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WO2012144291A1 - Composition de formation de film à base de silice pour jet d'encre, procédé de formation de film à base de silice, dispositif à semi-conducteurs, et système de cellules solaires - Google Patents

Composition de formation de film à base de silice pour jet d'encre, procédé de formation de film à base de silice, dispositif à semi-conducteurs, et système de cellules solaires Download PDF

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Publication number
WO2012144291A1
WO2012144291A1 PCT/JP2012/057555 JP2012057555W WO2012144291A1 WO 2012144291 A1 WO2012144291 A1 WO 2012144291A1 JP 2012057555 W JP2012057555 W JP 2012057555W WO 2012144291 A1 WO2012144291 A1 WO 2012144291A1
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WO
WIPO (PCT)
Prior art keywords
solvent
butyrolactone
added
silica
boiling point
Prior art date
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Ceased
Application number
PCT/JP2012/057555
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English (en)
Japanese (ja)
Inventor
悠平 岡田
貴浩 吉川
茂 野部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
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Filing date
Publication date
Priority claimed from JP2011183951A external-priority patent/JP2014132044A/ja
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of WO2012144291A1 publication Critical patent/WO2012144291A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/129—Passivating
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a silica-based film forming composition for inkjet, a method for forming a silica-based film, a semiconductor device, and a solar cell system.
  • Silica-based coatings are applied in various fields because they are excellent in insulation, heat resistance, transparency and wear resistance.
  • semiconductor devices are applied to applications such as insulating films between wires, element isolation films and mask materials from the viewpoint of insulation, heat resistance and barrier properties.
  • insulating films between wires, element isolation films and mask materials from the viewpoint of insulation, heat resistance and barrier properties.
  • heat resistance and barrier properties In liquid crystal devices, insulation, heat resistance and From the viewpoint of transparency, it is applied to applications such as protective films for elements.
  • a gas phase growth method and a coating method are known as general methods for obtaining a silica-based film.
  • the gas layer growth method is widely applied and has a feature that a dense silica-based film can be obtained.
  • the coating method has features such that film formation can be performed with a relatively simple apparatus and film formation on a large-sized substrate is relatively easy. Examples of the coating method include spin coating, spraying, dipping, roll coating, and screen printing.
  • Patent Document 1 An inkjet method has been studied as a method for easily and inexpensively forming a pattern. Since the inkjet method can form a desired pattern at a desired position, it is not necessary to form a silica-based coating on the entire surface of the substrate unlike the photolithography method, and the amount of material to be used can be greatly reduced. There are also significant environmental benefits.
  • Patent Documents 2 and 3 As a method for obtaining an ink jet-compatible silica-based film forming composition, a sol-gel method using alkoxysilane as a raw material is known (Patent Documents 2 and 3).
  • Patent Document 2 when ethanol or water is used as a solvent, or as described in Patent Document 3, a solvent at 100 ° C. or less may occupy 70 to 90% by weight of the entire composition. In such a case, nozzle clogging is likely to occur if the operations of non-ejection and ejection by ink jet drawing are repeated. In mass production, since such discharge and non-discharge are repeated, the conventional silica-based film-forming composition is not yet sufficient for practical use.
  • the silica-based film forming composition for ink jet it is desirable for the silica-based film forming composition for ink jet to have a cross-sectional shape that is rectangular or close to rectangular when a pattern is drawn using this.
  • the pattern cross-sectional shape is not rectangular (that is, the thickness of the insulating film decreases toward the film edge), and the insulating property May be locally reduced, resulting in degradation of device characteristics.
  • the ink containing the silica-based film forming composition is: (1) The ink does not dry at the nozzle tip, (2) When a small droplet of ink lands on the surface to be coated, the droplet is difficult to spread and spread; It is necessary to achieve both of these characteristics. However, it is very difficult to achieve both of these characteristics.
  • the present invention is for an ink jet that can discharge without causing clogging of the ink jet nozzle even when the operations of non-discharge and discharge are repeated, and can form a drawing pattern having a cross-sectional shape closer to a rectangle. It is an object of the present invention to provide a silica-based film forming composition, a method for forming a silica-based film using the composition, a semiconductor device, and a solar cell system.
  • the present invention provides a silica-based film-forming composition for inkjet as described in the following (1) and (2), a method for forming a silica-based film as described in (3) below, (4) And the solar cell system described in the following (5).
  • (1) Contains a silicon compound obtained by hydrolysis / polycondensation of a compound represented by the following general formula (I), a solvent, and a surface conditioner.
  • the solvent is ⁇ -butyrolactone and has a boiling point of 80
  • R 1 n SiX 4-n (I) [Wherein R 1 represents an organic group having 1 to 20 carbon atoms, X represents a hydrolyzable group, and n represents an integer of 0 to 2. However, when n is 2, a plurality of R 1 may be the same or different, and when n is 0 to 2, a plurality of X 1 may be the same or different. ]
  • the surface conditioner is a silicone-based surface conditioner.
  • a silica-based film comprising: a step of forming a drawing pattern film by discharging the composition according to (1) or (2) by an inkjet method; and a step of curing the drawing pattern film. Forming method.
  • a semiconductor device comprising a substrate and a silica-based film formed on the substrate by the method according to (3).
  • a solar cell system comprising the semiconductor device according to (4).
  • a silica-based film forming composition for inkjet, a method for forming a silica-based film using the composition, a semiconductor device, and a solar cell system are provided.
  • the ink containing the silica-based film-forming composition for ink-jet is not used to cause clogging of the ink-jet nozzle even when the non-ejection and ejection operations are repeated and to bring the pattern cross-sectional shape at the time of drawing closer to a rectangle.
