Negative-type photosensitive composition, cured film, method for producing the same, and member and electronic component provided therewith

Abstract

To provide a photosensitive composition and a cured film thereof, which contain a high proportion of inorganic components, have a high refractive index, and can be subjected to patterning.SOLUTION: A negative-type photosensitive composition comprises (A) a metalloxane comprising a structural unit represented by the general formula (1), (B) a photoacid generator, and (C) a solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive composition, a cured film, a method for producing the same, and a member and an electronic component equipped with the same. [Background technology]

[0002] Films made of metal oxides have properties such as high heat resistance, high transparency, high refractive index, and high dielectric constant, and are therefore useful in a wide variety of applications, such as condenser lenses, anti-reflection films, planarizing layers, interlayer insulating films, etc. In these applications, desired patterns can be obtained by using a photosensitive composition.

[0003] Various methods for forming films made of metal oxides have been investigated. For example, a method has been proposed in which a thin film is obtained by applying and curing a metal alkoxide or its condensate, metalloxane (see, for example, Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2022 / 138541 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-72619 [Patent Document 3] Patent Publication No. 2021-33090 Summary of the Invention [Problem to be solved by the invention]

[0005] In the technology described in Patent Document 1, a polymetalloxane that can exist stably in a homogeneous state in a solution is obtained by reacting a specific organic group with a metal alkoxide. A thin film is formed by coating and curing the obtained polymetalloxane, but there was no information about its photosensitivity.

[0006] The technology described in Patent Document 2 is a technology for obtaining a substrate having a convex structure, and a metalloxane compound is cited as one of the materials for the layer having the concave-convex structure. Furthermore, photolithography is cited as one example of a method for forming a layer having the concave-convex structure. However, photosensitization using a metalloxane compound other than siloxane and the specific method for doing so are not clearly stated, and it has been difficult to form a clear pattern using a metalloxane-based photosensitive composition.

[0007] In the technology described in Patent Document 3, a negative pattern is formed using a resist material containing a condensate or hydrolysis condensate of a metal alkoxide, a photoacid generator, and a photobase generator. However, these patterns can be achieved by exposure to short wavelengths such as EUV or electron beams, and it has been difficult to form patterns using exposure with wavelengths such as i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm).

[0008] The present invention was made in view of the drawbacks of the prior art, and its object is to provide a metalloxane-based photosensitive composition and a cured film thereof that are capable of forming high-resolution patterns using commonly used exposure wavelengths such as i-line, h-line, and g-line. [Means for solving the problem]

[0009] The present invention has the following configuration. [1] A negative-type photosensitive composition comprising (A) a metalloxane containing a structural unit represented by the following general formula (1) (hereinafter referred to as "(A) metalloxane"), (B) a photoacid generator, and (C) a solvent:

[0010] [ka]

[0011] (R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a silicon atom-containing organic group, and a plurality of R1 In the formula (A), the silicon atom-containing organic group is present in an amount of 1 to 200 parts by mole per 100 parts by mole of the metal atom in the metalloxane (A). 2 is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, a group represented by the following general formula (2), or a group having a metalloxane bond.

[0012] [ka]

[0013] R 3 and R 4 are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms, and b is an integer of 0 to 2. M is a metal atom selected from the group consisting of Al, Ti, Y, Zr, Nb, Sn, and Hf. m is an integer indicating the valence of the metal atom M, and a is an integer of 1 to (m-2). [2] (A) Multiple R in metalloxane 2 The negative photosensitive composition according to the above [1], wherein the group represented by the general formula (2) is present in an amount of 1 to 150 parts by mole per 100 parts by mole of metal atoms in the (A) metalloxane. [3] The negative photosensitive composition according to the above [1] or [2], wherein the silicon atom-containing organic group is a group represented by the following general formula (3):

[0014] [ka]

[0015] (R 5 R is an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. 6 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. n is an integer of 0 to 3. R 5 and R 6If there are multiple, they may be the same or different.) [4] (A) Multiple R in metalloxane 1 The negative photosensitive composition according to any one of the above [1] to [3], wherein the group represented by the general formula (3) is 1 to 100 parts by mole per 100 parts by mole of metal atoms in the (A) metalloxane. [5] (A) Multiple R in metalloxane 2 The negative photosensitive composition according to any one of the above [1] to [4], wherein the group represented by the general formula (2) is present in an amount of 50 to 120 parts by mole per 100 parts by mole of metal atoms in the (A) metalloxane. [6] The negative photosensitive composition according to any one of the above [1] to [5], wherein the weight-average molecular weight of the (A) metalloxane is 10,000 or more and 2,000,000 or less. [7] A cured film obtained by curing the negative photosensitive composition according to any one of the above [1] to [6]. [8] A method for producing a cured film, comprising the steps of forming a coating film of the negative photosensitive composition according to any one of the above [1] to [6], exposing and developing the coating film, and heating the developed film. [9] The method for producing a cured film according to the above [8], wherein the developer used in the developing step is an organic developer.

