JPH0559154B2 - - Google Patents
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- Publication number
- JPH0559154B2 JPH0559154B2 JP1022041A JP2204189A JPH0559154B2 JP H0559154 B2 JPH0559154 B2 JP H0559154B2 JP 1022041 A JP1022041 A JP 1022041A JP 2204189 A JP2204189 A JP 2204189A JP H0559154 B2 JPH0559154 B2 JP H0559154B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- oxide film
- solution
- coating liquid
- present
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1212—Zeolites, glasses
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Silicon Polymers (AREA)
- Local Oxidation Of Silicon (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Formation Of Insulating Films (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明な半導体の表面保護又は層間絶縁用酸化
物日膜形成用塗布液および酸化物被膜の製造法に
関し、さらに詳しくは熱的に安定で、かつ成膜性
の良好な半導体の表面保護又は層間絶縁用の酸化
物被膜の製造法およびこの酸化物被膜形成用塗布
液に関する。Detailed Description of the Invention (Field of Industrial Application) More specifically, the present invention relates to a coating solution for forming an oxide film for surface protection or interlayer insulation of semiconductors, and a method for producing an oxide film. The present invention also relates to a method for producing an oxide film for surface protection or interlayer insulation of semiconductors, which has good film formability, and a coating solution for forming the oxide film.
（従来の技術）
従来、IC、LSI等の半導体素子の層間絶縁の方
法として、シラノール化合物の加水分解・縮合物
を焼成し、酸化物被膜を形成する方法がよく知ら
れている。テトラエトキシシラン（エチルシリケ
ート）等の４官能シランを用いる方法が最も多く
検討されているが、４官能シランのみを用いる方
法では、焼成してシリカ被膜を形成する際、三次
元加橋構造が密になり剛直となるため、膜厚が厚
くなるとクラツクが発生するという欠点がある。
この欠点の改善のために２官能や３官能シランを
共加水分解する方法が特開昭57−191219号公報等
に示されているが、これらの方法では縮合物また
は膜の中に多量の炭素が含まれ、焼成によつて膜
の中に炭素が残存する場合は、その後の半導体製
造工程でクラツクが発生するという欠点がある。
また膜の中に含まれる炭素を脱離するためには、
500℃以上の高温が必要であり、炭素の脱離によ
る膜の収縮または脱離後の膜とシリコン、アルミ
等の基体との熱膨張係数の差が大きいため、膜に
クラツクが発生する欠点がある。(Prior Art) Conventionally, as a method for interlayer insulation of semiconductor elements such as ICs and LSIs, a method of forming an oxide film by baking a hydrolyzed/condensed product of a silanol compound is well known. The most studied method is to use tetrafunctional silanes such as tetraethoxysilane (ethyl silicate), but in the method of using only tetrafunctional silanes, the three-dimensional cross-linked structure becomes dense when firing to form a silica film. Since it becomes rigid and rigid, it has the disadvantage that cracks occur when the film thickness increases.
In order to improve this drawback, methods of co-hydrolyzing bifunctional and trifunctional silanes have been shown in Japanese Patent Application Laid-open No. 191219/1983, but these methods do not contain a large amount of carbon in the condensate or film. If carbon is contained in the film and carbon remains in the film after firing, there is a drawback that cracks will occur in the subsequent semiconductor manufacturing process.
In addition, in order to remove carbon contained in the film,
High temperatures of 500°C or higher are required, and the film shrinks due to carbon desorption, or cracks occur in the film due to the large difference in thermal expansion coefficient between the desorbed film and the substrate such as silicon or aluminum. be.
（発明が解決しようとする課題）
本発明の目的は、前記従来技術の欠点を除去
し、熱的に安定で、かつ成膜性の良好な半導体の
表面保護又は層間絶縁用酸化物被膜の製造法及び
この酸化物形成用塗布液を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to eliminate the drawbacks of the prior art and to produce an oxide film for semiconductor surface protection or interlayer insulation that is thermally stable and has good film formability. An object of the present invention is to provide a method and a coating solution for forming an oxide.