  • Ink does not dry at the nozzle tip (hereinafter sometimes referred to as “non-drying property at the nozzle tip”);
  • a mixed solvent containing a second solvent which is a low-boiling component, ⁇ -butyrolactone which is a high-boiling component, and a third solvent as a solvent for a silica-based film forming composition for inkjet It is important to use In this mixed solvent, it is extremely important to adjust the respective contents so that the mass ratio of ⁇ -butyrolactone and the second solvent to the total mass in the solvent falls within a specific numerical range.
  • the non-drying property at the nozzle tip is mainly controlled by the action of ⁇ -butyrolactone and the third solvent, and the wetting of the droplets upon ink landing is suppressed mainly by the action of ⁇ -butyrolactone and the second solvent.
  • the boiling point of the second solvent is 80 to 100 ° C.
  • the boiling point of the third solvent is 180 to 230 ° C.
  • the mass ratio of ⁇ -butyrolactone to the total mass of the solvent is 0.2 or more
  • the mass ratio of the second solvent to the total mass of the solvent is 0.2 to 0.5.
  • the silica-based film-forming composition for inkjet contains a surface conditioner. This is also considered to be a factor.
  • the wetting and spreading of the droplets upon landing of the ink is suppressed by controlling the wettability to the coating object and the fluidity of the silica-based resin. More specifically, the wetting and spreading of the droplets upon landing of the ink is locally caused by non-uniform wetting of the ink to the coated object (such as repelling) and non-uniformity of the solvent evaporation of the ink during ejection.
  • the surface conditioner in the present invention is (1) a compound having the action of uniformizing the surface tension of the coating film in the drying process and improving the wettability to the coating object, and (2) the solvent from the coating film surface. It is defined as at least one compound selected from compounds having the effect of homogenizing evaporation and reducing local viscosity increase and surface tension change.
  • the silica-based film-forming composition for inkjet according to the present embodiment contains the following components (A) to (C).
  • (A) A silicon compound obtained by hydrolysis and polycondensation of a compound represented by the following general formula (I).
  • R 1 n SiX 4-n (I) [Wherein R 1 represents an organic group having 1 to 20 carbon atoms, X represents a hydrolyzable group, and n represents an integer of 0 to 2. However, when n is 2, a plurality of R 1 may be the same or different, and when n is 0 to 2, a plurality of X 1 may be the same or different. ]
  • (B) containing ⁇ -butyrolactone, a second solvent having a boiling point of 80 to 100 ° C. and a third solvent having a boiling point of 180 to 230 ° C.
  • composition Silicon Compound
  • composition is a compound obtained by hydrolysis / polycondensation of the compound represented by the general formula (I).
  • silicon compound is an essential component.
  • hydrolysis / polycondensation means that the compound represented by the general formula (I) is hydrolyzed, condensed while dehydrating (H 2 O), and polymerized. To do.
  • X in the general formula (I) those known as a group capable of leaving by hydrolysis can be selected without particular limitation. Specifically, for example, an alkoxy group, a halogen group, an acetoxy group, An isocyanate group and a hydroxyl group are mentioned, Among these, an alkoxy group is preferable. By making X an alkoxy group, the liquid stability of the resulting silicon compound and the halogen concentration in the resulting composition can be suppressed.
  • the compound represented by the general formula (I) is alkoxysilane.
  • the alkoxysilane include a tetraalkoxysilane represented by the following general formula (I-1), a trialkoxysilane represented by the following general formula (I-2), and a dialkoxysilane represented by the following general formula (I-3).
  • An alkoxysilane etc. are mentioned.
  • An alkoxysilane may be used individually by 1 type, and may be used in combination of 2 or more type.
  • R 2 Si (OR 2 ) 4 (I-1) [Wherein R 2 may be the same or different and each independently represents an alkyl group. ]
  • R 5 2 Si (OR 6 ) 2 (I-3) [In the formula, R 5 may be the same or different, each independently represents an alkyl group or a phenyl group, the phenyl group may have a substituent, and R 6 may be the same or different, Each independently represents an alkyl group. ]
  • the number of carbon atoms of the alkoxy group R (R 2 , R 4 and R 6 ) is not particularly limited, Usually, it has 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms from the viewpoint of availability.
  • R (R 2 , R 4, and R 6 ) of the alkoxy group may be one in which a part of hydrogen atoms is substituted with fluorine atoms.
  • Examples of the tetraalkoxysilane represented by the general formula (I-1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, and tetrabutoxysilane.
  • tetraethoxysilane is preferably used from the viewpoint that the reactivity and the handling of reaction byproducts are easy.
  • trialkoxysilanes represented by the general formula (I-2) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.
  • methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, and phenyltriethoxysilane are preferable, and phenyltriethoxysilane is more preferable because of the reactivity and easy handling of reaction byproducts. preferable.
  • dialkoxysilanes represented by the general formula (I-3) include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-iso-propoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and diethyldiethoxysilane.
  • the alkoxysilanes represented by the general formula (I-1), general formula (I-2) and general formula (I-3) may be used alone or in combination of two or more. Also good.
  • the alkoxysilanes represented by the general formula (I-1), general formula (I-2) and general formula (I-3) are used in combination of two or more, the mixing ratio is not particularly limited.
  • the general formula (I -1) The molar amount M 2 of the trialkoxysilane represented by the general formula (I-2) and the dialkoxy represented by the general formula (I-3) with respect to the molar amount M 1 of the tetraalkoxysilane represented by -1)
  • the ratio (M 2 + M 3 ) / M 1 of the total amount of the silane molar amount M 3 is preferably 0.1 or more, more preferably 0.3 or more, and more preferably 0.5 or more.
  • (M 2 + M 3 ) / M 1 is preferably 4.0 or less, more preferably 2.5 or less, and 1.5 or less. It is very preferable that
  • the component (B) may be used as a solvent, or a solvent other than the component (B) may be used.