[10] A member comprising the cured film described in [7] above.

[11] An electronic component comprising the member described in

[10] above. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a metalloxane-based photosensitive composition that can form a high-resolution pattern using commonly used exposure wavelengths such as i-line, h-line, and g-line, thereby making it possible to easily obtain a high-resolution pattern of a metalloxane-based cured film. DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with various modifications depending on the purpose and application.

[0018] The negative photosensitive composition according to an embodiment of the present invention is a negative photosensitive composition containing (A) a metalloxane, (B) a photoacid generator, and (C) a solvent.

[0019] [(A) Metalloxane] The metalloxane used in the present invention has a structural unit represented by the following general formula (1).

[0020] [ka]

[0021] In general formula (1), R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a silicon atom-containing organic group, and a plurality of R 1 In the formula (A), the silicon atom-containing organic group is present in an amount of 1 to 200 parts by mole per 100 parts by mole of the metal atom in the metalloxane (A). 2 is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, a group represented by the following general formula (2), or a group having a metalloxane bond.

[0022] [ka]

[0023] In general formula (2), R 3 and R 4are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms, and b is an integer of 0 to 2. M is a metal atom selected from the group consisting of Al, Ti, Y, Zr, Nb, Sn, and Hf. m is an integer indicating the valence of the metal atom M, and a is an integer of 1 to (m-2).

[0024] (A) metalloxane is a polymer having a metal-oxygen-metal bond as its main chain. The metal atoms constituting the (A) metalloxane of the present invention are selected from the group consisting of Al, Ti, Y, Zr, Nb, Sn, and Hf. When the (A) metalloxane contains these metal atoms, the refractive index and other properties of the film obtained by curing the composition according to the embodiment of the present invention (hereinafter simply referred to as the "cured film") can be improved. The metal atoms contained in the (A) metalloxane may be of one type or multiple types.

[0025] R 1 Examples of the alkyl group having 1 to 12 carbon atoms used in the above include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

[0026] (A) Multiple R in metalloxane 1 In the formula (A), the silicon atom-containing organic group is present in an amount of 1 to 200 parts by mole per 100 parts by mole of metal atoms in the metalloxane (A), so that the dissolution rate of the negative photosensitive composition in the developer can be changed.

[0027] The silicon atom-containing organic group is preferably a group represented by the following general formula (3).

[0028] [ka]

[0029] R 5 R is an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. 6 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. n is an integer of 0 to 3. R 5 and R 6 When there are a plurality of, they may be the same or different.

[0030] When the silicon atom-containing organic group is a group represented by general formula (3), the dissolution rate of the negative photosensitive composition in a developer can be further improved.

[0031] (A) Multiple R in metalloxane 1 In the above, the amount of the group represented by general formula (3) is preferably 1 to 100 molar parts per 100 molar parts of metal atoms in the (A) metalloxane. By adjusting the amount of the group represented by general formula (3) to 1 molar part or more per 100 molar parts of metal atoms in the metalloxane, the solubility of the negative photosensitive composition in the developer can be improved, and pattern processing with less residue can be achieved. The amount of the group represented by general formula (3) is more preferably 10 molar parts or more per 100 molar parts of metal atoms in the (A) metalloxane. On the other hand, by adjusting the amount of the group represented by general formula (3) to 100 molar parts or less per 100 molar parts of metal atoms in the metalloxane, the composition becomes more susceptible to the effect of the acid generated from the photoacid generator, and film loss in exposed areas can be suppressed. The amount of the group represented by general formula (3) is more preferably 50 molar parts or less per 100 molar parts of metal atoms in the (A) metalloxane.

[0032] When the amount of the group represented by general formula (3) is large or the molecular weight is large, it is preferable to increase the content of the photoacid generator (B) in order to suppress film loss in the exposed area.

[0033] Preferred examples of the silicon-containing organic group will be given later in the description of the method for producing metalloxane.

[0034] R 2 Examples of the alkoxy group having 1 to 12 carbon atoms used in the above include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, a pentoxy group, a hexyloxy group, a heptoxy group, an octoxy group, a 2-ethylhexyloxy group, a nonyl group, and a decyloxy group.

[0035] R 2 is a group having a metalloxane bond, R 2 is directly bonded to the metal atom M of another metalloxane chain.

[0036] The structure represented by general formula (2) is derived from a diketone or ketoester. This structure exhibits keto-enol tautomerism. For convenience, general formula (2) shows the enol structure bonded to the metal atom M in the metalloxane main chain. However, this is equivalent to the structure in the keto structure where two oxygen atoms are coordinated to the metal atom M in the metalloxane main chain, and there is no structural difference between the two.

[0037] In consideration of the ease with which the structure represented by general formula (2) bonds or coordinates to the metal atom M in the metalloxane, b is preferably 0. In other words, the structure represented by general formula (2) is preferably a β-diketone or a β-ketoester. Preferred specific examples will be shown later in the description of the method for producing metalloxane.

