JP3144165B2 - Thin film generator - Google Patents
Thin film generatorInfo
- Publication number
- JP3144165B2 JP3144165B2 JP17839893A JP17839893A JP3144165B2 JP 3144165 B2 JP3144165 B2 JP 3144165B2 JP 17839893 A JP17839893 A JP 17839893A JP 17839893 A JP17839893 A JP 17839893A JP 3144165 B2 JP3144165 B2 JP 3144165B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- hollow
- thin film
- hollow electrode
- film
- 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
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- Chemical Vapour Deposition (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、化合物ガスを電極間に
発生するグロー放電を用いて分割して基体上にアモルフ
ァス半導体等の薄膜を形成する薄膜生成装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film forming apparatus for forming a thin film of an amorphous semiconductor or the like on a substrate by dividing a compound gas using glow discharge generated between electrodes.
【０００２】[0002]
【従来の技術】化合物ガスをプラズマ放電により分解さ
せる薄膜生成方法には、従来は平行平板電極を用いたグ
ロー放電やあるいは高周波を用いたＲＦ放電が使用され
てきた。これら平行平板電極を用いた放電法では、SiＨ
4 、GeＨ4 、Ｃ2 Ｈ2 等の化合物ガスおよびＢ2 Ｈ6 、
ＰＨ3 等のドーピングガス、あるいはこれらを組合わせ
た形で混合したガスを分解してSi−Ge合金あるいはSi−
Ｃ合金の非晶質薄膜を生成するとき、分解の効率がそれ
ぞれ異なるため、最適条件でプラズマによる分解を可能
にすることが困難であった。そこで、これらの混合ガス
を用いて合金膜を作製する際に、より高密度なプラズマ
を発生させることが可能な中空円筒状の金属電極 (以下
ホロー電極と記す) を用いれば分解効率の異なる混合ガ
スに適用する際再現性のよい膜を得ることが可能であ
る。すなわち、一つの共通電極に複数のホロー電極をそ
の開口部を対向させて配置し、基板を共通電極側に設置
した上でホロー電極の内部空間に原料ガス導入管を連通
させ、共通電極に正、ホロー電極に負の電圧を印加して
グロー放電を発生させる薄膜生成装置が特開昭62−1594
19号公報で公知である。2. Description of the Related Art Conventionally, a glow discharge using a parallel plate electrode or an RF discharge using a high frequency has been used as a thin film forming method for decomposing a compound gas by plasma discharge. In the discharge method using these parallel plate electrodes, SiH
4 , compound gas such as GeH 4 and C 2 H 2 and B 2 H 6 ,
Doping gas of PH 3, etc., or to decompose the mixed gas in the form of a combination of these Si-Ge alloy or Si-
When an amorphous thin film of a C alloy is formed, it is difficult to enable decomposition by plasma under optimum conditions because the decomposition efficiencies differ from one another. Therefore, when forming an alloy film using these mixed gases, if a hollow cylindrical metal electrode (hereinafter referred to as a hollow electrode) capable of generating higher-density plasma is used, mixing with different decomposition efficiencies will be used. When applied to a gas, a film with good reproducibility can be obtained. That is, a plurality of hollow electrodes are arranged on one common electrode with their openings facing each other, a substrate is placed on the common electrode side, and a raw material gas introduction pipe is communicated with the internal space of the hollow electrode. Japanese Unexamined Patent Publication No. Sho 62-1594 discloses a thin film forming apparatus for generating a glow discharge by applying a negative voltage to a hollow electrode.
It is publicly known in JP-A-19.
【０００３】[0003]
【発明が解決しようとする課題】従来、ホローカソード
による成膜法ではその膜質が平行平板電極を用いた通常
の放電による成膜法に比べ劣るという問題があった。こ
の一つの原因として、基板がホロー電極から離れたとこ
ろに位置するため、この距離を膜形成前駆体が移動する
際、比較的大きなポリマー的な構造をもつものが形成さ
れ、膜堆積を行う時これらが集まり粗雑な膜となること
が考えられる。さらに、ポリマー構造をもつものが成長
する確率を押さえるためホロー電極のそばに基板を置く
ことは、電界が集中した高密度のプラズマ領域に基板を
さらすことになり、イオンなどの衝突の影響により良質
膜は形成不可能である。またこれとは別に、大面積太陽
電池用にホロー電極を用いた場合膜厚の不均一性が問題
となっていた。Heretofore, there has been a problem that the film quality of the hollow cathode film formation method is inferior to that of a normal discharge film formation method using parallel plate electrodes. One of the causes is that the substrate is located far from the hollow electrode, so when the film forming precursor moves over this distance, a relatively large polymer-like structure is formed, and when the film is deposited, It is conceivable that these gather to form a rough film. Furthermore, placing the substrate near the hollow electrode in order to reduce the probability of growth of those with a polymer structure exposes the substrate to a high-density plasma region where the electric field is concentrated, and provides good quality due to the impact of ions and the like. A film cannot be formed. Separately, when a hollow electrode is used for a large-area solar cell, nonuniformity of the film thickness has been a problem.
