WO2005036270A1 - 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路 - Google Patents
放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路 Download PDFInfo
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- WO2005036270A1 WO2005036270A1 PCT/JP2004/014852 JP2004014852W WO2005036270A1 WO 2005036270 A1 WO2005036270 A1 WO 2005036270A1 JP 2004014852 W JP2004014852 W JP 2004014852W WO 2005036270 A1 WO2005036270 A1 WO 2005036270A1
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- radiation
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- curable composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/115—Cationic or anionic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/12—Nitrogen compound containing
Definitions
- the present invention relates to a radiation-curable composition, a method for storing the composition, a method for forming a cured film, a method for forming a pattern, a method for using a pattern, an electronic component, and an optical waveguide.
- an SiO film formed by a CVD method and an organic SOG (Spin) formed by a coating method because of its excellent heat resistance and electrical reliability.
- On Glass film and inorganic SOG film are often used. However, it is impossible to directly form wiring trenches and via holes with the conventional insulating film. Usually, after patterning photoresist on the insulating film, dry etching by plasma or chemical etching Then, a pattern is formed through a resist removing step and a cleaning step. On the other hand, if photosensitive properties are imparted to an insulating film material that is excellent in heat resistance, electrical reliability, transparency, etc., the resist material required in the above process is no longer necessary, and dry etching treatment using plasma can be performed. It becomes possible to omit a wet etching process using a chemical solution, a resist removal process and a cleaning process.
- Patent Documents 1 and 2 disclose a photosensitive resin composition comprising an alkali-soluble siloxane polymer from which water and a catalyst have been removed, a photoacid generator, and a solvent.
- Patent Documents 3 and 4 disclose photosensitive polysilazane compositions containing polysilazane and a photoacid generator.
- Patent Document 5 discloses a radiation-curable composition comprising a hydrolyzable silane compound, a photoacid generator and an acid diffusion controller.
- Patent Document 1 JP-A-6-148895
- Patent Document 2 JP-A-10-246960
- Patent document 3 JP-A-2000-181069
- Patent document 4 JP 2002-72502 A
- Patent Document 5 Japanese Patent Application Laid-Open No. 2001-288364
- a radiation-curable composition comprising a hydrolyzable silane compound, a photoacid generator and an acid diffusion controller disclosed in Patent Document 5
- an acid diffusion controller suppresses the diffusion of an acid generated by radiation.
- the pattern accuracy of the silane ligature can be improved.
- the acid diffusion controller deactivates (neutralizes) the acid, the amount of photoacid generator is small! / In some cases or the amount of exposure is small, the curability decreases and the pattern accuracy decreases. There are concerns. Conversely, it has become clear that the pursuit of improved pattern accuracy increases the amount of exposure and is suitable for mass production.
- the present invention has been made in view of vigorous circumstances, and a radiation-curable composition capable of obtaining a cured product excellent in pattern accuracy even with a relatively small amount of exposure, a method for storing the composition, and a cured film.
- An object of the present invention is to provide a forming method and a pattern forming method, and a pattern using method, an electronic component and an optical waveguide using the same.
- the present invention provides (a) a component: a siloxane resin, (b) a photoacid generator or a photobase generator, (c) a component: a solvent capable of dissolving the (a) component, and (d) Component: Provided is a radiation curable composition containing a curing acceleration catalyst.
- siloxane resin is represented by the following general formula (1):
- R 1 represents an H atom or an F atom, or a group containing a B atom, an N atom, an A1 atom, a P atom, a Si atom, a Ge atom or a Ti atom, or an organic group having 120 carbon atoms.
- X represents a hydrolysable group
- n represents an integer of 0 to 2
- each R 1 may be the same or different.
- n is 1 to 2
- each X is the same or different. It may be.
- the radiation-curable composition comprises a resin obtained by hydrolyzing and condensing a compound represented by the formula (I).
- the present invention provides the above radiation-curable composition, wherein the curing acceleration catalyst is an onium salt.
- the foam salt is preferred from the viewpoint of improving the electrical properties and mechanical strength of the obtained cured product and further improving the stability of the composition.
- the present invention provides the radiation-curable composition, wherein the curing acceleration catalyst is a quaternary ammonium salt.
- the curing acceleration catalyst is a quaternary ammonium salt.
- the present invention includes a step of applying the radiation-curable composition on a substrate and drying to obtain a coating film, and a step of exposing the coating film.
- a method for forming a cured film without heating According to this method, the diffusion of acid due to heating and the increase in production cost are sufficiently suppressed, and the pattern accuracy of the obtained cured film is sufficiently excellent.
- the present invention provides a step of applying the radiation-curable composition on a substrate and drying to obtain a coating film, a step of exposing the coating film, and a step of heating the coating film after the exposing step.
- a method for forming a cured film having the following is provided.
- the present invention provides the above-mentioned method for forming a cured film, wherein the coating film is heated to 70 to 110 ° C in the heating step. Thereby, diffusion of the acid during heating can be further suppressed.
- the present invention in the step of exposing the above, to provide the pattern forming method of exposing by irradiation of light of the light amount of the coating film 5- lOOmjZcm 2.
- the present invention provides a step of applying the radiation-curable composition on a substrate and drying to obtain a coating, a step of exposing the coating through a mask, and a step of exposing the coating after the exposing step. And a step of removing unexposed portions by development, and not heating the coating film after the exposing step.
- the diffusion of acid due to heating and the increase in production cost are sufficiently suppressed, and the patterning accuracy of the obtained cured film is sufficiently excellent.
- the “heating” here refers to heating in a stage before the above-described removing step, and thus heating may be performed after the above-described removing step.
- the present invention provides a step of applying the radiation-curable composition on a substrate and drying to obtain a coating film, a step of exposing the coating film via a mask, and a step of exposing the coating film after the exposing step.
- a pattern forming method including a heating step and a step of removing an unexposed portion of a coating film by development after the heating step.
- the present invention provides the above pattern forming method, wherein the coating is heated to 70 to 110 ° C. in the above heating step. Thereby, diffusion of the acid during heating can be further suppressed.
- the present invention provides the above-described pattern forming method, wherein in the above-mentioned exposing step, the coating film is exposed by irradiating a coating film with light of 5-lOOmjZcm 2 .
- the coating film is exposed by irradiating a coating film with light of 5-lOOmjZcm 2 .
- the present invention provides the above pattern forming method, wherein the removing step uses an aqueous solution of tetramethylammonium-dimethylhydroxide as a developing solution. As a result, contamination of the electronic component with the alkali metal during development can be sufficiently suppressed.