[0038] R 3 and R 4 Specific examples of the alkyl group having 1 to 12 carbon atoms used in the above include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, and a decyl group.

[0039] R 3 and R 4Examples of the alicyclic alkyl group having 5 to 12 carbon atoms used in the above include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

[0040] R 3 and R 4 Specific examples of the alkoxy group having 1 to 12 carbon atoms used in the above include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, a 2-ethylhexoxy group, a nonyloxy group, and a decyloxy group.

[0041] R 3 and R 4 Specific examples of the aryl group having 6 to 12 carbon atoms or the aryloxy group having 6 to 12 carbon atoms used in the above include a phenyl group, a phenoxy group, a benzyl group, a phenylethyl group, and a naphthyl group.

[0042] (A) Multiple R in metalloxane 2 In the formula (A), the amount of the group represented by general formula (2) is preferably 1 to 150 molar parts per 100 molar parts of metal atoms in the metalloxane (A). By setting the amount of the group represented by general formula (2) to at least the lower limit, the solubility of the negative photosensitive composition in a developer can be improved, and pattern processing with less residue can be achieved. The amount of the group represented by general formula (2) is more preferably 10 molar parts or more, and even more preferably 50 molar parts or more, per 100 molar parts of metal atoms in the metalloxane (A). On the other hand, by setting the amount of the group represented by general formula (2) to at most the upper limit, the bonding strength between the silicon-containing organic group and the metal atom can be ensured, and film loss in exposed areas can be suppressed. The amount of the group represented by general formula (2) is more preferably 120 molar parts or less per 100 molar parts of metal atoms in the metalloxane (A).

[0043] Although there are no particular limitations on the synthesis method for (A) metalloxane, it is preferable to include a step of chemically modifying and hydrolyzing a metal alkoxide as necessary, followed by partial condensation and polymerization. Here, partial condensation refers to leaving some M-OH in the resulting metalloxane, rather than condensing all of the M-OH in the hydrolyzate. Under the general condensation conditions described below, it is common for some M-OH to remain. There are no limitations on the amount of M-OH that remains.

[0044] The silicon atom-containing organic group and the group represented by general formula (2) may be hydrolyzed and (partially) condensed while bonded to the metal atom of the metal alkoxide, or may be bonded to the metal atom after condensation.

[0045] The silicon-containing organic group can be bonded to a metal atom, for example, by reacting a metal alkoxide or a (partially) condensed compound with a compound represented by the following general formula (4) in a predetermined molar ratio of 1 to 200 molar parts per 100 molar parts of the metal atom.

[0046] [ka]

[0047] R 5 , R 6 and n is as explained above.

[0048] Examples of the compound represented by general formula (4) include methoxytrimethylsilane, trimethylethoxysilane, dimethoxydimethylsilane, trimethylsilanol, triethylsilanol, t-butyldimethylsilanol, isopropoxytrimethylsilane, trimethoxymethylsilane, t-butoxytrimethylsilane, diethylisopropylsilanol, diethoxydimethylsilane, ethyltrimethoxysilane, tetramethoxysilane, ethoxytriethylsilane, trimethoxypropylsilane, diethoxydiethylsilane, triethoxymethylsilane, cyclohexyldimethoxymethylsilane, cyclopentyltrimethoxysilane, triethoxyethylsilane, methoxydimethyl-n-octylsilane, cyclohexyltrimethoxysilane, diisobutyldimethoxysilane, hexyltrimethoxysilane, and triethoxymethylsilane. Examples of the compound represented by general formula (4) include propylsilane, tetraethoxysilane, dimethoxymethyl-n-octylsilane, triethoxyisobutylsilane, butyltriethoxysilane, dicyclopentyldimethoxysilane, dimethylphenylsilanol, methoxydimethylphenylsilane, dimethoxymethylphenylsilane, trimethoxyphenylsilane, triethoxyphenylsilane, diethoxymethylphenylsilane, trimethoxy(p-tolyl)silane, triethoxy(p-tolyl)silane, benzyltriethoxysilane, benzyldiethoxysilanol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, diphenylethoxymethylsilane, t-butyldiphenylmethoxysilane, triphenylsilanol, methoxytriphenylsilane, and ethoxytriphenylsilane. Two or more of the compounds represented by general formula (4) may be used in combination.

[0049] The group represented by general formula (2) can be bonded to a metal atom, for example, by reacting a metal alkoxide or a (partially) condensed compound with a compound represented by the following general formula (5) in a predetermined molar ratio relative to the metal atom.

[0050] [ka]

[0051] 3 , R 4 and b are as explained above.

