JP3060185B2 - Method for manufacturing silicon oxide film of semiconductor device - Google Patents
Method for manufacturing silicon oxide film of semiconductor deviceInfo
- Publication number
- JP3060185B2 JP3060185B2 JP3194713A JP19471391A JP3060185B2 JP 3060185 B2 JP3060185 B2 JP 3060185B2 JP 3194713 A JP3194713 A JP 3194713A JP 19471391 A JP19471391 A JP 19471391A JP 3060185 B2 JP3060185 B2 JP 3060185B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- semiconductor device
- silicon oxide
- alkoxysilane
- liquid
- 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 - Fee Related
Links
Landscapes
- Formation Of Insulating Films (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＣＶＤ法（化学蒸着
法）による半導体装置のシリコン酸化膜の製造方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silicon oxide film of a semiconductor device by a CVD method (chemical vapor deposition method).
【０００２】[0002]
【従来の技術】半導体装置製造工程において、シリコン
酸化膜は電気的絶縁体、誘電体、空間充填体、保護膜等
として用いられている。従来、ＣＶＤ法によりシリコン
酸化膜を形成する主原料としてはモノシラン（Ｓｉ
Ｈ４）が用いられていた。2. Description of the Related Art In a semiconductor device manufacturing process, a silicon oxide film is used as an electrical insulator, a dielectric, a space filling material, a protective film, and the like. Conventionally, monosilane (Si) has been used as a main material for forming a silicon oxide film by a CVD method.
H 4 ) was used.
【０００３】しかし、半導体装置の最小設計寸法がＬＳ
Ｉの高集積化にともない極微細化するにつれ、モノシラ
ンを用いるＣＶＤ法では、凹凸の激しい面上では表面が
平滑な膜を得にくく、穴埋め作用もないこと、ダストを
生じ易いこと、モノシランは大気中で発火し易く取り扱
い上危険なこと等の欠点がある。However, the minimum design size of a semiconductor device is LS
As I becomes extremely fine with high integration, the CVD method using monosilane makes it difficult to obtain a film having a smooth surface on a surface with severe unevenness, there is no filling effect, it is easy to generate dust, and monosilane is used in the atmosphere. There are drawbacks such as easy ignition in the interior and dangerous handling.
【０００４】このため、モノシランに代わる原料として
アルコキシシラン（液体）、とくにＳｉ（ＯＣ２Ｈ５）
４（テトラエトキシシラン）を用いるＣＶＤ法が実用化
されてきている。[0004] Therefore, alkoxysilane (liquid), particularly Si (OC 2 H 5 ), is used as a raw material instead of monosilane.
4 The CVD method using (tetraethoxysilane) has been put to practical use.
【０００５】ＣＶＤ法におけるテトラエトキシシランの
成膜反応は、テトラエトキシシラン蒸気から化学反応に
より液体に変化したのち、該液体が固体化しＳｉＯ２膜
が形成されることによって行われる。[0005] The film formation reaction of tetraethoxysilane in the CVD method is performed by changing a liquid from tetraethoxysilane vapor to a liquid by a chemical reaction, and then solidifying the liquid to form an SiO 2 film.
【０００６】次に、モノシランとアルコキシシランのＳ
ｉＯ２膜を形成する成膜反応の基本的相違点を説明す
る。モノシランを酸素酸化してできる反応中間物質はほ
とんどが固体か気体であって、液体になっても揮発性で
ある。したがって、モノシランの酸化反応は固体として
基板に着床し、反応のほとんど全てが着床以前に起こる
空間反応型である。このため、基板の凹凸の平坦化作
用、穴埋め作用が起こらない。Next, S of monosilane and alkoxysilane
The fundamental difference of the film forming reaction for forming the iO 2 film will be described. Almost all reaction intermediates formed by oxygen oxidation of monosilane are solid or gaseous, and are volatile even when liquid. Therefore, the oxidation reaction of monosilane is implanted as a solid on the substrate, and almost all of the reaction is of a spatial reaction type that occurs before implantation. For this reason, the flattening action and the hole filling action of the unevenness of the substrate do not occur.
【０００７】これに対して、アルコキシシランが酸素酸
化してできる反応中間物質は液体が多い。したがって、
液体として基板に着床し、着床以降も反応が続行する表
面反応型である。着床した液体中間生成物は面上を流れ
て基板表面を平坦化する。この現象が平坦化作用、穴埋
め作用の基本である。On the other hand, reaction intermediates formed by oxygen oxidation of alkoxysilane are mostly liquid. Therefore,
This is a surface reaction type in which the liquid is landed on the substrate and the reaction continues after the landing. The liquid intermediate product that has landed flows on the surface and flattens the substrate surface. This phenomenon is the basis of the flattening action and the filling action.