  • Solvents used for hydrolysis and polycondensation of alkoxysilane include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, methyl-n- Pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, ⁇ -butyrolactone And ketone solvents such as ⁇
  • the solvent is removed or replaced by distillation after the reaction, and the resulting siloxane resin or siloxane resin solution is inkjetted. It can be used for preparation of a silica-based film forming composition.
  • the amount of the solvent when the general formula (I-1), the general formula (I-2) and the general formula (I-3) are hydrolyzed and polycondensed using the above-mentioned solvent is determined from the viewpoint of the uniformity of the reaction, etc.
  • the SiO 2 equivalent concentration is preferably in the range of 5% by mass to 35% by mass, the lower limit is more preferably 10% by mass or more, and the upper limit is more preferably 30% by mass or less.
  • a catalyst in order to shorten the reaction time and make the reaction uniform.
  • the catalyst include an acid catalyst, an alkali catalyst, a metal chelate compound, and the like. From the viewpoint of ensuring the stability of the resulting silica-based film-forming composition for inkjet, it is preferable to use an acid catalyst.
  • Examples of the acid catalyst include organic acids and inorganic acids.
  • organic acids include 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, heptanoic acid , Octanoic acid, nonanoic acid, decanoic acid, oxalic acid, adipic acid, sebacic acid, butyric acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzenesulfonic acid, benzoic acid, p-aminobenzoic acid, p- Examples include toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and trifluoroethanesulfonic acid.
  • inorganic acids examples include hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid, and hydrofluoric acid.
  • maleic acid as the organic acid and nitric acid as the inorganic acid.
  • the amount of catalyst used can be appropriately selected according to the type and amount of alkoxysilane, the type of catalyst, and the like.
  • a tetraalkoxysilane represented by the general formula (I-1), a trialkoxysilane represented by the general formula (I-2), and a dialkoxysilane represented by the general formula (I-3) are used in combination.
  • an acid catalyst is used as the catalyst, the molar ratio of the tetraalkoxysilane represented by the general formula (I-1) to the total number of moles of the alkoxysilane is represented by A and the trioxide represented by the general formula (I-2).
  • the amount (molar ratio) of the acid catalyst used is [(4A + 3B + 2C) / 3000] to [
  • the range of (4A + 3B + 2C) / 10] is preferable, and the range of [(4A + 3B + 2C) / 3000] to [(4A + 3B + 2C) / 100] is more preferable.
  • the amount of water to be used can be appropriately selected according to the type and amount of the alkoxysilane used.
  • a tetraalkoxysilane represented by general formula (I-1), a trialkoxysilane represented by general formula (I-2), and a dialkoxysilane represented by general formula (I-3) are used in combination.
  • the molar ratio of the tetraalkoxysilane represented by the general formula (I-1) to the total number of moles of alkoxysilane is A
  • the molar ratio of the trialkoxysilane represented by the general formula (I-2) is B
  • the molar ratio of the dialkoxysilane represented by the formula (I-3) is C
  • the amount of water (molar ratio) ranges from [(4A + 3B + 2C) ⁇ 0.5] to [(4A + 3B + 2C) ⁇ 2].
  • the range of [(4A + 3B + 2C) ⁇ 0.5] to [4A + 3B + 2C) ⁇ 1] is more preferable.
  • the weight average molecular weight (Mw) of the silicon compound as the component (A) is preferably 500 to 20000, more preferably 500 to 10,000, from the viewpoints of solubility in a solvent, inkjet dischargeability, and the like.
  • weight average molecular weight is within the above range, the film-formability of the silica-based film and the compatibility of the silicon compound and the solvent can be achieved at a high level.
  • “weight average molecular weight” is measured by gel permeation chromatography (hereinafter referred to as “GPC”) and converted using a standard polystyrene calibration curve. .
  • the weight average molecular weight (Mw) can be measured, for example, by GPC under the following conditions.
  • the content of the component (A) in the silica-based film-forming composition for inkjet is preferably 5 to 35% by mass. If the content of the component (A) is 5% by mass or more, the thickness of the silica-based film to be formed is not too thin and becomes an appropriate thickness. The possibility of being necessary can be reduced. Thereby, it becomes easy to suppress the increase in process time and the occurrence of bleeding of the drawing pattern due to the overlapping drawing. On the other hand, if the content of the component (A) is 35% by mass or less, the storage stability of the silica-based film-forming composition for inkjet tends to be improved, and 30% by mass or less from the same viewpoint. It is preferable that
  • Component (B) Solvent
  • the component (B) according to this embodiment contains ⁇ -butyrolactone, a second solvent having a boiling point of 80 to 100 ° C., and a third solvent having a boiling point of 180 to 230 ° C., A solvent in which the mass ratio of ⁇ -butyrolactone to the total mass of the solvent is 0.2 or more and the mass ratio of the second solvent to the total mass of the solvent is 0.2 to 0.5.
  • the “boiling point” means a boiling point at normal pressure (1 atm).
  • ⁇ -Butyrolactone is an organic solvent having a boiling point of 204 ° C. and a surface tension at 20 ° C. of 43.9 dyn / cm (43.9 ⁇ 10 ⁇ 3 N / m).
  • ⁇ -butyrolactone having such a boiling point and surface tension in the solvent, the non-drying property at the nozzle tip of the ink containing the ink-jet silica-based film-forming composition and the liquid upon ink landing It is considered that it is possible to achieve both suppression of dripping and spreading.
  • the second solvent has a boiling point of 80 ° C. to 100 ° C., and the boiling point is not particularly limited as long as the boiling point is within such a range, but the boiling point is preferably 80 ° C. to 95 ° C., preferably 80 ° C. to More preferably, it is 90 ° C.