[0052] Specific examples of compounds having a structure represented by general formula (5) include: When b = 0, examples of suitable solvents include acetylacetone, 1,3-pentanedione, 2,4-pentanedione, 3,5-heptanedione, 1,3-hexanedione, 2,4-hexanedione, 3,5-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, dimethyl malonate, methyl ethyl malonate, diethyl malonate, methyl butyl malonate, ethyl butyl malonate, dibutyl malonate, diisobutyl malonate, t-butyl malonate, diisopropyl malonate, methyl isopropyl malonate, ethyl isopropyl malonate, butyl isopropyl malonate, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, isopropyl acetoacetate, isobutyl acetoacetate, t-butyl acetoacetate, etc. Among these, acetylacetone, methyl acetoacetate, and ethyl acetoacetate are preferably used.

[0053] When b=1, 2,5-hexanedione, 2,5-heptanedione, 2,5-octanedione, 3,6-octanedione, 3,6-nonanedione, dimethyl succinate, diethyl succinate, dibutyl succinate, diisobutyl succinate, t-butyl succinate, diisopropyl succinate, methyl isopropyl succinate, ethyl isopropyl succinate, and butyl isopropyl succinate are preferably used.

[0054] When b=2, 2,6-heptanedione, 2,6-octanedione, dimethyl glutarate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, t-butyl glutarate, diisopropyl glutarate, methyl isopropyl glutarate, ethyl isopropyl glutarate, butyl isopropyl glutarate, and the like are preferably used.

[0055] As the compound represented by general formula (5), two or more of the above compounds may be used in combination.

[0056] The weight-average molecular weight of (A) metalloxane has a lower limit of 500 or more, preferably 1,000 or more, and more preferably 10,000 or more. The upper limit is 5,000,000 or less, preferably 3,000,000 or less, and more preferably 2,000,000 or less. When the weight-average molecular weight of the metalloxane is equal to or greater than the lower limit, polymer shrinkage during the heat treatment step is suppressed, improving the crack resistance of the cured film. When the molecular weight is equal to or less than the upper limit, the solubility of the metalloxane in solvents is improved, allowing for even application onto the substrate and producing a cured film with high in-plane uniformity. At the same time, the solubility of the metalloxane in the developer is also improved, enabling pattern processing with minimal residue.

[0057] The weight-average molecular weight in the present invention refers to a value measured by gel permeation chromatography (GPC) in terms of polystyrene. The weight-average molecular weight of metalloxane is determined by the following method. Metalloxane is dissolved in a developing solvent to a concentration of 0.2 wt% to prepare a sample solution. The sample solution is then injected into a column packed with a porous gel and developing solvent. The column eluate is detected with a differential refractive index detector, and the weight-average molecular weight is determined by analyzing the elution time. Note that a developing solvent capable of dissolving metalloxane at a concentration of 0.2 wt% is selected, but a developing solvent capable of dissolving metalloxane at a concentration of 0.02 mol / dm 3 When lithium chloride is dissolved in N-methyl-2-pyrrolidone solution, this is used.

[0058] In the synthesis of (A) metalloxane, the catalyst to be added as needed is not particularly limited, but an acidic catalyst or a basic catalyst is preferably used. Specific examples of acidic catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids, and their anhydrides. Specific examples of basic catalysts include diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and 2,2,6,6-tetramethylpiperidine.

[0059] [(B) Photoacid generator] In the present invention, the photoacid generator (B) is a compound that generates an acid upon irradiation with light, and known photoacid generators can be used. Although not particularly limited, the light referred to here refers to actinic radiation (radiation), such as visible light, ultraviolet light, electron beams, and X-rays. From the viewpoint of being able to use commonly used light sources, the light to be irradiated is preferably, for example, light from an ultra-high pressure mercury lamp light source capable of irradiating visible light or ultraviolet light, and more preferably j-rays (wavelength 313 nm), i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), or g-rays (wavelength 436 nm).

[0060] Upon exposure, the acid generated from the compound reacts with (A) the bond between the metal atom in the metalloxane and the oxygen atom to which the silicon atom-containing organic group is bonded (M and OR 1 and the bond between (A) and (B) is broken, and the organic group in the metalloxane (A) is released, thereby reducing the solubility in the developer. Therefore, when the negative-tone photosensitive composition of the present invention is applied and prebaked to prepare a prebaked film that is soluble in the developer, and the prebaked film is irradiated with actinic rays through a mask, only the exposed areas become insoluble, and the unexposed areas can be removed with the developer to form a negative-tone pattern.

[0061] Examples of photoacid generators include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, NAI-1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106, and PAI-1001 (all trade names, manufactured by Midori Chemical Co., Ltd.), SP-077, and SP-08 Examples of suitable surfactants include 2, SP-606, SP-171 (all trade names, manufactured by ADEKA Corporation), TPS-PFBS (trade name, manufactured by Toyo Gosei Co., Ltd.), CGI-MDT, CGI-NIT (all trade names, manufactured by Ciba Japan Co., Ltd.), WPAG-281, WPAG-336, WPAG-339, WPAG-342, WPAG-344, WPAG-350, WPAG-370, WPAG-372, WPAG-449, WPAG-469, WPAG-505, and WPAG-506 (all trade names, manufactured by Wako Pure Chemical Industries, Ltd.).

