JPH0457329A - Manufacture of silicon oxide film - Google Patents
Manufacture of silicon oxide filmInfo
- Publication number
- JPH0457329A JPH0457329A JP2169257A JP16925790A JPH0457329A JP H0457329 A JPH0457329 A JP H0457329A JP 2169257 A JP2169257 A JP 2169257A JP 16925790 A JP16925790 A JP 16925790A JP H0457329 A JPH0457329 A JP H0457329A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- oxide film
- silicon oxide
- group
- coating
- 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.)
- Granted
Links
Landscapes
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、基板上にシリコン酸化膜を形成する半導体装
置等のシリコン酸化膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method of manufacturing a silicon oxide film for semiconductor devices, etc., in which a silicon oxide film is formed on a substrate.
（従来の技術）
基板上にシリコン酸化膜を形成する方法として塗布法が
ある。(Prior Art) There is a coating method as a method of forming a silicon oxide film on a substrate.
塗布法にはスピンコード法、デイツプコート法、霧化コ
ート法等がある。Application methods include spin-coating, dip-coating, atomization-coating, and the like.
スピンコード法はＳｉを含む塗布剤を基板上に滴下し、
スピンナーで基板を回転させて塗布する方法である。In the spin code method, a coating agent containing Si is dropped onto a substrate.
This is a method of coating by rotating the substrate with a spinner.
デイツプコート法はＳｉを含む塗布剤に基板を浸漬し定
速で引き上げることによって基板に塗布する方法である
。The dip coating method is a method of coating a substrate by dipping the substrate in a coating agent containing Si and pulling it up at a constant speed.
霧化コート法は塗布剤を霧状にして基板に塗布する方法
である。The atomization coating method is a method in which a coating agent is atomized and applied to a substrate.
上記のような塗布法で塗布剤を基板上に薄く均一に塗布
したのち、適温かつ適当な雰囲気中で基板を加熱して乾
燥し、さらに、塗布物を基板上で分解することによって
、シリコン酸化膜を製造している。After coating the coating agent thinly and uniformly on the substrate using the coating method described above, the substrate is heated and dried in an appropriate atmosphere at an appropriate temperature, and the coating material is further decomposed on the substrate to form silicon oxide. Manufactures membranes.
塗布物を基板上で分解する方法としては、熱分解法、プ
ラズマ分解法あるいはオゾン分解法等が用いられる。As a method for decomposing the coated material on the substrate, a thermal decomposition method, a plasma decomposition method, an ozone decomposition method, or the like is used.
従来、塗布剤にはテトラエトキシシラン５ｉ（ＯＣ２Ｈ
５）４のようなアルコキシシランを有機酸あるいは無機
酸を用いて加水分解し、Ｓｉ−○−５ｉ結合をもつ分子
を含ませたものが一般的である。Conventionally, tetraethoxysilane 5i (OC2H
5) Generally, alkoxysilanes such as 4 are hydrolyzed using organic or inorganic acids to contain molecules having Si-○-5i bonds.
このようにＳ ｉ （ＯＣ２Ｈｓ ） ４を有機酸ある
いは無機酸で加水分解する理由は、Ｓ ｉ （ＯＣ２Ｈ
５）４は水のみては加水分解反応の進行が極めて遅いこ
とから、このような酸を加えて加水分解の進行を促進さ
せている。The reason for hydrolyzing S i (OC2Hs) 4 with an organic or inorganic acid is that S i (OC2Hs) 4 is
5) Since the hydrolysis reaction in 4 is extremely slow in the presence of water, such an acid is added to accelerate the progress of hydrolysis.
しかし、このような方法で製造した塗布剤では塗布剤中
に含まれる５ｉ−０−Ｓｉ結合をもつ分子の分子量が大
きく、かつ、塊状分子になり易い。このためこのような
塗布剤を用いて形成したシリコン酸化膜は膜中にクラッ
クが発生し易い欠点がある。However, in the coating agent produced by such a method, the molecular weight of molecules having 5i-0-Si bonds contained in the coating agent is large, and the molecules tend to form lumps. Therefore, a silicon oxide film formed using such a coating agent has the disadvantage that cracks are likely to occur in the film.
また、このような塗布剤は薄く均一に塗布できない欠点
があり、形成したシリコン酸化膜は平坦化性に劣る欠点
がある。Further, such a coating agent has the disadvantage that it cannot be applied thinly and uniformly, and the formed silicon oxide film has a disadvantage that it has poor planarization properties.