【０００４】本発明は、上記の問題を解決し、中空電極
を用い、しかもポリマー構造的な膜形成を押さえ、さら
に高密度プラズマ中でのイオンの影響を避けて均一な良
質膜を再現性よく形成できることのできる薄膜生成装置
を提供することにある。The present invention solves the above problems, uses a hollow electrode, suppresses the formation of a polymer-structured film, and avoids the influence of ions in high-density plasma to form a uniform high-quality film with good reproducibility. It is an object of the present invention to provide a thin film forming apparatus that can be formed.
【０００５】[0005]
【課題を解決するための手段】上記の目的を達成するた
めに、本発明の薄膜生成装置は、反応室内に負の電圧の
印加される筒状の中空電極と正の電圧の印加される対向
電極とが、中空電極の内部空間が対向電極に向かって開
口するように配置され、またその中空電極の内部空間に
向かって化合物ガスの導入口が開口し、中空電極の反対
向電極側に被成膜基体支持体が存在するものとする。そ
の被成膜基体支持体が中空電極と同電位であることが良
い。対向電極が内部に空洞を有し、その空洞が化合物ガ
ス導入管に連通し、対向電極の中空電極側の面に分散し
て貫通孔が明けられたことが効果的である。また、中空
電極が互いに側面を密着して結合された複数個の角筒状
電極よりなることが有効である。さらに、中空電極と被
成膜基体支持体との間に多孔質の熱源体が介在すること
も良い。In order to achieve the above object, a thin film forming apparatus according to the present invention comprises a tubular hollow electrode to which a negative voltage is applied and a counter electrode to which a positive voltage is applied. The electrode is arranged so that the internal space of the hollow electrode opens toward the counter electrode, the compound gas inlet opens toward the internal space of the hollow electrode, and the electrode is covered on the opposite side of the hollow electrode to the counter electrode. It is assumed that a film-forming substrate support exists. The substrate support on which the film is to be formed is preferably at the same potential as the hollow electrode. It is effective that the counter electrode has a cavity inside, and the cavity communicates with the compound gas introduction pipe, and is dispersed on the surface of the counter electrode on the hollow electrode side to form a through hole. In addition, it is effective that the hollow electrode is composed of a plurality of rectangular tubular electrodes which are bonded to each other with their side surfaces in close contact with each other. Further, a porous heat source body may be interposed between the hollow electrode and the substrate support.
【０００６】[0006]
【作用】被成膜基体を負電圧を印加した中空電極に近接
して設置することにより、膜形成前駆体の移動距離が短
くなってポリマー構造的の膜形成が抑制されると共に、
高密度のプラズマの影響が避けられ、しかも中空電極を
用いることによる利点、すなわち電極内部に供給される
分解効率の異なる混合ガスを最適条件で活性化できるこ
とが可能である。また、中空電極に角筒状のものを用い
れば、複数個の中空電極を密着して設置できるため、大
面積の成膜が容易にできる。中空電極と被成膜基体の間
に熱源体を介在させれば、気相中で成長したポリマー的
な構造を熱エネルギーによって分解し、より緻密な高品
質の再現性良く得ることが可能であることを特徴とす
る。By disposing the substrate on which the film is to be formed close to the hollow electrode to which the negative voltage is applied, the moving distance of the film forming precursor is shortened, and the formation of a polymer structural film is suppressed.
The effect of high-density plasma can be avoided, and the advantage of using a hollow electrode, that is, it is possible to activate mixed gas with different decomposition efficiencies supplied into the electrode under optimal conditions. Further, if a hollow cylindrical electrode is used as the hollow electrode, a plurality of hollow electrodes can be placed in close contact with each other, so that a large-area film can be easily formed. If a heat source is interposed between the hollow electrode and the substrate on which the film is to be formed, the polymer-like structure grown in the gas phase can be decomposed by thermal energy, and a denser, high-quality reproducible material can be obtained. It is characterized by the following.
