g-line stepper (FX-604F) was applied to the resist film to test patterns with various line widths of 1: 1 and line widths at various exposure doses, and 23 ° C and 60 ° C in a 2.38% by weight aqueous ammonium hydroxide solution. Develop for seconds. And the amount of exposure energy in which 5 micrometers of line and space are resolved by 1: 1 is observed as a sensitivity.
[148] (Applicability)
[149] The photosensitive composition was spun on a glass substrate (360 mm x 465 mm) with a chromium film, and baked at 100 ° C. for 90 seconds on a hot plate to obtain a 1.5 μm thick resist film. Subsequently, the film thickness measurement of 600 points | pieces in an inside is performed, in-plane maximum film thickness difference r and standard deviation (sigma) are measured, and applicability | paintability (film thickness uniformity) is confirmed.
[150] Example 14
[151] The same procedure as in Example 13 was repeated except that 20 parts by weight of an esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonyl chloride was used. To prepare a photosensitive composition. In the same manner as in Example 13, the sensitivity and the applicability of the photosensitive composition were measured. The results are shown in Table 3.
[152] Comparative Example 3
[153] The addition amount of the esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride is 25 parts by weight, and poly t-butyl methacrylate is added. Except not, it was carried out similarly to Example 13 to prepare a photosensitive composition. In the same manner as in Example 13, the sensitivity and the applicability of the photosensitive composition were measured. The results are shown in Table 3.
[154] Sensitivity (mJ / ㎠) Applicability γ (Å) δ (Å) Example 13 40 355 50 Example 14 80 490 80 Comparative Example 3 80 620 100
[155] Residual film rates of the photosensitive compositions of Examples 13 and 14 and Comparative Example 3 were 94.0, 99.0, and 93.5%. From the results of these Examples 13, 14 and Comparative Example 3, in the photosensitive composition of the present invention, not only can a high sensitivity and a high residual film ratio be achieved by reducing the amount of the photosensitive substance, but also excellent in the coating property of the photosensitive composition. It was found that
[156] Example 15
[157] 100 parts by weight of a mixture consisting of 100: 3 of a novolak resin having a weight average molecular weight of 6,000 and poly t-butyl methacrylate (PtBMA) having a weight average molecular weight of 10,000, and 2,3,4,4'-tetra 19 parts by weight of an esterified product of hydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride was dissolved in propylene glycol monomethyl ether acetate and radially generated on the resist film at the time of rotation coating. In order to prevent wrinkles and so-called striations, 300 ppm of a fluorine-based surfactant and fluoride-472 (manufactured by Sumitomo 3M) are added and stirred, followed by filtration with a 0.2 µm filter to adjust the photosensitive composition of the present invention.
[158] The sensitivity and the applicability of the photosensitive composition were measured in the same manner as in Example 13. In addition, in this embodiment, when forming a resist film for sensitivity measurement, baking temperature is set to 95 degreeC, 100 degreeC, and 105 degreeC, and the sensitivity with respect to the resist film baked at each baking temperature is calculated | required. The results are shown in Tables 4 and 5.
[159] Example 16
[160] The same procedure as in Example 15 was conducted except that a novolak resin having a weight average molecular weight of 15,000 was used, and the results of Table 4 and Table 5 were obtained.
[161] Novolak resin: PtBMA (weight ratio) Molecular Weight of Novolak Resin Amount of photosensitive material Sensitivity S (mJ / ㎠) 95 ℃ 100 ℃ 105 ℃ ΔS (105-95) Example 15 100: 3 6,000 19 18.5 21.2 23.4 4.9 Example 16 100: 3 15,000 19 26.3 30.3 34.0 7.7
[162] Applicability γ (Å) δ (Å) Example 15 350 60.0 Example 16 570 111.0
[163] In addition, neither the scum was confirmed in the resist patterns obtained in Examples 15 and 16, and the shape of the resist pattern was also good.
[164] From Tables 4 and 5, sensitivity difference ΔS (difference in sensitivity when baking temperature is 105 ° C and sensitivity when baking temperature is 95 ° C) due to the difference in coating properties and baking conditions, that is, process condition It was found that the uniformity of the line width uniformity of the resist pattern by the smaller the molecular weight of the novolak resin. In addition, if DELTA S is small, even if a temperature difference occurs due to a temperature distribution or the like within a certain exposure amount, the variation in the dimensions of the target resist pattern is small, that is, the line width uniformity is excellent.
[165] Example 17
[166] 100 parts by weight of a mixture consisting of a novolak resin having a weight average molecular weight of 15,000 and 100: 3 of a polymethyl methacrylate (PMMA) having a weight average molecular weight of 10,000, and 2,3,4,4'-tetrahydroxy 20 parts by weight of an esterified product of benzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride is dissolved in propylene glycol monomethylethyl acetate, and radial wrinkles are formed on the resist film during rotational application. In order to prevent so-called striation, 300 ppm of a fluorine-based surfactant and fluoride-472 (manufactured by Sumitomo 3M) were added and stirred, followed by filtration with a 0.2 µm filter to adjust the photosensitive composition of the present invention. The dissolution rate of this composition is computed based on the above-mentioned "dissolution rate measurement method of the photosensitive composition." Moreover, based on the sensitivity measurement method described in Example 13, sensitivity observation of the photosensitive composition is performed and the result of Table 6 is obtained.