さらに、アルコキシシランを有機酸を用いて加水分解し
た場合、形成したシリコン酸化膜中に多くのカーボン残
香を残す欠点がある。Furthermore, when alkoxysilane is hydrolyzed using an organic acid, there is a drawback that a large amount of carbon residue remains in the silicon oxide film formed.
また、加水分解のときに、Ｓｉ−〇−Ｓｉ結合の側鎖に
有機酸根が結合し、このため基板上の分解が困難になる
欠点がある。Furthermore, during hydrolysis, an organic acid group is bonded to the side chain of the Si-0-Si bond, which makes decomposition on the substrate difficult.
アルコキシシランを無機酸を用いて加水分解した場合、
塗布剤中に腐食成分を残す欠点がある。When alkoxysilane is hydrolyzed using an inorganic acid,
It has the disadvantage of leaving corrosive components in the coating agent.
本発明者等は、上記の欠点を除去し、基板上に薄く均一
に塗布でき、かつ、生成したシリコン酸化膜は平坦化性
に優れ、クラックのない膜を形成できる酸を使用しない
塗布剤の製造方法として、スピンコード剤の製造方法と
題し、平成２年６月４日特許を出願した。The inventors of the present invention have developed a coating agent that does not use acids, can eliminate the above drawbacks, can be applied thinly and uniformly on a substrate, and the resulting silicon oxide film has excellent planarization properties and can form a crack-free film. As a manufacturing method, a patent application was filed on June 4, 1990 entitled "Manufacturing method of spin code agent."
（解決しようとする問題点）
本発明は、塗布剤中に含まれるシリコン化合物の構造を
定めた塗布剤を用いて、形成したシリコン酸化膜は平坦
化性に優れ、クラックのない膜を形成できるシリコン酸
化膜の製造方法を提供しようとするものである。(Problems to be Solved) The present invention uses a coating agent in which the structure of the silicon compound contained in the coating agent is determined, so that the silicon oxide film formed has excellent planarization properties and can form a crack-free film. The present invention aims to provide a method for manufacturing a silicon oxide film.
（問題を解決するための手段）
本発明は、１分子中のケイ素原子数が８以上５００以下
のポリシロキサンを基板上に大気圧以下で塗布し、塗布
物を基板上で分解することによってシリコン酸化膜を製
造する方法である。(Means for Solving the Problems) The present invention applies polysiloxane having a silicon atom number of 8 to 500 in one molecule onto a substrate at atmospheric pressure or lower, and decomposes the applied material on the substrate. This is a method of manufacturing an oxide film.
化学式、Ｒ（ＳｉＯＲ２）。−１３ｊＲ３て表されるポ
リシロキサンのＲは、Ｈ基、○Ｈ基、ＣＨＪ基、ＯＣ２
Ｈｓ基、ｎ−ＯＣ３Ｈ７基、ｉ ＯＣ３Ｈ７基、ｎ
ＯＣ４）（ｓ基、ｊ ＯＣ４Ｈ９基、ｔ−ＯＣａ
Ｈ９基あるいは５ｅｅ−〇Ｃ４Ｈｅ基等である。Chemical formula, R(SiOR2). R of polysiloxane represented by -13jR3 is H group, ○H group, CHJ group, OC2
Hs group, n-OC3H7 group, i OC3H7 group, n
OC4) (s group, j OC4H9 group, t-OCa
These include H9 group or 5ee-〇C4He group.
本発明は、上記の鎖状分子のポリシロキサンを基板上に
減圧あるいは真空中で塗布することにより、同一圧力下
で、基板加熱、活性酸素供給、プラズマ等による表面エ
ネルギー供給を可能とし、平坦化性、無クラツク性、か
つ、残存異物のない極めて優れたシリコン酸化膜の形成
を可能にするものである。The present invention makes it possible to heat the substrate, supply active oxygen, supply surface energy by plasma, etc. under the same pressure by coating the above-mentioned polysiloxane with chain molecules on the substrate under reduced pressure or vacuum, and flatten the substrate. This makes it possible to form an extremely excellent silicon oxide film that is highly durable, crack-free, and free of residual foreign matter.
これは上記鎖状分子の場合、粘性率がほぼｌＰａ−８ｅ
ｃ以下であり、標準沸点が２５０℃以上、ＩＰａての沸
点が２００℃以上であり、低粘性、低揮発性であるとい
う物性に関係するものである。In the case of the above-mentioned chain molecules, the viscosity is approximately lPa-8e
c or less, the standard boiling point is 250°C or more, the IPa boiling point is 200°C or more, and it is related to the physical properties of low viscosity and low volatility.
