JPH07305028A - Coating liquid for silica-based film formation, its production, silica-based film, its production, and semiconductor element - Google Patents
Coating liquid for silica-based film formation, its production, silica-based film, its production, and semiconductor elementInfo
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- JPH07305028A JPH07305028A JP9738594A JP9738594A JPH07305028A JP H07305028 A JPH07305028 A JP H07305028A JP 9738594 A JP9738594 A JP 9738594A JP 9738594 A JP9738594 A JP 9738594A JP H07305028 A JPH07305028 A JP H07305028A
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- Prior art keywords
- silica
- coating
- coating liquid
- forming
- film
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- Formation Of Insulating Films (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はシリカ系被膜形成用塗布
液の製造法、塗布液及び該塗布液を用いて形成されるシ
リカ系被膜、シリカ系被膜の製造法およびこの被膜を用
いた半導体素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a coating liquid for forming a silica-based coating, a coating liquid, a silica-based coating formed by using the coating liquid, a method for producing a silica-based coating, and a semiconductor using this coating. Regarding the device.
【０００２】[0002]
【従来の技術】近年、半導体素子の高集積化にともない
配線幅が細く、その間隙は狭くなり、配線は多層化が進
んでいる。これらの結果、上層の配線に断線が生じた
り、またリソグラフィ工程においてフォーカスマージン
の確保が困難になってきている。これらの問題を解決す
るため、配線の層間絶縁膜による平坦化が重要な技術に
なってきている。層間絶縁膜による平坦化法としては、
バイアススパッタ法、ＣＶＤ（Chemical Vaper Deposit
ion）法、ＣＭＰ（Chemical Mechanical Polishing）法
などが検討されている。しかし、量産性、平坦性などの
観点から、ＳＯＧ（Spin On Glass）と呼ばれるシリカ
系被膜形成用塗布液をウエハ上に回転塗布し、加熱硬化
させることによりシリカ系被膜を形成するＳＯＧ法が広
く用いられている。このシリカ系被膜形成用塗布液は、
アルコキシシラン化合物を溶媒中、触媒の存在下、水を
添加してアルコキシ基を加水分解し、縮重合させてポリ
シロキサンを合成することにより製造される。しかし、
このシリカ系被膜形成用塗布液は経時的に粘度が増加
し、最後にはゲル化に至る。そのため、回転塗布したと
きにシリカ系被膜の膜厚が厚くなるため塗布条件を変更
する必要が生じたり、膜質が変化してエッチング速度が
変わったりする。2. Description of the Related Art In recent years, with the high integration of semiconductor elements, the wiring width has become narrower and the gap between them has become narrower, and the wiring has become multi-layered. As a result, disconnection occurs in the upper layer wiring, and it is becoming difficult to secure a focus margin in the lithography process. In order to solve these problems, planarization of wiring by an interlayer insulating film has become an important technique. As a planarization method using an interlayer insulating film,
Bias sputtering method, CVD (Chemical Vaper Deposit)
Ion) method, CMP (Chemical Mechanical Polishing) method and the like are being studied. However, from the viewpoint of mass productivity and flatness, the SOG method of forming a silica-based coating by spin-coating a coating solution for forming a silica-based coating called SOG (Spin On Glass) on a wafer and heating and curing is widely used. It is used. The coating liquid for forming a silica-based film is
It is produced by adding water to an alkoxysilane compound in a solvent in the presence of a catalyst to hydrolyze an alkoxy group and polycondensing it to synthesize a polysiloxane. But,
The viscosity of the coating liquid for forming a silica-based film increases with time and finally gels. Therefore, when the spin coating is performed, the thickness of the silica-based coating becomes large, so that it is necessary to change the coating conditions, or the film quality changes and the etching rate changes.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、塗布膜厚や
エッチング速度などの膜質が変化する原因である経時的
な粘度増加を抑制し、保存安定性に優れたシリカ系被膜
形成用塗布液、その製造法、シリカ系被膜、その製造法
およびこの被膜を配線層間膜とした半導体素子を提供す
るものである。DISCLOSURE OF THE INVENTION The present invention provides a coating solution for forming a silica-based coating film, which suppresses an increase in viscosity over time, which is a cause of changes in coating quality such as coating thickness and etching rate, and which is excellent in storage stability. The present invention provides a method for producing the same, a silica-based coating, a method for producing the same, and a semiconductor element using the coating as an interconnection interlayer film.