【０００７】[0007]
【実施例】以下、図を引用して本発明の実施例について
述べる。図１に示す実施例では、真空槽１の中にホロー
電極２とシャワー電極３が対向配置されている。ホロー
電極２は、内径が20〜60mm、高さ30〜100mm である。シ
ャワー電極３は、絶縁性のガス導入管４に連通する空洞
を有し、ガス導入管４から供給される原料ガスをホロー
電極２の内部空間に向けて送り込むことができるよう
に、ホロー電極側はメッシュ状になっている。ホロー電
極２およびシャワー電極は、高圧抵抗51が直列接続され
た電源２に接続され、シャワー電極３が正、ホロー電極
２が負に印加される電圧は０〜２ＫＶの範囲で変えるこ
とができる。成膜基板６は、ホロー電極２同様に負の電
圧が印加されるトレイ７の上に載せられている。なお、
例えば電極あるいは槽壁に付着したフレークやほこりが
基板６に落下するのを防ぐために、基板が同じくカソー
ドとなるホロー電極を挟んで対向電極の上に設置される
デボアップ方式にすることもできる。基板６はヒータ８
により室温から350 ℃までの温度に制御される。ガス導
入管４から供給されるガスは、例えばSiＨ4 、GeＨ4 、
ＰＨ3 、Ｂ2 Ｈ6 であり、これらが単独あるいは混合さ
れ、排気管９からの真空排気により槽１内の圧力は0.１
〜0.５Torrに保たれる。基板６は、ホローカソード２の
すぐそばあるいは密着させて置くことができ、電子エネ
ルギーの高い領域に近づくことで効率よく分解された、
例えばSiＨ 4 、GeＨ4 等の活性種を早い段階で基板上に
非晶質Si−Ge合金薄膜として堆積させることが可能であ
る。この効果により従来問題となっていた膜質の悪さを
解決できる。BRIEF DESCRIPTION OF THE DRAWINGS FIG.
State. In the embodiment shown in FIG.
The electrode 2 and the shower electrode 3 are arranged to face each other. Hollow
The electrode 2 has an inner diameter of 20 to 60 mm and a height of 30 to 100 mm. Shi
The lower electrode 3 has a cavity communicating with the insulating gas introduction pipe 4.
And the source gas supplied from the gas introduction pipe 4 is hollow.
So that it can be fed into the internal space of the electrode 2
In addition, the hollow electrode side has a mesh shape. Hollow Den
A high-voltage resistor 51 is connected in series between the pole 2 and the shower electrode.
Connected to the power supply 2 and the shower electrode 3 is positive and the hollow electrode
The voltage applied to negative 2 can be changed in the range of 0 to 2 kV.
Can be. The film formation substrate 6 has a negative voltage, like the hollow electrode 2.
It is placed on a tray 7 to which pressure is applied. In addition,
For example, flakes and dust adhering to electrodes or tank walls
In order to prevent the board from dropping onto the board 6,
Placed on the opposite electrode with the hollow electrode serving as
It is also possible to use a devoted system. The substrate 6 has a heater 8
To control the temperature from room temperature to 350 ° C. Gas guide
The gas supplied from the inlet pipe 4 is, for example, SiHFour, GeHFour,
PHThree, BTwoH6These are used alone or in combination.
The pressure in the tank 1 is reduced to 0.1 by evacuation from the exhaust pipe 9.
It is kept at ~ 0.5 Torr. The substrate 6 has a hollow cathode 2
It can be placed right next to or close to
Decomposed efficiently by approaching the area with high energy,
For example, SiH Four, GeHFourActive species on the substrate at an early stage
Can be deposited as an amorphous Si-Ge alloy thin film
You. Due to this effect, the poor quality of the film
Solvable.
【０００８】図２に示す実施例は、カソード電極を多数
配置して大面積の基板上に成膜するための装置で、カソ
ード電極10は斜視図で概念的に示したように角筒状中空
電極の複数個 (図では８個) を密着させて基板６に近接
して配置したものである。図３に示す実施例では、ホロ
ー電極２と成膜基板６の間に、ステンレス鋼のメッシュ
体からなり、電源12に接続して電流を流すことにより10
0 〜500 ℃の温度に上げられる熱源体11が設置されてい
る。この熱源体11が、ホロー電極２から基板６に移動す
る膜形成前駆体に、ポリマー構造をもつものを分解する
熱エネルギーを与える。The embodiment shown in FIG. 2 is an apparatus for arranging a large number of cathode electrodes to form a film on a large-area substrate. The cathode electrode 10 has a rectangular hollow shape as conceptually shown in a perspective view. A plurality of electrodes (eight in the figure) are arranged in close contact with the substrate 6. In the embodiment shown in FIG. 3, between the hollow electrode 2 and the film-forming substrate 6, a stainless steel mesh body is connected.
A heat source 11 capable of raising the temperature to 0 to 500 ° C. is provided. The heat source 11 gives the film forming precursor moving from the hollow electrode 2 to the substrate 6 thermal energy for decomposing the precursor having a polymer structure.
【０００９】図４に示す実施例では、図２に示す実施例
と同様にカソード電極10を角筒状中空電極の複数個から
構成した大面積成膜用の装置において、ポリマー構造分
解用の熱源体11を設置している。以上の図２、図３、図
４に示した薄膜生成装置においても、デポアップ方式に
して膜質を向上させることが可能である。In the embodiment shown in FIG. 4, similarly to the embodiment shown in FIG. 2, a heat source for decomposing a polymer structure is used in a large area film forming apparatus in which the cathode electrode 10 is constituted by a plurality of rectangular hollow electrodes. Body 11 is installed. Also in the thin film generating apparatuses shown in FIGS. 2, 3 and 4, it is possible to improve the film quality by using a deposit-up method.