[0062] These photoacid generators can be used alone or in combination of two or more. The content of the photoacid generator is preferably 0.1 parts by mass or more, more preferably 3 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by weight of the (A) metalloxane. When the content of the (B) photoacid generator is equal to or greater than the lower limit, dissolution contrast between exposed and unexposed areas is easily achieved. On the other hand, when the content of the (B) photoacid generator is equal to or less than the upper limit, compatibility with the (A) metalloxane is improved, a more homogeneous film is obtained, and coloration due to decomposition of the photoacid generator during thermal curing can be suppressed.

[0063] [(C) Solvent] The solvent (C) may be the same as that in the metalloxane solution obtained in the production of the metalloxane (A), or may be a solution to which another solvent has been added.

[0064] The solvent contained in the negative photosensitive composition is not particularly limited, but it is preferable to use the same solvent as that used in the synthesis of the metalloxane, and an aprotic polar solvent is preferred. The use of an aprotic polar solvent improves the stability of the metalloxane (A) in the composition. This allows for a negative photosensitive composition with excellent storage stability and with little increase in viscosity even during long-term storage.

[0065] Specific examples of aprotic polar solvents include acetone, tetrahydrofuran, ethyl acetate, dimethoxyethane, N,N-dimethylformamide, dimethylacetamide, dipropylene glycol dimethyl ether, tetramethylurea, diethylene glycol ethyl methyl ether, dimethyl sulfoxide, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, propylene carbonate, N,N′-dimethylpropyleneurea, N,N-dimethylisobutyramide, and 2,6-dimethyl-4-heptanone.

[0066] The content of the (C) solvent in the negative photosensitive composition is preferably in the range of 100 to 1000 parts by mass per 100 parts by mass of the (A) metalloxane.

[0067] The solid content concentration in the negative photosensitive composition is preferably 1% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 40% by mass or less. By setting the solid content concentration of the composition within the above range, it is possible to obtain a coating film with good thickness uniformity in the coating step described below. The solid content concentration of the composition is obtained by weighing 1.0 g of the negative photosensitive composition into an aluminum cup, heating it on a hot plate at 250°C for 30 minutes to evaporate the liquid, weighing the solid content remaining in the aluminum cup after heating, and calculating the remaining ratio to the original 1.0 g.

[0068] The viscosity of the negative photosensitive composition of the present invention at 25°C is preferably from 1 mPa·s to 1000 mPa·s, more preferably from 1 mPa·s to 500 mPa·s, and even more preferably from 1 mPa·s to 200 mPa·s. By setting the viscosity of the composition within the above range, it is possible to obtain a coating film with good thickness uniformity in the coating step described below. The viscosity of the composition can be measured by setting the composition temperature to 25°C and using an E-type viscometer at an arbitrary rotation speed.

[0069] [Other ingredients] The negative photosensitive composition according to the embodiment of the present invention may contain other components, such as inorganic particles, surfactants, silane coupling agents, crosslinking agents, and crosslinking accelerators.

[0070] (cured film) A method for producing a cured film using a negative-tone photosensitive composition according to an embodiment of the present invention will be described. This method includes the steps of forming a coating film of the negative-tone photosensitive composition, exposing and developing the coating film, and heating the developed film.

[0071] First, the negative photosensitive composition according to the embodiment of the present invention is applied onto a base substrate by a known method such as spinning, dipping, or slitting, and then prebaked using a heating device such as a hot plate or oven. Prebaking is carried out at a temperature in the range of 50 to 150°C for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.01 to 15 μm.

[0072] After pre-baking, UV-visible exposure is performed using a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), or other UV-visible exposure device at 10 to 4000 J / m 2 The desired exposure is performed through a desired mask.

[0073] It is preferable to subject the exposed film to a post-exposure bake (hereinafter referred to as "PEB"). PEB can promote the above-mentioned effect of the acid generated from the (B) photoacid generator. PEB is preferably performed at a temperature in the range of 50 to 150°C for 30 seconds to 30 minutes.

[0074] After exposure, the unexposed areas are dissolved by development to obtain a negative pattern. The development method is preferably immersion in a developer for 5 seconds to 10 minutes by showering, dipping, puddling, or other methods.

[0075] Examples of the developer include an alkaline developer and an organic developer. Examples of the alkaline developer include an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. A surfactant may be added to these. Examples of organic developers include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphortriamide, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate methanol, ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate, and butyl acetate. These developers can be used alone or in combination of two or more. The developer is preferably an organic developer from the viewpoint of solubility of unexposed areas.

[0076] After development, the film is rinsed with water and then dried. Dry baking can also be performed at temperatures between 50 and 150°C.

