WO2007111271A1 - シリカ系被膜形成用組成物およびシリカ系被膜 - Google Patents

シリカ系被膜形成用組成物およびシリカ系被膜 Download PDF

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Publication number
WO2007111271A1
WO2007111271A1 PCT/JP2007/056091 JP2007056091W WO2007111271A1 WO 2007111271 A1 WO2007111271 A1 WO 2007111271A1 JP 2007056091 W JP2007056091 W JP 2007056091W WO 2007111271 A1 WO2007111271 A1 WO 2007111271A1
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WO
WIPO (PCT)
Prior art keywords
silica
composition
forming
based film
acid
Prior art date
Application number
PCT/JP2007/056091
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English (en)
French (fr)
Japanese (ja)
Inventor
Kiyoshi Ishikawa
Toshiyuki Ogata
Hideo Hada
Shogo Matsumaru
Original Assignee
Tokyo Ohka Kogyo Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Ohka Kogyo Co., Ltd. filed Critical Tokyo Ohka Kogyo Co., Ltd.
Publication of WO2007111271A1 publication Critical patent/WO2007111271A1/ja

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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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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

Definitions

  • the present invention relates to a composition for forming a silica-based film and a silica-based film. More specifically, the present invention relates to a composition for forming a silica-based film capable of forming a film at a low temperature and a silica-based film.
  • a composition for forming a silica-based film is mainly used for reducing a step in a semiconductor wiring or filling a groove between wirings to form a silica-based film. Since the liquid is applied, the pattern recess on the wafer can be easily embedded, and the wiring can be flattened with good reproducibility.
  • This silica-based film is particularly preferably used as an interlayer insulating film.
  • Such a silica-based coating is generally obtained by applying a composition for forming a silica-based coating on a substrate, heating at 80 ° C. to 300 ° C., and baking at a temperature of 350 ° C. or higher. (For example, refer to Patent Document 1).
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-171067
  • the present invention has been made in view of the above-described problems, and provides a composition for forming a silica-based film that can form a silica-based film by heating at a low temperature. With the goal.
  • the present inventors have made extensive studies focusing on the additive agent added to the silica-based film forming composition. As a result, it generates acid or base by the action of heat. It has been found that the above problems can be solved by using a compound, and the present invention has been completed. More specifically, the present invention provides the following.
  • a first invention of the present invention is a composition for forming a silica-based film comprising a siloxane polymer (A) and a compound (B) that generates an acid or a base by the action of heat.
  • the second invention of the present invention is a silica-based coating obtained from the above-mentioned composition for forming a silica-based coating.
  • the composition for forming a silica-based film of the present invention contains a compound that generates an acid or a base by the action of heat. Thereby, a silica-based film can be easily formed at a temperature of less than 350 ° C.
  • FIG. 1 is a diagram showing a FT-IR chart of Example 1.
  • FIG. 2 is a diagram showing an FT-IR chart of Comparative Example 1.
  • FIG. 3 is a diagram showing an FT-IR chart of Example 2.
  • FIG. 4 is a diagram showing an FT-IR chart of Comparative Example 3.
  • FIG. 5 is a graph comparing the BHF resistance of silica-based coatings in Example 2 and Comparative Example 3.
  • composition for forming a silica-based film of the present invention comprises a siloxane polymer (A) and a compound (B) that generates an acid or a base by the action of heat.
  • the siloxane polymer of the present invention (hereinafter also referred to as “component (A)”) is not particularly limited, and is a polymer having a Si 2 O 3 Si bond.
  • hydrolysis-condensation products of alkoxysilanes can be suitably used.
  • Any kind of alkoxysilane can be used as the alkoxysilane.
  • Examples of such alkoxysilane include, for example, the following general formula (a): Mention may be made of the compounds represented.
  • R 1 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group
  • R 2 is a monovalent organic group
  • n is an integer of 0 to 2.
  • examples of the monovalent organic group include an alkyl group, aryl group, aryl group, and glycidyl group.
  • an alkyl group and an aryl group are preferable.
  • the number of carbon atoms of the alkyl group is preferably 1 to 5, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the alkyl group may be linear or branched, and hydrogen may be substituted with fluorine.
  • the aryl group those having 6 to 20 carbon atoms are preferred, and examples thereof include a phenyl group and a naphthyl group.
  • examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane,
  • n l
