WO2007111270A1 - 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
WO2007111270A1
WO2007111270A1 PCT/JP2007/056090 JP2007056090W WO2007111270A1 WO 2007111270 A1 WO2007111270 A1 WO 2007111270A1 JP 2007056090 W JP2007056090 W JP 2007056090W WO 2007111270 A1 WO2007111270 A1 WO 2007111270A1
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WO
WIPO (PCT)
Prior art keywords
silica
composition
forming
based film
compound
Prior art date
Application number
PCT/JP2007/056090
Other languages
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 WO2007111270A1 publication Critical patent/WO2007111270A1/ja

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Classifications

    • 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 added to the silica-based film-forming composition. As a result, dehydration or dealk The present inventors have found that the above-mentioned problems can be solved by using a compound that causes a polyol reaction, and have completed the present invention. 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 causes a dehydration or dealcoholization reaction by the action of heat. is there.
  • 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 causes a dehydration or dealcohol reaction 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.
  • composition for forming a silica-based film of the present invention comprises a siloxane polymer (A) and a compound (B) that causes a dehydration or dealcoholization reaction 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.
  • alkoxysilanes hydrolysis-condensation products of alkoxysilanes can be suitably used.
  • Any kind of alkoxysilane can be used as the alkoxysilane.
  • Examples of such alkoxysilanes include compounds represented by the following general formula (a).
  • R 2 is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group
  • R 3 is a monovalent organic group
  • m 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, such as a phenol group and a naphthyl group.
  • examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
  • dialkyl dialkoxysilane diphenyl such as dimethylenoresimethoxymethoxy, dimethylenoresetoxysilane, dimethylenoresipropoxysilane, getinoresioxymethoxysilane, getinolegetoxysilane, getinoresidipropoxysilane, etc.
  • diphenyl dialkoxysilane such as dimethoxysilane and diphenyljetoxysilane.
  • the weight average molecular weight of the siloxane polymer (A) is preferably 200 or more and 50000 or less, more preferably 1000 or more and 3000 or less. Within this range, the coating properties of the silica-based film-forming composition are improved. Can be raised.
  • 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 added water is 1.0 to LO: 0 times the total number of moles of alkoxysilane represented by the chemical formula (a). More preferably, it is added in a proportion of 5 to 8.0 moles.
  • 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: LOO time.
  • the reaction is performed by adding an acid catalyst aqueous solution dropwise to the organic solvent containing one or more alkoxysilanes represented by the chemical formula (a) to cause a reaction. It is also possible to complete the reaction in the reaction time.
  • the hydrolyzed alkoxysilane is then subjected to a condensation reaction. As a result, a Si-O-Si network is formed.
  • component (B) Compounds that cause dehydration or dealcoholization reaction by the action of heat (hereinafter referred to as “component (B)
  • a silica-based film By adding a compound that causes dehydration or dealcoholization reaction by the action of heat to the composition for forming a silica-based film, a silica-based film can be formed without firing at a high temperature of, for example, 350 ° C or higher. Can do. Thereby, heating (for example, drying and firing) after applying the composition for forming a silica-based film can be simplified.
  • Such a substance is preferably a silicon compound having an isocyanate group, and more preferably a compound represented by the following general formula (b).
  • R 1 is an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 0 to 3.
  • Examples of the compound represented by the general formula (b) include tetraisocyanate. Nate silane, methyl triisocyanate silane, etyl triisocyanate silane, propyl triisocyanate silane, butyl triisocyanate silane, dimethyl diisocyanate silane, jetyl diisocyanate silane, dipropyl diisocyanate silane, dibuty Examples thereof include noresisocyanate silane, trimethylenoisocyanate silane, triethinoreisocyanate silane, tripropinoreisocyanate silane, and tributylisocyanate silane.
  • these components (B) may be used alone or in combination of two or more.
  • the content of component (B) is 0.1% by mass or more and 20 quality with respect to the SiO equivalent mass of 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 ethenore, ethylene glycol monomono chineno ethenore, ethylene glycol enore Monopropinoreethenole, Ethyleneglycolenomonobutenoreethenore
  • 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 means, temperature, time, etc. of the heat treatment are not particularly limited, but can be heated for about 1 to 6 minutes on a hot plate of about 80 to 300 ° C.
  • the heat treatment promotes the dehydration reaction or dealcoholization reaction of the component (A) by the component (B).
  • This dehydration reaction or dealcoholization reaction forms a Si—O—Si network, so that a dense silica-based film can be obtained.
  • the temperature of the heat treatment is increased in three steps or more. 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.
  • Tetraisocyanate silane was added so as to be 1% by mass with respect to the solid content in the spin-on glass material to produce a composition for forming a silica-based film.
  • 6 inch silico The composition for forming a silica-based film was applied onto a 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 was formed in the same manner as in Example 1 using OCD T-12 1000V.
  • Comparative Example 1 after heating, a silica-based film was formed by baking at 400 ° C. in a nitrogen atmosphere.
  • Example 1 in which the additive was calorie compared to Comparative Example 1 in which the additive (tetraisocyanate silane) had a strong force was obtained by heating at 200 ° C or lower. It was confirmed that the network was formed.
  • the ratio of Si—OZS i—H is comparable to that in Comparative Example 2 where firing was performed at 400 ° C., and the same Si—O—Si network was formed as when firing was performed. ! / I was able to confirm.