[0077] It is preferable to carry out bleaching exposure after that. By carrying out bleaching exposure, unreacted quinone diazide compounds remaining in the film are photodecomposed, and the optical transparency of the film is further improved. As a method of bleaching exposure, an ultraviolet-visible exposure machine for PLA or the like is used, and 100 to 20,000 J / m 2 The entire surface is exposed to approximately 1000 ppm of light (equivalent to 365 nm wavelength exposure).

[0078] This film is then heated (cured) for approximately 30 seconds to 10 hours at a temperature between 100°C and 500°C, preferably between 150°C and 400°C, using a heating device such as a hot plate or oven. This results in a cured film containing metalloxane. Heating causes the metalloxane molecules to bond together, further increasing the molecular weight. By setting the heating temperature above the lower limit, the curing of the metalloxane progresses, increasing the film density of the cured film. By setting the heating temperature below the upper limit, damage to the substrate, inorganic solid material, and surrounding components due to heating can be suppressed. The thickness of this cured film is preferably 0.01 to 15 μm.

[0079] The cured film obtained in this manner is a film mainly composed of a resin having metal atoms with high electron density in the main chain, so the density of metal atoms in the cured film can be increased, and a high film density can be easily obtained.In addition, since the cured film is a dielectric film with no free electrons, a cured film with high heat resistance and dielectric constant can be obtained.

[0080] The refractive index of the resulting cured film at a wavelength of 633 nm is preferably 1.50 or more and 2.20 or less, and more preferably 1.60 or more and 2.10 or less.

[0081] The refractive index of the cured film at a wavelength of 633 nm can be obtained by a prism coupling method using a prism coupler.

[0082] (Application) The cured film described above has excellent refractive index and insulating properties, and is therefore suitable for use as a component for electronic components such as solid-state imaging devices and displays. The term "component" refers to a component used to assemble electronic components. That is, the component according to the embodiment of the present invention comprises a cured film containing the metalloxane or its composition described above. The electronic component according to the embodiment of the present invention comprises such a cured film. For example, components for solid-state imaging devices include condenser lenses, optical waveguides connecting condenser lenses and optical sensors, and anti-reflection films. Components for displays include index matching materials, planarizing materials, and insulating protective materials.

[0083] Furthermore, the cured film according to the embodiment of the present invention can also be used as a protective film or dry etching resist in a multi-layer NAND flash memory, a buffer coat for a semiconductor device, a planarizing film for a TFT substrate, an interlayer insulating film, and various protective films. [Example]

[0084] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0085] (Measurement of weight average molecular weight) The weight-average molecular weight (Mw) was determined by the following method. Lithium chloride was dissolved in N-methyl-2-pyrrolidone as a developing solvent, and the resulting solution was diluted to 0.02 mol / dm 3 A lithium chloride solution in N-methyl-2-pyrrolidone was prepared. Metalloxane was dissolved in the developing solvent to a concentration of 0.2 wt% to prepare the sample solution. The developing solvent was packed into a porous gel column (one each of TSKgel α-M and α-3000, manufactured by Tosoh) at a flow rate of 0.5 mL / min, and 0.2 mL of the sample solution was injected into the column. The column eluate was detected using a differential refractive index detector (RI-201, manufactured by Showa Denko K.K.), and the weight-average molecular weight (Mw) was determined by analyzing the elution time.

[0086] (Materials used in Examples and Comparative Examples) (Synthesis Example 1) Synthesis of zirconium compound (M-1) A 500 ml three-neck flask was charged with 32.8 g (0.1 mol) of tetrapropoxyzirconium, and the flask was immersed in a 40°C oil bath and stirred for 30 minutes. Then, 10.0 g (0.1 mol) of acetylacetone was added over 1 hour using a dropping funnel, and the mixture was stirred for another 1 hour. The contents of the flask were transferred to a 200 ml eggplant-shaped flask, and the purified propanol was removed to obtain a yellow liquid zirconium compound (M-1).

[0087] (Synthesis Example 2) Synthesis of zirconium compound (M-2) A yellow liquid zirconium compound (M-2) was obtained by synthesis and purification in the same manner as in Synthesis Example 1, except that the amount of acetylacetone was changed to 15.0 g (0.15 mol).

[0088] When these zirconium compounds (M-1) and (M-2) were analyzed by FT-IR, the absorption peak of C=O (1595 cm) derived from the chelate ring formation of acetylacetone was observed. -1 ) and the C=C absorption peak (1532 cm -1 ) was observed, and the absorption peak of C=O derived from acetylacetone before the reaction (1725 cm -1 ) was not observed, it was confirmed that the structure was one in which the n-propoxy groups of tetrapropoxyzirconium were substituted with acetylacetone.