【０００４】[0004]
【課題を解決するための手段】本発明は前記課題に鑑
み、鋭意研究を重ねた結果なされたもので、本発明は、
下記一般式（Ｉ）SUMMARY OF THE INVENTION The present invention has been made as a result of intensive studies in view of the above problems.
The following general formula (I)
【化２】 （式中Ｒ及びＲ′は、水素または炭素数１〜３のアルキ
ル基を示し、ＲおよびＲ′は同じでもよく、ｎは１〜２
の整数を示す）で表されるアルコキシシラン化合物を溶
媒中で加水分解、縮重合させてシリカ系被膜形成用塗布
液を製造する際に、該アルコキシシラン化合物１モルに
対し０．０１モル以上（４−ｎ）モル以下の水を用いる
シリカ系被膜形成用塗布液の製造法、この製造法によっ
て得られたシリカ系被膜形成用塗布液、この塗布液を用
いたシリカ系被膜の製造法、この塗布液を用いて形成し
たシリカ系被膜およびこの被膜を配線層間膜とした半導
体素子に関する。[Chemical 2] (In the formula, R and R'represent hydrogen or an alkyl group having 1 to 3 carbon atoms, R and R'may be the same, and n is 1 to 2
When an alkoxysilane compound represented by the formula (1) is hydrolyzed and polycondensed in a solvent to produce a coating liquid for forming a silica-based coating film, 0.01 mol or more (1 mol of the alkoxysilane compound) 4-n) a method for producing a coating liquid for forming a silica-based coating film using water in an amount of 4 or less moles, a coating liquid for forming a silica-based coating film obtained by this production method, a method for producing a silica-based coating film using this coating liquid, The present invention relates to a silica-based coating formed using a coating liquid and a semiconductor element using this coating as a wiring interlayer film.
【０００５】本発明に用いられる前記の一般式（Ｉ）で
表されるアルコキシシラン化合物としては、テトラメト
キシシラン、テトラエトキシシラン、テトラプロポキシ
シラン、テトラブトキシシラン、トリメトキシシラン、
メチルトリメトキシシラン、メチルトリエトキシシラ
ン、メチルトリプロポキシシラン、メチルトリブトキシ
シラン、ジメトキシシラン、ジメチルジメトキシシラ
ン、ジメチルジエトキシシラン、ジメチルジプロポキシ
シラン、ジメチルジブトキシシランなどがある。これら
のアルコキシシラン化合物はそれぞれ２種以上を併用し
てもよい。２種以上のアルコキシシラン化合物を併用す
る時はそれぞれのアルコキシシラン化合物１モルに対し
０．０１モル以上（４−ｎ）モル以下の水が用いられ
る。Examples of the alkoxysilane compound represented by the general formula (I) used in the present invention include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, trimethoxysilane,
Examples include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, and dimethyldibutoxysilane. Two or more of these alkoxysilane compounds may be used in combination. When two or more alkoxysilane compounds are used in combination, 0.01 mol or more (4-n) mol of water is used with respect to 1 mol of each alkoxysilane compound.
