WO2020187685A1 - Positive type photosensitive polysiloxane composition - Google Patents
Positive type photosensitive polysiloxane composition Download PDFInfo
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- WO2020187685A1 WO2020187685A1 PCT/EP2020/056648 EP2020056648W WO2020187685A1 WO 2020187685 A1 WO2020187685 A1 WO 2020187685A1 EP 2020056648 W EP2020056648 W EP 2020056648W WO 2020187685 A1 WO2020187685 A1 WO 2020187685A1
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- 0 CC(C)(C)*N(C)O Chemical compound CC(C)(C)*N(C)O 0.000 description 1
Classifications
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
-
- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
-
- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
- G03F7/327—Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts
-
- 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
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a positive type
- the present invention relates to a method for manufacturing a cured film using the same and an electronic device comprising the cured film.
- a material for such a planarization film for a TFT substrate a material combining an acrylic resin with a quinoned iazide compound is known. Since these materials have planarizing properties and photosensitivity, contact holes and other patterns can be formed . However, as resolution and frame frequency are increased, planarization becomes severe due to more complicated wiring, so that it becomes d ifficult for these materials to cope with this problem.
- silsesquioxane As a material having high heat resistance and high transparency, polysiloxane, in particular silsesquioxane, is known.
- Silsesquioxane is polymer composed of a trifunctional siloxane structural unit RSi(Oi.s) and is an intermediate existence between inorganic silica (S1O2) and organic silicone (R2S1O) in terms of chemical structure.
- the cured product thereof is a specific compound having high heat resistance, which is characteristic of inorganic silica.
- a pattern is formed by exposure and development using a positive type photosensitive composition
- a cured film comprising such polysiloxane and a photosensitizer, and a cured film can be formed by heating .
- the film surface does not sometimes become flat and wrinkles may occur.
- a curing auxiliary is sometimes added, or flood exposure is sometimes performed after exposure and development.
- the present invention has been made on the basis of the above-described circumstances, and it is an object of the present invention to provide a positive type
- composition accord ing to the present invention comprises:
- the method for manufacturing a cured film according to the present invention comprises the following processes:
- composition accord ing to the present invention on a substrate to form a composition layer
- composition layer (2) exposing the composition layer
- present invention comprises the cured film manufactured by the above-described method .
- the pattern shape of the cured film can also be made into a shape, which is a shape desirable for subsequent processes and in which an opening part is gentle.
- an anti-reflection plate an optical filter, a high-intensity light-emitting diode, a touch panel, a solar cell and the like, and further as an optical device, such as an optical waveguide.
- an element of a concept can be expressed by a plurality of species, and when the amount (for example, mass% or mol%) is described, it means sum of the plurality of species. "And/or” includes a combination of all elements and also includes single use of the element.
- the hydrocarbon means one including carbon and hydrogen, and optionally including oxygen or nitrogen.
- the hydrocarbyl group means a monovalent or d ivalent or hig her valent hyd rocarbon.
- the aliphatic hydrocarbon means a linear, branched or cyclic aliphatic hydrocarbon
- the aliphatic hyd rocarbon g roup means a monovalent or divalent or hig her valent aliphatic hyd rocarbon.
- the aromatic hyd rocarbon means a hydrocarbon comprising an aromatic ring which may optionally not only comprise an aliphatic hydrocarbon group as a substituent but also be condensed with an alicycle.
- the aromatic hydrocarbon g roup means a monovalent or d ivalent or higher valent aromatic hyd rocarbon.
- the aromatic ring means a hydrocarbon comprising a conjugated unsaturated ring structure
- the alicycle means a hyd rocarbon having a ring structure but comprising no conjugated unsaturated ring structure.
- the alkyl means a g roup obtained by removing any one hydrogen from a linear or branched, saturated hydrocarbon and includes a linear alkyl and branched alkyl
- the cycloalkyl means a g roup obtained by removing one hyd rogen from a saturated hydrocarbon comprising a cyclic structure and optionally includes a linear or branched alkyl in the cyclic structure as a side chain.
- the aryl means a group obtained by removing any one hyd rogen from an aromatic hyd rocarbon.
- the alkylene means a g roup obtained by removing any two hydrogens from a linear or branched, saturated hydrocarbon.
- the arylene means a
- hydrocarbon group obtained by removing any two hydrogens from an aromatic hydrocarbon.
- Ci- 6 alkyl means alkyl having 1 to 6 carbons (such as methyl, ethyl, propyl, butyl, pentyl and hexyl) .
- fluoroalkyl as used in the present specification refers to one in which one or more hyd rogen in alkyl is replaced with fluorine, and the fluoroaryl is one in which one or more hyd rogen in aryl are replaced with fluorine.
- repeating units when polymer has a plural types of repeating units, these repeating units copolymerize. These copolymerization are any of alternating copolymerization, random copolymerization, block copolymerization, g raft copolymerization, or a mixture of any of these.
- Celsius is used as the temperature unit.
- 20 deg rees means 20 deg rees Celsius.
- composition comprises (I) a polysiloxane, (II) a carboxylic acid compound, (III) a diazonaphthoquinone derivative, and (IV) a solvent.
- the structure of polysiloxane used in the present invention is not particularly limited and can be selected from any ones according to the purpose.
- the skeleton structure of polysiloxane can be classified as follows: a silicone skeleton (the number of oxygen atoms bonded to a silicon atom is 2), a silsesquioxane skeleton (the number of oxygen atoms bonded to a silicon atom is 3), and a silica skeleton (the number of oxygen atoms bonded to a silicon atom is 4) . In the present invention, any of these may be used .
- the polysiloxane molecules may contain multiple combinations of these backbone structures.