【０００８】この面流がより効果的に起こるには、その
中間生成物の粘性率が小さい方が好ましい。また、着床
した液体中間生成物が再揮発せずに基板表面に留まるに
は、シロキサン結合（−Ｓｉ−Ｏ−Ｓｉ−）の縮合が進
んで揮発性がなくなる必要がある。In order for this surface flow to occur more effectively, it is preferable that the viscosity of the intermediate product is small. In addition, in order for the liquid intermediate product that has landed to remain on the substrate surface without re-evaporation, it is necessary that condensation of siloxane bonds (—Si—O—Si—) proceeds and volatility is lost.
【０００９】直線状にシロキサン結合した分子ではＳｉ
数が数万個まで液体になると推定されている。殊に、ア
ルコキシ基を側鎖にもつシロキサン結合は電気的分極が
小さく、これらの側鎖が外側を覆うことにより高分子に
なるまで粘性率が低い液体になる。すなわち、より大き
なＳｉ数まで流動性を維持し基板の平坦化の効果を上げ
るには、分子の側鎖をいかに分極させずに縮合させてシ
ロキサン結合を長くするかということが重大な問題点で
ある。In the case of a molecule having a linear siloxane bond, Si
It is estimated that up to tens of thousands will be liquid. In particular, a siloxane bond having an alkoxy group as a side chain has a small electric polarization, and the side chain covers the outside, so that a liquid having a low viscosity until a polymer is formed is obtained. In other words, in order to maintain the fluidity up to a larger Si number and improve the flattening effect of the substrate, a serious problem is how to extend the siloxane bond by condensing the side chains of the molecules without polarizing them. is there.
【００１０】そこでアルコキシシランの蒸気を速やかに
揮発性のない低粘性液体に変え、基板の平坦化効果を高
める技術が要望されるところとなる。また、アルコキシ
シランは熱酸化膜等の表面には馴染みにくい欠点があ
る。Therefore, there is a need for a technique for quickly changing the vapor of alkoxysilane to a low-viscosity liquid having no volatility to enhance the flattening effect of the substrate. In addition, alkoxysilane has a disadvantage that it is difficult to adapt to the surface of a thermal oxide film or the like.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、アルコキシ
シランの蒸気を速やかに揮発性のない低粘性液体に変
え、基板の平坦化効果を高めると同時に、アルコキシシ
ランを熱酸化膜等の表面に馴染み易くする半導体装置の
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。SUMMARY OF THE INVENTION According to the present invention, the alkoxysilane vapor is quickly changed to a low-viscosity liquid having no volatility to enhance the flattening effect of the substrate, and at the same time, the alkoxysilane is deposited on the surface of a thermal oxide film or the like. An object of the present invention is to provide a method for manufacturing a silicon oxide film of a semiconductor device which is easy to be used.
【００１２】[0012]
【課題を解決するための手段】本発明は、主原料として
アルコキシシランとジシロキサン（Ｈ３ＳｉＯＳｉ
Ｈ３）を併用し、これらを酸素あるいはオゾンを用いて
酸化することによって、半導体装置のシリコン酸化膜を
製造する方法である。According to the present invention, alkoxysilane and disiloxane (H 3 SiOSi) are used as main raw materials.
This is a method of manufacturing a silicon oxide film of a semiconductor device by using H 3 ) in combination and oxidizing these with oxygen or ozone.
【００１３】また、本発明は、主原料としてのアルコキ
シシランとジシロキサンとの混合比を、アルコキシシラ
ン１モルに対して、ジシロキサン０．０１モル以上、
０．２モル以下として使用するものである。In the present invention, the mixing ratio of the alkoxysilane and the disiloxane as the main raw materials is not less than 0.01 mol of the disiloxane to 1 mol of the alkoxysilane.
It is used as 0.2 mol or less.
【００１４】ジシロキサンとアルコキシシランの一例と
してのテトラエトキシシランとの反応は次の通りであ
る。Ｈ３ＳｉＯＳｉＨ３はＳｉ（ＯＣ２Ｈ５）４よりも
酸化され易く、Ｈ基はＯＨ基に置換された型になる。置
換されたジシロキサンはテトラエトキシシランと速やか
に反応して、エタノールを放出して縮合する。この時の
反応は、下記の化学式１によって示すことができる。The reaction between disiloxane and tetraethoxysilane as an example of alkoxysilane is as follows. H 3 SiOSiH 3 is more easily oxidized than Si (OC 2 H 5 ) 4 , and the H group becomes a type in which the OH group is substituted. The substituted disiloxane reacts quickly with tetraethoxysilane, releasing ethanol and condensing. The reaction at this time can be represented by the following chemical formula 1.