  • monoalkyltrialkoxysilanes such as silane and monopropyltriethoxysilane
  • monophenyltrialkoxysilanes such as monophenyltrimethoxysilane
  • monophenyltriethoxysilane monophenyltriethoxysilane.
  • dialkyl dialkoxysilane diphenyl such as dimethylenoresimethoxysilane, dimethylenoresetoxysilane, dimethylenoresipropoxysilane, getinoresioxymethoxysilane, methinoresoxyoxysilane, methinoresidipropoxysilane, etc.
  • diphenyl dialkoxysilanes such as dimethoxysilane and diphenyljetoxysilane.
  • the weight average of the siloxane polymer (A) is preferably 200 or more and 50000 or less, more preferably 1000 or more and 3000 or less. If it is this range, the applicability
  • Hydrolytic condensation of alkoxysilane is obtained by reacting alkoxysilane as a polymerization monomer in an organic solvent in the presence of an acid catalyst or a base catalyst.
  • the alkoxysilane used as the polymerization monomer may be used alone or may be condensed by combining plural kinds.
  • trialkylalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, triethylmethoxysilane, triethyloxysilane, triethylpropoxysilane, tripylpyroxysilane, tripropylethoxysilane, Triphenylalkoxysilane such as triphenylmethoxysilane and triphenylethoxysilane may be added during hydrolysis.
  • the degree of hydrolysis of alkoxysilane which is a precondition for condensation, can be adjusted by the amount of water to be added.
  • the amount of water added is 1.0 to L: 0.0 times the total number of moles of alkoxysilane represented by the chemical formula (a). More preferably, it is added at a molar ratio of 5 to 8.0.
  • the degree of hydrolysis can be sufficiently increased, and the film formation can be improved.
  • gelling can be prevented and the storage stability can be improved by controlling the molarity to 10.0 mol or less.
  • an acid catalyst in the condensation of the alkoxysilane represented by the chemical formula (a), it is preferable to use an acid catalyst.
  • the acid catalyst that is preferably used is not particularly limited and is conventionally used. Any organic acid or inorganic acid can be used. Examples of the organic acid include organic carboxylic acids such as acetic acid, propionic acid, and butyric acid, and examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the like.
  • the acid catalyst may be added directly to the mixture of alkoxysilane and water, or may be added to the alkoxysilane as an acidic aqueous solution together with water.
  • the hydrolysis reaction is usually completed in about 5 to about L00 hours.
  • component (B) As a compound that generates an acid or base by the action of heat (hereinafter also referred to as “component (B)”)
  • the compound that generates an acid or a base is preferably a compound that generates an acid or a base at 100 ° C. or higher and 300 ° C. or lower.
  • the composition for forming a silica-based film can form a silica-based film without firing at a high temperature of, for example, 350 ° C or higher. Thereby, heating (for example, drying and baking) after applying the composition for forming a silica-based film can be simplified.
  • thermal acid generators examples include thermal acid generators and thermal base generators.
  • the thermal acid generator is not particularly limited, but 2, 4, 4, 6-tetrabromocyclohexagenone, benzoin tosylate, 2--trobendiltosylate, and other alkyls of organic sulfonic acid.
  • Esters can be used. Specific examples include sulphonium salts, iodine salts, benzothiazonium salts, ammonium salts, phosphonium salts, and the like. Of these, particularly preferred are ododonium salts, sulfo-salts and benzothiazo-salts.
  • sulfo-um salt and the benzothiazo-um salt include, for example, 4-acetoxyphenol dimethylsulfo-hexafluoroarsenate, benzyl 4-hydroxyphenol methylsulfo-hexafluoro Antimonate, 4-acetoxyphenol pendylmethylsulfo-hexafluoroantimonate, dibenzyl 4-hydroxyphenolsulfo-hexafluoroantimonate, 4-acetoxyphenol pendylsulfo-hexaflux Examples include oloantimonate and 3-benzylbenzothiazolium hexafluoroantimonate.
  • the thermal base generator is not particularly limited, but 1-methyl 1- (4 —Biphenyl-ethyl) ethyl carbamate, forceful rubamate derivatives such as 1,1-dimethyl-2-cyanoethylcarbamate, urea derivatives such as urea and N, N-dimethyl-N'methylurea, 1,4-dihydronicotine Dihydropyridine derivatives such as amides, quaternized ammonium salts of organic silanes and organic boranes, dicyandiamide and the like are used.
  • trichlorodiethyl acetate guanidine trichlorodimethylacetate acetate, potassium trichlorodiacetate
  • phenylsulfonylacetate guanidine p-diphenylsulfolacetate guanidine
  • p-methanesulfursulfate -Lusulfol acetate guanidine phenol-potassium propylpropiolate, guanidine propylpropiolate, cesium ferropropiolate, p-chlorophenol guanidine propylpropiolate, p-phthalene bisphenol
  • examples include guanidine lupropiolic acid, tetramethylammonium phenolsulfol acetate, and tetramethylammonium phenolpropiolate.
  • these compounds generating an acid or a base may be used alone or in combination of two or more.