（課題を解決するための手段）
本発明者らは、前記目的を達成するため種々研
究した結果、シリコン、アルミ等の基体上でクラ
ツクが発生せず、さらにその後の酸素プラズマ処
理によつてもクラツクの発生のない酸化物被膜を
形成するためには、(1)焼成時の硬化収縮歪を小さ
くする、(2)膜の寧膨張係数を基体の値に近づけ
る、(3)膜の中の炭素含有量を極めて少なくするか
または無くするという条件を満たす塗布液を用い
ることが必要であり、該塗布液は、特定の化合物
を溶剤の存在下に触媒を用いて加水分解、縮合さ
せて得られることを見出し、本発明に到達した。(Means for Solving the Problems) As a result of various studies to achieve the above object, the present inventors found that cracks do not occur on substrates such as silicon and aluminum, and that cracks do not occur even during subsequent oxygen plasma treatment. In order to form a crack-free oxide film, (1) reduce the curing shrinkage strain during firing, (2) bring the film's coefficient of expansion close to that of the substrate, and (3) reduce the It is necessary to use a coating solution that satisfies the condition of extremely low or no carbon content, and the coating solution is obtained by hydrolyzing and condensing a specific compound using a catalyst in the presence of a solvent. The present invention was achieved based on the discovery that
本発明は、(A)一般式RmSi（OR）4-n（式中、Ｒ
は炭素数１〜４のアルキル基またはアリール基、
ｍは０〜２の整数を意味する）で表されるシラン
化合物と、(B)一般式Ｍ（OR′）ｎ（式中、Ｍはマグ
ネシウム、硼素または燐の金属原子、R′は炭素
数１〜４のアルキル基またはアリール基、ｎは金
属原子Ｍの原子価を意味する）で表される金属ア
ルコキシド化合物とを、溶媒の存在下に触媒を用
いて加水分解、縮合させて得られる反応物を含ん
でなる半導体の表面保護又は層間絶縁溶酸化物被
膜形成用塗布液およびこの塗布液を用いた酸化物
被膜の製造法に関する。 The present invention provides (A) general formula RmSi(OR) 4-n (wherein R
is an alkyl group or aryl group having 1 to 4 carbon atoms,
m means an integer of 0 to 2), and (B) a silane compound represented by the general formula M(OR')n (wherein M is a metal atom of magnesium, boron or phosphorus, and R' is the number of carbon atoms A reaction obtained by hydrolyzing and condensing a metal alkoxide compound represented by 1 to 4 alkyl groups or aryl groups (n means the valence of the metal atom M) using a catalyst in the presence of a solvent. The present invention relates to a coating liquid for forming an oxide film for surface protection or interlayer insulation of a semiconductor containing a compound, and a method for producing an oxide film using this coating liquid.
本発明に用いられるシラン化合物は、前記一般
式RmSi（OR）4-nで表され、具体的にはSi
（OCH3）4、Si（OC2H5）4、Si（OC3H7）4等の４官能
シラン、CH3Si（OCH3）3、CH3Si（OC2H5）3、
CH3Si（OC3H7）3、C2H5Si（OCH3）3、C6H5Si
（OH3）3、CH3Si（OC6H5）3等の３官能シラン、
（CH3）2Si（OCH3）2、（CH3）2Si（OC2H5）2、
（CH3）2Si（OC3H7）2、（C2H5）2Si（OCH3）2、
（C6H5）2Si（OCH3）2、（CH3）2Si（OC6H5）2等の２
官能シランが挙げられる。これらのシラン化合物
は単独でまたは２種以上混合して用いることがで
きる。 The silane compound used in the present invention is represented by the general formula RmSi(OR) 4-n , and specifically, Si
Tetrafunctional silanes such as ( OCH3 ) 4 , Si( OC2H5 ) 4 , Si( OC3H7 ) 4 , CH3Si ( OCH3 ) 3 , CH3Si ( OC2H5 ) 3 ,
CH3Si ( OC3H7 ) 3 , C2H5Si ( OCH3 ) 3 , C6H5Si
Trifunctional silanes such as (OH 3 ) 3 , CH 3 Si(OC 6 H 5 ) 3 ,
( CH3 ) 2Si ( OCH3 ) 2 , ( CH3 ) 2Si ( OC2H5 ) 2 ,
( CH3 ) 2Si ( OC3H7 ) 2 , ( C2H5 ) 2Si ( OCH3 ) 2 ,
(C 6 H 5 ) 2 Si (OCH 3 ) 2 , (CH 3 ) 2 Si (OC 6 H 5 ) 2 , etc.
Examples include functional silanes. These silane compounds can be used alone or in combination of two or more.
