【０００１】[0001]
【発明の属する技術分野】本発明は、シリカ系被膜形成
用塗布液、シリカ系被膜の製造法及び半導体装置に関す
る。The present invention relates to a coating solution for forming a silica-based film, a method for producing a silica-based film, and a semiconductor device.
【０００２】[0002]
【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、シリカ系被膜を形成する方法がよく用い
られている。テトラエトキシシラン等の４官能シランを
用いる方法が最も多く知られているが、４官能シランの
みを用いる方法では、焼成してシリカ系被膜を形成する
際に発生する収縮応力が大きいために、膜厚が厚くなる
とクラックが発生するのと被膜の吸湿性が高いために誘
電率が高いという問題がある。一方、ヒドロポリシラザ
ンを用いたシリカ系被膜の形成法（特開平４−３４１７
０５号公報、特開平５−１０５４８６号公報）が提案さ
れているが５００℃程度の熱処理では得られる膜の吸水
性が大きく、ＣＶＤ等で形成されるシリカ膜と比較して
誘電率が高い等の問題がある。2. Description of the Related Art Conventionally, as a method for interlayer insulation of semiconductor devices such as ICs and LSIs, a method of forming a silica-based coating by hydrolyzing a silanol compound and baking a condensate is often used. A method using tetrafunctional silane such as tetraethoxysilane is most known, but a method using only tetrafunctional silane causes a large shrinkage stress generated when a silica-based film is formed by sintering. When the thickness is large, there is a problem that cracks occur and the dielectric constant is high because the film has high hygroscopicity. On the other hand, a method for forming a silica-based coating using hydropolysilazane (Japanese Patent Laid-Open No. 4-3417)
No. 05, Japanese Patent Application Laid-Open No. 5-105486), but a film obtained by heat treatment at about 500 ° C. has a large water absorption, and has a higher dielectric constant than a silica film formed by CVD or the like. There is a problem.
【０００３】[0003]
【発明が解決しようとする課題】請求項１記載の発明
は、成膜性が良好で且つ、低誘電率なシリカ系被膜の形
成可能なシリカ系被膜形成用塗布液を提供するものであ
る。請求項２記載の発明は、低誘電率なシリカ系被膜を
容易に歩留りよく製造できるシリカ系被膜の製造法を提
供するものである。請求項３記載の発明は、高信頼性で
高品位な半導体装置を提供するものである。SUMMARY OF THE INVENTION The first aspect of the present invention provides a coating solution for forming a silica-based coating film having good film-forming properties and capable of forming a silica-based coating film having a low dielectric constant. The second aspect of the present invention provides a method for producing a silica-based coating capable of easily producing a low-dielectric-constant silica-based coating with good yield. The third aspect of the present invention provides a highly reliable and high quality semiconductor device.
【０００４】[0004]
【課題を解決するための手段】本発明は、（Ａ）一般式
（Ｉ）According to the present invention, there is provided (A) a compound represented by the following general formula (I):
【化５】（Ｒは炭素数１〜４のアルキル基を示す）で表されるテ
トラアルコキシシラン、（Ｂ）一般式（II）Embedded image (R represents an alkyl group having 1 to 4 carbon atoms), (B) a general formula (II)
【化６】（Ｒは炭素数１〜４のアルキル基を示す）で表されるト
リフルオロプロピルトリアルコキシシラン、（Ｃ）一般
式（III）Embedded image (R represents an alkyl group having 1 to 4 carbon atoms), (C) a general formula (III)
【化７】（Ｒは炭素数１〜４のアルキル基を示す）で表されるメ
チルトリアルコキシシラン及び（Ｄ）一般式（IV）Embedded image (R represents an alkyl group having 1 to 4 carbon atoms), and (D) a general formula (IV)
【化８】（Ｒは炭素数１〜４のアルキル基を示す）で表されるジ
メチルジアルコキシシランを溶媒の存在下に水と触媒を
添加して加水分解、縮重合して得られるシロキサンオリ
ゴマーを含むシリカ系被膜形成用塗布液に関する。Embedded image (R represents an alkyl group having 1 to 4 carbon atoms) Silica-based siloxane oligomer containing siloxane oligomer obtained by adding water and a catalyst in the presence of a solvent, adding water and a catalyst, and hydrolyzing and condensation-polymerizing the dimethyldialkoxysilane. The present invention relates to a coating solution for forming a film.
【０００５】また、本発明は、前記のシリカ系被膜形成
用塗布液を、基体表面上に塗布後、５０〜２００℃で乾
燥し、ついで３００〜５００℃で焼成するシリカ系被膜
の製造法に関する。また、本発明は、前記シリカ系被膜
を用いた半導体装置に関する。The present invention also relates to a method for producing a silica-based coating, which comprises applying the above-mentioned coating liquid for forming a silica-based coating on a substrate surface, drying the coating at 50 to 200 ° C., and then firing at 300 to 500 ° C. . The present invention also relates to a semiconductor device using the silica-based coating.