- the polysiloxane used in the present invention comprises a repeating unit represented by the following formula (la) :
- R Ia is hydrogen, or a Ci-30, linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon g roup,
- the aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxy or alkoxy, and
- methylene is not replaced, or one or more methylene are replaced with oxy, amino, imino or carbonyl, provided that R Ia is not hydroxy or alkoxy) .
- the above-described methylene includes a terminal methyl.
- substituted with fluorine, hyd roxy or alkoxy means that a hydrogen atom directly bonded to a carbon atom in an aliphatic
- hydrocarbon g roup and aromatic hydrocarbon group is replaced with fluorine, hydroxy or alkoxy.
- R Ia includes, for example, (i) alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and decyl, (ii) aryl, such as phenyl, tolyl and benzyl, (iii) fluoroalkyl, such as trifluoromethyl, 2,2,2-trifluoroethyl and
- fluoroalkyl perfluoroalkyl is preferred, and trifluoromethyl and pentafluoroethyl are particularly preferred .
- the compound wherein R Ia is methyl is preferred, since raw material thereof is easily obtained, it has hig h film hard ness after curing and it has high chemical resistance. Further, the compound wherein R Ia is phenyl is preferred, since it increases solubility of the polysiloxane in the solvent and the cured film becomes to hard ly crack. Further, it is preferred that R Ia has hyd roxy, glycidyl, isocyanate or amino, since the ad hesion to the substrate is improved .
- the polysiloxane used in the present invention can further comprise a repeating unit represented by the following formula (lb) :
- R Ib is a group obtained by removing plural hydrogen from a nitrogen and/or oxygen-containing cycloaliphatic hydrocarbon compound having an amino g roup, an imino group and/or a carbonyl group) .
- R Ib is preferably a group
- 6-membered ring containing nitrogen as a member For example, groups obtained by removing two or three hyd rogen from piperid ine, pyrrolid ine or isocyanurate.
- R Ib connects Si each other included in plural repeating units.
- the polysiloxane used in the present invention can further comprise a repeating unit represented by the following formula (Ic) .
- it is preferably 40 mol% or less with, and more preferably 20 mol% or less, based on the total number of the repeating units of polysiloxane.
- the polysiloxane used in the present invention can further comprise a repeating unit represented by the following formula (Id) :
- R Id each independently represents hydrogen, or a Ci-30, linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group;
- methylene is not replaced or replaced with oxy, imide or carbonyl, and the carbon atom is unsubstituted or substituted with fluorine, hydroxy or alkoxy) .
- R Id includes, for example, (i) alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and decyl, (ii) aryl, such as phenyl, tolyl and benzyl, (iii) fluoroalkyl, such as trifluoromethyl, 2,2,2-trifluoroethyl and
- fluoroalkyl perfluoroalkyl is preferred, and trifluoromethyl and pentafluoroethyl are particularly preferred .
- the compound wherein R Id is methyl is preferred, since raw material thereof is easily obtained, it has hig h film hard ness after curing and it has high chemical resistance. Further, the compound wherein R Id is phenyl is preferred, since it increases solubility of the polysiloxane in the solvent and the cured film becomes to hard ly crack. Further, it is preferred that R Id has hyd roxy, glycidyl, isocyanate or amino, since the ad hesion to the substrate is improved .
- the polysiloxane according to the present invention can partially have a linear structure. Flowever, since heat resistance is reduced, it is preferable that portions of linear structure are few.
- the repeating unit of the formula (Id) is preferably 30 mol% or less based on the total number of the repeating units of the
- polysiloxane used in the present invention can further comprises a repeating unit
- L Ie is -(CR Ie 2 )n- or
- n is an integer of 1 to 3
- R Ie each independently represents hydrogen, methyl or ethyl).
- L Ie is preferably -(CR Ie 2 )n-
- R Ie is identical or different in one repeating unit or in the polysiloxane molecule. All R Ie in one molecule are preferably identical, and it is preferred that all are hyd rogen.
- the polysiloxane used in the present invention can contain two or more types of repeating units.
- it can contain three types of repeating units, which have repeating units represented by the formula (la) in which R Ia is methyl or phenyl and a repeating unit represented by the formula (Ic) .
- composition according to the present invention can contain two or more types of polysiloxane.
- polysiloxane containing any of the repeating units of the formulae (la) to (Id) described above can be used, and as the second type, polysiloxane containing the repeating unit of the formula (Ie) and the repeating unit other than that of the formula (Ie)
- one or more polysiloxane comprises a repeating unit, which is a bulky group, in at least one of R Ia of the formula (la), R Ib of the formula (lb) and/or R Id of the formula (Id), and it is further preferred to use polysiloxane comprising a repeating unit in which R Ia of the formula (la) is a bulky, C3-20, satu rated or unsaturated, cyclic aliphatic hyd rocarbon group or an aromatic hyd rocarbon group (for example, phenyl, naphthyl and anthracene) and the repeating unit of the formula (Ie) .
- R Ia of the formula (la) is a bulky, C3-20, satu rated or unsaturated, cyclic aliphatic hyd rocarbon group or an aromatic hyd rocarbon group (for example, phenyl, naphthyl and anthrac
- the ratio of the total number of the repeating unit (Ie) and the repeating unit (la) to the total number of the repeating units contained in the polysiloxane is preferably 60 mol% or more, and more preferably 70 mol% or more. Further, it is preferred that (la) is 20 to 95 mol% and (Ie) is 5 to 40 mol%.
- (lb) and (Id) containing the above bulky g roup is preferably 10 mol% or more based on the total number of repeating units contained in the polysiloxane.
- the polysiloxane used in the present invention has a structure in which the above-described repeating units are bonded, but preferably has a silanol at its terminal.
- a silanol group is one in which -O 0.5 FI is bonded to the bonding hand of the above-described repeating units or blocks.
- polysiloxane used in the present invention is not particularly limited .