- the present invention provides a pattern using method using a pattern formed by the above pattern forming method as a resist mask.
- the present invention provides an electronic component having a pattern formed by the pattern forming method.
- the present invention provides an optical waveguide including a pattern formed by the pattern forming method.
- the present invention provides a method for storing the radiation-curable composition, which stores the radiation-curable composition at a temperature of 0 ° C or lower.
- the storage stability becomes better than when storing the composition at a temperature higher than 0 ° C.
- the amount of exposure is low. Even if the amount is relatively small, it is possible to form a cured product having excellent pattern accuracy, and it is possible to solve the conventional problems that the amount of exposure and the excellent pattern accuracy cannot be achieved at the same time.
- the radiation-curable composition of the present invention can provide a cured product having excellent pattern accuracy even when the exposure amount is relatively small. Therefore, the present invention is useful for a method of using a pattern, an electronic component, and an optical waveguide.
- FIG. 1 is a schematic sectional view showing a preferred embodiment of an electronic component according to the present invention.
- FIG. 2 is an SEM photograph showing a pattern shape according to an example of the present invention.
- FIG. 3 is an SEM photograph showing a pattern shape according to a comparative example of the present invention.
- the component (a) is a siloxane resin, and a known resin can be used, but it is preferable that the resin has an OH group at a terminal or a side chain. This is for further promoting the hydrolysis-condensation reaction for curing the radiation-curable composition.
- the siloxane resin has a weight average molecular weight (Mw) force of 500 to 1,000,000, preferably S to 500 to 500,000, from the viewpoint of solubility in a solvent, mechanical properties, moldability, and the like. More preferably, the force is 500-100,000, even more preferably, the force is 500-10000, and S is particularly preferably 500-5000. If the weight average molecular weight is less than 500, the film formability of the cured product tends to be inferior, and if the weight average molecular weight exceeds 1,000,000, the compatibility with the solvent tends to decrease. In this specification, the weight average molecular weight is measured by gel permeation chromatography (hereinafter, referred to as “GPC”) and converted using a standard polystyrene calibration curve.
- GPC gel permeation chromatography
- the weight average molecular weight (Mw) can be measured by, for example, GPC under the following conditions.
- Standard polystyrene Standard polystyrene manufactured by Tosoh Corporation (molecular weight: 190,000, 17900)
- siloxane resin for example, the following general formula (1);
- R 1 is an H atom or an F atom, or a group containing a B atom, an N atom, an A1 atom, a P atom, a Si atom, a Ge atom, or a Ti atom, or an organic group having 1 to 20 carbon atoms.
- X represents a hydrolyzable group; n represents an integer of 0-2; when n is 2, each R 1 is the same or different When X is SO-2, each X may be the same or different.
- Examples of the hydrolyzable group X include an alkoxy group, a halogen atom, an acetoxy group, an isocyanate group, and a hydroxyl group.
- an alkoxy group is preferable in terms of the liquid stability of the composition itself, the coating properties, and the like.
- Examples of the compound (alkoxysilane) of the general formula (1) in which the hydrolyzable group X is an alkoxy group include tetraalkoxysilane, trialkoxysilane, and diorganodialkoxysilane.
- tetraalkoxysilane for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane
- trialkoxysilanes include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropanesilane, Methyl tree iso-propoxy silane, methyl tree n-butoxy silane, methyl tree iso-butoxy silane, methyl tree tert-butoxy silane, methyl triphenoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, ethyl tri- n —propoxy silane, ethyl tree iso-propoxysilane, ethyltri- n -butoxysilane, ethyl-iso-butoxysilane, ethyl-tri-tert-butoxysilane, ethyl-triphenoxy
- diorganodialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethinoresipropoxysilane, dimethinoresi isopropoxysilane, dimethyldi-n-butoxysilane, dimethyldisec-butoxysilane, dimethylditert-butoxysilane, dimethyisilane Noresiphenoxysilane, Jetinoresimethoxysilane, Jetinoresiediethoxysilane, Jetinoresipropoxysilane, Jetinoresi isopropoxysilan, Jetirzy n -butoxysilane, Jetirzy sec butoxysilane, Jetirzy tert butoxysilane, Jetinoresphenoxysilane, G-propynolexy methoxysilane, g-propyl propyl ethoxysilane, g-propyl propyl n-propoxysilane, g-
- R 1 is an organic group having 1 one 20 carbon atoms (1), as the compound other than the above, for example, bis (trimethoxysilyl) methane, bis (triethoxysilyl ) Methane, bis (tree n propoxysilyl) methane, bis (tree isopropoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (tree n propoxysilyl) ethane, bis (tree n isopropoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) propane, bis (tri-n-propoxysilyl) propane, bis (tri-isopropoxysilyl) propane, bis (trimethoxysilyl) benzene, bis (Triethoxysilyl) benzene, bis (tree n
- Examples of the compound of the general formula (1) in which R 1 is a group containing a Si atom include, for example, hexamethoxydisilane, hexetoxydisilane, hexanol n-propoxydisilane, hexar isopropoxydisilane, and the like.
- dialkyltetraalkoxydisilanes such as orchids.
- Examples of the compound (halogenated silane) of the general formula (1) in which the hydrolyzable group X is a halogen atom (halogen group) include, for example, the case where the alkoxy group in each of the above-mentioned alkoxysilane molecules is a halogen atom. And those substituted with an atom.
- examples of the compound (acetoxysilane) of the general formula (1) in which the hydrolyzable group X is an acetyloxy group include, for example, those in which the alkoxy group in each of the above-mentioned alkoxysilane molecules is substituted with an acetyloxy group. I can do it.
- the compound (isocyanate silane) of the general formula (1) in which the hydrolyzable group X is an isocyanate group for example, the compound represented by the above formula (1) is substituted with an alkoxy group and a sulfur isocyanate group in each alkoxysilane molecule described above. And the like.
- examples of the compound (hydroxysilane) of the general formula (1) in which the hydrolyzable group X is a hydroxyl group include, for example, those in which the alkoxy group in each of the above alkoxysilane molecules is substituted with a hydroxyl group. Is mentioned.
- a resin obtained by hydrolyzing and condensing a partial condensate such as a polymer of the compound represented by the general formula (1), a portion of a polymer such as the polymer of the general formula (1)
- Fats, resins obtained by hydrolyzing and condensing a partial condensate such as a polymer of a compound represented by the general formula (1) with a compound represented by the general formula (1) and other compounds. Can also be used.