【０００６】[0006]
【発明の実施の形態】本発明に用いられる（Ａ）テトラ
アルコキシシランは、前記一般式（Ｉ）で表せ、具体的
には、BEST MODE FOR CARRYING OUT THE INVENTION The (A) tetraalkoxysilane used in the present invention can be represented by the above general formula (I).
【化９】等が挙げられる。Embedded image And the like.
【０００７】また（Ｂ）トリフルオロプロピルトリアル
コキシシランは、前記一般式（II）で表せ、具体的に
は、The trifluoropropyl trialkoxysilane (B) can be represented by the above general formula (II).
【化１０】等が挙げられる。Embedded image And the like.
【０００８】また（Ｃ）メチルトリアルコキシシラン
は、前記一般式（III）で表せ、具体的には、The (C) methyl trialkoxysilane can be represented by the above general formula (III).
【化１１】等が挙げられる。Embedded image And the like.
【０００９】また（Ｄ）ジメチルジアルコキシシラン
は、前記一般式（IV）で表せ、具体的には、Further, (D) dimethyldialkoxysilane can be represented by the above general formula (IV).
【化１２】等が挙げられる。Embedded image And the like.
【００１０】これら４種の混合比は、（Ａ）テトラアル
コキシシラン１モルに対して、（Ｂ）メチルトリアルコ
キシシラン０．５〜２モル、（Ｃ）トリフルオロプロピ
ルトリアルコキシシランが０．１〜０．５モル、（Ｄ）
メチルフェニルジアルコキシシランが０．２〜０．５モ
ルの範囲とすることが好ましい。The mixing ratio of these four kinds is such that 0.5 mol to 2 mol of (B) methyl trialkoxysilane and 0.1 mol of (C) trifluoropropyl trialkoxysilane to 1 mol of (A) tetraalkoxysilane. ~ 0.5 mol, (D)
It is preferable that methylphenyldialkoxysilane be in the range of 0.2 to 0.5 mol.
【００１１】また、加水分解、縮重合反応に用いられ触
媒としては、酸触媒、塩基性触媒のいずれでも良く、具
体的にはリン酸、硝酸、硫酸、マレイン酸、フマル酸、
ギ酸、酢酸などの酸触媒或いはアンモニアなどの塩基性
触媒が挙げられる。また、これらの添加量は、アルコキ
シシラン１モルに対して０．１〜０．００１モルの範囲
が好ましい。添加する水の量としては、アルコキシシラ
ン１モルに対して０．１〜１０モルの範囲が好ましく、
０．５〜１．５モルの範囲がより好ましい。本発明に用
いられる溶媒としては、アルコール、ケトン、グリコー
ルエーテル、酢酸エステル類などが挙げられ、これらは
単独で又は２種以上を組み合わせて用いられる。The catalyst used in the hydrolysis and polycondensation reactions may be either an acid catalyst or a basic catalyst. Specifically, phosphoric acid, nitric acid, sulfuric acid, maleic acid, fumaric acid,
Examples thereof include an acid catalyst such as formic acid and acetic acid and a basic catalyst such as ammonia. The amount of these additives is preferably in the range of 0.1 to 0.001 mol per 1 mol of alkoxysilane. The amount of water to be added is preferably in the range of 0.1 to 10 mol per mol of alkoxysilane,
A range of 0.5 to 1.5 mol is more preferred. Examples of the solvent used in the present invention include alcohols, ketones, glycol ethers, acetates, and the like. These may be used alone or in combination of two or more.
【００１２】次に、このようにして得られたシリカ系被
膜形成用塗布液を用いてシリカ系被膜を形成するには、
この塗布液をガラス、セラミックス、シリコンウエハ
ー、回路の形成されたシリコンウエハー等の基体上に、
浸漬法、回転塗布法等の方法で塗布した後、５０〜２０
０℃、好ましくは１００〜１５０℃で乾燥し、ついで３
００〜５００℃で焼成する。Next, in order to form a silica-based film using the silica-based film-forming coating solution thus obtained,
This coating solution is applied onto a substrate such as glass, ceramics, a silicon wafer, or a silicon wafer having circuits formed thereon.
After coating by a method such as a dipping method or a spin coating method, 50 to 20
Dry at 0 ° C., preferably 100-150 ° C., then
Bake at 00-500 ° C.