- the mass average molecular weight of the polysiloxane is usually 500 or more and 25,000 or less, and preferably 1,000 or more and 20,000 or less from the viewpoint of solubility in an organic solvent and solubility in an alkali developer.
- the mass average molecular weight means a mass average molecular weight in terms of polystyrene, which can be measured by the gel permeation chromatography based on polystyrene.
- the polysiloxane used in the present invention is contained in a composition having positive type
- a cured film is formed through coating on a substrate, imagewise exposure and development. At this time, it is necessary that a difference in solubility occurs between the exposed area and the unexposed area, and the coating film in the exposed area should have above certain solubility in a developer. For example, it is considered that a pattern can be formed by
- TMAH tetramethylammonium hydroxide
- ADR alkali dissolution rate
- the dissolution rate in the 2.38 mass% TMAH aqueous solution is preferably 50 to 5,000 A/sec, and more preferably 200 to 3,000 A/sec.
- polysiloxane having any ADR within the above range can be selected depending on the application and required characteristics. Further, by combining some polysiloxane having different ADR, a mixture having a desired ADR can be prepared .
- Polysiloxane having different alkali dissolution rates and mass average molecular weig hts can be prepared by chang ing catalyst, reaction temperature, reaction time or polymer. Using a combination of polysiloxane having different alkali dissolution rates, it is possible to improve reduction of remaining insoluble matter after development, reduction of pattern reflow, pattern stability, and the like.
- Such polysiloxane includes, for example:
- composition having a desired dissolution rate can be obtained by mixing with :
- the alkali dissolution rate of polysiloxane or a mixture thereof is measured and calculated as described below.
- Polysiloxane is diluted with PGM EA so as to be 35 mass% and dissolved while stirring at room temperature with a stirrer for 1 hour. In a clean room under an atmosphere of temperature of 23.0 ⁇ 0.5°C and humid ity of 50 ⁇ 5.0%, using a pipette, lcc of the prepared polysiloxane solution is dropped on the center area of a
- the silicon wafer having this film is gently immersed in a glass petri d ish having a diameter of 6 inches, into which 100 ml of a TMAH aqueous solution adjusted to 23.0 ⁇ 0.1 °C and having a predetermined concentration is put, then allowed to stand, and the time until the film d isappeared is measured .
- the d issolution rate is determined by dividing by the time until the film in the area 10 mm of inside from the wafer edge disappears.
- the wafer is immersed in a TMAH aqueous solution for a certain period and then heated for 5 minutes on a hot plate at 200°C to remove moisture taken in the film during the dissolution rate measurement. Thereafter, film thickness is measured, and the dissolution rate is calculated by dividing the variation amount between before and after the immersion, by the immersion time. The above measurement method is performed 5 times, and the average of the obtained values is taken as the d issolution rate of the polysiloxane.
- polysiloxane used in the present invention is not
- silane monomer represented by the following formula, if necessary, in the presence of an acidic catalyst or a basic catalyst:
- R ia is hydrogen, or a Ci-30, linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group,
- methylene is not replaced or replaced with oxy, imide or carbonyl, and the carbon atom is unsubstituted or substituted with fluorine, hydroxy or alkoxy, and
- R ia' is linear or branched Ci- 6 alkyl) .
- R ia' includes methyl, ethyl, n-propyl, isopropyl, n-butyl and the like.
- a plurality of R ia' are contained, and each R ia' can be identical or different.
- Preferred R ia' is the same as the above-described preferred R Ia .
- Exemplified embod iments of the silane monomer represented by the formula (ia) include, for example, methyltrimethoxysilane, methyltriethoxysilane,
- methyltriisopropoxysilane methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
- ethyltriisopropoxysilane ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane,
- methyltripropoxysilane, and phenyltrimethoxysilane are preferable.
- Two or more types of silane monomers represented by the formula (ia) can be combined .
- silane monomer represented by the following formula (ic) can be combined .
- silane monomer represented by the formula (ic) is used, polysiloxane comprising the repeating unit (Ic) can be obtained .
- R ic' is linear or branched, Ci- 6 alkyl.
- R ic' includes methyl, ethyl, n-propyl, isopropyl, n-butyl and the like.
- a plurality of R ic' are included, and each R ic' can be identical or different.
- R ib' is linear or branched Ci- 6 alkyl, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like.
- a plurality of R ib' are contained in one monomer, and each R ib' can be identical or d ifferent.
- R ib is a group obtained by removing plural, preferably two or three, hydrogen from a nitrogen and/or oxygen-containing cyclic aliphatic hydrocarbon compound having an amino group, an imino group and/or a carbonyl group.
- Preferred R ib is the same as the above-described preferred R Ib .
- silane monomer represented by the following formula (id) can be combined .
- silane monomer represented by the formula (id) is used, polysiloxane containing the repeating unit (Id) can be obtained .
- R id' is each independently a linear or branched Ci- 6 alkyl, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like.
- a plurality of R id are contained in one monomer, and each R id can be identical or different,
- R id each independently represents hydrogen, or a
- Ci-30 linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group, and
- hyd rocarbon group methylene is not replaced or replaced with oxy, amino, imino or carbonyl, and the carbon atom is unsubstituted or substituted with fluorine, hydroxy or alkoxy.
- Preferred R id is the same as the above-described preferred R Id .
- silane monomer represented by the following formula (ie) can be combined .
- R ie' is each independently a linear or branched Ci- 6 alkyl, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like.
- L ie is -(CR ie 2 )n- or
- n is each independently an integer of 1 to 3
- R ie is each independently hydrogen, methyl or ethyl.
- the carboxylic acid compound used in the present invention is 200 to 50,000 ppm of monocarboxylic acid or dicarboxylic acid based on the total mass of the composition.
- the first acid dissociation constant pKai of the monocarboxylic acid is 5.0 or less.