- Examples of the partial condensate such as a multimer of the compound represented by the general formula (1) include, for example, hexamethoxydisiloxane, hexaethoxydisiloxane, hexa-n-propoxydisiloxane, hexaiso- Hexaalkoxydisiloxane such as propoxydisiloxane, trisiloxane, tetrasiloxane, oligosiloxane, etc., with advanced partial condensation are included.
- Examples of the "other compound” include a compound having a polymerizable double bond or triple bond.
- Compounds having a polymerizable double bond include, for example, ethylene, propylene, isobutene, butadiene, isoprene, butyl chloride, butyl acetate, butyl propionate, butyl caproate, butyl stearate, methyl butyl ether, Ruby ether, propyl butyl ether, acrylonitrile, styrene, methacrylic acid
- the resin thus obtained is used alone or in combination of two or more.
- the amount of water used for hydrolyzing and condensing the compound represented by the general formula (1) is preferably 0.1 to 1000 mol per mol of the compound represented by the general formula (1). Even more preferably 0.5-100 moles.
- the amount of water is less than 0.1 mol, the hydrolysis-condensation reaction does not tend to proceed sufficiently, and when the amount of water exceeds 1000 mol, gelling tends to occur during hydrolysis or condensation.
- a catalyst in the hydrolytic condensation of the compound represented by the general formula (1).
- examples of the type of such a catalyst include an acid catalyst, an alkali catalyst, and a metal compound.
- Examples of the acid catalyst include organic acids and inorganic acids.
- Organic acids include, for example, formic acid, maleic acid, fumaric acid, phthalic acid, malonic acid, succinic acid, tartaric acid, malic acid, lactic acid, citric acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptaic acid Acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, adipic acid, sebacic acid, butyric acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzenesulfonic acid, benzoic acid, P-aminobenzoic acid , P-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulf
- hydrochloric acid for example, hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid, hydrofluoric acid and the like can be mentioned. These are used alone or in combination of two or more.
- Examples of the alkali catalyst include an inorganic alkali and an organic alkali.
- the inorganic alkali examples include sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and the like.
- the organic alkali for example, pyridine, monoeta Nolamine, diethanolamine, triethanolamine, dimethyl monoethanolamine, monomethyl ethanolamine, ammonia, tetramethylammonium hydroxide oxide, tetraethylammonium hydroxide oxide, tetrapropylammonium hydroxide oxide, Methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, norylamine, decylamine, pendecacilamine, dodecacilamine, cyclopentylamine, cyclohexylamine, N, N-dimethylamine, N, N-ethylamine , N-dipropylamine, N, N-dibut
- metal chelate conjugates examples include trimethoxy'mono (acetylacenate) titanium, triethoxy'mono (acetylacenate) titanium, tree n-propoxy mono (acetylacenate) titanium, and tree iso-propoxy.
- the material may be affected by corrosion or the like.
- the catalyst may be removed from the composition or reacted with another compound to deactivate the function as a catalyst.
- the hydrolyzate obtained from the compound represented by the general formula (1) may be extracted from the composition by reprecipitation or the like.
- a method of deactivating the function as a catalyst by a reaction for example, when the catalyst is an alkali catalyst, a method of adding an acid catalyst and neutralizing the acid by an acid-base reaction or adjusting the pH to an acidic side.
- the amount of the catalyst to be used is preferably in the range of 0.0001-1 mol per 1 mol of the compound represented by the general formula (1). If the amount is less than 0.0001 mol, the reaction does not substantially proceed, and if it exceeds 1 mol, gelling tends to be promoted during hydrolysis and condensation. In the direction.
- the alcohol by-produced by this hydrolysis is a protic solvent, it is preferable to remove the alcohol using an evaporator or the like.
- the resin thus obtained has a weight-average molecular weight of 500 to 1,000,000, preferably S, and more preferably 500 to 500,000. More preferably, the force is 500-100,000, more preferably, the force is 500-10000, and particularly preferably, 500-5000. If the weight average molecular weight is less than 500, the film formability of the cured product tends to be inferior, and if the weight average molecular weight exceeds 1,000,000, the compatibility with the solvent tends to decrease.
- H atom, F atom, B atom, N atom, A1 atom, P atom, and Si atom are used for 1 mole of Si atom in general formula (1).
- Ge atom, Ti atom, and C atom the total content of at least one atom selected from the group consisting of the total number (M) of specific bonding atoms (R 1 in general formula (1)) ) Is preferably 1.3-0.2 mol, more preferably 1.0-0.2 mol, and particularly preferably 0.90-0.2 mol. It is very preferable that the amount is 0.8-0.2 mol. By doing so, it is possible to suppress a decrease in adhesiveness and mechanical strength of the cured product to another film (layer).
- the dielectric properties when the cured product is used as an insulating film tend to be inferior. It tends to have poor adhesion to other films (layers) and mechanical strength.
- at least one selected from the group consisting of H atoms, F atoms, N atoms, Si atoms, Ti atoms, and C atoms in terms of film formability of the cured product It is preferable to include at least one kind of atom whose group force is selected from the group consisting of H atom, F atom, N atom, Si atom and C nuclear atom in terms of dielectric properties and mechanical strength. More preferably, it is included.
- the total number (M) of the specific bonding atoms can be determined by the charged amount of the siloxane resin.
- the following formula (A) is the following formula (A).
- Ml is the total number of atoms that are bonded to a single (and only one) Si atom of a particular bond atom
- M2 is the Indicates the total number of atoms bonded to two silicon atoms
- M3 indicates the total number of atoms bonded to three of the specific bonded atoms
- Msi indicates the total number of Si atoms .
- Such siloxane resins are used alone or in combination of two or more.
- a method of combining two or more siloxane resins for example, a method of combining two or more siloxane resins having different weight average molecular weights, or two methods obtained by hydrolyzing and condensing different compounds as essential components A method of combining the above siloxane resins is exemplified.
- the component (b) is a photoacid generator or a photobase generator, and upon irradiation, releases an acid active substance or a basic active substance capable of photocuring (hydrolytic polycondensation) the component (a). It is defined as a compound that can be issued.
- Examples of the photoacid generator include diaryl sulfonium salt, triaryl sulfonium salt, dialkylphenacyl sulfonium salt, diallydonium salt, aryl diazonium salt, and aromatic.
- Examples of the photobase generator include a compound group represented by the following general formulas (2) to (5), a nonionic photobase generator such as nifedipine, a cobalt amine complex, (6), ionic photobase generators such as quaternary ammonium salts represented by the following general formula (7), and the like. These are used alone or in combination of two or more. Also, they can be used in combination with other sensitizers and the like.