[167] Examples 18-21, Comparative Examples 4-6
[168] The results of Table 6 were obtained in the same manner as in Example 17, except that the mixing ratio of the novolak resin and PMMA and the addition amount of the photosensitive material were as described in Table 6.
[169] Novolak resin: PMMA (weight ratio) Addition amount of the photosensitive substance with respect to 100 weight part of alkali-soluble resins (weight part) Dissolution Rate (Å / min) Sensitivity (mJ / ㎠) Example 17 100: 3 20 120 35 Example 18 100: 3 15 2100 25 Example 19 100: 3 10 3710 24 Example 20 100: 5 5 120 50 Example 21 100: 5 One 1500 60 Comparative Example 4 100: 5 0.5 2400 180 Comparative Example 5 100: 0 One 33000 No pattern formation Comparative Example 6 100: 0 15 22800 No pattern formation
[170] Examples 22-26, Comparative Example 7
[171] Instead of PMMA, poly (methyl methacrylate-co-styrene) [P (MMA-St)] having a weight average molecular weight of about 10,000 was used, and the mixing ratio and photosensitive material of P (MMA-St) with a novolak resin The addition amount of was carried out in the same manner as in Example 17 except that the addition amount was as described in Table 7, to obtain the result of Table 7.
[172] Novolak resin: P (MMA-St) (weight ratio) Addition amount of the photosensitive substance with respect to 100 weight part of alkali-soluble resins (weight part) Dissolution Rate (Å / min) Sensitivity (mJ / ㎠) Example 22 100: 3 20 110 32 Example 23 100: 3 15 1900 23 Example 24 100: 3 10 3350 22 Example 25 100: 5 5 110 45 Example 26 100: 5 One 1350 53 Comparative Example 7 100: 5 0.5 2100 90
[173] From the said Table 6 and Table 7, the dissolution rate with respect to 2.38 weight% of tetramethylammonium hydroxide of a photosensitive composition is 5000 Pa / min or less, and the usage-amount of the photosensitive material becomes 1 weight part or more with respect to 100 weight part of resin compositions, In addition to maintaining high residual film, it has been found that practical sensitivity can be obtained. In addition, scum is not confirmed in any of the resist patterns obtained in Examples 17 to 26, and the shape of the resist pattern is also good.
[174] Example 27
[175] An acrylic copolymer having a novolak resin having a weight average molecular weight of 6,000 and a monomer ratio (weight fraction) of methyl methacrylate: n-butyl methacrylate: acrylic acid = 50: 50: 1 and having a weight average molecular weight of 13,000. 100 parts by weight of a mixture consisting of a mixture ratio of 100: 3 with 19 parts by weight of an esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride Except for using, the same operation as in Example 17 was carried out. The alkali dissolution rate of the photosensitive composition is 570 dl / min, and the sensitivity is 25 mJ / cm 2. In addition, scum is not confirmed in the obtained resist pattern, and the shape of a resist pattern is also favorable.
[176] Example 28
[177] As an acryl-type copolymer, except the copolymer which consists of a monomer ratio (weight fraction) of methyl methacrylate: n-butyl methacrylate: acrylic acid = 70: 30: 1, and uses a weight average molecular weight of 13,000, It carried out similarly to Example 27. The alkali dissolution rate of the photosensitive composition is 590 Pa / min, and the sensitivity is 20 mJ / cm 2. Scum is not confirmed in the obtained resist pattern, and the shape of a resist pattern is also favorable.
[178] Example 29
[179] As the acryl-based copolymer, except that a copolymer having a monomer ratio (weight fraction) having methyl methacrylate: n-butyl methacrylate = 70: 30 and having a weight average molecular weight of 13,000 was used. Do the same. The alkali dissolution rate of the photosensitive composition is 550 Pa / min, and the sensitivity is 22 mJ / cm 2. Scum is not confirmed in the obtained resist pattern, and the shape of a resist pattern is also favorable.
[180] The results of Examples 27 to 29 are summarized in Table 8 below.
[181] Novolak resin: Acrylic copolymer (weight ratio) Addition amount of photosensitive material with respect to 100 weight part of acrylic soluble resins (weight part) Dissolution Rate (Å / min) Sensitivity (mJ / ㎠) Example 27 100: 3 19 570 25 Example 28 100: 3 19 590 20 Example 29 100: 3 19 550 22
[182] Example 30
[183] 100 parts by weight of a mixture consisting of a novolak resin having a weight average molecular weight of 6,000 and a polymer ratio of 100: 3 (weight ratio) of the polymer described in Synthesis Example 1, 2,3,4,4'-tetrahydroxybenzophenone and 1 19 parts by weight of an esterified product of 2-naphthoquinone diazide-5-sulfonyl chloride is dissolved in propylene glycol monomethyl ether acetate to prevent radiation wrinkles and so-called striations occurring on the resist film at the time of rotation coating. To this end, further, 300 ppm of a fluorine-based surfactant and fluoride-472 (manufactured by Sumitomo 3M) were added and stirred, followed by filtration with a 0.2 µm filter to prepare the photosensitive composition of the present invention. The sensitivity and residual film rate of this composition are measured. In addition, a sensitivity is measured by the method similar to Example 13. The results are shown in Table 9.