- the first acid dissociation constant pKai of the dicarboxylic acid is 4.0 or less, and more preferably 3.5 or less.
- the monocarboxylic acid is represented by the formula (i) :
- R' is hyd rogen, or a saturated or unsaturated Ci-4 hyd rocarbon group, and more preferably a C1-3
- Examples of the monocarboxylic acid used in the present invention include acetic acid, formic acid and acrylic acid, and preferably acetic acid .
- the dicarboxylic acid is represented by the formula (ii) :
- Ci-6 unsubstituted alkylene, hydroxy-substituted alkylene or amino-substituted alkylene
- alkenylene means a divalent group having one or more double bonds.
- alkynylene means a divalent g roup having one or more triple bonds.
- L is N
- L is a sing le bond, a C1-2 unsubstituted alkylene, vinylene, hydroxyethylene or phenylene.
- Exemplified embod iments of the d icarboxylic acid used in the present invention include oxalic acid, maleic acid, fumaric acid, o-phthalic acid, succinic acid, glutaconic acid, aspartic acid, glutamic acid, malic acid, itaconic acid, 3-aminohexanedioic acid and malonic acid, and preferably oxalic acid, maleic acid, fumaric acid, o-phthalic acid, malic acid or malonic acid .
- the carboxylic acid compound used in the present invention is more preferably a dicarboxylic acid, and above all, one can take a cyclic structure by intramolecular dehydration condensation is particularly preferable.
- dicarboxylic acids examples include oxalic acid, maleic acid, succinic acid, o-phthalic acid, glutaconic acid, and itaconic acid .
- dicarboxylic acids having a temperature at which intramolecular dehydration condensation reaction occurs at 100°C to 250°C are preferable, and maleic acid, succinic acid and oxalic acid are further preferable.
- the carboxylic acid compound can be used in any combination of any two or more kinds thereof.
- the content of the carboxylic acid compound is any one of the carboxylic acid compound.
- the content of the compound (II) is preferably 300 to 10,000 ppm, and more preferably 500 to 5,000 ppm.
- the content of the compound (II) is preferably 1,000 to 30,000 ppm, and more preferably 3,000 to 10,000 ppm.
- composition according to the present invention contains a specific amount of a specific carboxylic acid compound, thereby suppressing the wrinkles of the cured film and producing an effect of improving the smoothness of the pattern surface. Although not desiring to be bound by theory, this is considered to be due to the following .
- the positive type polysiloxane composition is applied, exposed, developed with an alkaline developer, rinsed, and cured by heating . Although the developer is washed away by rinsing, an alkali component remaining in the film, particularly on the film surface, excessively accelerates the curing reaction on the film surface.
- composition according to the present invention contains a specific amount of a specific carboxylic acid compound, excessive acceleration of the curing reaction does not occur and generation of the wrinkles can be suppressed by neutralizing an alkali component with an alkali developer even if there is no flood exposure process.
- the carboxylic acid compound is a compound that can form a cyclic structure by an intramolecular dehydration reaction at a specific
- the silanol group of the polysiloxane is protected with the carboxylic acid group before heating for curing .
- stepwise curing occurs, that is, at the time of heating for curing, curing is performed from unprotected silanol groups, carboxylic acid compounds are converted into anhydrides and removed from the film, and unprotected silanol groups are then cured . Therefore, it is considered that the effect of suppressing the wrinkles becomes higher.
- Alkali developers are classified into organic and inorganic types, and inorganic developers have a smaller molecular size compared with organic developers and can easily enter into the film during development, so that the amount of acid required for neutralization also becomes more. Therefore, when an inorganic developer is used, the content of the carboxylic acid compound is more.
- the composition according to the present invention comprises a diazonaphthoquinone derivative.
- the composition comprising the d iazonaphthoquinone derivative forms a positive image that is removed by development when the exposed area becomes soluble in an alkaline developer. That is, the composition according to the present invention generally functions as a positive type photoresist composition.
- the diazonaphthoquinone derivative of the present invention is a compound in which naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxy group, and the structure is not particularly limited but is preferably an ester compound with a compound having one or more phenolic hyd roxy groups.
- naphthoquinone diazide sulfonic acid 4-naphthoquinone d iazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used .
- the 4-naphthoquinonediazide sulfonic acid ester compound has absorption in i-line (wavelength : 365 nm) region, it is suitable for i-line exposure. Further, the 5-naphthoquinoned iazide sulfonic acid ester compound has absorption in a broad wavelength range and is therefore suitable for exposure in a broad wavelength range. It is preferable to select an a 4-naphthoquinone diazide sulfonic acid ester compound or a
- 5-naphthoquinone d iazide sulfonic acid ester compound according to the wavelength to be exposed .
- a mixture of a 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone d iazide sulfonic acid ester compound can also be used .
- the compound having a phenolic hydroxy is not particularly limited, but examples thereof include bisphenol A, BisP-AF, BisOTBP-A, Bis26B-A, BisP-PR,
- BisP-LV BisP-OP, BisP-NO, BisP-DE, BisP-AP, BisOTBP-AP, TrisP-HAP, BisP-DP, TrisP-PA, BisOTBP-Z, BisP-FL,
- diazonaphthoquinone derivative is concerned, optimal amount thereof varies depend ing on the esterification ratio of naphthoquinone diazide sulfonic acid, or the physical properties of the polysiloxane used, the required photosensitivity, and the dissolution contrast between the exposed area and the unexposed area, but is preferably 1 to 20 parts by mass, and more preferably 2 to 15 parts by mass, based on 100 parts by mass of the total amount of polysiloxane.