【００１３】このような方法により本発明のシリカ系被
膜形成用塗布液を用いて形成したシリカ系被膜は、成膜
性も良好で、しかも誘電率も低くなるので、半導体の多
層配線における層間絶縁膜等として好適であり、このシ
リカ系被膜を用いた半導体装置は、信頼性に優れ、高品
位である。The silica-based coating film formed by using the coating solution for forming a silica-based coating film of the present invention has good film-forming properties and a low dielectric constant. It is suitable as a film or the like, and a semiconductor device using this silica-based film has excellent reliability and high quality.
【００１４】[0014]
【実施例】以下、本発明を実施例により説明する。The present invention will be described below with reference to examples.
【００１５】実施例１ Ｓｉ(ＯＣＨ3)4８０ｇ、ＣＦ3Ｃ2Ｈ4Ｓｉ(ＯＣＨ3)
3４５ｇ、ＣＨ3Ｓｉ(OCH3)3１３０ｇと(ＣＨ3)2Ｓ
ｉ(ＯＣＨ3)2２５ｇをイソピロピルアルコール４００
ｇに溶解し、これに水８０ｇと硝酸０．５ｇの混合液を
１時間で滴下した後、更に室温下で２４時間反応させシ
リカ膜形成用塗布液を調整した。この反応物溶液をスピ
ナーを用いて２０００rpmでシリコンウエハー上に塗布
した後、１５０℃さらに２５０℃に制御されたホットプ
レート上で各１分間乾燥し、ついで電気炉で４５０で大
気中１時間焼成したところ、無色透明でクラックのない
被膜が得られた。該被膜の膜厚を測定したところ０．６
μｍであった。この被膜上にアルミニウム被膜を１μｍ
スパッタ法で形成し、この試料の誘電率をＬＦインピー
ダンスメータを用いて周波数１０〜１００００Hzで測定
したところ、２．４であった。Example 1 80 g of Si (OCH3 )4 , CF3 C2 H4 Si (OCH3 )
3 45 g, 130 g of CH3 Si (OCH3 )3 and (CH3 )2 S
25 g of i (OCH3 )2 was added to isopropyl alcohol 400
g, and a mixed solution of 80 g of water and 0.5 g of nitric acid was added dropwise over 1 hour, and the mixture was further reacted at room temperature for 24 hours to prepare a coating solution for forming a silica film. The reaction product solution was applied on a silicon wafer at 2000 rpm using a spinner, dried on a hot plate controlled at 150 ° C. and 250 ° C. for 1 minute each, and then fired in an electric furnace at 450 for 1 hour in air. However, a colorless, transparent and crack-free film was obtained. When the film thickness of the coating was measured, it was 0.6
μm. 1 μm of aluminum coating on this coating
The sample was formed by sputtering, and the dielectric constant of this sample was measured at a frequency of 10 to 10000 Hz using an LF impedance meter, and was 2.4.
【００１６】比較例１ Ｓｉ(ＯＣＨ3)4５０ｇ、ＣＨ3Ｓｉ(ＯＣＨ3)3５０
ｇと(ＣＨ3)2Ｓｉ(ＯＣＨ3)2４０ｇをイソピロピルア
ルコール４００ｇに溶解し、これに水６３ｇと硝酸１．
０ｇの混合液を１時間で滴下した後、更に室温下で２４
時間反応させシリカ膜形成用塗布液を調整した。この反
応物溶液をスピナーを用いて２０００rpmでシリコンウ
エハー上に塗布した後、１５０℃に制御されたホットプ
レート上で１分間乾燥し、ついで電気炉で４５０℃で大
気中１時間焼成したところ、無色透明でクラックのない
被膜が得られた。該被膜の膜厚を測定したところ０．４
μｍであった。この被膜上にアルミニウム被膜を１μｍ
スパッタ法で形成し、この試料の誘電率をＬＦインピー
ダンスメータを用いて周波数１０〜１００００Hzで測定
したところ３．０であった。[0016] Comparative Example1 Si (OCH 3) 4 50g , CH 3 Si (OCH 3) 3 50
g of (CH3 )2 Si (OCH3 )2 and 40 g of isopropyl alcohol were dissolved in 400 g of isopropyl alcohol.
0 g of the mixed solution was added dropwise over 1 hour, and further added at room temperature for 24 hours.
The reaction was carried out for a period of time to prepare a coating liquid for forming a silica film. The reaction solution was applied on a silicon wafer at 2,000 rpm using a spinner, dried on a hot plate controlled at 150 ° C. for 1 minute, and then baked in an electric furnace at 450 ° C. for 1 hour in the air to obtain a colorless solution. A transparent and crack-free coating was obtained. When the film thickness of the coating was measured, it was 0.4
μm. 1 μm of aluminum coating on this coating
The sample was formed by sputtering, and the dielectric constant of this sample was measured at a frequency of 10 to 10000 Hz using an LF impedance meter, and was found to be 3.0.