【０００６】また加水分解、縮重合反応を行うときに用
いられる溶媒としては、メタノール、エタノール、ブタ
ノール、プロパノール、イソプロパノール、イソブタノ
ール、２−ブタノール、テトラブタノール、ペンチルア
ルコール、２−ペンチルアルコール、３−ペンチルアル
コール、イソペンチルアルコール等のアルコール類、酢
酸メチル、酢酸エチル、酢酸イソプロピル、酢酸プロピ
ル、酢酸ブチル、酢酸イソブチル、酢酸sec−ブチル等
のエステル類、エチレングリコールジエチルエーテル、
エチレングリコールモノヘキシルエーテル、ジプロピレ
ングリコールモノプロピルエーテル、プロピレグリコー
ルモノプロピルエーテル、プロピレングリコールモノブ
チルエーテル、プロピレングリコールモノフェニルエー
テル等のグリコールエーテル類、ベンゼン、トルエン、
キシレン等の芳香族溶媒があげられる。これらの溶媒は
単独で用いても、また、２種以上を組み合わせて用いて
もよい。Further, as a solvent used for the hydrolysis and polycondensation reaction, methanol, ethanol, butanol, propanol, isopropanol, isobutanol, 2-butanol, tetrabutanol, pentyl alcohol, 2-pentyl alcohol, 3- Alcohols such as pentyl alcohol and isopentyl alcohol, esters such as methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, ethylene glycol diethyl ether,
Glycol ethers such as ethylene glycol monohexyl ether, dipropylene glycol monopropyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, benzene, toluene,
An aromatic solvent such as xylene can be used. These solvents may be used alone or in combination of two or more kinds.
【０００７】触媒としては、蟻酸、マレイン酸、フマル
酸、酢酸等の有機酸および塩酸、燐酸、硝酸、ほう酸、
硫酸等の無機酸が用いられる。この触媒は、原料となる
アルコキシシラン化合物の量に応じて適当量で用いられ
るが、好ましくはアルコキシシラン化合物１モルに対し
０．００１〜１モルの範囲とされる。As the catalyst, organic acids such as formic acid, maleic acid, fumaric acid, acetic acid and the like, hydrochloric acid, phosphoric acid, nitric acid, boric acid,
An inorganic acid such as sulfuric acid is used. This catalyst is used in an appropriate amount depending on the amount of the alkoxysilane compound as a raw material, but is preferably in the range of 0.001 to 1 mol with respect to 1 mol of the alkoxysilane compound.
【０００８】加水分解のために用いる水は、滴下ロート
などを用い、徐々に加えることが好ましい。一度に添加
すると加水分解の発熱により液温が急激に上昇し、縮重
合が進み、ポリシロキサンが高分子量化し、シリカ系被
膜形成用塗布液の安定性が低下する傾向がある。液温を
５０℃以下になるように滴下速度を調節することが好ま
しい。水の量は、上記のアルコキシシラン化合物１モル
に対し、０．０１モル以上（４−ｎ）モル以下とされる
が、０．０１モル未満であれば塗布膜に加熱硬化時にク
ラックが生じ、（４−ｎ）モルを超えると分子量、膜厚
の変化が大きく、保存安定性に劣る。Water used for hydrolysis is preferably added gradually using a dropping funnel or the like. When added all at once, the temperature of the liquid rapidly rises due to the heat of hydrolysis, polycondensation proceeds, the polysiloxane has a high molecular weight, and the stability of the coating liquid for forming a silica-based coating tends to decrease. It is preferable to adjust the dropping rate so that the liquid temperature becomes 50 ° C. or lower. The amount of water is 0.01 mol or more and (4-n) mol or less with respect to 1 mol of the above-mentioned alkoxysilane compound, but if it is less than 0.01 mol, cracks are generated in the coating film during heat curing, If it exceeds (4-n) moles, the change in molecular weight and film thickness is large, resulting in poor storage stability.