- R 3 and m have the same meanings as in the above formula (2), and R 4 and R 5 each independently represent a monovalent organic group having 130 carbon atoms, and To form a ring structure.
- R 2 has the same meaning as in general formula (2) above, and R 6 and R 7 each independently represent a monovalent organic group having 110 to 130 carbon atoms, V may form the structure, or either one of them may be a hydrogen atom.
- R. And R 7 have the same meanings as in the above general formula (4), and R 8 represents a monovalent organic group having 130 to 130 carbon atoms, and an alkoxy group, a nitro group, an amino group, an alkyl-substituted amino group on the side chain.
- R 9 which may contain an aromatic ring having an alkylthio group is a divalent organic group having 1 to 30 carbon atoms.
- R 11 and R 12 each independently represent a monovalent organic group having 1 to 30 carbon atoms or a hydrogen atom
- X 1 represents Any of the following general formulas (6A), (6B), (6C), (6D), (6E), and (6F) (hereinafter referred to as “(6A) — (6F)”).
- R 13 , R 14 , R 15 and R 16 each independently represent a monovalent organic group having 130 carbon atoms
- R 17 , R 18 and R 19 each independently represent 1 carbon atom. It represents 30 divalent organic groups or single bonds
- R 2G and R 21 each independently represent a trivalent organic group having 130 carbon atoms.
- R, R and R, Z—, t, p, and q are the same as those in the above general formula (6), and X 2 is any of the following general formulas (7A) to (7D) Represents a divalent group represented by [0073]
- R 13 , R “, R 15 , R 16 , R 17 , R 18 , R 19 , R 2 ° and R 21 have the same meanings as those in the general formula (6A)-(6F). is there.
- R NI may be a photoacid generator or a photo salt to be used.
- the range is wide because it depends on the sensitivity and efficiency of the base generator, the light source used, the desired thickness of the cured product, and the like.
- the amount of the component (b) used is preferably 0.0001 to 50% by weight based on the total amount of the component (a) in the radiation-curable composition, and 0.0001 to 20% by weight. Is more preferably 0.01 to 10% by weight. If the amount is less than 0.0001% by weight, the photocurability tends to decrease or a large amount of exposure is required for curing. If the amount exceeds 50% by weight, the stability of the composition and film formation are increased. The properties tend to be inferior, and the electrical properties and process compatibility of the cured product tend to decrease.
- a photosensitizer may be used in combination with the above-described photoacid generator or photobase generator.
- the photosensitizer By using the photosensitizer, the energy ray of radiation can be efficiently absorbed, and the sensitivity of the photoacid generator or photobase generator can be improved.
- the photosensitizer include an anthracene derivative, a perylene derivative, an anthraquinone derivative, a thioxanthone derivative, and coumarin.
- the radiation-curable composition is stored in two parts for the purpose of improving storage stability, it is preferable to store the component (b) and the component (a) separately.
- the radiation-curable composition When the radiation-curable composition is stored as a single solution, it is preferable to store the radiation-curable composition at a temperature of 0 ° C or lower, for example.
- the lower limit of this temperature is determined by the condensation of the solvent in the radiation-curable composition. It is preferable that the temperature is not less than the solid point, and it is preferable that the temperature is ⁇ 50 ° C.
- the component (c) is a solvent capable of dissolving the component (a), and includes, for example, an aprotic solvent and a protic solvent, and preferably contains an aprotic solvent.
- an aprotic solvent may be effective in reducing the amount of exposure and improving the pattern accuracy.
- a protic solvent represented by an alcohol has a hydrogen atom bonded to an oxygen atom having a high electronegativity.
- the protic solvent molecules form hydrogen bonds with nucleophiles and solvate. That is, since the protic solvent solvates with the siloxane resin obtained by hydrolyzing the compound represented by the general formula (1), the solvent must be capable of removing this solvent molecule in order for the siloxane resin to condense. Therefore, it is considered that curing at low temperature tends to be hindered.
- an aprotic solvent is a solvent having no hydrogen atom on an element having a high electronegativity, and is considered to have a smaller factor of inhibiting the reaction than a protic solvent. Therefore, in the exposed area, the curing reaction proceeds with the generation of acidic active substances and basic active substances, and it is considered that pattern precision tends to be improved, where pattern precision is unlikely to decrease due to diffusion of acids and bases. This is different from the mechanism of improving the pattern accuracy by inactivating (neutralizing) the acid generated by the conventional acid diffusion controller. Accordingly, it is considered that when the aprotic solvent is contained in the component (c), the effects of improving the pattern accuracy and reducing the exposure amount are more effectively exerted.
- Examples of the aprotic solvent contained in the component (c) include acetone, methylethylketone, methyl-n-propylketone, methyl-iso-propylketone, methyl-n-butylketone, methyl-iso-butylketone, methyl-n-pentylketone, Kishiruketon to methyl-n-, di Echiruketon, dipropyl ketone, Gee iso- butyl ketone, trimethyl Roh Nanon, cyclohexane key Sanon, cyclohexanone cyclopentanone, methylcyclohexane, 2, 4-pentanedione, Asetoniru acetone, .gamma.
- ether solvents Preferred are ether solvents, ester solvents, ether acetate solvents and ketone solvents. Further, it is preferable that the solvent does not have a nitrogen atom. Among these, the inventors believe that ether acetate solvents are preferred first, ether solvents are preferred second, and ketone solvents are preferred third. These are used alone or in combination of two or more.
- component (c) is soluble in water or water. It is preferable that the compound has both water solubility and water solubility, which are preferable. Therefore, when the aprotic solvent has no solubility in water or has no solubility in water, it is preferable to add a protic solvent. When the aprotic solvent has poor solubility in water or water, and does not contain a protic solvent, the compatibility of the component (a) with the solvent tends to decrease, and the stability tends to decrease. When sensitivity is required even if the stability is somewhat sacrificed, it is better to use less protic solvent.
- Examples of such a protic solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, and 2-methyl.
- the proportion of the aprotic solvent used is preferably 50% by weight or more of the total solvent. More preferably, it is at least 90% by weight, particularly preferably at least 95% by weight. If the use ratio is small, the exposed portion tends not to be sufficiently cured when the exposure amount is small. Alternatively, if the use ratio is small, a heat treatment at a higher temperature is required to sufficiently cure, and the generated acid or base is easily diffused, and the pattern accuracy tends to deteriorate.
- the method of using the component (c) is not particularly limited.
- a method of using the component (a) as a solvent for preparing the component a method of adding the component (a) after preparation, and a method of exchanging the solvent.