本発明に用いられる金属アルコキシド化合物
は、前記一般式Ｍ（OR′）ｎで表され、具体的に
はＢ（O-iC3H7）3、Mg（OC3H7）2、Ｐ（O-iC3H7）3
等が挙げられる。これらの金属アルコキシド化合
物は単独でまたは２種以上混合して用いることが
できる。また前記一般式中のＲとR′は等しくて
も異なつていてもよい。 The metal alkoxide compound used in the present invention is represented by the general formula M(OR')n, and specifically includes B(O -i C 3 H 7 ) 3 , Mg(OC 3 H 7 ) 2 , P( O -i C 3 H 7 ) 3
etc. These metal alkoxide compounds can be used alone or in combination of two or more. Furthermore, R and R' in the general formula may be equal or different.
本発明に用いられる前記シラン化合物と金属ア
ルコキシド化合物との共重合組成としては、成膜
性、炭素残渣等の点から、シラン化合物70〜90モ
ル％および金属アルコキシド化合物10〜30モル％
の範囲が好ましく、またこれらのシラン化合物
が、４官能シランSi（OR）4であるか、４官能シラ
ンSi（OR）420〜40モル％、３官能シランRSi
（OR）320〜60モル％、および２官能シランR2Si
（OR）20〜40モル％の混合物であることが好まし
い。 The copolymerization composition of the silane compound and metal alkoxide compound used in the present invention is 70 to 90 mol% of the silane compound and 10 to 30 mol% of the metal alkoxide compound from the viewpoint of film formability, carbon residue, etc.
It is preferable that these silane compounds are tetrafunctional silane Si(OR) 4 , 20 to 40 mol% of tetrafunctional silane Si(OR) 4 , trifunctional silane RSi
(OR) 3 20-60 mol%, and difunctional silane R 2 Si
(OR) 2 It is preferable that it is a mixture of 0 to 40 mol%.
本発明に用いられる溶媒としては、成膜性の点
から、シラン化合物中のアルキル基またはアリー
ル基の炭素を有するアルコール、アルキル基また
はアリール基と反応しないＮ，Ｎ−ジメチルホル
ムアミド等のアミド系の溶媒などが用いられる。
これは混合して用いてもよい。 From the viewpoint of film-forming properties, the solvents used in the present invention include alcohols having carbon atoms in alkyl or aryl groups in the silane compound, and amide-based solvents such as N,N-dimethylformamide that do not react with the alkyl or aryl groups. A solvent or the like is used.
These may be used in combination.
本発明に用いられる反応触媒としては、例えば
塩酸、硫酸、燐酸、硼酸、フツ酸などの無機酸、
五酸化燐、酸化硼素などの酸化物、シユウ酸など
の有機酸等が用いられる。該触該の添加量は、シ
ラン化合物と金属アルコキシド化合物に対して合
計量0.1〜５重量％が好ましい。 Examples of the reaction catalyst used in the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and hydrofluoric acid;
Oxides such as phosphorus pentoxide and boron oxide, organic acids such as oxalic acid, and the like are used. The amount of the catalyst added is preferably 0.1 to 5% by weight in total based on the silane compound and metal alkoxide compound.
本発明の塗布液は、前記アルコキシシラン化合
物と金属アルコキシド化合物とを溶媒の存在下に
前記触媒を用いて加水分解、縮合させて得られ
る。また該溶液を用いて得られる酸化物被膜の熱
膨張係数は、選定する金属アルコキシド化合物の
種類および量によつて任意に変化させることがで
きる。 The coating liquid of the present invention is obtained by hydrolyzing and condensing the alkoxysilane compound and the metal alkoxide compound using the catalyst in the presence of a solvent. Further, the thermal expansion coefficient of the oxide film obtained using the solution can be arbitrarily changed depending on the type and amount of the metal alkoxide compound selected.
本発明の塗布液を用いて酸化物被膜を形成する
に際しては、シリコン、ガラス、セラミツクス、
アルミ等の基体表面に、スピナー、ハケ、スプレ
ー等で塗布液を塗布したのち、通常50〜200℃、
好ましくは100〜150℃で乾燥し、次いで通常400
〜800℃、好ましくは400〜500℃で焼成する。 When forming an oxide film using the coating liquid of the present invention, silicon, glass, ceramics,
After applying the coating liquid to the surface of a substrate such as aluminum using a spinner, brush, spray, etc., the temperature is usually 50 to 200℃.
Dry preferably at 100-150℃, then usually at 400℃
Calcinate at ~800°C, preferably 400-500°C.