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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)
  • Silicon Polymers (AREA)
PCT/JP2007/056090 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 WO2007111270A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-083733 2006-03-24
JP2006083733A JP2007254678A (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

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JP (1) JP2007254678A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
TW (1) TW200745265A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO2007111270A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5991846B2 (ja) * 2012-04-24 2016-09-14 東京応化工業株式会社 膜形成用組成物、拡散剤組成物、膜形成用組成物の製造方法、及び拡散剤組成物の製造方法
JP6013150B2 (ja) * 2012-11-22 2016-10-25 メルクパフォーマンスマテリアルズマニュファクチャリング合同会社 ポジ型感光性シロキサン組成物の製造方法
JP2015052101A (ja) * 2013-08-06 2015-03-19 東京応化工業株式会社 膜形成用材料
JP6533443B2 (ja) * 2014-10-03 2019-06-19 東京応化工業株式会社 半導体基板の製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58216194A (ja) * 1982-06-10 1983-12-15 Matsumoto Seiyaku Kogyo Kk シリケ−ト組成物
JPS6366264A (ja) * 1986-09-09 1988-03-24 Matsumoto Seiyaku Kogyo Kk 耐熱絶縁塗料組成物
JPS63110263A (ja) * 1986-10-27 1988-05-14 Matsumoto Seiyaku Kogyo Kk 表面処理方法
JPH0499029A (ja) * 1990-08-07 1992-03-31 Nec Corp 絶縁膜の形成方法
JP2003171616A (ja) * 2001-12-04 2003-06-20 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
WO2003087228A1 (fr) * 2002-04-12 2003-10-23 Clariant International Ltd. Composition de copolymere contenant du silicium, copolymere contenant du silicium reticule soluble dans un solvant, et articles durcis obtenus a partir de ladite composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58216194A (ja) * 1982-06-10 1983-12-15 Matsumoto Seiyaku Kogyo Kk シリケ−ト組成物
JPS6366264A (ja) * 1986-09-09 1988-03-24 Matsumoto Seiyaku Kogyo Kk 耐熱絶縁塗料組成物
JPS63110263A (ja) * 1986-10-27 1988-05-14 Matsumoto Seiyaku Kogyo Kk 表面処理方法
JPH0499029A (ja) * 1990-08-07 1992-03-31 Nec Corp 絶縁膜の形成方法
JP2003171616A (ja) * 2001-12-04 2003-06-20 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
WO2003087228A1 (fr) * 2002-04-12 2003-10-23 Clariant International Ltd. Composition de copolymere contenant du silicium, copolymere contenant du silicium reticule soluble dans un solvant, et articles durcis obtenus a partir de ladite composition

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TWI358427B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2012-02-21
TW200745265A (en) 2007-12-16

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