【００１５】[0015]
【化１】 Embedded image
【００１６】上記の反応によって生成した縮合物は沸点
が３００℃程度であり、分子の側鎖が分極していない揮
発性のない低粘性液体である。上記のように、テトラエ
トキシシランは酢酸基、ヒドロキシエトキシ基等のエト
キシ基が酸化された基をもたないＳｉ数８〜２４個程度
の分子になり易いこと、縮合過程で環状分子になりにく
く、縮合分子が短い側鎖をもった線状分子になり易い等
の理由で、テトラエトキシシランにジシロキサンを混合
することによって、速やかに縮合が進み揮発性のない低
粘性液体を基板上に着床することができる。このことに
より、優れた平坦化性、穴埋め性を発揮することができ
る。The condensate produced by the above reaction is a low-viscosity liquid having a boiling point of about 300 ° C. and a non-volatile liquid in which the side chains of the molecules are not polarized. As described above, tetraethoxysilane is apt to be a molecule having about 8 to 24 Si atoms without an oxidized group such as an ethoxy group such as an acetic acid group or a hydroxyethoxy group, and is unlikely to be a cyclic molecule in the condensation process. By mixing disiloxane with tetraethoxysilane, condensation progresses quickly and a non-volatile low-viscosity liquid is deposited on the substrate because the condensed molecules tend to be linear molecules with short side chains. Can be floor. As a result, excellent flattening property and hole filling property can be exhibited.
【００１７】また、このような縮合物は熱酸化膜等の表
面に対して濡れ性がよく、基板選択性が改善される。さ
らに、ジシロキサンは気体であるが、モノシランのよう
な自然発火性がなく取り扱い上安全である。Further, such a condensate has good wettability to the surface of a thermal oxide film or the like, and the selectivity of the substrate is improved. Furthermore, although disiloxane is a gas, it is not pyrophoric like monosilane and is safe to handle.
【００１８】本発明の主原料としてのアルコキシシラン
は、Ｓｉ（ＯＣ２Ｈ５）４、ＳｉＨ（ＯＣ２Ｈ５）３、
Ｓｉ［ＯＣＨ（ＣＨ３）２］４、ＳｉＨ［ＯＣＨ（ＣＨ
３）２］３、ＳｉＨ［ＯＣＨ（ＣＨ３）Ｃ２Ｈ５］３、
Ｓｉ［ＯＣＨ（ＣＨ３）Ｃ２Ｈ５］４、ＳｉＨ ［ＯＣ
（ＣＨ３）３］３、Ｓｉ［ＯＣ（ＣＨ３）３］４等の物
質である。Alkoxysilanes as main raw materials of the present invention include Si (OC 2 H 5 ) 4 , SiH (OC 2 H 5 ) 3 ,
Si [OCH (CH 3 ) 2 ] 4 , SiH [OCH (CH
3 ) 2 ] 3 , SiH [OCH (CH 3 ) C 2 H 5 ] 3 ,
Si [OCH (CH 3) C 2 H 5] 4, SiH [OC
(CH 3 ) 3 ] 3 and Si [OC (CH 3 ) 3 ] 4 .
【００１９】[0019]
【実施例】５００Ｐａ（３．７５Ｔｏｒｒ）の反応室内
に設置したアルミ格子パターンシリコン基板を３５０℃
に加熱するとともに、ジシロキサン、テトラエトキシシ
ラン、オゾンを流量比率で１：１０：４０となるように
供給してＳｉＯ２膜を成膜した。作成した膜を顕微鏡で
観察した結果、アルミ上、シリコン基板上、熱酸化膜上
等に成膜状態、膜厚等の差は見られず、極めて平坦化性
に富む膜であった。EXAMPLE An aluminum lattice pattern silicon substrate set in a reaction chamber at 500 Pa (3.75 Torr) was heated to 350 ° C.
, And disiloxane, tetraethoxysilane, and ozone were supplied at a flow ratio of 1:10:40 to form a SiO 2 film. As a result of observing the formed film with a microscope, no difference in the state of film formation, film thickness and the like was observed on aluminum, a silicon substrate, a thermal oxide film and the like, and the film was extremely flat.