本発明の塗布液を用いて得られる酸化物被膜
は、従来のシラノール縮合物を用いて得られる酸
化膜被膜と比較して、炭素含有量が少なく、また
第２成分としてマグネシウム、硼素または燐の酸
化物が含まれ、これらがSiO2と共重合体を形成
するために熱的に安定であり、成膜性も良好とな
る。 The oxide film obtained using the coating solution of the present invention has a lower carbon content than the oxide film obtained using conventional silanol condensates, and also contains magnesium, boron, or phosphorus as a second component. Since it contains oxides and forms a copolymer with SiO 2 , it is thermally stable and has good film-forming properties.
（実施例） 以下、本発明を実施例により詳しく説明する。(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例 １
Si（OCH3）451ｇ、CH3Si（OCH3）345ｇ、
（CH3）2Si（OCH3）212ｇ、Ｂ（ｉ−OC3H7）331ｇ、
Mg（OC3H7）210ｇをＮ，Ｎ−ジメチルホルムア
ミド160ｇおよびメチルアルコール40ｇの混合溶
媒中に溶解し、この溶液にさらにシユウ酸0.6ｇ
を溶解させた水55ｇを添加して加水分解、縮合を
行い、反応物溶液を作製した。Example 1 Si(OCH 3 ) 4 51g, CH 3 Si(OCH 3 ) 3 45g,
( CH3 ) 2Si ( OCH3 ) 212g , B (i- OC3H7 ) 331g ,
10 g of Mg(OC 3 H 7 ) 2 was dissolved in a mixed solvent of 160 g of N,N-dimethylformamide and 40 g of methyl alcohol, and 0.6 g of oxalic acid was added to this solution.
55 g of water in which was dissolved was added to perform hydrolysis and condensation to prepare a reactant solution.
この溶液をスピナーを用いて3000rpmでSiウエ
ハー上に塗布した後、150℃で１時間乾燥し、次
いで電気炉中、400℃で１時間焼成したところ、
無色透明でクラツクのないシリカ系被膜が得られ
た。 This solution was applied onto a Si wafer at 3000 rpm using a spinner, dried at 150°C for 1 hour, and then baked at 400°C for 1 hour in an electric furnace.
A colorless, transparent and crack-free silica-based coating was obtained.
該シリカ系被膜の膜厚を、表面あらさ計（商品
名タリステツプ、ランクテーラーホブソン社製）
を用いて測定したところ、0.7μｍであつた。また
該被膜の吸収スペクトルを赤外分光光度計を用い
て測定いしたところ、Si−Ｏ−Si吸収の他に、
Mg−Ｏ、Ｂ−Ｏ結合の吸収が観察され、完全な
酸化膜であることが確認された。さらに本酸化膜
をバレル型酸素プラズマ灰化装置PR−501A型
（ヤマト科学社製）を用いて400Wで20分間処理し
たが、膜中にクラツクは認められなかつた。 The thickness of the silica coating was measured using a surface roughness meter (trade name Talystep, manufactured by Rank Taylor Hobson).
When measured using a , it was 0.7 μm. When the absorption spectrum of the film was measured using an infrared spectrophotometer, it was found that in addition to Si-O-Si absorption,
Absorption of Mg-O and B-O bonds was observed, and it was confirmed that the film was a complete oxide film. Furthermore, this oxide film was treated at 400W for 20 minutes using a barrel type oxygen plasma incineration device PR-501A (manufactured by Yamato Scientific Co., Ltd.), but no cracks were observed in the film.
また前記溶液を、厚さ0.7μｍ、ラインアンドス
ペース幅0.5〜5μｍのアルミパターンが蒸着され
たSiウエハー上に前記と同様の条件で成膜したと
ころ、無色透明でクラツクのない酸化被膜が得ら
れた。 Furthermore, when the solution was deposited under the same conditions as above on a Si wafer on which an aluminum pattern with a thickness of 0.7 μm and a line-and-space width of 0.5 to 5 μm was deposited, a colorless and transparent oxide film without cracks was obtained. Ta.