[184] Example 31
[185] The same procedure as in Example 30 was carried out except that the polymer described in Synthesis Example 2 was used instead of the polymer described in Synthesis Example 1 to obtain the results of Table 9.
[186] Example 32
[187] The same procedure as in Example 30 was carried out except that the polymer described in Synthesis Example 5 was used instead of the polymer described in Synthesis Example 1 to obtain the results of Table 9.
[188] Example 33
[189] 100 parts by weight, 2,3,4,4'-tetrahydroxybenzophenone and a mixture consisting of a mixture ratio (weight ratio) of 100: 3 between a novolak resin having a weight average molecular weight of 6,000 and the polymer described in Synthesis Example 2 Except for using 4 parts by weight of an ester of 2, naphthoquinonediazide-5-sulfonylchloride, it was carried out in the same manner as in Example 30 to obtain the results of Table 9.
[190] Example 34
[191] The same procedure as in Example 30 was carried out except that the polymer described in Synthesis Example 3 was used instead of the polymer described in Synthesis Example 1 to obtain the results of Table 9.
[192] Example 35
[193] The same procedure as in Example 30 was carried out except that the polymer described in Synthesis Example 4 was used instead of the polymer described in Synthesis Example 1 to obtain the results of Table 9.
[194] Example 36
[195] Instead of the polymer described in Synthesis Example 1, the same procedure as in Example 30 was carried out except that the polymer described in Synthesis Example 6 was used to obtain the results of Table 9.
[196] Comparative Example 8
[197] Except that the polymer described in Synthesis Example 1 was not used, it was carried out in the same manner as in Example 30 to obtain the results of Table 9.
[198] Comparative Example 9
[199] Addition amount of esterified products of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride with respect to 100 parts by weight of novolac resin having a weight average molecular weight of 6,000 Is 4 parts by weight, and the result of Table 9 is obtained in the same manner as in Example 33 except that the polymer described in Synthesis Example 2 is not used.
[200] Comparative Example 10
[201] Addition amount of esterified products of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride with respect to 100 parts by weight of a novolak resin having a weight average molecular weight of 10,000 Is 25 parts by weight, and the result of Table 9 is obtained in the same manner as in Example 30, except that the polymer described in Synthesis Example 1 is not used.
[202] Acrylic resin Photosensitizer addition amount (phr ^** ) Sensitivity (mJ / ㎠) Residual Rate (%) Copolymerization Component ^* Mw Acid value (mg KOH / g) Amount (phr ^** ) Example 30 MMA, tBuMA, AA 15,000 80 300/103 19 16.8 96.0 Example 31 MMA, tBuMA, AA 13,000 8 Same as above 19 17.6 97.0 Example 32 MMA, tBuMA, AA 13,000 One Same as above 19 18.4 98.2 Example 33 MMA, tBuMA, AA 13,000 8 Same as above 4 25.3 97.0 Example 34 MMA, nBuMA, AA 13,000 8 Same as above 19 16.4 97.5 Example 35 MMA, cHMA, AA 12,000 8 Same as above 19 17.8 97.3 Example 36 MMA, tBuMA 13,000 0.3 Same as above 19 22.0 98.8 Comparative Example 8 - - - 0 19 No pattern formation No pattern formation Comparative Example 9 - - - 0 4 No pattern formation No pattern formation Comparative Example 10 - - - 0 25 35.0 97.0^* MMA: methyl methacrylate, tBuMA: t-butyl methacrylate, AA: acrylic acid, cHMA: cyclohexyl methacrylate, nBuMA: n-butyl methacrylate ^** amount per 100 parts by weight of resin in photosensitive composition (parts by weight) )
[203] In addition, neither scum is confirmed in the resist patterns obtained in Examples 30 to 36, and the line width uniformity of the resist pattern and the shape of the resist pattern are also good.
[204] However, from the above Table 9, when the acid value of the acrylic copolymer exceeds the range of 1 to 80 mg KOH / g, for example, when the amount of the photosensitive substance added is 19 parts by weight, the sensitivity is somewhat lower, and the acid value of the acrylic copolymer is 1 In the range of from 80 mg KOH / g, even when the amount of the photosensitive substance is decreased, since a photosensitive composition having both good sensitivity and a residual film ratio is obtained, the acid value of the acrylic copolymer is preferably 1 to 80 mg KOH / g. I knew that. In addition, when an acryl-type copolymer is not used, since a residual film rate is too bad, a pattern is not formed.
[205] Example 37
[206] (NMR Measurement of Resin Composition)
[207] The ¹ H-NMR spectrum measurement of the heavy acetone solution of the resin composition which mixed the novolak resin with a weight average molecular weight of 10,000, and the poly n-butyl methacrylate with a weight average molecular weight of 13,000 in the mixing ratio (weight) of 100: 3 is performed. do. From the obtained chart, the peak integrated value A in the range of 7.2 to 5.6 ppm and the peak integrated value B in the range of 1.3 to 0.95 ppm excluding the propylene glycol monomethyl ether acetate solvent peak were calculated, and the value X of B / A. X is 0.042.