  • the content of the component (B) is 0.1% by mass or more and 20 quality with respect to the SiO equivalent mass of the component (A).
  • the amount is 0.5% by mass or more and 15% by mass or less.
  • blend surfactant It is preferable to mix
  • the composition for forming a silica-based film of the present invention preferably contains a solvent for the purpose of improving coating properties and film thickness uniformity.
  • a solvent for the purpose of improving coating properties and film thickness uniformity.
  • an organic solvent generally used conventionally can be used.
  • Specific examples include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol; methyl 3-methoxypropionate, ethyl 3-ethoxy Alkyl carboxylic acid esters such as propionate; polyhydric alcohols such as ethylene glycol, diethylene glycol, and propylene glycol; ethylene glycol monomethino enoenoate, ethylene glycol monometheno enoenoate, Tylene glycol monopropinoreateol, ethylene glycol monobutinoleatenore, propylene glyconole monomethinoatenor
  • the amount of the solvent is not particularly limited, but it is preferable that the concentration of components (solid content) other than the solvent is 5 to: LOO mass% 20 to 50 mass % Is more preferable. By making it in this range, the coatability can be improved.
  • a composition for forming a silica-based coating is applied on a substrate.
  • a method for applying the composition for forming a silica-based film on the substrate for example, any method such as a spray method, a spin coat method, a dip coat method, a roll coat method can be used. Is used.
  • the silica-based film-forming composition applied on the substrate is heat-treated.
  • the heat treatment is not particularly limited with respect to its means, temperature, time, etc. In general, it may be performed on a hot plate at about 80 to 300 ° C. for about 1 to 6 minutes.
  • composition for forming a silica-based film of the present invention an acid or a base is generated by heating with a heat treatment. Hydrolysis is promoted by the generated acid or base, so that the alkoxy group becomes a hydroxyl group and alcohol is generated. After that, the two molecules of alcohol condense and a Si-O-Si network is formed. A dense silica-based film can be obtained.
  • the heat treatment is preferably performed in three steps or more and in steps. Specifically, after the first heat treatment for about 30 seconds to 2 minutes on a hot plate at about 60 to 150 ° C in the atmosphere or an inert gas atmosphere such as nitrogen, 100 to 220 ° The second heat treatment is performed for about 30 seconds to 2 minutes at about C, and the third heat treatment is performed for about 30 seconds to 2 minutes at about 150 to 300 ° C.
  • stepwise heat treatment of three or more steps preferably about 3 to 6 steps, a silica-based film can be formed at a lower temperature.
  • the above-mentioned compound (b-1) was added so as to be 7.5% by mass with respect to the solid content in the spin-on glass material to produce a composition for forming a silica-based film.
  • a composition for forming a silica-based film was applied on a 6-inch silicon wafer using a coater (SS8261NUU: manufactured by Tokyo Ohka Kogyo Co., Ltd.) at a rotation speed of lOOOOrpm. Next, heating was performed on a hot plate at 80 ° C. for 60 seconds, 150 ° C. for 60 seconds, and 200 ° C. for 60 seconds to form a silica-based film.
  • a silica-based film forming composition was produced by adding 7% by mass with respect to the solid content in the non-on glass material.
  • the composition for forming a silica-based film was applied onto a 6-inch silicon wafer at a rotational speed of lOOOOrpm using a coater (SS8261NUU: manufactured by Tokyo Ohka Kogyo Co., Ltd.). Next, heat on a hot plate at 300 ° C for 60 seconds to form a silica coating. Made.
  • a silica-based film was produced in the same manner as in Example 1 using OCD T-12 1000V.
  • Comparative Example 1 after heating, firing was further performed at 400 ° C. in a nitrogen atmosphere to form a silica-based film.
  • a silica-based film was formed in the same manner as in Example 2 using OCD T-7 7000WK80A.
  • Comparative Example 3 after heating, firing was further performed at 400 ° C. in a nitrogen atmosphere to form a silica-based film.
  • Example 1 and Comparative Examples 1 and 2 were evaluated based on the ratio of the peak area of Si—O bond to the peak area of Si—H bond. Further, Example 2 and Comparative Examples 3 and 4 were evaluated based on the ratio of the peak area of the Si—O bond and the peak area of the Si—C bond.
  • the FT-IR chart of Example 1 is shown in FIG. 1
  • the FT-IR chart of Comparative Example 1 is shown in FIG. 2
  • the FT-IR chart of Example 2 is shown in FIG. 3
  • the FT-IR chart of Comparative Example 3 is shown.
  • Figure 4 shows the IR chart.
  • the second embodiment the silica-based film of Comparative Example 3, 3 parts by mass 0/0 resistance Noffa for one Dofu' (BHF) acid concentration, time after applying the BHF onto the silica-based film It confirmed by measuring the amount of film
  • Example 2 had higher chemical resistance than Comparative Example 3.