さらに前記溶液を150℃で３時間乾燥した後、
得られた粉末を直径12mmのペレツト状に圧縮成形
し、電気炉中で1000℃で１時間焼成した。この試
料の熱膨張係数を理学電機社製、熱物理試験機
TMA8150型で測定したところ、室温から450℃
までの平均線熱膨張係数は7.0×10-6であつた。 Furthermore, after drying the solution at 150°C for 3 hours,
The obtained powder was compression molded into pellets with a diameter of 12 mm, and fired at 1000° C. for 1 hour in an electric furnace. The thermal expansion coefficient of this sample was measured using a thermophysical testing machine manufactured by Rigaku Denki Co., Ltd.
When measured with the TMA8150 model, the temperature ranged from room temperature to 450℃.
The average linear thermal expansion coefficient up to this point was 7.0×10 -6 .
実施例 ２
Si（OC2H5）4145ｇ、Ｐ（OC3H7）341ｇ、Mg
（OC3H7）214ｇをエチルアルコール300ｇに溶解
し、この液にさらにシユウ酸0.8ｇを溶解させた
水66ｇを添加して加水分解、縮合を行い反応物溶
液を作製した。Example 2 Si(OC 2 H 5 ) 4 145g, P(OC 3 H 7 ) 3 41g, Mg
14 g of (OC 3 H 7 ) 2 was dissolved in 300 g of ethyl alcohol, and 66 g of water in which 0.8 g of oxalic acid had been dissolved was further added to the solution for hydrolysis and condensation to prepare a reaction product solution.
この液を実施例１と同様な条件でSiウエハー上
に塗布、乾燥、焼成したところ、膜厚0.5μｍの無
色透明でクラツクのないシリカ系被膜が得られ
た。また前記溶液を実施例１と同様な条件でアル
ミパターンを蒸着したSiウエハー上に成膜したと
ころ、無色透明でクラツクのない酸化物被膜が得
られた。 When this liquid was applied onto a Si wafer under the same conditions as in Example 1, dried, and baked, a colorless, transparent, crack-free silica-based film with a thickness of 0.5 μm was obtained. When the solution was applied to a Si wafer on which an aluminum pattern had been deposited under the same conditions as in Example 1, a colorless and transparent oxide film without cracks was obtained.
実施例 ３
Si（OC2H5）469ｇ、CH3Si（OC2H5）359ｇ、
（CH3）2Si（OC2H5）225ｇ、Ｂ（O-iC3H7）331ｇをエ
チルアルコール26ｇおよびＮ，Ｎ−ジメチルホル
ムアミド105ｇの混合溶媒中に溶解し、この溶液
にさらにシユウ酸0.6ｇを溶解させた水56ｇを添
加して加水分解、縮合を行い、反応物溶液を作製
した。Example 3 Si(OC 2 H 5 ) 4 69g, CH 3 Si(OC 2 H 5 ) 3 59g,
25 g of (CH 3 ) 2 Si(OC 2 H 5 ) 2 and 31 g of B(O -i C 3 H 7 ) 3 were dissolved in a mixed solvent of 26 g of ethyl alcohol and 105 g of N,N-dimethylformamide, and added to this solution. Furthermore, 56 g of water in which 0.6 g of oxalic acid was dissolved was added to perform hydrolysis and condensation to prepare a reactant solution.
この溶液を実施例１と同様な条件でSiウエハー
およびアルミパターンを蒸着したSiウエハー上に
成膜したところ、膜厚0.7μｍの無色透明でクラツ
クのない酸化物被膜が得られた。 When this solution was deposited under the same conditions as in Example 1 on a Si wafer and a Si wafer on which an aluminum pattern had been deposited, a colorless, transparent, crack-free oxide film with a thickness of 0.7 μm was obtained.
実施例 ４
Si（OCH3）4、51ｇ、CH3Si（OCH3）330ｇ、
C6H5Si（OCH3）322ｇ、（CH3）2Si（OCH3）212ｇ、
Ｂ（O-iC3H7）331ｇ、Mg（OC3H7）210ｇをジエチ
レングリコールジエチルエーテル200ｇに溶解し、
この溶液に燐酸0.5ｇを溶解させた水55ｇを添加
して加水分解、縮合を行い、反応物溶液を作製し
た。Example 4 Si(OCH 3 ) 4 , 51 g, CH 3 Si(OCH 3 ) 3 30 g,
C 6 H 5 Si(OCH 3 ) 3 22g, (CH 3 ) 2 Si(OCH 3 ) 2 12g,
Dissolve 31 g of B(O -i C 3 H 7 ) 3 and 10 g of Mg(OC 3 H 7 ) 2 in 200 g of diethylene glycol diethyl ether,
55 g of water in which 0.5 g of phosphoric acid was dissolved was added to this solution to perform hydrolysis and condensation to prepare a reactant solution.