- diazonaphthoquinone derivative is 1 part by mass or less, the dissolution contrast between the exposed area and the unexposed area is too low, and there is no realistic photosensitivity. Further, in order to obtain more excellent dissolution contrast, 2 parts by mass or more is preferable. On the other hand, when the addition amount of the d iazonaphthoquinone derivative is more than 20 parts by mass, whitening of the coating film occurs due to poor compatibility between the polysiloxane and the quinoned iazide compound, or colorless
- quinoned iazide compound that occurs during thermal curing becomes remarkable. Further, since heat resistance of diazonaphthoquinone derivatives is inferior to that of polysiloxane, if the addition amount is increased, thermal decomposition causes deterioration of the electrical insulation of the cured film and outgassing, resulting sometimes in problems in subsequent processes. Furthermore, resistance of the cured film to a photoresist stripper, which is mainly composed of monoethanolamine or the like, is sometimes lowered .
- the solvent is not particularly limited as long as it uniformly dissolves or disperses the above-described polysiloxane and the carboxylic acid compound as well as the add itives that are optionally added .
- the solvent that can be used in the present invention include ethylene g lycol monoalkyl ethers, such as ethylene g lycol monomethyl ether, ethylene g lycol monoethyl ether, ethylene g lycol monopropyl ether and ethylene g lycol monobutyl ether; diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol d iethyl ether, d iethylene glycol d ipropyl ether and diethylene glycol d ibutyl ether; ethylene glycol alkyl ether acetates, such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monoalkyl ether
- ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone
- alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin
- esters such as ethyl lactate, ethyl 3-ethoxypropionate, methyl
- g-butyrolactone Such a solvent can be used alone or in combination of two or more of any of these, and the amount used thereof varies depending on coating method or requirement of the film thickness after the coating .
- the content of the solvent in the composition according to the present invention can be selected suitably according to the mass average molecular weight of polysiloxane to be used, its distribution and its structure.
- composition according to the present invention comprises a solvent of generally 40 to 90 mass%, and preferably 60 to 80 mass%, based on the total mass of the composition.
- composition accord ing to the present invention essentially comprises the above (I) to (IV), but further compounds can be optionally combined . These materials which can be combined are described below.
- content of the components other than (I) to (IV) contained in the total composition is preferably 10 mass% or less, and more preferably 5 mass% or less, based on the total mass.
- composition according to the present invention can comprise a silanol condensation catalysts selected from the g roup consisting of a photoacid generator, a photobase generator, a photothermal acid generator, and a photothermal base generator. It is preferable that these are selected accord ing to the polymerization reaction and the crosslinking reaction used in the cured film manufacturing process.
- the photoacid generator does not include the above-described
- optimal amounts thereof vary depend ing on type of the active substance generated by decomposition, the amount generated, and the required photosensitivity/dissolution contrast between the exposed area and the unexposed area, but are preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total mass of polysiloxane.
- the addition amount is less than 0.1 parts by mass, the amount of acid or base to be generated is too small and pattern reflow easily occurs.
- the add ition amount is more than 10 parts by mass, the cured film to be formed may be cracked, or prominently colored due to decomposition thereof, which sometimes invites reduction of the colorless transparency of the cured film.
- the photoacid generator or photobase generator refers to a compound that generates an acid or base by causing bond cleavage upon exposure to light.
- the generated acid or base is considered to contribute to the polymerization of the polysiloxane.
- examples of the light include visible light, ultraviolet ray, infrared ray, X ray, electron beam, a ray, y ray, and the like.
- the photoacid generator or photobase generator preferably generates an acid or base through not an image-wise exposure for projecting a pattern (hereinafter referred to as the first exposure) but the flood exposure that is subsequently performed, and preferably has small less absorption at the wavelength of at the time of first exposure.
- the photoacid generator or photobase generator preferably has a greater absorbance at wavelength of 365 nm than that at 436 nm and/or 405 nm.
- absorbance at wavelength of 365 nm/absorbance at wavelength of 405 nm is preferably 2 or more, more preferably 5 or more, further preferably 10 or more, and most preferably 100 or more.
- the UV-visible absorption spectrum is measured using dichloromethane as the solvent.
- the measuring device is not particularly limited, but examples thereof include Cary 4000 UV-Vis spectrophotometer (manufactured by Ag ilent Technologies Japan, Ltd .) .
- the photoacid generator can be freely selected from generally used ones and includes diazomethane
- N-(nonafluorobutylsulfonyloxy)naphthyl-imide and the like.
- Examples of the photobase generator include
- multi-substituted amide compounds having an amide group, lactams, imide compounds or those containing the structure thereof.
- an ionic photobase generator includ ing an amide anion, a methide anion, a borate anion, a
- phosphate anion a sulfonate anion, a carboxylate anion, and the like as an anion can also be used .
- the photothermal acid generator or photothermal base generator refers to a compound that changes its chemical structure but does not generate an acid or base upon exposure to lig ht, and then causes a bond cleavage by heat to generate an acid or base.
- the photothermal base generator is preferred .
- the photothermal base generator one represented by the following general formula (II), more preferably hyd rate or solvate thereof is mentioned .
- the compound represented by the general formula (II) inverts to cis-form by exposure to lig ht and becomes unstable, so that the decomposition temperature decreases and the base is generated even if the baking temperature is about 100°C in the subsequent process.
- the photothermal base generator does not need to be adjusted with the absorption wavelength of the diazonaphthoquinone derivative.
- R a' to R r are each independently hyd rogen, halogen, hyd roxy, mercapto, sulfide, silyl, silanol, nitro, nitroso, sulfino, sulfo, sulfonato, phosphino, phosphinyl,
- substituent a C6-22 aromatic hydrocarbon group optionally having a substituent, a Ci-20 alkoxy optionally having a substituent, or a C6-20 aryloxy group optionally having a substituent.
- R a' to R d' particularly hydrogen, hyd roxy, a Ci-6 aliphatic hydrocarbon group, or Ci-6 alkoxy is preferable, and for R e' and R r , particularly hydrogen is preferable.