【００２０】[0020]
【発明の効果】本発明によれば、極めて段差被覆性に優
れた半導体装置のシリコン酸化膜を製造することができ
ると同時に、基板選択性を改善することができる特徴が
ある。また、原料の反応効率が高く経済性が高い特徴が
ある。さらに、ダストの発生も抑制される特徴がある。According to the present invention, it is possible to manufacture a silicon oxide film of a semiconductor device having extremely excellent step coverage, and at the same time, it is possible to improve the substrate selectivity. Further, there is a feature that the reaction efficiency of the raw material is high and the economy is high. Further, there is a feature that generation of dust is suppressed.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/316 ＩＮＳＰＥＣ（ＤＩＡＬＯＧ）（ジシロ キサン＊ＴＥＯＳ) ＪＩＣＳＴファイル（ＪＯＩＳ）（ＤＩ ＳＩＬＯＸＡＮＥ＊ＴＥＯＳ) ＷＰＩ（ＤＩＡＬＯＧ）（ＤＩＳＩＬＯ ＸＡＮＥ＊ＴＥＯＳ)──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. 7 , DB name) H01L 21/316 INSPEC (DIALOG) (Disiloxane * TEOS) JICST file (JOIS) (DI SILOXANE * TEOS) WPI ( DIALOG) (DISILO XANE * TEOS)
Claims (3)
キサンを併用し、酸素あるいはオゾンを用いて酸化する
ことを特徴とする半導体装置のシリコン酸化膜の製造方
法。1. A method of manufacturing a silicon oxide film for a semiconductor device, comprising using an alkoxysilane and a disiloxane in combination as main raw materials and oxidizing using oxygen or ozone.
の混合比が、アルコキシシラン１モルに対して、ジシロ
キサンが０．０１モル以上、０．２モル以下であること
を特徴とする請求項１の半導体装置のシリコン酸化膜の
製造方法。2. The method according to claim 1, wherein the mixing ratio of the alkoxysilane to the disiloxane is 0.01 to 0.2 mol per 1 mol of the alkoxysilane. A method for manufacturing a silicon oxide film of a semiconductor device.
４、ＳｉＨ（ＯＣ２Ｈ５）３、Ｓｉ［ＯＣＨ（ＣＨ３）
２］４、ＳｉＨ［ＯＣＨ（ＣＨ３）２］３、ＳｉＨ［Ｏ
ＣＨ（ＣＨ３）Ｃ２Ｈ５］３、Ｓｉ［ＯＣＨ（ＣＨ３）
Ｃ２Ｈ５］４、ＳｉＨ［ＯＣ（ＣＨ３）３］３、Ｓｉ
［ＯＣ（ＣＨ３）３］４等であることを特徴とする請求
項１の半導体装置のシリコン酸化膜の製造方法。3. The method of claim 1, wherein the alkoxysilane is Si (OC 2 H 5 ).
4 , SiH (OC 2 H 5 ) 3 , Si [OCH (CH 3 )
2 ] 4 , SiH [OCH (CH 3 ) 2 ] 3 , SiH [O
CH (CH 3) C 2 H 5] 3, Si [OCH (CH 3)
C 2 H 5 ] 4 , SiH [OC (CH 3 ) 3 ] 3 , Si
2. The method for producing a silicon oxide film for a semiconductor device according to claim 1, wherein [OC (CH 3 ) 3 ] 4 or the like is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3194713A JP3060185B2 (en) | 1991-05-01 | 1991-05-01 | Method for manufacturing silicon oxide film of semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3194713A JP3060185B2 (en) | 1991-05-01 | 1991-05-01 | Method for manufacturing silicon oxide film of semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04329639A JPH04329639A (en) | 1992-11-18 |
| JP3060185B2 true JP3060185B2 (en) | 2000-07-10 |
Family
ID=16329014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3194713A Expired - Fee Related JP3060185B2 (en) | 1991-05-01 | 1991-05-01 | Method for manufacturing silicon oxide film of semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3060185B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2914095A (en) * | 1994-06-28 | 1996-01-25 | Fei Company | Charged particle deposition of electrically insulating films |
| JP4591651B2 (en) * | 2003-02-27 | 2010-12-01 | 東ソー株式会社 | Insulating film material comprising organosilane compound, method for producing the same, and semiconductor device |
| US10384254B2 (en) | 2013-07-02 | 2019-08-20 | Jfe Steel Corporation | Method of manufacturing hot-pressed member |
| SG11201703196WA (en) | 2014-10-24 | 2017-05-30 | Versum Materials Us Llc | Compositions and methods using same for deposition of silicon-containing films |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992012535A1 (en) | 1991-01-08 | 1992-07-23 | Fujitsu Limited | Process for forming silicon oxide film |
-
1991
- 1991-05-01 JP JP3194713A patent/JP3060185B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992012535A1 (en) | 1991-01-08 | 1992-07-23 | Fujitsu Limited | Process for forming silicon oxide film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04329639A (en) | 1992-11-18 |
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