この溶液を実施例１と同様な条件でSiウエハー
およびアルミパターンを蒸着したSiウエハー上に
成膜したところ、膜厚0.8μｍの無色透明でクラツ
クのない酸化物被膜が得られた。 When this solution was deposited under the same conditions as in Example 1 on a Si wafer and a Si wafer on which an aluminum pattern had been deposited, a colorless, transparent, crack-free oxide film with a thickness of 0.8 μm was obtained.
比較例 １
Si（OC2H5）435ｇを、エチルアルコール64ｇお
よび酢酸エチル26ｇの混合溶媒に溶解し、この溶
液にさらにシユウ酸0.5ｇを溶解させた水12ｇを
添加して加水分解、縮合を行い、シラノールオリ
ゴマー溶液を作製した。Comparative Example 1 35 g of Si(OC 2 H 5 ) 4 was dissolved in a mixed solvent of 64 g of ethyl alcohol and 26 g of ethyl acetate, and 12 g of water in which 0.5 g of oxalic acid was dissolved was added to this solution for hydrolysis and condensation. A silanol oligomer solution was prepared.
この溶液を実施例１と同様にしてSiウエハー上
に塗布したところ、約0.4μｍの膜が得られたが、
膜には多数のクラツクが存在していた。 When this solution was applied onto a Si wafer in the same manner as in Example 1, a film of approximately 0.4 μm was obtained.
There were many cracks in the membrane.
比較例 ２
Si（OCH3）417ｇ、CH3Si（OCH3）325ｇおよび
（CH3）2Si（OCH3）25ｇを、Ｎ，Ｎ−ジメチルホル
ムアミド48ｇおよびメタノール６ｇの混合溶媒に
溶解し、この溶液にさらに燐酸0.5ｇを溶解させ
た水20ｇを添加して加水分解、縮合を行い、シラ
ノールオリゴマー溶液を作製した。Comparative Example 2 17g of Si( OCH3 ) 4 , 25g of CH3Si ( OCH3 ) 3 and 5g of ( CH3 ) 2Si ( OCH3 ) 2 are dissolved in a mixed solvent of 48g of N,N-dimethylformamide and 6g of methanol. Then, 20 g of water in which 0.5 g of phosphoric acid was dissolved was further added to this solution to perform hydrolysis and condensation to prepare a silanol oligomer solution.
この溶液を実施例１と同様にしてSiウエハー上
に塗布したところ、約0.7μｍの膜が得られた。該
膜の吸収スペクトルを赤外分光光度計を用いて測
定したところ、Si−Ｏ−Si吸収の他にSi−CH3の
強い吸収がみられ、完全にSiO2膜になつていな
いことが確認された。またこの膜を実施例１と同
様にして400Wで20分間酸素プラズマ処理したと
ころ、膜中にクラツクが発生した。 When this solution was applied onto a Si wafer in the same manner as in Example 1, a film of about 0.7 μm was obtained. When the absorption spectrum of the film was measured using an infrared spectrophotometer, strong absorption of Si-CH 3 was observed in addition to Si-O-Si absorption, confirming that it had not completely become a SiO 2 film. It was done. Further, when this film was subjected to oxygen plasma treatment at 400 W for 20 minutes in the same manner as in Example 1, cracks occurred in the film.
（発明の効果）
本発明の酸化物被膜形成用塗布液は、熱的に安
定で成膜性に優れるため、該塗布液を用いて基体
表面上に形成した酸化膜被膜には、1.5μｍ程度の
厚さとしてもクラツクの発生がなく、本発明の酸
化物被膜形成用塗布液は、半導体の表面保護又は
層間絶縁用として好適であり電子部品、特に半導
体の多層配線における層間段差の被膜、磁気バブ
ルメモリー等の素子表面の平坦化等に有効であ
る。(Effects of the Invention) The coating liquid for forming an oxide film of the present invention is thermally stable and has excellent film forming properties, so that the oxide film formed on the surface of the substrate using the coating liquid has a thickness of about 1.5 μm The coating liquid for forming an oxide film of the present invention is suitable for surface protection of semiconductors or interlayer insulation, and is suitable for use as a coating on interlayer steps in electronic components, especially in multilayer wiring of semiconductors, and magnetic It is effective for flattening the surface of devices such as bubble memories.