- Two or more of R a' to R d' can be bonded to form a cyclic structure. At this time, the cyclic structure can contain a hetero atom.
- N is a constituent atom of a nitrogen-containing heterocyclic ring
- the nitrogen-containing heterocyclic ring is a 3- to 10-membered ring
- nitrogen-containing heterocyclic ring can further have a
- Ci-20-, in particular Ci-6-, aliphatic hydrocarbon group which can contain one or more substituents that are different from Cxh xOH shown in the formula (II) .
- R a' to R d' are appropriately
- unsaturated hydrocarbon bonding functional groups such as vinyl and alkynyl which shift the absorption wavelength to g-, h- and i-line, alkoxy, nitro and the like are used, and particularly methoxy and ethoxy are preferred .
- the thermal acid generator or thermal base generator refers to a compound that causes bond cleavage by heat to generate an acid or base.
- thermal acid generator examples include salts and esters that generate organic acids, such as various aliphatic sulfonic acids and salts thereof; various aliphatic carboxylic acids such as citric acid, acetic acid and maleic acid, and salts thereof; various aromatic carboxylic acids such as benzoic acid and phthalic acid, and salts thereof; aromatic sulfonic acids and ammonium salts thereof; various amine salts; aromatic diazonium salts; and phosphonic acids and salts thereof, provided that the thermal acid generator used for the present invention does not include above mentioned (II) carboxylic acid compound.
- thermal acid generators in particular, a salt composed of an organic acid and an organic base is preferred, and a salt composed of sulfonic acid and an organic base is further preferred .
- Preferred sulfonic acids include p-toluenesulfonic acid,
- benzenesulfonic acid p-dodecylbenzenesulfonic acid, 1,4-naphthalene-disulfonic acid, methanesulfonic acid, and the like.
- acid generators can be used alone or in combination.
- thermal base generator examples include a compound that generates a base, such as imidazole, tertiary amine and quaternary ammonium, and mixtures thereof.
- a base such as imidazole, tertiary amine and quaternary ammonium, and mixtures thereof.
- the base to be released examples include imidazole derivatives such as
- surfactants As the other additives, surfactants, developer dissolution accelerators, scum removers, ad hesion enhancers, polymerization inhibitors, antifoaming agents, and sensitizers are mentioned .
- the surfactant can improve coating properties, using it is preferable.
- the surfactant that can be used in the polysiloxane composition in the present invention include nonionic surfactants, anionic surfactants, amphoteric surfactants, and the like.
- surfactant include, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; polyoxyethylene fatty acid d iester; polyoxyethylene fatty acid monoester;
- acetylene alcohol acetylene g lycol
- acetylene alcohol derivatives such as polyethoxylate of acetylene alcohol
- acetylene glycol derivatives such as polyethoxylate of acetylene g lycol
- fluorine-containing surfactants such as Fluorad (trade name, manufactured by 3M Japan Limited), Megafac (trade name, manufactured by DIC Corporation), Surufuron (trade name, AGC Inc.) ; or organosiloxane surfactants, such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd .) .
- fluorine-containing surfactants such as Fluorad (trade name, manufactured by 3M Japan Limited), Megafac (trade name, manufactured by DIC Corporation), Surufuron (trade name, AGC Inc.)
- organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd .
- acetylene glycol include 3-methyl-l-butyne-3-ol
- examples of the anionic surfactant include ammonium salt or organic amine salt of alkyl diphenyl ether disulfonic acid, ammonium salt or organic amine salt of alkyl diphenyl ether sulfonic acid, ammonium salt or organic amine salt of alkyl benzene sulfonic acid, ammonium salt or organic amine salt of polyoxyethylene alkyl ether sulfuric acid, ammonium salt or organic amine salt of alkyl sulfuric acid and the like.
- amphoteric surfactant examples include 2-alkyl-N-carboxymethyl-N-hyd roxyethyl imidazolium betaine, lauric acid amide propyl
- surfactants can be used alone or as a mixture of two or more kinds, and the compound ing ratio thereof is usually 50 to 10,000 ppm, preferably 100 to 5,000 ppm, based on the total mass of the composition.
- remover adjusts solubility of the formed coating film in the developer and has action of preventing scum from remaining on the substrate after development.
- crown ether can be used as such an additive.
- the add ition amount thereof is preferably 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the total mass of the polysiloxane.
- a sensitizer can be added as necessary.
- Coumarins, ketocoumarins and their derivatives, acetophenones, as well as sensitizing dyes such as pyrylium salts and thiopyrylium salts, and anthracene skeleton-containing compounds can be included .
- phenoxazine, hindered amine and derivatives thereof and an ultraviolet absorber can be added .
- the addition amount thereof is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total mass of the polysiloxane.
- alcohols such as oleic acid and stearic acid, higher fatty acid esters such as glycerin monolaurate, polyethers such as polyethylene g lycols (PEG) (Mn : 200 to 10,000) and polypropylene glycols (PPG) (Mn : 200 to 10,000), silicone compounds such as d imethyl silicone oil, alkyl-mod ified silicone oil and fluorosilicone oil, and
- organosiloxane-based surfactants are mentioned . These can be used alone or in combination of a plurality of these. The addition amount thereof is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the total mass of the polysiloxane.
- the adhesion enhancer has an effect of preventing a pattern from being peeled off by stress applied after curing when a cured film is formed using the composition according to the present invention.
- the adhesion enhancer imidazoles and silane coupling agents are preferable.
- combination of a plurality of these, and the addition amount thereof is 20 parts by mass or less, preferably 0.05 to 15 parts by mass, with respect to 100 parts by mass of the total mass of the polysiloxane.