- removing the components by distilling off the solvent and adding (c) a solvent a solvent.
- the radiation-curable composition of the present invention may contain water as necessary, but may preferably contain water, but is preferably in a range that does not impair desired properties.
- the amount of water used is preferably 10% by weight or less, more preferably 5% by weight or less, more preferably 2% by weight or less, based on the total amount of the radiation-curable composition. preferable. If the water usage exceeds 10% by weight, the applicability and the stability of the coating solution tend to deteriorate. Although the details are not clear, it is possible to reduce the exposure amount by adding a little water.
- the amount of the solvent (the sum of the aprotic solvent and the protic solvent) used is preferably such that the concentration of the component (a) (siloxane resin) is 3 to 60% by weight. . If the amount of the solvent is too large and the concentration of the component (a) is less than 3% by weight, it tends to be difficult to form a cured product having a desired film thickness. If the amount of the solvent is too small and the concentration of the component (a) is 60% by weight. %, The film formability of the cured product and the like tend to deteriorate, and the stability of the composition itself tends to decrease.
- the component (d) in the present invention is a curing accelerating catalyst, and when added to the radiation-curable composition, reduces the amount of photoacid generator or photobase generator, reduces the amount of exposure, or reduces the amount of PEB. It is considered that the effect of lowering the temperature can be expected.
- This curing accelerating catalyst is different from a usual photoacid generator or photobase generator which generates an active substance by the light of the component (b). Therefore, they are usually distinguished from hondium salts used as photoacid generators or photobase generators. However, any material having both photoacid generating ability or photobase generating ability and curing promoting catalytic ability can be used.
- the catalyst does not show a catalytic action in a solution, but is active in the coated film after application.
- the curing reaction by the curing accelerating catalyst progresses along with the generation of acidic active substances and basic active substances.Therefore, it is more difficult for the pattern accuracy to decrease due to the diffusion of acids and bases. Presumed.
- a composition comprising component (a) and component (c) is prepared.
- composition prepared in 1 above was added with 0.01% by weight, based on the total amount of component (a), of a compound whose curing promoting catalytic ability was to be confirmed, to obtain the composition.
- Examples of the curing-promoting catalyst that is the component (d) include alkali metals such as sodium hydroxide, sodium chloride, potassium hydroxide, potassium chloride, and the like, and potassium salts. Can be These are used alone or in combination of two or more.
- quaternary ammonium salts are preferred from the viewpoint that the electrical properties and mechanical strength of the obtained cured product can be improved and the stability of the composition can be enhanced. It is more preferable to be salt! / ,.
- one of the polymer salt conjugates for example, at least one selected from (d-1) a nitrogen-containing compound, (d-2) an ionic group-containing compound, and a halogen atom And salts formed from
- the atoms bonded on the nitrogen of the (d-1) nitrogen-containing compound are H atom, F atom, B atom, N atom, A1 atom, P atom, Si atom, Ge atom, Ti atom, and C atom. It is preferably at least one selected from the group consisting of atoms.
- the above-mentioned ionic group and Examples thereof include a hydroxyl group, a nitrate group, a sulfate group, a carbonyl group, a carboxyl group, a carbonate group, and a phenoxy group.
- ammonium salt compounds include, for example, ammonium hydroxide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium ammonium iodide.
- ammonium moiety of the above-mentioned ammonium salt compound may be methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, ethylammonium, getylammonium.
- Amm triethylammonium, tetraethylammonium, propylammonium, dipropylammonium, tripropylammonium, tetrapropylammonium, butylammonium, dibutylammonium, Examples thereof include an ammonium salt substituted compound substituted with tributylammonium, tetrabutylammonium, ethanolammonium, diethanolammonium, triethanolammonium and the like.
- tetra-ammonium nitrate tetramethyl-ammonium acetate
- tetramethyl-ammonium-dimethyl propionate are used in these rubber salt conjugates.
- Ammonium salt is preferred.
- the amount of the component (d) used is 0.1% based on the total amount of the component (a) in the radiation-curable composition.
- 0001—preferably 5% by weight 0.000001—1% by weight is more preferable. If this amount is less than 0.0001% by weight, a large amount of exposure tends to be required for curing. If the amount used exceeds 5% by weight, the stability and film formability of the composition tend to be poor, and the electrical properties and process compatibility of the cured product tend to decrease.
- the amount of the curing acceleration catalyst used as the component (d) is 0.0001-0.000 to the total amount of the component (a) in the radiation-curable composition.
- force S preferably 1 wt%, more preferably be force S 0. 0001- is 0.05 weight 0/0, and particularly preferably is 01% by weight 0. 0005- 0.! /,.
- oxalates may be dissolved or diluted in water or a solvent, if necessary, and then added to obtain a desired concentration.
- the timing of addition is not particularly limited. For example, there are times when the component (a) is hydrolyzed, during hydrolysis, at the end of the reaction, before and after the solvent is distilled off, and when an acid generator is added.
- a dye may be added to the radiation-curable composition of the present invention.
- a dye for example, an effect of adjusting sensitivity, an effect of suppressing a standing wave effect, and the like can be obtained.
- a thermally decomposable compound such as a surfactant, a silane coupling agent, a thickener, an inorganic filler, and polypropylene glycol may be used.
- Compounds may be added! It is preferable that the thermally decomposable compound and the volatile compound can be decomposed or volatilized by heat (preferably 250 to 500 ° C.) to form voids.
- the siloxane resin as the component (a) may be provided with a void-forming ability.
- the metal ion in the composition may be used.
- the concentration is preferably 100 ppm or less, more preferably 1 ppm or less.
- the concentration of these metal ions exceeds 100 ppm, the metal ions easily flow into electronic components such as semiconductor elements having a cured product obtained from the composition, and the Performance may itself be adversely affected. Therefore, if necessary, it is effective to remove the alkali metal or alkaline earth metal from the composition using, for example, an ion exchange filter.
- the purpose is not impaired unless the purpose is impaired!
- a method for forming a patterned cured product on a substrate by using such a radiation-curable composition of the present invention will be described by taking, as an example, a spin coating method which is generally excellent in film formability and film uniformity. .
- the method for forming a cured product is not limited to the spin coating method.
- the substrate may have a flat surface, or may have electrodes and the like formed thereon and have irregularities.
- the radiation-curable composition is spin-coated on a substrate such as a silicon wafer or a glass substrate at preferably 500 to 5000 rotations Z, more preferably 500 to 3000 rotations Z to form a film. If the number of rotations is less than 500 rotations Z, the film uniformity tends to be poor, and if it exceeds 5000 rotations Z, the film formability may be poor.