[208] In addition, instead of the said resin thin film, in the measurement, the measurement sample was created from the resist film obtained using the photosensitive composition manufactured below, and the NMR spectrum measurement was performed, and it is the same as the measurement result of X value by a resin composition. Obtain the results.
[209] (Adjustment of the photosensitive composition)
[210] 100 parts by weight of the above resin composition and 18 parts by weight of an esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride are propylene glycol monomethyl ether Dissolved in acetate and added with 300 ppm of fluorine-based surfactant and fluoride-472 (manufactured by Sumitomo 3M) to prevent radiation wrinkles and so-called striations occurring on the resist film during rotation coating, followed by stirring at 0.2 µm. It filters by the filter of and prepares the photosensitive composition of this invention.
[211] The sensitivity, residual film ratio and applicability of the obtained photosensitive composition were measured. In addition, measurement of a sensitivity and applicability is performed by the method similar to Example 13. The results are shown in Table 10.
[212] Example 38
[213] In the same manner as in Example 37, except that poly (methyl methacrylate-co-n-butyl methacrylate) [70:30] having a weight average molecular weight of 13,000 was used instead of poly n-butyl methacrylate. The results are obtained in Table 10.
[214] Example 39
[215] Instead of poly n-butyl methacrylate, except using poly (methyl methacrylate-co-n-butylmethacrylate-co-acrylic acid) [70: 29: 1] having a weight average molecular weight of 13,000, The same procedure as in Example 37 was carried out to obtain the results of Table 10.
[216] Example 40
[217] In the same manner as in Example 37, except that instead of poly n-butyl methacrylate, a mixture (70:30) of polymethyl methacrylate and poly n-butyl methacrylate having a weight average molecular weight of 13,000 is used. The results in Table 10 are obtained.
[218] Comparative Example 11
[219] A ¹ H-NMR spectrum measurement of a heavy acetone solution of a novolak resin having a weight average molecular weight of 10,000 was carried out, and the ratio B between the peak integration value A in the range of 7.2 to 5.6 ppm and the peak integration value B in the range 1.3 to 0.95 ppm was determined. The value X of / A is zero.
[220] 23 parts by weight of an esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride using 100 parts by weight of the above resin is propylene glycol monomethyl ether After dissolving in acetate, it carried out similarly to Example 37, and evaluates a sensitivity, a residual film ratio, and applicability | paintability. The results are shown in Table 10.
[221] Comparative Example 12
[222] As in Comparative Example 11, except that the esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride was 18 parts by weight. Conduct. The results are shown in Table 10.
[223] X = B / A Sensitivity (mJ / ㎠) Residual Rate (%) Applicability γ (Å) δ (Å) Example 37 0.042 27 96 360 50 Example 38 0.042 25 96 350 47 Example 39 0.042 23 96 350 47 Example 40 0.042 25 96 350 52 Comparative Example 11 0 40 85 620 100 Comparative Example 12 0 No pattern formation 0 - -
[224] Example 41
[225] The mixing ratio of the novolak resin and poly n-butyl methacrylate used in Example 37 was 100: 10 by weight, and 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonedia were used. The sensitivity and the residual film ratio were evaluated in the same manner as in Example 37, except that the amount of the esterified product of the zide-5-sulfonyl chloride was 12 parts by weight. The results are shown in Table 11.
[226] Example 42
[227] In the same manner as in Example 41, except that poly (methyl methacrylate-co-n-butyl methacrylate) [70:30] having a weight average molecular weight of 13,000 was used instead of poly n-butyl methacrylate. To obtain the results in Table 11.
[228] Example 43
[229] Instead of poly n-butyl methacrylate, except using poly (methyl methacrylate-co-n-butyl methacrylate-co-acrylic acid) [70: 29: 1] having a weight average molecular weight of 13,000, The results of Table 11 were obtained in the same manner as in Example 41.
[230] Example 44
[231] In the same manner as in Example 41, except that instead of poly n-butyl methacrylate, a mixture (70:30) of polymethyl methacrylate and poly n-butyl methacrylate having a weight average molecular weight of 13,000 is used. The results in Table 11 are obtained.
[232] Comparative Example 13
[233] The same procedure as in Example 41 was conducted except that no poly n-butyl methacrylate was used to obtain the results of Table 11.
[234] X = B / A Sensitivity (mJ / ㎠) Residual Rate (%) Example 41 0.12 80 100 Example 42 0.12 70 100 Example 43 0.12 60 100 Example 44 0.12 70 100 Comparative Example 13 0 No pattern formation 0
[235] Example 45
[236] The mixing ratio of the novolak resin and poly n-butyl methacrylate used in Example 37 was 100: 0.25 by weight, and 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonedia were used. Except for using 23 parts by weight of an esterified product of the zide-5-sulfonyl chloride, it was carried out in the same manner as in Example 37 to obtain the results of Table 12.
[237] Example 46
[238] In the same manner as in Example 45, except that poly (methyl methacrylate-co-n-butyl methacrylate) [70:30] having a weight average molecular weight of 13,000 was used instead of poly n-butyl methacrylate. To obtain the results in Table 12.
[239] Example 47