ことに、分子の標準沸点が２δＯ℃以上という条件は基
板からの塗布剤の再蒸発の防止に役立つものである。In particular, the condition that the normal boiling point of the molecule is 2 δO° C. or higher is useful for preventing re-evaporation of the coating agent from the substrate.
塗布剤中のＳｉを含む分子が環状分子あるいは分校状分
子である場合、高粘性化あるいは固体化が進み好ましく
ない。When the Si-containing molecules in the coating agent are cyclic molecules or branched molecules, the coating agent becomes highly viscous or solidified, which is undesirable.
本塗布剤には有機希釈剤を適当量添加することによって
、基板上に均一な薄い膜ができ平坦化性に富む膜が得ら
れる。By adding an appropriate amount of an organic diluent to this coating agent, a uniform thin film can be formed on the substrate and a film with excellent flatness can be obtained.
本発明における基板への塗布剤の塗布方法は、スピンコ
ード法、デイツプコート法、霧化コート法等どのコート
法を用いてもよいが、好ましくはスピンコード法あるい
は霧化コート法である。The coating agent may be applied to the substrate in the present invention by any coating method such as a spin code method, dip coating method, or atomization coating method, but preferably a spin code method or an atomization coating method.
また、塗布物を基板上で分解してＳｉ酸化膜とする方法
は、熱分解法、プラズマ分解法、オゾン分解法等どの分
解法を用いてもよいが、好ましくはプラズマ分解法ある
いはオゾン分解法である。Furthermore, any decomposition method such as thermal decomposition, plasma decomposition, or ozone decomposition may be used to decompose the coated material on the substrate to form a Si oxide film, but preferably plasma decomposition or ozone decomposition is preferred. It is.
すなわち、大気圧以下で分解が行われることが、分解副
生成物を形成する酸化膜外に除去する上で有効である。That is, performing the decomposition at atmospheric pressure or lower is effective in removing decomposition byproducts from the oxide film that forms.
ことに、ポリシロキサンのＲがＨ基、ＯＨ基、ＯＣ３Ｈ
７基あるいはＯＣ４Ｈ９基およびそれらの異性体の場合
、より低温で分解することができる。In particular, R of polysiloxane is H group, OH group, OC3H
7 or OC4H9 groups and their isomers can be decomposed at lower temperatures.
また、本塗布剤を溶剤で希釈することにより、１回の塗
布による膜厚を調整することができる。Further, by diluting this coating agent with a solvent, the film thickness after one coating can be adjusted.
（実施例１）
装置内の圧力０．５ＫＰａ、基板温度３００°Ｃで、５
“シリコンウェハー上にポリジプロポキシシロキサンを
０．２ｍｌ噴霧したのち、同圧力、同温度でオゾンを２
０秒流し、基板上にシリコン酸化膜を形成した。(Example 1) At a pressure of 0.5 KPa in the device and a substrate temperature of 300°C, 5
“After spraying 0.2ml of polydipropoxysiloxane onto a silicon wafer, 2 ml of ozone was sprayed at the same pressure and temperature.
The flow was continued for 0 seconds to form a silicon oxide film on the substrate.
上記の操作を１０回繰り返し、膜厚を１μｍとした。The above operation was repeated 10 times to give a film thickness of 1 μm.
形成されたシリコン酸化膜にはクラックがなく、極めて
平坦化性に優れた膜であった。The formed silicon oxide film had no cracks and had extremely excellent planarization properties.
（実施例２）
装置内の圧力０．５ＫＰａ、基板温度３００℃で、５“
シリコンウェハー上にポリジプロポキシシロキサンを０
．２ｍｌ噴霧したのち、同圧力、同温度で２０秒、酸素
プラズマに５０Ｖのバイアスをかけ、基板上に圧縮性の
シリコン酸化膜を形成した。(Example 2) At a pressure of 0.5 KPa in the device and a substrate temperature of 300°C, 5"
0 polydipropoxysiloxane on silicon wafer
．． After spraying 2 ml, a bias of 50 V was applied to the oxygen plasma for 20 seconds at the same pressure and temperature to form a compressible silicon oxide film on the substrate.
上記の操作を１０回繰り返し、膜厚な１μｍとした。The above operation was repeated 10 times to obtain a film thickness of 1 μm.
形成されたシリコン酸化膜にはクラックがなく、極めて
平坦化性に優れた膜であった。The formed silicon oxide film had no cracks and had extremely excellent planarization properties.
（発明の効果）
本発明によれば、塗布剤を基板上に薄く極めて均一に塗
布できる特徴がある。(Effects of the Invention) According to the present invention, a coating agent can be applied thinly and extremely uniformly onto a substrate.