Claims (1)
１〜４のアルキル基またはアリール基、ｍは０〜
２の整数を意味する）で表されるシラン化合物
と、(B)一般式Ｍ（OR′）ｎ（式中、Ｍはマグネシウ
ム、硼素または燐の金属原子、R′は炭素数１〜
４のアルキル基またはアリール基、ｎは金属原子
Ｍの原子価を意味する）で表される金属アルコキ
ジド化合物とを、溶媒の存在下に触媒を用いて加
水分解、縮合させて得られる反応物を含んでなる
半導体の表面保護又は層間絶縁用酸化物被膜形成
用塗布液。 ２ 請求項１記載の塗布液を、基体表面上に塗布
後50〜200℃で乾燥し、ついで400〜800℃で焼成
する半導体の表面保護又は層間絶縁用酸化物被膜
の製造法。[Claims] 1 (A) General formula RmSi(OR) 4-n (wherein, R is an alkyl group or aryl group having 1 to 4 carbon atoms, m is 0 to
(B) a silane compound represented by the general formula M(OR')n (where M is a metal atom of magnesium, boron or phosphorus, and R' is a carbon number of 1 to 2);
A reaction product obtained by hydrolyzing and condensing a metal alkoxide compound represented by the alkyl group or aryl group of 4 (n means the valence of the metal atom M) using a catalyst in the presence of a solvent. A coating liquid for forming an oxide film for surface protection or interlayer insulation of semiconductors. 2. A method for producing an oxide film for semiconductor surface protection or interlayer insulation, which comprises applying the coating liquid according to claim 1 onto the surface of a substrate, drying at 50 to 200°C, and then baking at 400 to 800°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1022041A JPH021778A (en) | 1988-02-02 | 1989-01-31 | Coating liquid for forming oxide coating film and production of oxide coating film |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2237088 | 1988-02-02 | ||
| JP63-22370 | 1988-02-02 | ||
| JP1022041A JPH021778A (en) | 1988-02-02 | 1989-01-31 | Coating liquid for forming oxide coating film and production of oxide coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH021778A JPH021778A (en) | 1990-01-08 |
| JPH0559154B2 true JPH0559154B2 (en) | 1993-08-30 |
Family
ID=12080747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1022041A Granted JPH021778A (en) | 1988-02-02 | 1989-01-31 | Coating liquid for forming oxide coating film and production of oxide coating film |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0327311B1 (en) |
| JP (1) | JPH021778A (en) |
| DE (1) | DE68918124T2 (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02258839A (en) * | 1989-03-31 | 1990-10-19 | Fuji Xerox Co Ltd | Production of inorganic and organic composite material |
| JPH02258841A (en) * | 1989-03-31 | 1990-10-19 | Fuji Xerox Co Ltd | Production of inorganic and organic composite material |
| JP2576065B2 (en) * | 1989-03-31 | 1997-01-29 | 富士ゼロックス株式会社 | Semiconductive polymer composition |
| JP2576066B2 (en) * | 1989-03-31 | 1997-01-29 | 富士ゼロックス株式会社 | Semiconductive polymer composition |
| BE1008162A5 (en) * | 1989-09-27 | 1996-02-06 | Air Prod & Chem | Carbonated manufactured products and method for producing same |
| DE4018984A1 (en) * | 1990-06-13 | 1991-12-19 | Wacker Chemitronic | METHOD FOR THE PRODUCTION OF STORAGE-STABLE SURFACES OF POLISHED SILICON DISC |
| JP2739916B2 (en) * | 1992-02-18 | 1998-04-15 | キヤノン株式会社 | Glass blank for manufacturing optical element and method for manufacturing optical element using the same |
| DE4225106C2 (en) * | 1992-07-30 | 1995-10-05 | Heraeus Kulzer Gmbh | Method and device for producing a metal-plastic composite |
| EP0768352A4 (en) * | 1994-06-30 | 1997-12-10 | Hitachi Chemical Co Ltd | Material for forming silica-base coated insulation film, process for producing the material, silica-base insulation film, semiconductor device, and process for producing the device |
| DE19714949A1 (en) * | 1997-04-10 | 1998-10-15 | Inst Neue Mat Gemein Gmbh | Process for providing a metallic surface with a glass-like layer |
| JP4499907B2 (en) * | 2000-12-07 | 2010-07-14 | 富士化学株式会社 | Method for producing inorganic polymer compound, inorganic polymer compound, and inorganic polymer compound film |