- composition accord ing to the present invention on a substrate to form a composition layer
- composition layer (2) exposing the composition layer
- the above-described composition is applied on a substrate.
- Formation of the coating film of the composition in the present invention can be carried out by any method conventionally known as a method for applying a photosensitive composition. Specifically, it can be freely selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating and the like.
- a suitable substrate such as a silicon substrate, a glass substrate, a resin film, or the like can be used as the substrate on which the composition is applied.
- Various semiconductor devices and the like can be formed on these substrates as needed .
- the substrate is a film
- gravure coating can also be utilized .
- a drying process can be additionally provided after applying the film. Further, if necessary, the applying process can be repeated once or twice or more to make the film thickness of the coating film to be formed as desired .
- pre-baking heat treatment
- the pre-baking process can be carried out at a temperature of generally 70 to
- 150°C preferably 90 to 120°C, in the case of a hot plate, for 10 to 300 seconds, preferably 30 to 120 seconds and in the case of a clean oven, for 1 to 30 minutes.
- the coating film surface is then irradiated with light.
- this process is sometimes referred to as the first exposure.
- a lig ht source to be used for the light irradiation any one conventionally used for a pattern forming method can be used .
- a light source a hig h-pressure mercury lamp, a low-pressure mercury lamp, a lamp such as metal halide and xenon, a laser diode, an LED and the like can be included .
- Ultraviolet ray such as g-line, h-line and i-line is usually used as the irradiation lig ht.
- the energy of the irradiation light is generally 5 to 2,000 mJ/cm 2 , preferably 10 to 1,000 mJ/cm 2 , although it depends on the light source and the film thickness of the coating film. If the irradiation light energy is lower than 5 mJ/cm 2 , sufficient resolution cannot be obtained in some cases. On the other hand, when the irrad iation light energy is hig her than 2,000 mJ/cm 2 , the exposure becomes excess and occurrence of halation is sometimes brought.
- photomask can be used .
- Such a photomask can be freely selected from well-known ones.
- the environment at the time of irradiation is not particularly limited, but it can generally be set as an ambient atmosphere (in the air) or nitrogen atmosphere.
- an ambient atmosphere in the air
- nitrogen atmosphere in the case of forming a film on the entire surface of the substrate
- light irrad iation can be performed over the entire surface of the substrate.
- the pattern film also includes such a case where a film is formed on the entire surface of the substrate.
- the coating film is developed .
- the developer includes an organic developer and an inorganic developer, and examples of the organic developer include a TMAH aqueous solution, a tetrabutylammonium hydroxide aqueous solution, methyl isobutyl ketone and isopropyl alcohol, preferably a TMAH aqueous solution, and more preferably, a 2.38 mass% TMAH aqueous solution.
- alkali metal salts are included, and preferably a potassium hydroxide aqueous solution or a sodium hydroxide aqueous solution, a sodium carbonate aqueous solution, a sodium bicarbonate aqueous solution, a sodium silicate aqueous solution, a sodium metasilicate aqueous solution, aqueous ammonia, and particularly preferably a potassium hydroxide aqueous solution are included .
- a potassium hyd roxide aqueous solution this concentration is preferably 0.1 to 3.0 mass%, and more preferably 0.5 to 2.0 mass%.
- a water-soluble organic solvent such as methanol and ethanol, or a surfactant can be further contained, if necessary.
- the developing method can also be freely selected from conventionally known methods. Specifically, methods such as d ipping in a developer (d ip), padd le, shower, slit, cap coat, spray and the like can be included .
- the development temperature is preferably a normal temperature (20 to 25°C), but can be heated to 30 to 50°C.
- the development time is preferably 15 to 180 seconds, and more preferably 30 to 60 seconds.
- a pattern can be obtained, and it is preferable that rinsing (washing with water) is conducted after the development is performed with a developer.
- the rinsing is preferably conducted using water, and can be conducted in the same manner as the development, and is conducted preferably by showering for 60 seconds or more.
- the method of the flood exposure there is a method for exposing light over the entire surface with about 100 to 2,000 mJ/cm 2 (in terms of exposure amount at wavelength of 365nm) using an ultraviolet visible exposure machine PLA (for example, PLA-501 F, manufactured by Canon Inc.) .
- PLA for example, PLA-501 F, manufactured by Canon Inc.
- the heating temperature in this process is not particularly limited as long as it is a temperature at which curing of the coating film can be performed and can be freely determined .
- a relatively high temperature is generally selected as the heating temperature.
- the curing temperature is more preferably 300°C or lower, and particularly preferably 250°C or lower.
- the curing temperature is preferably 70°C or hig her, more preferably 90°C or higher, and particularly preferably 100°C or hig her.
- the heating time is not particularly limited and is generally 10 minutes to 24 hours, and preferably 30 minutes to 3 hours. In add ition, this heating time is a time from when the temperature of the pattern film reaches a desired heating temperature. Usually, it takes about several minutes to several hours for the pattern film to reach a desired temperature from the temperature before heating .
- the wrinkles generated on the surface of the cured film in this curing process can be suppressed .
- the wrinkle means unevenness which generates in the vicinity of or at a portion away from the pattern part of a cured film.
- Figure 1 shows electron micrograph
- the rough indication of the d ifference among no wrinkles (Figure 1 (P)), small wrinkles (Figure 1 (Q)) and large wrinkles (Figure 1 (R)) is that when with respect to a distance of 1.5 cm, the film surface is measured at a portion away from the pattern after curing, with a force of 3 mg over 50 seconds using a stylus type surface
- the surface unevenness means as follows:
- no wrinkles level difference of about lower than 30 nm
- large wrinkles level difference of larger than 100 nm.
- the cured film thus obtained can achieve excellent flatness, electrical insulation properties, and the like.
- the relative dielectric constant of 4 or less can also be achieved .