- the film thickness of the cured product differs depending on the intended use.
- the film thickness used for an interlayer insulating film such as an LSI is preferably 0.01-1 / zm when used for a passivation layer.
- the film thickness is preferably 2 to 40 m.
- Thickness for use in liquid crystal applications is preferably 0.1-20 m.
- Thickness for use in photoresists is preferably 0.1-2 m.
- the film thickness at the time of this process be 1-150 m.
- the thickness is generally preferably 0.01-1-10 m, more preferably 0.01-1-5 m, and more preferably 0.01-1-3 m.
- the concentration of the component (a) in the composition may be adjusted.
- the film thickness can be adjusted by adjusting the number of rotations and the number of coatings.
- the concentration of the component (a) is controlled by adjusting the concentration of the component (a), for example, when increasing the film thickness, the concentration of the component (a) is increased, and when decreasing the film thickness, the component (a) is used.
- the spin coating method for example, when the film thickness is increased, the number of rotations is reduced, or when the number of coatings is increased, and when the film thickness is reduced, the rotation speed is reduced. Adjust by increasing the number or reducing the number of applications Can do.
- the solvent in the coating is dried on a hot plate or the like at preferably 50 to 200 ° C, more preferably 70 to 150 ° C, and the coating dissolves under various conditions during the subsequent development. It is necessary to adjust the drying temperature as follows. If the drying temperature is lower than 50 ° C, the solvent tends to be insufficiently dried. If the drying temperature is higher than 200 ° C, the solvent does not dissolve during development and a pattern may not be formed.
- radiation is exposed through a mask having a desired pattern.
- this dose is 2 particularly preferred instrument 5-LOOmjZcm be a signaling 5-500MjZcm 2 and more preferable is that preferred instrument 5-LOOOmjZcm 2 be 5-5000MjZcm 2 .
- the exposure amount is less than 5 mjZcm 2 , it may be difficult to control depending on the light source, and if it exceeds 5000 mjZcm 2 , the exposure time becomes longer and the productivity tends to deteriorate.
- the exposure amount of a conventional general siloxane-based radiation curable composition is about 500-5 OOOiujZcm 2 .
- the radiation at this time is, for example, a force capable of using visible light, ultraviolet light, infrared light, X-ray, ⁇ -ray, j8-ray, ⁇ -ray, or the like, particularly preferably ultraviolet light.
- the ultraviolet light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metalno, a ride lamp, an excimer lamp and the like.
- the unexposed area has sufficient solubility in the developing solution, but the exposed area generates an acidic active substance or a basic active substance, and a hydrolytic condensation reaction occurs, resulting in poor solubility in the developing solution. descend. Thereby, a pattern is formed.
- a heating step (post-Etas plunger bake: ⁇ ) may be followed by additional heating.
- This heating is for heating the film with a hot plate or the like.
- the heating is preferably performed in a temperature range where the solubility of the unexposed portion in the developing solution does not decrease. This temperature is preferably 50-200 ° C 70-150 ° C is more preferable 70-110 ° C is particularly preferable 70-100 ° C Is very preferred. Generally, the higher the temperature, the easier the generated acid is to diffuse, so the lower the temperature, the better.
- the heating temperature of the conventional general siloxane radiation curable composition in the PEB step is about 115 to 120 ° C.
- a developing solution such as an alkaline aqueous solution
- the alkaline aqueous solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, etc .; primary amines such as ethylamine, n-propylamine, etc .; secondary amines such as n-propylamine; tertiary amines such as triethylamine and methylethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; tetramethylammonium-dimethyl hydroxide ( Quaternary ammonium salts such as TMAH), tetraethylammonium and idroxide.
- TMAH tetraethylammonium and idroxide
- an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or a surfactant to these alkaline aqueous solutions can also be used. Since electronic parts do not like the contamination of alkali metals, tetramethylammonium-dumno and an aqueous solution of idroxide are preferred as the developer.
- a suitable development time depends on the film thickness and the solvent, but is preferably 5 seconds to 5 minutes, more preferably 30 seconds to 13 minutes, and more preferably 30 seconds to 1 minute. Is particularly preferred. If the development time is less than 5 seconds, it may be difficult to control the time on the entire surface of the wafer or the substrate, and if it exceeds 5 minutes, the productivity tends to deteriorate.
- the processing temperature during development is generally 20-30 ° C.
- a developing method for example, a method such as spraying, paddle, dipping, and ultrasonic wave can be used.
- the pattern formed by development can be rinsed with distilled water or the like as necessary.
- the cured product patterned according to the present invention can be used as it is as a resist mask.
- the cured product patterned according to the present invention is left as an interlayer insulating film, a clad layer, or the like, for example, it is preferable to perform final curing by baking the coating at a heating temperature of 100 to 500 ° C. This final curing is performed in the atmosphere or under reduced pressure in an inert atmosphere such as N, Ar, or He.
- the heating temperature is lower than 100 ° C, sufficient curing tends not to be achieved, and the electrical insulation tends to be poor. If the heating temperature exceeds 500 ° C, the material used for the lower layer may be deteriorated.
- the heating time for final curing is preferably 2 to 240 minutes, and is preferably 2 to 120 minutes. More preferably. If the heating time exceeds 240 minutes, it may not be suitable for mass production.
- the heating device include a furnace such as a quartz tube furnace, a hot plate, and a heat treatment device such as a rabbit thermal annealing (RTA).
- Examples of an electronic component that is a use example having a hardened product include a device having an insulating film such as a semiconductor element and a multilayer wiring board.
- an insulating film such as a semiconductor element
- a multilayer wiring board it can be used as an interlayer insulating film.
- the semiconductor element for example, an individual semiconductor such as a diode, a transistor, a compound semiconductor, a thermistor, a noristor, and a thyristor, a DRAM (dynamic "random access” memory), and an SRAM (static random access “memory”) , EPROM (erasable programmable read-only memory), mask ROM (mask read-only memory), EEPROM (electrically erasable programmable read-only memory), flash memory, etc.
- an individual semiconductor such as a diode, a transistor, a compound semiconductor, a thermistor, a noristor, and a thyristor, a DRAM (dynamic "random access” memory), and an SRAM (static random access "memory”)
- EPROM erasable programmable read-only memory
- mask ROM mask read-only memory
- EEPROM electrically erasable programmable read-only memory
- flash memory etc.