[240] Instead of poly n-butyl methacrylate, except using poly (methyl methacrylate-co-n-butyl methacrylate-co-acrylic acid) [70: 29: 1] having a weight average molecular weight of 13,000, The same procedure as in Example 45 was carried out to obtain the results of Table 12.
[241] X = B / A Sensitivity (mJ / ㎠) Residual Rate (%) Example 45 0.012 40 92 Example 46 0.012 40 92 Example 47 0.012 40 92
[242] From Table 12, it was found that even with the addition of a small amount of the mixed resin, the sensitivity and the residual film ratio can be improved, and there is also a possibility of improving the sensitivity.
[243] In addition, the chart obtained by the ¹ H-NMR spectrum measurement of the mixed resin film sample whose novolak resin: acryl polymer = 100: 10 is shown in FIG.1 and FIG.2, and the resist film sample created using this mixed resin as a resin composition. The chart obtained from the ¹ H-NMR spectral measurement is shown. As shown in these charts, in the chart obtained from the mixed resin film sample and the chart obtained from the resist film sample, slight spectral differences based on the difference in the components contained in the sample are observed, but in the range of 7.2 to 5.6 ppm. There is almost no difference in the value X of B / A, which is the ratio between the peak integral value A and the peak integral value B in the range of 1.3 to 0.95 ppm except for the propylene glycol monomethyl ether acetate solvent peak. This is not limited to the resin composition used to obtain the chart shown, but the same applies to the resin composition of each of the above-described examples. Although Example 37 described this in detail, also about the resin composition of an Example other than this, the value of X obtained by the resin film sample and the resist film sample of each Example shows substantially the same value.
[244] Example 48
[245] Esterate of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride with respect to 100 weight part of novolak resins with a weight average molecular weight of 7,000 20 In order to dissolve 3.0 parts by weight of polystyrene (PSt) having a weight part and a weight average molecular weight of 14,000 in propylene glycol monomethyl ether acetate, and to prevent radiation wrinkles and so-called striations occurring on the resist film during rotation coating, the fluorine-based 300 ppm of surfactant and Floride-472 (manufactured by Sumitomo 3M) are added and stirred, followed by filtration with a 0.2 µm filter to prepare the photosensitive resin composition of the present invention. The composition was spun onto a 4 inch silicon wafer and baked on a hot plate at 100 ° C. for 90 seconds to obtain a 1.5 μm thick resist film. Nikon's g-line stepper (FX-604F) was used to expose a test pattern with various line widths having 1: 1 line and space widths at various exposure doses, followed by a 2.38 wt% tetramethylammonium hydroxide aqueous solution. It develops at 23 degreeC and 60 second. The residual film ratio was calculated from the measurement of the film thickness before and after the development, and the observation was performed using the exposure energy amount of 5 µm line and space resolved at 1: 1 as sensitivity to obtain the results shown in Table 13.
[246] Example 49
[247] Instead of polystyrene (PSt) having a weight average molecular weight of 14,000, the same procedure as in Example 48 was carried out except that polystyrene (PSt) having a weight average molecular weight of 7,000 was used to obtain the results in Table 13.
[248] Example 50
[249] Instead of polystyrene (PSt) having a weight average molecular weight of 14,000, the same as in Example 48 except that a copolymer of styrene and methyl methacrylate having a weight average molecular weight of 7,000 (PSt / MMA, monomer ratio 90/10) was used. To the results of Table 13.
[250] Example 51
[251] A low molecular weight compound having a phenolic hydroxyl group, based on 100 parts by weight of the novolak resin having a weight average molecular weight of 7,000, and 5 parts by weight of o-cresol, 2,3,4,4'-tetrahydroxybenzophenone and 1 The procedure was carried out in the same manner as in Example 48, except that 21.5 parts by weight of an esterified product of 2-, naphthoquinonediazide-5-sulfonyl chloride and 3.2 parts by weight of polystyrene (PSt) having a weight average molecular weight of 14,000 were used. 13 results are obtained.
[252] Comparative Example 14
[253] The same procedure as in Example 48 was carried out except that polystyrene (PSt) having a weight average molecular weight of 14,000 was used to obtain the results in Table 13.
[254] Example 52
[255] Instead of polystyrene (PSt) having a weight average molecular weight of 14,000, it carried out in the same manner as in Example 48 except that the polymethyl methacrylate having a weight average molecular weight of 10,000 was obtained to obtain the results in Table 13.
[256] Resin blended with novolac resin Residual Rate (%) Sensitivity (mJ / ㎠) Example 48 PSt 98.5 23.9 Example 49 PSt 99.0 28.9 Example 50 PAt / MMA 99.3 32.0 Example 51 PSt (addition of low molecular weight compound having phenolic resin group) 98.2 21.0 Comparative Example 14 - 52.0 (pattern cannot be formed) - Example 52 PMMA 98.0 35.0
[257] Example 53
[258] The procedure was carried out in the same manner as in Example 48 except that the esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonyl chloride was 25 parts by weight. 14 results are obtained.
[259] Comparative Example 15
[260] The same procedure as in Example 53 was carried out except that polystyrene (PSt) having a weight average molecular weight of 14,000 was used to obtain the results in Table 14.