- it can be suitably utilized in many fields as a planarization film for the above-described various devices such as a flat panel display (FPD), an interlayer insulating film for low
- HLC-8220 GPC type high-speed GPC system (trade name, manufactured by Tosoh Corporation) and Super Multipore HZ-N type GPC column (trade name, manufactured by Tosoh Corporation).
- the measurement was performed using monodisperse polystyrene as a standard sample and tetrahydrofuran as an eluent, under the analytical cond itions of a flow rate of 0.6 ml/min and a column temperature of 40°C.
- TMAH aqueous solution 600 ml of isopropyl alcohol (IPA) and 4.0 g of water were charged, and then a mixed solution of 68.0 g of methyltrimethoxysilane, 79.2 g of phenyltrimethoxysilane and 15.2 g of tetramethoxysilane was prepared in a d ropping funnel.
- the mixed solution was added d ropwise at 40°C, and the resulting product was stirred at the same temperature for 2 hours and then neutralized by adding a 10 mass% HCI aqueous solution.
- 400 ml of toluene and 600 ml of water were added to separate the resulting product into two phases, and the aqueous phase was removed .
- the resulting product was washed three times with 300 ml of water, the obtained organic phase was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to prepare a solid content concentration of 35 mass%.
- Synthesis was performed in the same manner as in Synthesis Example 1 except that the amount of the TMAH aqueous solution was changed to 32.5 g .
- bis(triethoxysilyl)methane was prepared .
- the mixed solution was added dropwise at 40°C, and the mixture was stirred at the same temperature for 2 hours, and then neutralized by adding a 10 mass% HCI aqueous solution.
- 400 ml of toluene and 600 ml of water were added to separate the resulting product into two phases, and the aqueous phase was removed .
- the resulting product was washed 3 times with 400 ml of water, the obtained organic phase was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to prepare a solid content concentration of 35 mass%.
- thermometer and a condenser tube 102 g of a 25 mass% TMAH aqueous solution, 600 ml of isopropyl alcohol (IPA) and 4.0 g of water were charged, and then in a dropping funnel, a mixed solution of 68.0 g of TMAH aqueous solution, 600 ml of isopropyl alcohol (IPA) and 4.0 g of water were charged, and then in a dropping funnel, a mixed solution of 68.0 g of
- methyltrimethoxysilane, 79.2 g of phenyltrimethoxysilane and 54.0 g of bis(trimethoxysilyl)ethane was prepared .
- the mixed solution was added dropwise at 40°C, and the mixture was stirred at the same temperature for 2 hours, and then neutralized by adding a 10 mass% HCI aqueous solution.
- 400 ml of toluene and 600 ml of water were added to separate the resulting product into two phases, and the aqueous phase was removed . Further, the resulting product was washed 3 times with 400 ml of water, the obtained organic phase was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to prepare a solid content concentration of 35 mass%.
- ADR of the whole polysiloxane for the 2.38 mass% TMAH aqueous solution after prebaking were as follows:
- KF-53 manufactured by Shin-Etsu Chemical Co., Ltd .
- the evaluation criteria are as follows, and the evaluation results are as described in Table 1.
- SEM scanning electron microscope
- compositions of Examples 101 to 105 were applied by spin coating so that the film thickness after pre-baking was 1.6 pm.
- the obtained coating film was subjected to pre-baking at 110°C for 90 seconds to volatilize the solvent.
- a contact hole having a size of 5 pm was pattern-exposed with an optimal exposure amount using a g + h lines mask aligner (FX-604F type, manufactured by Nikon Corporation) .
- paddle development was performed for 70 seconds using a 2.38 mass% TMAFI aqueous solution, followed by rinsing with pure water for 60 seconds and drying .
- the exposure amount at which the bottom width of the contact hole after curing when patterned with a 5 micron mask was 5 microns was determined as the optimal exposure amount.
- the exposure amount of less than 500 mJ was the optimal exposure amount, and the photosensitivity was sufficient for practical use.
- Example 101 using the same composition as in Example 101 except that maleic acid was 80,000 ppm, the optimal exposure amount was determined in the same manner as described above, but no pattern could be formed even when the exposure amount was increased .
- Examples 201 to 204 containing the compounds shown in Table 2 below and the balance being PGM EA were prepared .
- KF-53 manufactured by Shin-Etsu Chemical Co., Ltd .
- Each composition was applied by spin coating so that the film thickness after pre-baking was 1.6 pm.
- the obtained coating film was subjected to pre-baking at 110°C for 90 seconds to volatilize the solvent. Thereafter, a contact hole having a size of 5 pm was pattern-exposed with an optimal exposure amount using a g + h lines mask aligner (FX-604F type, manufactured by N ikon
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Citations (3)
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US3350309A (en) * | 1965-07-14 | 1967-10-31 | Mobil Oil Corp | Stabilization of silicone fluids with an iron compound and a polycarboxylic acid |
JP2011002517A (en) | 2009-06-16 | 2011-01-06 | Jsr Corp | Positive radiation-sensitive composition, interlayer insulating film, and forming method of the same |
EP3255494A1 (en) * | 2015-02-04 | 2017-12-13 | Sakai Display Products Corporation | Positive photosensitive siloxane composition, active matrix substrate, display device, and method for producing active matrix substrate |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3350309A (en) * | 1965-07-14 | 1967-10-31 | Mobil Oil Corp | Stabilization of silicone fluids with an iron compound and a polycarboxylic acid |
JP2011002517A (en) | 2009-06-16 | 2011-01-06 | Jsr Corp | Positive radiation-sensitive composition, interlayer insulating film, and forming method of the same |
EP3255494A1 (en) * | 2015-02-04 | 2017-12-13 | Sakai Display Products Corporation | Positive photosensitive siloxane composition, active matrix substrate, display device, and method for producing active matrix substrate |
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