- Storage elements microprocessors, logic circuit elements such as DSPs and ASICs, integrated circuit elements such as compound semiconductors represented by MMICs (monolithic 'microwave integrated circuits), hybrid integrated circuits (hybrid ICs), light-emitting diodes, charge-coupled devices Photoelectric conversion elements such as elements .
- MMICs monolithic 'microwave integrated circuits
- hybrid ICs hybrid integrated circuits
- Photoelectric conversion elements such as elements .
- Examples of the multilayer wiring board include a high-density wiring board such as an MCM.
- FIG. 1 is a schematic end view showing an embodiment of a TFT (thin film transistor) according to the present invention, which is an electronic component provided in a TFT liquid crystal display.
- a conductive layer 3 also having a polysilicon force is provided on an undercoat film 2 formed on a glass substrate 1, and a source 4 and a drain 5 are sandwiched between the conductive layers 3 in an in-plane direction.
- a gate electrode is formed on the conductive layer 3 via a gate oxide film 6 made of SiO.
- the gate oxide film 6 is provided so as not to bring the conductive layer 3 into direct contact with the gate electrode 7.
- the undercoat film 2, the conductive layer 3, the source 4, the drain 5, the gate oxide film 6, and the gate electrode 7 are covered with a first interlayer insulating film 8 to prevent a short circuit.
- a part of the first interlayer insulating film 8 is removed at the time of forming the TFT, and the metal wiring 9 is drawn out while being connected to the source 4 and the drain 5 respectively.
- the metal wiring 9, which is drawn out in a state of being connected to the drain 5, is electrically connected to the transparent electrode 11, and the other parts are not short-circuited so as not to be short-circuited. It is covered with.
- the cured film obtained from the radiation-curable composition of the present invention may be mainly used as the second interlayer insulating film 10 for the first interlayer insulating film 8 provided in the TFT. .
- These interlayer insulating films 8 and 10 are formed, for example, as follows. First, the radiation-curable composition of the present invention is applied on a substrate by a spin coating method or the like and dried to obtain a coating film. Next, the coating film is exposed through a mask having a predetermined pattern to expose a predetermined portion (a portion other than the portion where the metal wiring 9 is to be formed in the case of the first interlayer insulating film 8, and a transparent electrode in the case of the second interlayer insulating film 10).
- interlayer insulating films 8 and 10 may have the same composition or different compositions.
- the radiation-curable composition was used until the photocurable composition or the photobase generator was not developed until the step of developing the radiation-curable composition was completed.
- the work was performed in an environment that did not include the photosensitive wavelength of the photobase generator and the sensitizer.
- the amount of component (a) used was 15% by weight based on the total amount of the radiation-curable composition, and the amount of component (b) was 1.9% by weight based on the total amount of the radiation-curable composition.
- the amount of component (d) used was 0.075% by weight based on the total amount of the radiation-curable composition.
- TMAH tetramethylammonium - ⁇ beam Hydro O sulfoxide
- Tetraethoxysilane 96. 13 g and a methylolmelamine Honoré triethoxysilane 165. 44 g and the propylene glycol 3 one Honoré methylcarbamoyl Honoré ether Honoré Seteto 562. 99 g [This dissolved the solution [This, prepared 0.644 wt 0/0 18.9 g of an aqueous tetramethylammonium nitrate solution (PH3.6) adjusted to 75.47 g of the prepared nitric acid and 2.38% by weight were added dropwise over 5 minutes with stirring.
- PH3.6 aqueous tetramethylammonium nitrate solution
- the amount of component (a) used was 20% by weight based on the total amount of the radiation-curable composition, and the amount used of component (b) was 0.4% by weight based on the total amount of the radiation-curable composition.
- the amount of the component (d) used was 0.1% by weight based on the total amount of the radiation-curable composition.
- the wafer was immersed in a developing solution consisting of an aqueous solution of tetramethylammonium-palladium hydroxide (TMAH) by weight for 30 seconds to perform paddle development to dissolve unexposed portions. Thereafter, the wafer was washed with water and spin-dried. Then, using a furnace, the wafer after spin drying was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a radiation cured product on the wafer. Observation of the pattern shape of the radiation-cured product from above using an optical microscope and observation of the cross-sectional shape using an SEM revealed that the lines were formed accurately and that the pattern accuracy was 2 m.
- Figure 2 shows an SEM photograph of the cross-sectional shape.
- a radiation-curable composition was prepared by mixing 0.40 g of a photobase generator (NBC-101, manufactured by Midori Kagaku) with 10. Og of the polysiloxane solution for radiation-curable composition obtained in Example 2. .
- the amount of the component (a) used was 20% by weight based on the total amount of the radiation-curable composition, and the amount used of the component (b) was 0.4% by weight based on the total amount of the radiation-curable composition.
- the amount of the component used was 0.1% by weight based on the total amount of the radiation-curable composition.
- Polysiloxane solution for radiation-curable composition obtained in Example 2. 10. Og in 0.040 g of photoacid generator (PAI-101, manufactured by Midori Kagaku Co., Ltd.), and polypropylene glycol as a thermally degradable conjugate (Aldrich, PPG725) was mixed with 0.5 g to prepare a radiation-curable composition.
- the amount of the component (a) used was 20% by weight based on the total amount of the radiation-curable composition, and the amount used of the component (b) was 0.4% by weight based on the total amount of the radiation-curable composition.
- the amount of component (d) used was 0.1% by weight based on the total amount of the radiation-curable composition.
- the radiation-curable composition was dropped in a volume of 2 mL at the center of a 6-inch silicon wafer, and a coating film was formed on the wafer by a spin coating method (700 rotations, Z minutes and 30 seconds rotation). Dry on a hot plate at 30 ° C. for 30 seconds. Then, the exposed coating film was exposed to UV light through an exposure machine (FPA-3000 iW, manufactured by Canon Inc.) through a negative mask having a line pattern with a minimum line width of 2 m. cm 2 was irradiated.
- FPA-3000 iW manufactured by Canon Inc.
- TMAH tetramethylammonium hydroxide
- the thickness of the radiation cured product was 3.0 m, but no defects such as cracks were observed. Observation of the pattern shape of the radiation-cured material using an optical microscope and observation of the cross-sectional shape using an SEM revealed that the lines were formed with high accuracy and that the pattern accuracy was 2 m.
- a photoacid generator (PAI-1001, manufactured by Midori Kagaku) was mixed with 10. Og of the polysiloxane solution for radiation-curable composition to prepare a radiation-curable composition.
- the amount of component (a) used was 15% by weight based on the total amount of the radiation-curable composition, and the amount of component (b) was 1.5% by weight based on the total amount of the radiation-curable composition.