【０００９】このような方法により製造されたシリカ系
被膜形成用塗布液は、主に回転塗布によりウエハなどの
基板上に塗布される。塗布方法としては、この他にディ
ップ、スプレーなどがある。また、塗布基板としてはガ
ラス、セラミック、金属などがある。これらの方法で塗
布した後、１００〜２００℃で予備硬化し、３００〜７
００℃で本硬化させることによりシリカ系被膜が形成さ
れる。このシリカ系被膜を配線層間膜として半導体素子
を得ることができる。The coating liquid for forming a silica-based coating film produced by such a method is applied onto a substrate such as a wafer mainly by spin coating. In addition to this, the application method includes dip, spray, and the like. Further, the coated substrate may be glass, ceramic, metal or the like. After applying by these methods, pre-cured at 100 to 200 ° C., 300 to 7
A silica coating is formed by main curing at 00 ° C. A semiconductor element can be obtained by using this silica-based film as a wiring interlayer film.
【００１０】以下本発明を実施例及び比較例により説明
するが、本発明はこれらの実施例に限定されるものでは
ない。 実施例１〜７、比較例１〜３ 表１および表２に示した配合でシリカ系被膜形成用塗布
液を合成した。合成は１リットルの４つ口フラスコに表
１および表２に示したアルコキシシラン化合物と溶媒を
入れ、撹はんした。次に触媒を水に溶解させ、これを滴
下ロートに入れ、５００ml／時間の速度でフラスコ中に
滴下した。このとき、液温が５０℃以下になるように滴
下速度を調節した。滴下終了後、１０時間撹はんし、シ
リカ系被膜形成用塗布液を得た。The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Examples 1 to 7 and Comparative Examples 1 to 3 A coating liquid for forming a silica-based coating film was synthesized with the formulations shown in Table 1 and Table 2. In the synthesis, the alkoxysilane compounds shown in Tables 1 and 2 and the solvent were placed in a 1-liter four-necked flask and stirred. Next, the catalyst was dissolved in water, placed in a dropping funnel, and dropped into the flask at a rate of 500 ml / hour. At this time, the dropping rate was adjusted so that the liquid temperature was 50 ° C. or lower. After completion of dropping, the mixture was stirred for 10 hours to obtain a coating liquid for forming a silica-based film.
【００１１】[0011]
【表１】 [Table 1]
【００１２】[0012]
【表２】 [Table 2]
【００１３】得られたシリカ系被膜形成用塗布液につい
て液体クロマトグラフィー（日立製作所製 Ｌ−６００
０型）を用い、ポリシロキサンの平均分子量を測定し
た。カラムは日立化成製ゲルパーミエーションＣＧＰ
Ｃ）用カラムＲ４２０、Ｒ４３０およびＲ４４０を直列
に接続し、溶離液にはテトラヒドロフランを使用した。
また、ＳＯＧコータ（大日本スクリーン社製 Ｄ−ＳＰ
ＩＮ６３６型）を用い、シリカ系被膜形成用塗布液をウ
エハに回転塗布し、干渉膜厚計（大日本スクリーン社製
ラムダエース）で膜厚を測定した。シリカ系被膜形成
用塗布液を冷蔵庫に入れ、７℃の条件で保管した。そし
て、経日的に重量平均分子量と膜厚の変化量を観測し
た。その結果を表３に示す。The obtained silica-based coating liquid for forming a coating film was subjected to liquid chromatography (Hitachi L-600).
0 type) was used to measure the average molecular weight of the polysiloxane. Column is Hitachi Chemical's gel permeation CGP
C) columns R420, R430 and R440 were connected in series, and tetrahydrofuran was used as an eluent.
In addition, SOG coater (D-SP manufactured by Dainippon Screen Co., Ltd.
The coating liquid for forming a silica-based coating film was spin-coated on the wafer using IN636 type), and the film thickness was measured with an interference film thickness meter (Lambda Ace manufactured by Dainippon Screen Co., Ltd.). The silica-based coating forming solution was placed in a refrigerator and stored at 7 ° C. Then, the changes in the weight average molecular weight and the film thickness were observed over time. The results are shown in Table 3.