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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)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Formation Of Insulating Films (AREA)
PCT/JP2007/056091 2006-03-24 2007-03-23 シリカ系被膜形成用組成物およびシリカ系被膜 WO2007111271A1 (ja)

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JP2006083732A JP2007254677A (ja) 2006-03-24 2006-03-24 シリカ系被膜形成用組成物およびシリカ系被膜
JP2006-083732 2006-03-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020090420A (ja) * 2018-12-07 2020-06-11 住友金属鉱山株式会社 黒鉛製またはセラミックス製の基板、基板の製造方法、炭化珪素の成膜方法および炭化珪素基板の製造方法

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JP5329281B2 (ja) * 2009-03-31 2013-10-30 東京応化工業株式会社 塗布液及び当該塗布液を用いるシリカ系被膜の形成方法
US10544329B2 (en) 2015-04-13 2020-01-28 Honeywell International Inc. Polysiloxane formulations and coatings for optoelectronic applications

Citations (4)

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JP2005134908A (ja) * 2003-10-28 2005-05-26 Samsung Electronics Co Ltd 絶縁膜形成用組成物及びこれを用いた絶縁膜または絶縁膜パターンの形成方法
JP2005136429A (ja) * 2004-11-12 2005-05-26 Hitachi Chem Co Ltd シリカ系被膜形成用組成物、シリカ系被膜及びその形成方法、並びにシリカ系被膜を備える電子部品
JP2005350558A (ja) * 2004-06-10 2005-12-22 Shin Etsu Chem Co Ltd 多孔質膜形成用組成物、パターン形成方法、及び多孔質犠性膜
JP2006137932A (ja) * 2004-10-12 2006-06-01 Toray Ind Inc コーティング用組成物およびそれを用いた表示装置

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JP3300089B2 (ja) * 1993-02-15 2002-07-08 クラリアント インターナショナル リミテッド ポジ型放射感応性混合物
JP5087807B2 (ja) * 2006-02-22 2012-12-05 東京応化工業株式会社 有機半導体素子の製造方法及びそれに用いる絶縁膜形成用組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005134908A (ja) * 2003-10-28 2005-05-26 Samsung Electronics Co Ltd 絶縁膜形成用組成物及びこれを用いた絶縁膜または絶縁膜パターンの形成方法
JP2005350558A (ja) * 2004-06-10 2005-12-22 Shin Etsu Chem Co Ltd 多孔質膜形成用組成物、パターン形成方法、及び多孔質犠性膜
JP2006137932A (ja) * 2004-10-12 2006-06-01 Toray Ind Inc コーティング用組成物およびそれを用いた表示装置
JP2005136429A (ja) * 2004-11-12 2005-05-26 Hitachi Chem Co Ltd シリカ系被膜形成用組成物、シリカ系被膜及びその形成方法、並びにシリカ系被膜を備える電子部品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020090420A (ja) * 2018-12-07 2020-06-11 住友金属鉱山株式会社 黒鉛製またはセラミックス製の基板、基板の製造方法、炭化珪素の成膜方法および炭化珪素基板の製造方法

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TW200740939A (en) 2007-11-01
TWI358431B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2012-02-21

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