  • the second solvent include 1-propanol, 2-propanol, 2-methyl-2-propanol, and 2-butanol.
  • the second solvent contained in the composition may be one type or two or more types.
  • the third solvent has a boiling point of 180 ° C. to 230 ° C.
  • the boiling point of the ⁇ -butyrolactone is within this range, but is excluded from the third solvent.
  • the boiling point of the third solvent is more preferably 180 ° C. to 220 ° C., further preferably 180 ° C. to 210 ° C., and particularly preferably 180 ° C. to 200 ° C.
  • ⁇ -butyrolactone must be used to achieve both non-drying properties at the ink nozzle tip and suppression of droplet wetting and spreading when the ink lands.
  • a solvent other than ⁇ -butyrolactone and ⁇ -butyrolactone It is preferable to use together.
  • the third solvent examples include ether solvents, glycol solvents, alkylene glycol monoalkyl ether solvents, alkylene glycol dialkyl ether solvents, and alkylenes exemplified in the description of the solvent used when hydrolyzing and polycondensing alkoxysilane.
  • examples thereof include glycol alkyl ether acetate solvents, and among them, alkylene glycol monoalkyl ether solvents and glycol solvents are preferably used because they are excellent in compatibility with ⁇ -butyrolactone and the second solvent.
  • the 3rd solvent contained in a composition may be 1 type, or 2 or more types.
  • the mass ratio of ⁇ -butyrolactone to the total mass of the solvent containing ⁇ -butyrolactone, the second solvent having a boiling point of 80 to 100 ° C., and the third solvent having a boiling point of 180 to 230 ° C. is 0. .2 or more, preferably 0.2 to 0.7, more preferably 0.2 to 0.6.
  • the second solvent has a total mass of ⁇ -butyrolactone, the second solvent having a boiling point of 80 to 100 ° C., and the third solvent having a boiling point of 180 to 230 ° C.
  • the mass ratio is 0.2 to 0.5, preferably 0.25 to 0.5, and more preferably 0.3 to 0.5.
  • Component (C) Surface Conditioner
  • the composition of the present embodiment contains a surface conditioner as the component (C).
  • a surface conditioner it is possible to control the wettability of the ink to the substrate surface and prevent bleeding of the drawing pattern, and the cross-sectional shape of the drawing pattern can be controlled to a shape closer to a rectangle.
  • a commercially available compound as a “surface conditioner” can be used without particular limitation.
  • a fluorine-based surface conditioner, a silicone-based surface conditioner, and a nonionic surface conditioner Etc. can be used.
  • the use of a silicone-based surface conditioner is particularly effective in suppressing the wetting and spreading of liquid droplets upon ink landing.
  • the content of the component (C) is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and further preferably 0.2% by mass or more with respect to the component (A). Moreover, 1.0 mass% or less is preferable with respect to (A) component, as for content of (C) component, 0.9 mass% or less is more preferable, and 0.8 mass% or less is further more preferable. In addition, (C) component may be used individually by 1 type or in combination of 2 or more types.
  • a method for forming a silica-based film according to the present embodiment includes a step of forming a drawing pattern film by discharging the composition by ink jetting to form a drawing pattern film, a step of pre-curing the drawing pattern film, and a drawing pattern. Curing the film.
  • Pattern drawing by the inkjet method can be performed using an inkjet apparatus.
  • Ink jet devices are generally roughly classified into two types, a continuous type (continuous discharge type) and an on-demand type.
  • the continuous type is a system in which ink is always ejected continuously even when a pattern is not drawn on a substrate.
  • On-demand type is a method of drawing a pattern on a substrate by ejecting ink in a necessary amount when necessary.
  • the on-demand type includes an inkjet apparatus using a piezoelectric element that deforms when a voltage is applied, and a thermal inkjet apparatus that discharges using bubbles generated by heating.
  • the silica-based film-forming composition for inkjet according to the present embodiment may basically use either device, but it is preferable to use an inkjet device using a piezo element from the viewpoint of suppressing ink composition change. .
  • the substrate on which the pattern is drawn may be drawn while being heated in the range of 50 to 100 ° C.
  • the quick drying property of the ink on the substrate can be further improved, and the disorder of the drawing pattern can be prevented.
  • a step of precuring the drawing pattern film may be provided before the step of curing the drawing pattern film.
  • the polycondensation reaction of the siloxane resin in the drawing pattern film is promoted and organic using a hot plate or the like where the first-stage baking temperature is set to 80 to 140 ° C. and the second-stage baking temperature is set to 180 to 250 ° C.
  • the drying of the solvent may be performed in stages. Further, the first stage and / or the second stage bake may be further multi-staged. By the multi-stage baking, the siloxane resin is uniformly cured, and it is possible to prevent the drawing pattern from being disturbed due to the thermal convection when the solvent is removed.
  • the final curing is performed, for example, by baking the drawing pattern film (which may not be precured) at a heating temperature of 350 to 1000 ° C.
  • the heating temperature of the final curing is 350 ° C. or higher, sufficient curing is easily achieved, and if it is 1000 ° C. or lower, the influence of the high temperature on the substrate can be made difficult to occur.
  • the heating time for the final curing is preferably 2 to 60 minutes, more preferably 2 to 30 minutes. If this heating time is 60 minutes or less, the amount of heat input will not increase excessively, and thus the deterioration of the substrate will be suppressed gradually.
  • a heating device it is preferable to use a heat treatment device such as a quartz tube furnace, other furnaces, a hot plate, rapid thermal annealing (RTA), UV irradiation annealing, and EB irradiation annealing.
  • the atmosphere of the gas at the time of final curing may be an atmosphere of an inert gas such as nitrogen, argon or helium, or an atmosphere of an active gas such as oxygen or ozone, as long as it does not adversely affect the substrate. Good.