【００１４】[0014]
【表３】 [Table 3]
【００１５】実施例１〜５はアルコキシシラン化合物１
モルに対し、（４−ｎ）モルの割合で水を加えた。実施
例６及び７はアルコキシシラン化合物１モルに対し、
（４−ｎ）／２モル、（４−ｎ）／１０モルの割合で水
を加えた。これらのシリカ系被膜形成用塗布液は重量平
均分子量並びに膜厚ともに変化量が小さい。添加した水
の量を減らした実施例６及び７は特に変化量が小さく保
存安定性が極めて良好である。比較例１は実施例７よ
り、さらに水を減らしたものであるが、シリカ系被膜形
成時にクラックが生じてしまい被膜としては使用できな
いことが示された。比較例２及び３はアルコキシシラン
化合物１モルに対し、１．２×（４−ｎ）モルの割合で
水を加えた、これらのシリカ系被膜形成用塗布液は高分
子量化し、膜厚の変化量が５００（Å）を上回ってしま
い、保存安定性が極めて低下していることが示された。
実施例で得られた保存安定性に優れたシリカ系被膜形成
用塗布液を配線段差１μｍの半導体素子基板にスピン塗
布した。塗布は前述のＳＯＧコータを用い、回転数２５
００rpm／３０secで行った。スピン塗布後、１５０℃、
２５０℃で各々３０秒加熱した後、オーブンで４５０
℃、３０分加熱硬化した。硬化後、断面を走査型電子顕
微鏡（日立製作所製、Ｓ５７０型）で観察した。配線上
に形成されたシリカ系被膜の膜厚を観察したところ、シ
リカ系被膜形成用塗布液の製造直後と６ヶ月、７℃で保
管したものとで、差はほとんど認められなかった。これ
により、塗布硬化条件を変えることなく、塗布液を塗布
しても、膜厚が変らず、その後のエッチバックも同一条
件で行うことが可能となり、素子の信頼性の向上が示さ
れる。Examples 1 to 5 are alkoxysilane compounds 1
Water was added at a ratio of (4-n) mol to mol. In Examples 6 and 7, 1 mol of the alkoxysilane compound was used.
Water was added at a ratio of (4-n) / 2 mol and (4-n) / 10 mol. These silica-based coating forming liquids have small changes in both weight average molecular weight and film thickness. In Examples 6 and 7 in which the amount of added water was reduced, the amount of change was particularly small and the storage stability was extremely good. Comparative Example 1 was obtained by further reducing the amount of water as compared with Example 7, but it was shown that cracks were generated during the formation of the silica-based coating and it could not be used as a coating. In Comparative Examples 2 and 3, water was added at a ratio of 1.2 × (4-n) moles to 1 mole of the alkoxysilane compound. These silica-based coating film forming coating liquids had a high molecular weight and a change in film thickness. The amount exceeded 500 (Å), indicating that the storage stability was extremely low.
The silica-based coating film forming coating liquid having excellent storage stability obtained in Example was spin-coated on a semiconductor element substrate having a wiring step difference of 1 μm. For coating, use the above-mentioned SOG coater and rotate at 25
It was performed at 00 rpm / 30 sec. After spin coating, 150 ℃,
Heat at 250 ° C for 30 seconds each and then in the oven 450
It was cured by heating at 30 ° C for 30 minutes. After curing, the cross section was observed with a scanning electron microscope (Hitachi, S570 type). When the film thickness of the silica-based film formed on the wiring was observed, almost no difference was observed between immediately after the production of the coating liquid for forming the silica-based film and when it was stored at 7 ° C. for 6 months. As a result, even if the coating liquid is applied without changing the coating and curing conditions, the film thickness does not change, and the subsequent etch back can be performed under the same conditions, and the reliability of the device is improved.
【００１６】[0016]
【発明の効果】本発明になるシリカ系被膜形成用塗布液
により、保存安定性に優れ、半導体素子に適用した場合
に、信頼性の高いシリカ系被膜を形成することができ
る。The coating solution for forming a silica-based coating according to the present invention has excellent storage stability and can form a highly reliable silica-based coating when applied to a semiconductor device.