[261] Resin blended with novolac resin Residual Rate (%) Sensitivity (mJ / ㎠) Example 53 PSt 100.0 32.0 Comparative Example 15 - 92.0 32.0
[262] Example 54
[263] To 100 parts by weight of a novolak resin having a weight average molecular weight of 5,000, an esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride was obtained. Except for using the weight part, it carried out similarly to Example 48 and obtained the result of Table 15.
[264] Comparative Example 16
[265] The same procedure as in Example 54 was carried out except that polystyrene (PSt) having a weight average molecular weight of 14,000 was used to obtain the results in Table 15.
[266] Resin blended with novolac resin Residual Rate (%) Sensitivity (mJ / ㎠) Example 54 PSt 100.0 26.0 Comparative Example 16 - 92.0 25.0
[267] Example 55
[268] An esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride was used with respect to 100 parts by weight of the novolak resin having a weight average molecular weight of 10,000. The result of Table 16 was obtained like Example 48 except having set it as weight part and 4.0 weight part of polystyrene (PSt) whose weight average molecular weight is 14,000.
[269] Comparative Example 17
[270] Except not using polystyrene (PSt) having a weight average molecular weight of 14,000, it was carried out in the same manner as in Example 55 to obtain the results of Table 16.
[271] Resin blended with novolac resin Residual Rate (%) Sensitivity (mJ / ㎠) Example 55 PSt 98.5 27.0 Comparative Example 17 - No pattern formation -
[272] In the resist patterns obtained in Examples 48 to 55, neither scum was confirmed, the line width of the resist pattern was uniform, and the shape of the resist pattern was good. And from Tables 13 to 16, it was found that when a styrene resin was used as the resin additive, a photosensitive composition having excellent residual film ratio and sensitivity was obtained. In addition, even when PMMA was selected as the resin used in combination with the novolak resin, the residual film ratio and the sensitivity were improved. However, when PSt was used, a more sensitive photosensitive resin composition was obtained than when PMMA was used. I found it from 13. It is thought that the difference in refractive index between the PMMA and the PSt used in the present invention can be seen between the novolak resin and the improvement of the sensitivity of the photosensitive resin composition is expected by this, but the difference in the refractive index between the novolak resin and the PSt is The refractive index difference of PSt is small compared with the refractive index difference of novolak resin and PMMA, and the refractive index difference of PSt becomes a suitable refractive index difference from the viewpoint of the sensitivity improvement of the photosensitive resin composition, and thereby the utilization efficiency of a photosensitive material It is considered that this improved. In addition, from Table 15, when using a styrene resin as a resin additive, even when adding a large amount of photosensitive substance, it turned out that the photosensitive resin composition of this invention can maintain a high sensitivity and a high residual film, ie, process dependency is low.
[273] Effects of the Invention
[274] According to the first invention of the present invention, the effect of the photosensitive substance is enhanced by using one or more sets of resins having a refractive index difference (Δn) of 0.03 or more as the resin of the resin composition used in the photosensitive composition. Thereby, the usage-amount of the photosensitive substance in a photosensitive composition can be reduced, and throughput can be improved by high sensitivity of a photosensitive composition. In addition, according to the second invention of the present invention, the photosensitive composition composed of an alkali-soluble resin and a quinonediazide group contains a resin that functions as a dissolution inhibitor as a resin additive, thereby reducing the amount of the photosensitive substance used. Even when the sensitivity of the photosensitive material is increased, a photosensitive composition excellent in residual film property can be obtained. Furthermore, according to the present invention, a photosensitive composition having high resolution, good developability and excellent pattern formation property can be produced, and furthermore, a photosensitive composition having excellent processability and excellent line width uniformity of the photosensitive composition and low process dependency Can be obtained.
[275] As described above, according to the present invention, it is possible to obtain a photosensitive composition having high sensitivity and excellent properties such as developability, residual film property, coating property, and line width uniformity of resist pattern, and at the same time, the amount of the photosensitive material used can be reduced. have. Therefore, in the present invention, significant cost reduction is possible in the manufacture of semiconductor integrated circuits, FPDs, and circuit boards such as thermal heads by improving throughput and reducing the amount of photosensitive materials used. Done.
[276] As mentioned above in detail, the photosensitive composition of this invention is used suitably as a photoresist material in the case of manufacture of semiconductor integrated circuits, such as LSI, FPD manufacture, and circuit boards, such as a thermal head.