【００１７】[0017]
【発明の効果】請求項１記載のシリカ系被膜形成用塗布
液は、成膜性が良好で且つ、低誘電率なシリカ系被膜の
形成可能なものである。請求項２記載のシリカ系被膜の
製造法は、低誘電率なシリカ系被膜を容易に歩留りよく
製造できるものである。請求項３記載の半導体装置は、
高信頼性で高品位なものである。The coating liquid for forming a silica-based film according to the first aspect is capable of forming a silica-based film having good film-forming properties and a low dielectric constant. According to the method for producing a silica-based coating according to the second aspect, a silica-based coating having a low dielectric constant can be easily produced with high yield. The semiconductor device according to claim 3 is
High reliability and high quality.
フロントページの続き (72)発明者 榎本 和宏 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社山崎工場内 (72)発明者 桜井 治彰 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社山崎工場内 (72)発明者 寺田 信子 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社山崎工場内 Ｆターム(参考） 4J038 DL051 DL071 JC31 JC32 PA19 PB09 PC03 5F058 AA10 AC03 AF04 AG01 AH01 AH02Continued on front page (72) Inventor Kazuhiro Enomoto 4-3-1 Higashicho, Hitachi City, Ibaraki Prefecture Inside the Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Haruaki Sakurai 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Nobuko Terada 4-3-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Plant F-term (reference) 4J038 DL051 DL071 JC31 JC32 PA19 PB09 PC03 5F058 AA10 AC03 AF04 AG01 AH01 AH02
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11150050AJP2000336312A (en) | 1999-05-28 | 1999-05-28 | Coating solution for forming silica-based coating film, production of silica-based coating film and semiconductor device |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11150050AJP2000336312A (en) | 1999-05-28 | 1999-05-28 | Coating solution for forming silica-based coating film, production of silica-based coating film and semiconductor device |
| Publication Number | Publication Date |
|---|---|
| JP2000336312Atrue JP2000336312A (en) | 2000-12-05 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11150050APendingJP2000336312A (en) | 1999-05-28 | 1999-05-28 | Coating solution for forming silica-based coating film, production of silica-based coating film and semiconductor device |
| Country | Link |
|---|---|
| JP (1) | JP2000336312A (en) |
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|---|---|---|---|---|
| JP2006213908A (en)* | 2004-12-21 | 2006-08-17 | Hitachi Chem Co Ltd | Composition for forming silica-based film, method for forming silica-based film, silica-based film and electronic part |
| CN100367472C (en)* | 2002-01-31 | 2008-02-06 | 东粟株式会社 | Material for insulating film containing organic silane compound, method for producing the same, and semiconductor device |
| JPWO2006068181A1 (en)* | 2004-12-21 | 2008-06-12 | 日立化成工業株式会社 | Coating, silica-based coating and method for forming the same, composition for forming silica-based coating, and electronic component |
| CN100415752C (en)* | 2002-01-31 | 2008-09-03 | 东粟株式会社 | Material for insulating film containing organosilane compound, method for producing same, and semiconductor device |
| EP2246384A4 (en)* | 2008-02-22 | 2012-05-23 | Nippon Soda Co | Solution for formation of organic thin film, and method for production thereof |
| KR101369446B1 (en) | 2012-02-29 | 2014-03-04 | 충남대학교산학협력단 | Fluorinated hydrophobic polymer film and method for manufacturing the same |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100367472C (en)* | 2002-01-31 | 2008-02-06 | 东粟株式会社 | Material for insulating film containing organic silane compound, method for producing the same, and semiconductor device |
| CN100415752C (en)* | 2002-01-31 | 2008-09-03 | 东粟株式会社 | Material for insulating film containing organosilane compound, method for producing same, and semiconductor device |
| JP2006213908A (en)* | 2004-12-21 | 2006-08-17 | Hitachi Chem Co Ltd | Composition for forming silica-based film, method for forming silica-based film, silica-based film and electronic part |
| JPWO2006068181A1 (en)* | 2004-12-21 | 2008-06-12 | 日立化成工業株式会社 | Coating, silica-based coating and method for forming the same, composition for forming silica-based coating, and electronic component |
| EP2246384A4 (en)* | 2008-02-22 | 2012-05-23 | Nippon Soda Co | Solution for formation of organic thin film, and method for production thereof |
| US9303124B2 (en) | 2008-02-22 | 2016-04-05 | Nippon Soda Co., Ltd. | Solution for formation of organic thin film, and method for production thereof |
| KR101369446B1 (en) | 2012-02-29 | 2014-03-04 | 충남대학교산학협력단 | Fluorinated hydrophobic polymer film and method for manufacturing the same |
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