  • the use of the silica-based film formed by the method for forming a silica-based film according to the present embodiment is not particularly limited, and examples thereof include use for devices including an insulating film such as a semiconductor device (element) or a multilayer wiring board. .
  • an insulating film such as a semiconductor device (element) or a multilayer wiring board.
  • a semiconductor device it can be used as a surface protective film (passivation film), a buffer coat film, an interlayer insulating film, a diffusion prevention film, and the like.
  • a multilayer wiring board it can be suitably used as an interlayer insulating film.
  • the semiconductor device of this embodiment includes a substrate and a silica-based film having a predetermined pattern formed on the substrate by the method for forming a silica-based film.
  • Such semiconductor devices include, for example, individual semiconductors such as diodes, transistors, compound semiconductors, thermistors, varistors, and thyristors, DRAMs (Dynamic Random Access Memory), SRAMs (Static Random Access Memory), EPROMs.
  • high-density wiring boards such as MCM, are mentioned, for example.
  • the solar cell system of this embodiment includes the semiconductor device.
  • the photoelectric conversion element is a semiconductor device used in a solar cell system, and has been actively developed due to the influence of recent environmental problems.
  • a typical photoelectric conversion element includes a semiconductor Si wafer in which an impurity called a dopant is diffused to form a pn junction.
  • an element in which a non-diffusion region and a diffusion region of a dopant are mixed on one Si wafer is sometimes produced in order to increase the efficiency of the solar cell. In such a case, it is necessary to form a diffusion prevention mask in the non-diffusion region.
  • a diffusion prevention mask has been obtained by patterning a silica-based film formed by CVD or the like by a photolithography method.
  • the silica-based film forming composition for inkjet according to the present embodiment is used, a silica-based film patterned by inkjet can be obtained, which is useful because the number of steps and the necessary materials can be reduced.
  • the silica-based coating according to the present embodiment can be used for applications such as liquid crystal parts, optical waveguides, and photoresists, but the usage is not limited to this.
  • silicon compound A distilled off under reduced pressure using the evaporator until the said silicon compound solution whole quantity became 95 g or less. Thereafter, dipropylene glycol monomethyl ether was added until the total amount of the silicon compound solution reached 100 g to obtain silicon compound A.
  • the siloxane resin solid content concentration of the silicon compound A at this time was 60% by mass.
  • solid content means the solid part except the volatile substances, such as water and a solvent, and shows a non volatile matter. The same applies to the following.
  • the siloxane resin solid content concentration of the silicon compound B at this time was 60% by mass.
  • the siloxane resin solid content concentration of the silicon compound C was 60% by mass.
  • the siloxane resin solid concentration of the silicon compound D was 60% by mass.
  • the siloxane resin solid content concentration of the silicon compound E was 60% by mass.
  • the siloxane resin solid content concentration of the silicon compound F was 60% by mass.
  • Example 1 To the silicon compound A, 0.3 g of Dispalon 1711 (trade name, manufactured by Enomoto Kasei Co., Ltd., registered trade name) is added and stirred to the silicon compound A, and 13.3 g of ⁇ -butyrolactone (boiling point 204 ° C.) is added. And 13.3 g of 2-propanol (boiling point 82 ° C.) were added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-propanol to the total mass of the solvent was 0.2. At this time, the siloxane resin solid content concentration was 47.4%.
  • Example 2 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 16.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 24.0 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-propanol to the total mass of the solvent was 0.3. Moreover, the siloxane resin solid content concentration at this time was 42.9%.
  • Example 3 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 20.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 40.0 g of 2-propanol (boiling point 82 ° C.). was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-propanol to the total mass of the solvent was 0.4. Moreover, the siloxane resin solid content concentration at this time was 37.5%.
  • Example 4 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 26.7 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 66.7 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content concentration at this time was 31.0%.
  • Example 5 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner was added and stirred, and 40.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 20.0 g of 2-propanol (boiling point 82 ° C.). was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-propanol to the total mass of the solvent was 0.2. Moreover, the siloxane resin solid content concentration at this time was 37.5%.
  • Example 6 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner was added and stirred, and 53.4 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 40.1 g of 2-propanol (boiling point 82 ° C.). was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-propanol to the total mass of the solvent was 0.3. Moreover, the siloxane resin solid content concentration at this time was 31.0%.
  • Example 7 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 80.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 80.0 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-propanol to the total mass of the solvent was 0.4. Moreover, the siloxane resin solid content concentration at this time was 23.1%.
  • Example 8 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 160.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 200.0 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content density
  • Example 9 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, 120.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 40.0 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.6, and the mass ratio of 2-propanol to the total mass of the solvent was 0.2. Moreover, the siloxane resin solid content concentration at this time was 23.1%.
  • Example 10 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner is added and stirred, and 240.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 120.0 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.6, and the mass ratio of 2-propanol to the total mass of the solvent was 0.3. Moreover, the siloxane resin solid content density
  • Example 11 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 280.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 80.0 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.7, and the mass ratio of 2-propanol to the total mass of the solvent was 0.2. Further, the siloxane resin solid content concentration at this time was 13.0%, and this was used as a silica-based film-forming composition for inkjet.
  • Example 12 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 13.3 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 13.3 g of 2-methyl-2-propanol ( (Boiling point 83 ° C.) was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-methyl-2-propanol to the total mass of the solvent was 0.2. At this time, the siloxane resin solid content concentration was 47.4%.
  • the mass composition ratio of ⁇ -butyrolactone / 2-methyl-2-propanol / dipropylene glycol monomethyl ether is 0.2 / 0.2 / 0.6 until the solid content of the siloxane resin is 13.0%.
  • a mixed solvent was added to produce a silica-based film-forming composition for inkjet.