- TMAH Hydro O sulfoxide
- the development was performed in the same manner as in Comparative Example 1 except that the exposure to ultraviolet light of 200 mjZcm 2 was changed to that of ultraviolet light of 100 mJZ cm 2 .
- the wafer was washed with water and spin-dried. And the furnace body The spin-dried wafer was heated at 350 ° C for 30 minutes in a nitrogen atmosphere to obtain a radiation-cured product.
- Observation of the pattern shape of the radiation-cured product from above by an optical microscope and observation of its cross-sectional shape by SEM showed that although a line with a width of 10 / zm was formed, the shape was not good.
- Figure 3 shows an SEM photograph of the cross-sectional shape.
- a photoacid generator (PAI-1001, manufactured by Midori Kagaku) was added to 10. Og of the polysiloxane solution for the radiation-curable composition, but the solution was dissolved.
- the amount of component (a) used was 20% by weight based on the total amount of the radiation-curable composition, and the amount of component (b) was 1.5% by weight based on the total amount of the radiation-curable composition.
- Table 1 shows the results of Examples 14 to 14 and Comparative Examples 13 to 13 described above.
- Example 2 When the radiation-curable composition obtained in Example 2 was stored in an atmosphere at 20 ° C for 30 days, the storage stability was higher than that when the same radiation-curable composition was stored in an atmosphere at room temperature for 30 days. Excellent! The radiation-curable composition stored in an atmosphere at 20 ° C could be puttered after storage for 30 days, but the radiation-curable composition stored in an atmosphere at room temperature for 30 days could be stored after 7 days. You can no longer putter Jung. This is considered to be due to the fact that the condensation of the siloxane resin progressed in the radiation-curable composition stored for 7 days in an atmosphere at normal temperature, and water was generated accordingly.
- the present invention is useful for a method of using a pattern, an electronic component, and an optical waveguide.
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EP04792149A EP1672427A4 (en) | 2003-10-07 | 2004-10-07 | RADIODURCISSABLE COMPOSITION, METHOD FOR STORING THE SAME, METHOD FOR FORMING CURED FILM, METHOD FOR FORMING PATTERN, METHOD FOR USING PATTERN, ELECTRONIC COMPONENT, AND OPTICAL WAVEGUIDE |
JP2005511732A JP3758669B2 (ja) | 2003-10-07 | 2004-10-07 | 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路 |
US11/166,415 US7297464B2 (en) | 2003-10-07 | 2005-06-27 | Radiation curable composition, storing method thereof, forming method of cured film, patterning method, use of pattern, electronic components and optical waveguide |
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Cited By (15)
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US8901268B2 (en) | 2004-08-03 | 2014-12-02 | Ahila Krishnamoorthy | Compositions, layers and films for optoelectronic devices, methods of production and uses thereof |
JP2007031696A (ja) * | 2005-06-10 | 2007-02-08 | Hitachi Chem Co Ltd | 樹脂組成物、シリカ系被膜及びその製造方法、積層体、並びに、電子部品 |
JP2007031697A (ja) * | 2005-06-10 | 2007-02-08 | Hitachi Chem Co Ltd | 被アルカリ処理被膜形成用組成物、被アルカリ処理被膜及びその製造方法、積層体、反射防止膜、並びに電子部品 |
JP4655914B2 (ja) * | 2005-12-13 | 2011-03-23 | 東レ株式会社 | 感光性シロキサン組成物、それから形成された硬化膜、および硬化膜を有する素子 |
JP2007163720A (ja) * | 2005-12-13 | 2007-06-28 | Toray Ind Inc | 感光性シロキサン組成物、それから形成された硬化膜、および硬化膜を有する素子 |
US8158981B2 (en) | 2006-09-25 | 2012-04-17 | Hitachi Chemical Company, Ltd. | Radiation-sensitive composition, method of forming silica-based coating film, silica-based coating film, apparatus and member having silica-based coating film and photosensitizing agent for insulating film |
JP2010117439A (ja) * | 2008-11-11 | 2010-05-27 | Jsr Corp | ポジ型感放射線性組成物、硬化パターン形成方法及び硬化パターン |
JP2010243773A (ja) * | 2009-04-06 | 2010-10-28 | Sanyo Chem Ind Ltd | 光塩基発生剤を含有する感光性組成物 |
JP2010282031A (ja) * | 2009-05-01 | 2010-12-16 | Jsr Corp | ネガ型感放射線性組成物、硬化パターン形成方法及び硬化パターン |
JP2011026495A (ja) * | 2009-07-28 | 2011-02-10 | Asahi Kasei E-Materials Corp | ポリオルガノシロキサンの保存方法 |
JP2011048200A (ja) * | 2009-08-27 | 2011-03-10 | Jsr Corp | ネガ型感放射線性組成物、硬化パターン形成方法及び硬化パターン |
US8864898B2 (en) | 2011-05-31 | 2014-10-21 | Honeywell International Inc. | Coating formulations for optical elements |
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US9411231B2 (en) | 2011-10-12 | 2016-08-09 | Central Glass Company, Limited | Silane composition and cured film thereof, and method for forming negative resist pattern using same |
US9638998B2 (en) | 2011-10-12 | 2017-05-02 | Central Glass Company, Limited | Silane composition and cured film thereof, and method for forming negative resist pattern using same |
JP2014126717A (ja) * | 2012-12-26 | 2014-07-07 | Tokyo Ohka Kogyo Co Ltd | 感光性樹脂組成物 |
JP2017504174A (ja) * | 2014-01-16 | 2017-02-02 | ヒューネット プラスHunet Plus | 有機電子素子及びその製造方法 |
US10411221B2 (en) | 2014-01-16 | 2019-09-10 | Hunet Plus | Organic electronic device and fabrication method thereof |
US10544329B2 (en) | 2015-04-13 | 2020-01-28 | Honeywell International Inc. | Polysiloxane formulations and coatings for optoelectronic applications |
Also Published As
Publication number | Publication date |
---|---|
TWI267703B (en) | 2006-12-01 |
US20050266344A1 (en) | 2005-12-01 |
JP3758669B2 (ja) | 2006-03-22 |
TW200513802A (en) | 2005-04-16 |
EP1672427A4 (en) | 2010-01-13 |
US7297464B2 (en) | 2007-11-20 |
KR20060026839A (ko) | 2006-03-24 |
JPWO2005036270A1 (ja) | 2006-12-21 |
KR100698391B1 (ko) | 2007-03-23 |
EP1672427A1 (en) | 2006-06-21 |
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