[0089] [Table 1]

[0090] [(A) Metalloxane] (Synthesis Example 3) Synthesis of Metalloxane (A-1) 36.8 g (0.1 mol) of the zirconium compound (M-1) and 32.1 g of N,N-dimethylisobutyramide (hereinafter abbreviated as DMIB) as a solvent were mixed to prepare Solution 1. 5.4 g (0.3 mol) of water, 49 g of isopropyl alcohol (hereinafter abbreviated as IPA) as a water-diluting solvent, and 0.98 g (0.005 mol) of dicyclohexylmethylamine as a polymerization catalyst were mixed to prepare Solution 2.

[0091] The entire amount of Solution 1 was placed in a 500 ml three-neck flask, and the flask was immersed in a 40°C oil bath and stirred for 30 minutes. Then, for the purpose of hydrolysis, the entire amount of Solution 2 was placed in a dropping funnel and added to the flask over 30 minutes. During the addition of Solution 2, no precipitation occurred in the flask, and the solution remained homogeneous and transparent. Then, for the purpose of polycondensation, the oil bath was heated to 140°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the solution was heated and stirred for 2 hours (internal temperature: 100-130°C). During the reaction, IPA, the by-product n-propanol, and water were distilled off. During the heating and stirring, no precipitation occurred in the flask, and the solution remained homogeneous and transparent.

[0092] After heating, the contents of the flask were cooled to room temperature, and 4.3 g (0.048 mol) of trimethylsilanol was added and stirred for 1 hour. DMIB was then added to obtain a metalloxane (A-1) solution with a weight-average molecular weight (Mw) of 179,000.

[0093] (Synthesis Examples 4 and 5) Synthesis of Metalloxanes (A-2) and (A-3) Synthesis was performed in the same manner as in Synthesis Example 3, except that the amount of trimethylsilanol was changed as shown in Table 2, to obtain metalloxane (A-2) to (A-3) solutions.

[0094] (Synthesis Example 6) Synthesis of Metalloxane (A-4) A metalloxane (A-4) solution was obtained in the same manner as in Synthesis Example 3, except that trimethylsilanol was changed to methoxytrimethylsilane and the amount added was changed as shown in Table 2.

[0095] (Synthesis Examples 7 to 9) Synthesis of Metalloxanes (A-5) to (A-7) Solutions of metalloxanes (A-5) to (A-7) were obtained in the same manner as in Synthesis Example 3, except that trimethylsilanol was changed to diphenylsilanediol and the amounts added were changed as shown in Table 2.

[0096] (Synthesis Example 10) Synthesis of Metalloxane (A-8) A metalloxane (A-8) solution was obtained in the same manner as in Synthesis Example 3, except that the zirconium compound was changed from (M-1) to (M-2).

[0097] (Synthesis Example 11) Synthesis of Metalloxane (A-9) Synthesis was performed in the same manner as in Synthesis Example 3, except that the amounts of water and IPA added were changed as shown in Table 2, to obtain a metalloxane (A-9) solution.

[0098] (Synthesis Example 12) Synthesis of Metalloxane (A-10) A metalloxane (A-10) solution was obtained in the same manner as in Synthesis Example 3, except that trimethylsilanol was not used.

[0099] (Synthesis Example 13) Synthesis of Metalloxane (A-11) A metalloxane (A-11) solution was obtained in the same manner as in Synthesis Example 3, except that trimethylsilanol was replaced with ethanol.

[0100] In all cases, no precipitation occurred and the solutions were uniform and transparent. The weight average molecular weight (Mw) of each metalloxane is shown in Table 2.

[0101] [Table 2]

[0102] [(B) Photoacid generator] (B-1) SP-606 Manufactured by ADEKA Corporation.

[0103] [(C) Solvent] DMIB: N,N'-dimethylisobutyramide (Mitsubishi Gas Chemical Company, Inc.) 2,6-Dimethyl-4-heptanone (Fujifilm Wako Pure Chemical Industries, Ltd.).

[0104] Example 1 First, 0.10 g of photoacid generator (B-1) and 2.4 g of a mixed solvent of DMIB and 2,6-dimethyl-4-heptanone were added to 8.0 g of the obtained 25 wt % metalloxane (A-1) solution, and the mixture was stirred to obtain composition 1.

[0105] Composition 1 was spin-coated onto a 4-inch silicon wafer using a spin coater ("1H-360S (trade name)" manufactured by Mikasa Co., Ltd.), and the substrate was heated at 90°C for 1 minute using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a pre-baked film. The produced film was exposed to an ultra-high pressure mercury lamp using PLA (PLA-501F manufactured by Canon Inc.) through a grayscale mask for sensitivity measurement, and then the substrate was subjected to PEB at 120°C for 1 minute using a hot plate.

[0106] After PEB, the film was developed by dipping in propylene glycol monomethyl ether for 1 minute to form a negative pattern.

[0107] The resulting film was cured using a hot plate at 230°C for 5 minutes to produce a cured film. The film thickness was measured using an optical interference film thickness meter (Lambda Ace STM602, manufactured by Dai Nippon Screen Mfg. Co., Ltd.).