权利要求:
Claims (15)
[1" claim-type="Currently amended] A photosensitive composition comprising a resin composition and a photosensitive material, wherein the resin composition is composed of two or more resins having different refractive indices, and the difference in refractive index of these resins is 0.03 or more.
[2" claim-type="Currently amended] The photosensitive composition as claimed in claim 1, wherein the resin composition comprises (a) a resin component composed of an alkali-soluble resin and (b) a resin additive composed of a resin having a refractive index difference of at least 0.03 with the resin of the resin component. .
[3" claim-type="Currently amended] A photosensitive composition containing a resin composition and a photosensitive material, wherein the resin composition is composed of a resin additive composed of at least (a) a resin component consisting of an alkali-soluble resin and (b) a resin functioning as a dissolution inhibitor, and the photosensitive material is ( c) a photosensitive material having a quinonediazide group.
[4" claim-type="Currently amended] The copolymer according to claim 2 or 3, wherein the resin additive is a copolymer obtained from at least two monomers selected from polyacrylic acid ester, polymethacrylic acid ester, polystyrene derivative or acrylic ester, methacrylic acid ester, styrene derivative or At least one resin selected from copolymers obtained from organic acid monomers having at least one monomer and a carboxyl group or carboxylic anhydride group.
[5" claim-type="Currently amended] The copolymer according to claim 4, wherein the acid value of the copolymer obtained from at least one monomer selected from acrylic acid esters, methacrylic acid esters and styrene derivatives and organic acid monomers having a carboxyl group or a carboxylic anhydride group is 1 to 80 mg KOH / g. Photosensitive composition.
[6" claim-type="Currently amended] The photosensitive composition according to claim 4, further comprising a polymer comprising at least 50 mol% of repeating units having a carboxyl group or a carboxylic anhydride group.
[7" claim-type="Currently amended] The photosensitive composition according to claim 2 or 3, wherein the dissolution rate of the photosensitive composition in an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide is 5000 m 3 / min or less.
[8" claim-type="Currently amended] The polystyrene reduced weight average molecular weight of this component resin is 7,000-20,000, and the said composition is 50 mol% or more, when the resin of the composition of a styrene-type monomer unit is used less than 50 mol% as a resin additive. When resin is used, the polystyrene reduced weight average molecular weight of the component resin is 3,000 to 25,000.
[9" claim-type="Currently amended] The B / A ratio according to claim 4, wherein when the peak integral value of 7.2 to 5.6 ppm of the ¹ H-NMR spectrum of the heavy acetone solution of the resin composition in the photosensitive composition is set to A, the peak integral value of 1.3 to 0.95 ppm is set to B. Photosensitive composition, characterized in that the value X is 0.01 to 0.13.
[10" claim-type="Currently amended] The photosensitive composition according to claim 2 or 3, wherein the resin component is a novolak resin.
[11" claim-type="Currently amended] The photosensitive composition according to claim 10, wherein the polystyrene reduced weight average molecular weight of the novolak resin is 3,000 to 15,000.
[12" claim-type="Currently amended] A resin according to claim 1 or 3, wherein when a resin having a styrene monomer unit composition of less than 50 mol% is used as the resin additive, the amount of the photosensitive material is 1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin in the photosensitive composition. When the resin having a composition of 50 mol% or more is used, the photosensitive composition, characterized in that 10 to 30 parts by weight.
[13" claim-type="Currently amended] The amount of the photosensitive material when the resin having a styrene monomer unit composition of less than 50 mol% is used as the resin additive is 1 to 18 parts by weight based on 100 parts by weight of the alkali-soluble resin in the photosensitive composition. Photosensitive composition.
[14" claim-type="Currently amended] The resin additive has a content of 1 to 20 parts by weight based on 100 parts by weight of a novolak resin, which is an alkali-soluble resin, when a resin having a styrene monomer unit composition of less than 50 mol% is used as the resin additive. And wherein the resin having a composition of 50 mol% or more is used, the content of the resin additive is 0.5 to 5 parts by weight.
[15" claim-type="Currently amended] The photosensitive composition of Claim 1 or 3 containing the low molecular compound which has a phenolic hydroxyl group represented by following formula (I).
Formula I