  • Example 13 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 26.7 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 66.7 g of 2-methyl-2-propanol ( (Boiling point 83 ° C.) was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-methyl-2-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content concentration at this time was 31.0%.
  • the mass composition ratio of ⁇ -butyrolactone / 2-methyl-2-propanol / dipropylene glycol monomethyl ether was 0.2 / 0.5 / 0.3 until the solid content of the siloxane resin reached 13.0%.
  • a mixed solvent was added to produce a silica-based film-forming composition for inkjet.
  • Example 14 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner was added and stirred, and then 40.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 20.0 g of 2-methyl-2-propanol ( (Boiling point 83 ° C.) was added and stirred. At this time, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-methyl-2-propanol to the total mass of the solvent was 0.2. Moreover, the siloxane resin solid content concentration at this time was 37.5%.
  • the mass composition ratio of ⁇ -butyrolactone / 2-methyl-2-propanol / dipropylene glycol monomethyl ether is 0.4 / 0.2 / 0.4 until the siloxane resin solid concentration is 13.0%.
  • a mixed solvent was added to produce a silica-based film-forming composition for inkjet.
  • Example 15 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 160.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 200.0 g of 2-methyl-2-propanol ( (Boiling point 83 ° C.) was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-methyl-2-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content density
  • Example 16 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 280.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 80.0 g of 2-methyl-2-propanol ( (Boiling point 83 ° C.) was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.7, and the mass ratio of 2-methyl-2-propanol to the total mass of the solvent was 0.2. Further, the siloxane resin solid content concentration at this time was 13.0%, and this was used as a silica-based film-forming composition for inkjet.
  • Example 17 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, 13.3 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 13.3 g of 1-propanol (boiling point 97 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 1-propanol to the total mass of the solvent was 0.2. At this time, the siloxane resin solid content concentration was 47.4%.
  • Example 18 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner is added and stirred, 26.7 g of ⁇ -butyrolactone (boiling point 204 ° C.), and 66.7 g of 1-propanol (boiling point 97 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 1-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content concentration at this time was 31.0%.
  • Example 19 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner was added and stirred, and 40.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 20.0 g of 1-propanol (boiling point 97 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 1-propanol to the total mass of the solvent was 0.2. Moreover, the siloxane resin solid content concentration at this time was 37.5%.
  • Example 20 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner is added and stirred, and 160.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 200.0 g of 1-propanol (boiling point 97 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 1-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content density
  • Example 21 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 280.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 80.0 g of 1-propanol (boiling point 97 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.7, and the mass ratio of 1-propanol to the total mass of the solvent was 0.2. Further, the siloxane resin solid content concentration at this time was 13.0%, and this was used as a silica-based film-forming composition for inkjet.
  • Example 22 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 13.3 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 13.3 g of 2-butanol (boiling point 100 ° C.) was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-butanol to the total mass of the solvent was 0.2. At this time, the siloxane resin solid content concentration was 47.4%.
  • Example 23 To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 26.7 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 66.7 g of 2-butanol (boiling point 100 ° C.). was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-butanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content concentration at this time was 31.0%.
  • Example 24 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner was added and stirred, and then 40.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 20.0 g of 2-butanol (boiling point 100 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-butanol to the total mass of the solvent was 0.2. Moreover, the siloxane resin solid content concentration at this time was 37.5%.
  • Example 25 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 160.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 200.0 g of 2-butanol (boiling point 100 ° C.) was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-butanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content density
  • Example 26 To the silicon compound A, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 280.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 80.0 g of 2-butanol (boiling point 100 ° C.) was added and stirred. At this time, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.7, and the mass ratio of 2-butanol to the total mass of the solvent was 0.2. Further, the siloxane resin solid content concentration at this time was 13.0%, and this was used as a silica-based film-forming composition for inkjet.
  • Example 27 To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 13.3 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 13.3 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-propanol to the total mass of the solvent was 0.2. At this time, the siloxane resin solid content concentration was 47.4%.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 2-propanol / triethylene glycol dimethyl ether of 0.2 / 0.2 / 0.6 was added until the siloxane resin solid content concentration reached 13.0%. Then, a silica-based film forming composition for inkjet was prepared.
  • Example 28 To the silicon compound B, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 26.7 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 66.7 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content concentration at this time was 31.0%.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 2-propanol / triethylene glycol dimethyl ether of 0.2 / 0.5 / 0.3 was added until the siloxane resin solid concentration was 13.0%. Then, a silica-based film forming composition for inkjet was prepared.
  • Example 29 To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 40.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 20.0 g of 2-propanol (boiling point 82 ° C.). was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-propanol to the total mass of the solvent was 0.2. Moreover, the siloxane resin solid content concentration at this time was 37.5%.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 2-propanol / triethylene glycol dimethyl ether of 0.4 / 0.2 / 0.4 was added until the siloxane resin solid content concentration reached 13.0%. Then, a silica-based film forming composition for inkjet was prepared.
  • Example 30 To the silicon compound B, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 160.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 200.0 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.4, and the mass ratio of 2-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content density
  • Example 31 To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 280.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 80.0 g of 2-propanol (boiling point 82 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.7, and the mass ratio of 2-propanol to the total mass of the solvent was 0.2. Moreover, the siloxane resin solid content density
  • Example 32 To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 26.7 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 66.7 g of 2-methyl-2-propanol ( (Boiling point 83 ° C.) was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-methyl-2-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content concentration at this time was 31.0%.
  • the mass composition ratio of ⁇ -butyrolactone / 2-methyl-2-propanol / triethylene glycol dimethyl ether is 0.2 / 0.5 / 0.3 until the siloxane resin solid concentration is 13.0%.
  • a mixed solvent was added to prepare a silica-based film-forming composition for inkjet.