| US7015061B2 (en) * | 2004-08-03 | 2006-03-21 | Honeywell International Inc. | Low temperature curable materials for optical applications |
| US20060057418A1 (en) | 2004-09-16 | 2006-03-16 | Aeromet Technologies, Inc. | Alluminide coatings containing silicon and yttrium for superalloys and method of forming such coatings |
| PL3095895T3 (en) * | 2004-12-13 | 2019-10-31 | Mt Coatings Llc | Method of forming silicon-containing protective coatings on metal components |
| US9133718B2 (en) | 2004-12-13 | 2015-09-15 | Mt Coatings, Llc | Turbine engine components with non-aluminide silicon-containing and chromium-containing protective coatings and methods of forming such non-aluminide protective coatings |
| KR20070108658A (en) * | 2006-05-08 | 2007-11-13 | 유영선 | Method for producing coating liquid composition for insulating film formation of semiconductor device and prepared coating liquid composition |
| EP2046893A2 (en) * | 2006-08-04 | 2009-04-15 | Dow Corning Corporation | Silicone resin and silicone composition |
| US8557877B2 (en) | 2009-06-10 | 2013-10-15 | Honeywell International Inc. | Anti-reflective coatings for optically transparent substrates |
| RU2444540C1 (en) * | 2010-10-21 | 2012-03-10 | Общество с ограниченной ответственностью "Пента-91" | Method of producing polymetallosiloxanes |
| JP2014507516A (en) | 2011-01-05 | 2014-03-27 | ダウ コーニング コーポレーション | Polyheterosiloxane for high refractive index materials |
| RU2453550C1 (en) * | 2011-03-09 | 2012-06-20 | Федеральное государственное унитарное предприятие "Государственный ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП ГНИИХТЭОС) | Method of producing yttrium-containing organoaluminoxane siloxanes, binding and impregnating compositions based thereon |
| US8864898B2 (en) | 2011-05-31 | 2014-10-21 | Honeywell International Inc. | Coating formulations for optical elements |
| GB2496708A (en) * | 2011-11-17 | 2013-05-22 | Dow Corning | Solvent-borne scratch resistant coating compositions containing polymetallosiloxanes |
| JP6015389B2 (en) * | 2012-11-30 | 2016-10-26 | 株式会社リコー | Field effect transistor, display element, image display device, and system |
| JP6803842B2 (en) | 2015-04-13 | 2020-12-23 | ハネウェル・インターナショナル・インコーポレーテッドＨｏｎｅｙｗｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｉｎｃ． | Polysiloxane formulations and coatings for optoelectronic applications |
| CN110289204B (en) * | 2018-03-19 | 2023-08-15 | 株式会社理光 | Coating solution for oxide insulator film formation |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3847583A (en) * | 1969-08-13 | 1974-11-12 | Jenaer Glaswerk Schott & Gen | Process for the manufacture of multi-component substances |
| FR2123652A5 (en) * | 1970-02-19 | 1972-09-15 | Ibm | |
| IN152814B (en) * | 1978-08-08 | 1984-04-14 | Westinghouse Electric Corp | |
| JPS5534276A (en) * | 1978-09-04 | 1980-03-10 | Tokyo Denshi Kagaku Kabushiki | Preparation of coating liquid for silica-based film formation |
| JPS5638472A (en) * | 1979-09-06 | 1981-04-13 | Tokyo Denshi Kagaku Kabushiki | Formation of silica coating |
| US4318939A (en) * | 1980-08-21 | 1982-03-09 | Western Electric Co., Incorporated | Stabilized catalyzed organopolysiloxanes |
| JPS60258477A (en) * | 1984-06-02 | 1985-12-20 | Nippon Steel Corp | Formation of insulating film on silicon steel sheet |
-
1989
- 1989-01-31 JP JP1022041A patent/JPH021778A/en active Granted
- 1989-01-31 EP EP19890300927 patent/EP0327311B1/en not_active Expired - Lifetime
- 1989-01-31 DE DE1989618124 patent/DE68918124T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0327311A3 (en) | 1990-08-01 |
| EP0327311A2 (en) | 1989-08-09 |
| EP0327311B1 (en) | 1994-09-14 |
| DE68918124T2 (en) | 1995-02-23 |
| DE68918124D1 (en) | 1994-10-20 |
| JPH021778A (en) | 1990-01-08 |
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