また、本発明により形成したシリコン酸化膜は膜中にク
ラックが発生しにくく、平坦化性に富む極めて優れた膜
質である特徴がある。Further, the silicon oxide film formed according to the present invention is characterized by extremely excellent film quality, with less cracks occurring in the film and excellent planarization properties.
さらに、本発明によれば、シリコン酸化膜製造中にダス
トが発生しない利点がある。Further, according to the present invention, there is an advantage that no dust is generated during the manufacturing of the silicon oxide film.
Claims (2)
リシロキサンを基板上に大気圧以下で塗布し、シリコン
酸化膜を形成することを特徴とするシリコン酸化膜の製
造方法。(1) A method for producing a silicon oxide film, which comprises applying polysiloxane having 8 to 500 silicon atoms per molecule onto a substrate at atmospheric pressure or lower to form a silicon oxide film.
＿−＿１ＳｉＲ＿３で表され、ＲがＨ基、ＯＨ基、ＣＨ
＿３基、ＯＣ＿２Ｈ＿５基、ｎ−ＯＣ＿３Ｈ＿７基、ｉ
−ＯＣ＿３Ｈ＿７基、ｎ−ＯＣ＿４Ｈ＿９基、ｉ−ＯＣ
＿４Ｈ＿９基、ｔ−ＯＣ＿４Ｈ＿９基あるいはｓｅｃ−
ＯＣ＿４Ｈ＿９基である特許請求の範囲第１項記載のシ
リコン酸化膜の製造方法。(2) Polysiloxane has the chemical formula R(SiOR_2)_n
_-_1SiR_3, R is H group, OH group, CH
_3 groups, OC_2H_5 groups, n-OC_3H_7 groups, i
-OC_3H_7 groups, n-OC_4H_9 groups, i-OC
_4H_9 group, t-OC_4H_9 group or sec-
The method for manufacturing a silicon oxide film according to claim 1, wherein the silicon oxide film has OC_4H_9 groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2169257A JP2958466B2 (en) | 1990-06-27 | 1990-06-27 | Method for manufacturing silicon oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2169257A JP2958466B2 (en) | 1990-06-27 | 1990-06-27 | Method for manufacturing silicon oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0457329A true JPH0457329A (en) | 1992-02-25 |
| JP2958466B2 JP2958466B2 (en) | 1999-10-06 |
Family
ID=15883158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2169257A Expired - Fee Related JP2958466B2 (en) | 1990-06-27 | 1990-06-27 | Method for manufacturing silicon oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2958466B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003034508A1 (en) * | 2001-10-12 | 2003-04-24 | Nichia Corporation | Light emitting device and method for manufacture thereof |
| US7105857B2 (en) | 2002-07-08 | 2006-09-12 | Nichia Corporation | Nitride semiconductor device comprising bonded substrate and fabrication method of the same |
| WO2007046432A1 (en) * | 2005-10-19 | 2007-04-26 | Matsushita Electric Industrial Co., Ltd. | Method of forming metal oxide film, metal oxide film and optical electronic device |
-
1990
- 1990-06-27 JP JP2169257A patent/JP2958466B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003034508A1 (en) * | 2001-10-12 | 2003-04-24 | Nichia Corporation | Light emitting device and method for manufacture thereof |
| US7301175B2 (en) | 2001-10-12 | 2007-11-27 | Nichia Corporation | Light emitting apparatus and method of manufacturing the same |
| US7390684B2 (en) | 2001-10-12 | 2008-06-24 | Nichia Corporation | Light emitting apparatus and method of manufacturing the same |
| US7105857B2 (en) | 2002-07-08 | 2006-09-12 | Nichia Corporation | Nitride semiconductor device comprising bonded substrate and fabrication method of the same |
| US7378334B2 (en) | 2002-07-08 | 2008-05-27 | Nichia Corporation | Nitride semiconductor device comprising bonded substrate and fabrication method of the same |
| US8030665B2 (en) | 2002-07-08 | 2011-10-04 | Nichia Corporation | Nitride semiconductor device comprising bonded substrate and fabrication method of the same |
| WO2007046432A1 (en) * | 2005-10-19 | 2007-04-26 | Matsushita Electric Industrial Co., Ltd. | Method of forming metal oxide film, metal oxide film and optical electronic device |
| JP5006203B2 (en) * | 2005-10-19 | 2012-08-22 | パナソニック株式会社 | Method for forming metal oxide film, metal oxide film and optical electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2958466B2 (en) | 1999-10-06 |
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