  • Example 33 To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 280.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 80.0 g of 2-methyl-2-propanol ( (Boiling point 83 ° C.) was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.7, and the mass ratio of 2-methyl-2-propanol to the total mass of the solvent was 0.2. Moreover, the siloxane resin solid content density
  • Example 34 To the silicon compound B, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 26.7 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 66.7 g of 1-propanol (boiling point 97 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 1-propanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content concentration at this time was 31.0%.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 1-propanol / triethylene glycol dimethyl ether of 0.2 / 0.5 / 0.3 was added until the siloxane resin solid content concentration reached 13.0%. Then, a silica-based film forming composition for inkjet was prepared.
  • Example 35 To the silicon compound B, 0.3 g of Disparon 1711 which is a silicone surface conditioner is added and stirred, and 280.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 80.0 g of 1-propanol (boiling point 97 ° C.). Was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.7, and the mass ratio of 1-propanol to the total mass of the solvent was 0.2. Moreover, the siloxane resin solid content density
  • Example 36 To the silicon compound B, 0.3 g of Disparon 1711 which is a silicone surface conditioner was added and stirred, and 26.7 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 66.7 g of 2-butanol (boiling point 100 ° C.). was added and stirred. At this point, the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2, and the mass ratio of 2-butanol to the total mass of the solvent was 0.5. Moreover, the siloxane resin solid content concentration at this time was 31.0%.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 2-butanol / triethylene glycol dimethyl ether of 0.2 / 0.5 / 0.3 was added until the siloxane resin solid content concentration reached 13.0%. Then, a silica-based film forming composition for inkjet was prepared.
  • Example 37 0.3 g of Dispalon 1711 which is a silicone surface conditioner is added to the silicon compound B and stirred, and 280.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 80.0 g of 2-butanol (boiling point 100 ° C.) was added and stirred.
  • the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.7
  • the mass ratio of 2-butanol to the total mass of the solvent was 0.2.
  • concentration at this time is 13.0%, and let this be the silica-type film forming composition for inkjet.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 2-propanol / dipropylene glycol monomethyl ether of 0.1 / 0.2 / 0.7 is used until the solid content concentration of the siloxane resin becomes 13.0%. This was added to prepare a silica-based film-forming composition for inkjet.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / dipropylene glycol monomethyl ether of 0.8 / 0.2 was added until the solid content concentration of the siloxane resin reached 13.0%, and the silica-based coating film for inkjet A forming composition was made.
  • the mass composition ratio of ⁇ -butyrolactone / propylene glycol monopropyl ether / dipropylene glycol monomethyl ether is 0.2 / 0.2 / 0.6.
  • a solvent was added to prepare a silica-based film-forming composition for inkjet.
  • Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 16.0 g of ⁇ -butyrolactone (boiling point 204 ° C.) and 24.0 g of propylene glycol monopropyl ether (boiling point 150). ° C) was added and stirred.
  • the mass ratio of ⁇ -butyrolactone to the total mass of the solvent was 0.2
  • the mass ratio of propylene glycol monopropyl ether to the total mass of the solvent was 0.3.
  • the siloxane resin solid content concentration at this time was 42.9%.
  • the mass composition ratio of ⁇ -butyrolactone / propylene glycol monopropyl ether / dipropylene glycol monomethyl ether is 0.2 / 0.4 / 0.4.
  • a solvent was added to prepare a silica-based film-forming composition for inkjet.
  • the mass composition ratio of ⁇ -butyrolactone / propylene glycol monopropyl ether / dipropylene glycol monomethyl ether is 0.2 / 0.5 / 0.3.
  • a solvent was added to prepare a silica-based film-forming composition for inkjet.
  • Disparon 1711 which is a silicone-based surface conditioner is added and stirred, and 361.5 g of ⁇ -butyrolactone (boiling point 204 ° C.) is added and stirred to obtain a siloxane resin solid content concentration of 13.
  • a 0% silica-based film-forming composition for inkjet was prepared.
  • Dispalon 1711 which is a silicone-based surface conditioner is added and stirred, and 361.5 g of 2-propanol (boiling point 82 ° C.) is added and stirred to obtain a siloxane resin solid content concentration of 13.
  • a 0% silica-based film-forming composition for inkjet was prepared.
  • Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 17.2 g of 2-propanol (boiling point 82 ° C.) was added and stirred. At this point, the mass ratio of 2-propanol to the total mass of the solvent was 0.3. Moreover, the siloxane resin solid content concentration at this time was 51.2%. Accordingly, a mixed solvent having a mass composition ratio of 2-propanol / dipropylene glycol monomethyl ether of 0.3 / 0.7 is added until the solid content concentration of the siloxane resin becomes 13.0%, and the silica-based coating film for inkjet is used. A forming composition was made.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 2-propanol / tetraethylene glycol dimethyl ether of 0.2 / 0.2 / 0.6 was added until the siloxane resin solid content concentration reached 13.0%. Then, a silica-based film forming composition for inkjet was prepared.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 2-propanol / tetraethylene glycol dimethyl ether of 0.2 / 0.3 / 0.5 was added until the siloxane resin solid content concentration reached 13.0%. Then, a silica-based film forming composition for inkjet was prepared.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 2-propanol / tetraethylene glycol dimethyl ether of 0.2 / 0.4 / 0.4 was added until the siloxane resin solid content concentration reached 13.0%. Then, a silica-based film forming composition for inkjet was prepared.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / 2-propanol / tetraethylene glycol dimethyl ether of 0.2 / 0.5 / 0.3 was added until the siloxane resin solid content concentration reached 13.0%. Then, a silica-based film forming composition for inkjet was prepared.
  • a mixed solvent having a mass composition ratio of ⁇ -butyrolactone / acetone / dipropylene glycol monomethyl ether of 0.2 / 0.2 / 0.6 was added until the siloxane resin solid content concentration reached 13.0%.