[0108] (Possible film thickness) The thickness of the cured film to be produced was varied, and the surface was observed in sequence using an optical microscope (magnification: 5x). The maximum film thickness at which no cracks were observed in the cured film was determined as the film thickness that could be formed.

[0109] (Calculation of the remaining film rate in the unexposed area) The remaining film ratio of the unexposed area after development was calculated according to the following formula. Unexposed portion remaining film ratio (%)=unexposed portion film thickness after development / film thickness after pre-baking×100.

[0110] (Residue evaluation) The cured film after development was observed using an optical microscope to check for the degree of residue generation. The residue generation was evaluated using the following four-point scale. A: No residue is observed. B: Residue is observed in less than 5% of the entire cured film. C: Residue is observed in 5% or more of the entire cured film. -: The unexposed parts of the film do not dissolve during development, so no pattern can be formed.

[0111] (Examples 2 and 3) Compositions were prepared and evaluated in the same manner as in Example 1, except that the amount of photoacid generator (B-1) used was changed as shown in Table 3. The evaluation results are shown in Table 3.

[0112] Examples 4 to 6 Compositions were prepared and evaluated in the same manner as in Example 1, except that the type of metalloxane was changed from (A-1) to that shown in Table 3. The evaluation results are shown in Table 3.

[0113] Example 7 A composition was prepared and evaluated in the same manner as in Example 3, except that the type of metalloxane was changed from (A-1) to (A-5). The evaluation results are shown in Table 3.

[0114] (Examples 8 to 11) Compositions were prepared and evaluated in the same manner as in Example 1, except that the type of metalloxane was changed from (A-1) to that shown in Table 3. The evaluation results are shown in Table 3.

[0115] (Comparative Example 1) A composition was prepared and evaluated in the same manner as in Example 1, except that the type of metalloxane was changed from (A-1) to (A-10). Since the unexposed areas of the film did not dissolve during development, a pattern could not be obtained. The evaluation results are shown in Table 3.

[0116] (Comparative Example 2) A composition was prepared and evaluated in the same manner as in Example 1, except that no photoacid generator was used. The film was completely dissolved during development, making it impossible to obtain a pattern. The evaluation results are shown in Table 3.

[0117] (Comparative Example 3) A composition was prepared and evaluated in the same manner as in Example 1, except that the type of metalloxane was changed from (A-1) to (A-11). Since the unexposed areas of the film did not dissolve during development, a pattern could not be obtained. The evaluation results are shown in Table 3.

[0118] [Table 3]

Claims

1. A negative-type photosensitive composition comprising (A) a metalloxane containing a structural unit represented by the following general formula (1) (hereinafter referred to as "(A) metalloxane"), (B) a photoacid generator, and (C) a solvent: 【Chemical 1】 (R １ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a silicon atom-containing organic group, and (A) a plurality of R １ In the formula (A), the silicon atom-containing organic group is present in an amount of 1 to 200 parts by mole per 100 parts by mole of the metal atom in the metalloxane (A). ２ is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, a group represented by the following general formula (2), or a group having a metalloxane bond. 【Chemistry 2】 R ３ and R ４ are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms, and b is an integer of 0 to 2. M represents a metal atom selected from the group consisting of Al, Ti, Y, Zr, Nb, Sn and Hf. m is an integer indicating the valence of the metal atom M, and a is an integer from 1 to (m-2).

2. (A) Multiple R groups present in metalloxane ２ 2. The negative photosensitive composition according to claim 1, wherein the group represented by formula (2) is present in an amount of 1 to 150 parts by mole per 100 parts by mole of metal atoms in the metalloxane (A).

3. 2. The negative photosensitive composition according to claim 1, wherein the silicon atom-containing organic group is a group represented by the following general formula (3): 【Chemistry 3】 (R ５ is an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. ６ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. n is an integer of 0 to 3. R ５ and R ６ When there are multiple, they may be the same or different.)

4. (A) Multiple R groups present in metalloxane １ 4. The negative photosensitive composition according to claim 3, wherein the group represented by formula (3) is present in an amount of 1 to 100 parts by mole per 100 parts by mole of metal atoms in the metalloxane (A).

5. (A) Multiple R groups present in metalloxane ２ 2. The negative photosensitive composition according to claim 1, wherein the group represented by formula (2) is present in an amount of 50 to 120 parts by mole per 100 parts by mole of metal atoms in the metalloxane (A).

6. 2. The negative photosensitive composition according to claim 1, wherein the weight average molecular weight of the metalloxane (A) is from 10,000 to 2,000,000.

7. A cured film obtained by curing the negative photosensitive composition according to any one of claims 1 to 6.

8. A method for producing a cured film, comprising the steps of: forming a coating film of the negative photosensitive composition according to any one of claims 1 to 6; exposing and developing the coating film; and heating the developed film.

9. The method for producing a cured film according to claim 8 , wherein the developer used in the developing step is an organic developer.

10. A member comprising the cured film according to claim 7.

11. An electronic component comprising the member according to claim 10.

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