Claims (5)
ル基を示し、ＲおよびＲ′は同じでもよく、ｎは１〜２
の整数を示す）で表されるアルコキシシラン化合物を溶
媒中で加水分解、縮重合させてシリカ系被膜形成用塗布
液を製造する際に、該アルコキシシラン化合物１モルに
対し０．０１モル以上（４−ｎ）モル以下の水を用いる
ことを特徴とするシリカ系被膜形成用塗布液の製造法。1. A compound represented by the general formula (I): (In the formula, R and R'represent hydrogen or an alkyl group having 1 to 3 carbon atoms, R and R'may be the same, and n is 1 to 2
When an alkoxysilane compound represented by the formula (1) is hydrolyzed and polycondensed in a solvent to produce a coating liquid for forming a silica-based coating film, 0.01 mol or more (1 mol of the alkoxysilane compound) 4-n) A method for producing a coating liquid for forming a silica-based film, which comprises using water in an amount of at most mol.
シリカ系被膜形成用塗布液。2. A coating liquid for forming a silica-based coating film, which is obtained by the manufacturing method according to claim 1.
液を基板上に塗布し１００〜２００℃で予備硬化し、３
００〜７００℃で本硬化させるシリカ系被膜の製造法。3. A silica-based coating film forming coating solution according to claim 2 is applied onto a substrate and pre-cured at 100 to 200 ° C.
A method for producing a silica-based coating that is fully cured at 00 to 700 ° C.
シリカ系被膜。4. A silica-based coating film obtained by the manufacturing method according to claim 3.
膜とした半導体素子。5. A semiconductor device using the silica coating according to claim 4 as a wiring interlayer film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09738594A JP3520930B2 (en) | 1994-05-11 | 1994-05-11 | Method for producing coating liquid for forming silica-based coating, coating liquid for forming silica-based coating, method for producing silica-based coating, silica-based coating and semiconductor element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09738594A JP3520930B2 (en) | 1994-05-11 | 1994-05-11 | Method for producing coating liquid for forming silica-based coating, coating liquid for forming silica-based coating, method for producing silica-based coating, silica-based coating and semiconductor element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07305028A true JPH07305028A (en) | 1995-11-21 |
| JP3520930B2 JP3520930B2 (en) | 2004-04-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09738594A Expired - Lifetime JP3520930B2 (en) | 1994-05-11 | 1994-05-11 | Method for producing coating liquid for forming silica-based coating, coating liquid for forming silica-based coating, method for producing silica-based coating, silica-based coating and semiconductor element |
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| Country | Link |
|---|---|
| JP (1) | JP3520930B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006083319A (en) * | 2004-09-17 | 2006-03-30 | Toray Ind Inc | Coating composition and display device using the same |
| JP2007146031A (en) * | 2005-11-29 | 2007-06-14 | Shin Etsu Chem Co Ltd | Curable polymethylsiloxane resin, method for producing the same, curable polymethylsiloxane resin composition and article having cured film thereof |
| WO2014073543A1 (en) * | 2012-11-06 | 2014-05-15 | 旭硝子株式会社 | Coating liquid for water repellent films and article with water repellent film |
-
1994
- 1994-05-11 JP JP09738594A patent/JP3520930B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006083319A (en) * | 2004-09-17 | 2006-03-30 | Toray Ind Inc | Coating composition and display device using the same |
| JP2007146031A (en) * | 2005-11-29 | 2007-06-14 | Shin Etsu Chem Co Ltd | Curable polymethylsiloxane resin, method for producing the same, curable polymethylsiloxane resin composition and article having cured film thereof |
| WO2014073543A1 (en) * | 2012-11-06 | 2014-05-15 | 旭硝子株式会社 | Coating liquid for water repellent films and article with water repellent film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3520930B2 (en) | 2004-04-19 |
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