  • a silica-based film-forming composition for inkjet was prepared.
  • the cross-sectional shape of the drawing pattern was evaluated as follows. First, using NanoPrinter-1100 Standard, ink (each silica-based film forming composition for inkjet) was ejected, and a predetermined pattern was drawn on a mirror-surface Si wafer heated to 70 ° C. At this time, the drawing conditions of the apparatus were set to “width 800 ⁇ m, length 20000 ⁇ m, film thickness 1.2 ⁇ m”. And the drawn pattern cross-sectional shape was measured with the level difference meter. As a step meter, Dektak 150 manufactured by Veeco was used.
  • the ratio (%) of the cross-sectional width of the drawing pattern at the film thickness of 1.1 ⁇ m to the drawing pattern cross-sectional width at the film thickness of 0 ⁇ m (bottom side) was calculated as the rectangularity. And when the rectangularity was 85% or more, it was evaluated that the cross-sectional shape was rectangular.
  • Tables 1 to 9 show the compositions of the silica-based film-forming compositions for ink jets of Examples 1 to 37 and Comparative Examples 1 to 30 and the evaluation results.
  • the mass ratio of the three types of solvents used is fixed, and siloxane compounds (tetraethoxysilane and phenyltriethoxysilane) having the same composition are used although the solvents used in the synthesis are different. And evaluated.
  • the silica-based film-forming composition for inkjet of the present invention is composed of ⁇ -butyrolactone as a solvent, a second solvent having a boiling point of 80 to 100 ° C., and a third solvent having a boiling point of 180 to 230 ° C. It was confirmed that it was at least important to include a solvent.
  • the pattern cross-sectional shape also had a cross-sectional width at a film thickness of 1.1 ⁇ m of 85% or more with respect to the bottom width of the drawing pattern cross-section. It was a rectangle.
  • the silica-based film-forming composition for ink jet according to the present invention appropriately includes ⁇ -butyrolactone, a second solvent having a boiling point of 80 to 100 ° C., and a third solvent having a boiling point of 180 to 230 ° C. It was confirmed that by including it at a proper mass ratio, extremely excellent characteristics were exhibited.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

L'invention concerne une composition de formation de film à base de silice pour jet d'encre qui comprend : un composé silicium obtenu par hydrolyse/polycondensation d'un composé représenté par la formule générale R1 nSiX4-n; un solvant; et un régulateur de surface. Le solvant contient un γ-butyrolactone, un second solvant dont le point d'ébullition se situe entre 80 et 100°C, et un troisième solvant dont le point d'ébullition se situe entre 180 et 230°C. Pour la masse totale de solvant, le rapport de masse du γ-butyrolactone est supérieur ou égal à 0,2, et le rapport de masse du second solvant se situe entre 0,2 et 0,5. Dans la formule, R1 représente un groupe organique de 1 à 20 atomes de carbones, X représente un groupe hydrolysable, et n représente un entier de 0 à 2.
PCT/JP2012/057555 2011-04-22 2012-03-23 Composition de formation de film à base de silice pour jet d'encre, procédé de formation de film à base de silice, dispositif à semi-conducteurs, et système de cellules solaires Ceased WO2012144291A1 (fr)

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JP2011-095971 2011-04-22
JP2011095971 2011-04-22
JP2011-183951 2011-08-25
JP2011183951A JP2014132044A (ja) 2011-08-25 2011-08-25 インクジェット用シリカ系被膜形成組成物、シリカ系被膜の形成方法、半導体デバイス及び太陽電池システム

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
JP2014185207A (ja) * 2013-03-22 2014-10-02 Seiko Epson Corp インクジェット記録用の非水系インク組成物、インクジェット記録方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI575326B (zh) * 2013-04-09 2017-03-21 Jsr Corp A method for forming a resist film and a pattern forming method
DE112014004318T5 (de) * 2013-09-20 2016-07-07 Namiki Seimitsu Houseki Kabushiki Kaisha Substrat und Verfahren zu dessen Herstellung, Lichtemissionselement und Verfahren zu dessen Herstellung und Vorrichtung mit dem Substrat oder Lichtemissionselement

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Publication number Priority date Publication date Assignee Title
JP2001279134A (ja) * 2000-03-31 2001-10-10 Seiko Epson Corp 吐出組成物及び機能膜作製法
JP2003253203A (ja) * 2002-02-27 2003-09-10 Hitachi Chem Co Ltd シリカ系被膜形成用組成物、シリカ系被膜の製造方法及び電子部品
JP2005200469A (ja) * 2004-01-13 2005-07-28 The Inctec Inc インクジェットプリンター用油性インク
JP2007211081A (ja) * 2006-02-08 2007-08-23 Konica Minolta Holdings Inc インクジェットインク及びインクジェット記録方法
JP2008120992A (ja) * 2006-10-19 2008-05-29 Hitachi Maxell Ltd 顔料インク組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001279134A (ja) * 2000-03-31 2001-10-10 Seiko Epson Corp 吐出組成物及び機能膜作製法
JP2003253203A (ja) * 2002-02-27 2003-09-10 Hitachi Chem Co Ltd シリカ系被膜形成用組成物、シリカ系被膜の製造方法及び電子部品
JP2005200469A (ja) * 2004-01-13 2005-07-28 The Inctec Inc インクジェットプリンター用油性インク
JP2007211081A (ja) * 2006-02-08 2007-08-23 Konica Minolta Holdings Inc インクジェットインク及びインクジェット記録方法
JP2008120992A (ja) * 2006-10-19 2008-05-29 Hitachi Maxell Ltd 顔料インク組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014185207A (ja) * 2013-03-22 2014-10-02 Seiko Epson Corp インクジェット記録用の非水系インク組成物、インクジェット記録方法

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