In the above formula,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently H, C ₁ to C ₄ alkyl group, C ₁ to C ₄ alkoxyl group, cyclohexyl group, or a chemical formula Is a group of
R ₈ is H, a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ alkoxyl group or a cyclohexyl group,
m and n are each 0, 1 or 2,
a, b, c, d, e, f, g and h are 0 or an integer from 1 to 5 satisfying a + b ≦ 5, c + d ≦ 5, e + f ≦ 5, g + h ≦ 5 ,
i is 0, 1 or 2.

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同族专利:

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公开号 | 公开日

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EP1143298A1|2001-10-10|

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CN1208686C|2005-06-29|

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WO2001025853A1|2001-04-12|

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CN1327547A|2001-12-19|

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US6737212B1|2004-05-18|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1999-10-07|Priority to JP99-286418

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1999-10-07|Priority to JP28641899A

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1999-11-24|Priority to JP99-333048

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1999-11-24|Priority to JP33304899

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1999-12-21|Priority to JP36299499A

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1999-12-21|Priority to JP99-362994

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1999-12-24|Priority to JP99-367237

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1999-12-24|Priority to JP36723799A

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2000-02-23|Priority to JP2000-045430

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2000-02-23|Priority to JP2000045430A

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2000-02-24|Priority to JP2000-047391

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2000-02-24|Priority to JP2000047391A

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2000-07-04|Priority to JP2000201837A

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2000-07-04|Priority to JP2000-201837

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2000-08-25|Priority to JP2000255215A

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2000-08-25|Priority to JP2000-255215

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2000-10-04|Application filed by 데머 얀, 당코 제니아 떼., 클라리언트 인터내셔널 리미티드

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2000-10-04|Priority to PCT/JP2000/006903

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2001-12-20|Publication of KR20010112227A

优先权:

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申请号 | 申请日 | 专利标题

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JP99-286418|1999-10-07|

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JP28641899A|JP3615972B2|1999-10-07|1999-10-07|Photosensitive resin composition|

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JP99-333048|1999-11-24|

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JP33304899|1999-11-24|

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JP99-362994|1999-12-21|

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JP36299499A|JP3615977B2|1999-12-21|1999-12-21|Photosensitive resin composition|

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JP99-367237|1999-12-24|

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JP36723799A|JP2001183828A|1999-12-24|1999-12-24|Photosensitive resin composition|

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JP2000-045430|2000-02-23|

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JP2000045430A|JP3615981B2|1999-11-24|2000-02-23|Photosensitive resin composition|

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JP2000047391A|JP2001235859A|2000-02-24|2000-02-24|Photosensitive resin composition|

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JP2000-047391|2000-02-24|

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JP2000-201837|2000-07-04|

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JP2000201837A|JP3615995B2|2000-07-04|2000-07-04|Photosensitive resin composition|

---

JP2000-255215|2000-08-25|

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JP2000255215A|JP2002072473A|2000-08-25|2000-08-25|Photosensitive resin composition|

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PCT/JP2000/006903|WO2001025853A1|1999-10-07|2000-10-04|Photosensitive composition|