【００１０】なお、原料ガスにＣ2 Ｈ2 のようにSiＨ4
にくらべて分解しやすい化合物ガスを混合するときに
は、前記公報に記載されているようにSiＨ4 とＣ2 Ｈ2
とを互いに絶縁された中空電極に別個に導き、それぞれ
の電極に供給される電力を変えて、Ｃ2 Ｈ2 のための放
電電力をSiＨ4 のための放電電力の１／２ないし１／３
に低めることも効果的である。The source gas is SiH 4 such as C 2 H 2.
When compound gas which is more easily decomposed than in the case of mixing is used, as described in the above publication, SiH 4 and C 2 H 2
Are separately led to hollow electrodes insulated from each other, and the power supplied to each electrode is changed so that the discharge power for C 2 H 2 is reduced to １ ／ to の of the discharge power for SiH 4.
It is also effective to lower it.
【００１１】[0011]
【発明の効果】本発明によれば、変換効率の向上に有利
であるが、膜質の点に難点があった中空電極ＣＶＤ装置
を、中空カソード電極に近接して成膜基体を設置するこ
とにより、さらには中空カソード電極と成膜気体の間に
ポリマー構造分解のための熱エネルギーを与える熱源体
を設置することによって、ポリマー構造的な膜の形成を
抑制し、高密度のプラズマの影響を避けることにより、
改善することができた。これにより成膜コストを大幅に
引下げることが可能になり、特に非晶質合金膜を用いた
デバイスの製造上に得られる効果は大きい。According to the present invention, the hollow electrode CVD apparatus, which is advantageous for improving the conversion efficiency but has a problem in film quality, can be provided by installing a film-forming substrate close to the hollow cathode electrode. In addition, by installing a heat source between the hollow cathode electrode and the film-forming gas that gives thermal energy for polymer structure decomposition, the formation of polymer-structured films is suppressed and the effects of high-density plasma are avoided. By doing
Could be improved. As a result, the film formation cost can be significantly reduced, and the effect obtained particularly in the manufacture of a device using an amorphous alloy film is great.
【図１】本発明の一実施例の薄膜生成装置の断面図FIG. 1 is a sectional view of a thin film forming apparatus according to an embodiment of the present invention.
【図２】本発明の異なる実施例の薄膜生成装置の断面図FIG. 2 is a sectional view of a thin film forming apparatus according to another embodiment of the present invention.
【図３】本発明の異なる実施例の薄膜生成装置の断面図FIG. 3 is a sectional view of a thin film forming apparatus according to another embodiment of the present invention.
【図４】本発明の異なる実施例の薄膜生成装置の断面図FIG. 4 is a sectional view of a thin film forming apparatus according to another embodiment of the present invention.
１ 真空槽 ２ ホロー電極 ３ シャワー電極 ４ ガス導入管 ５、１２ 電源 ６ 成膜基板 ７ トレイ ８ ヒータ ９ 排気管 １０ カソード電極 １１ 熱源体 DESCRIPTION OF SYMBOLS 1 Vacuum tank 2 Hollow electrode 3 Shower electrode 4 Gas introduction pipe 5, 12 Power supply 6 Deposition substrate 7 Tray 8 Heater 9 Exhaust pipe 10 Cathode electrode 11 Heat source body
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−297578（ＪＰ，Ａ) 特開 平２−71516（ＪＰ，Ａ) 特開 平１−279761（ＪＰ，Ａ) 特開 平５−326426（ＪＰ，Ａ) 特開 平１−147068（ＪＰ，Ａ) 特開 昭62−119918（ＪＰ，Ａ) 特開 昭61−226925（ＪＰ，Ａ) 特開 昭62−159419（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/205 C23C 16/50 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-297578 (JP, A) JP-A-2-71516 (JP, A) JP-A-1-279761 (JP, A) JP-A-5-297 326426 (JP, A) JP-A-1-147068 (JP, A) JP-A-62-119918 (JP, A) JP-A-61-226925 (JP, A) JP-A-62-159419 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) H01L 21/205 C23C 16/50
Claims (5)
空電極と正の電圧の印加される対向電極とが、中空電極
の内部空間が対向電極に向かって開口するように配置さ
れ、またその中空電極の内部空間に向かって化合物ガス
の導入口が開口し、中空電極の反対向電極側に被成膜基
体支持体が存在することを特徴とする薄膜生成装置。A cylindrical hollow electrode to which a negative voltage is applied and a counter electrode to which a positive voltage is applied are arranged in the reaction chamber such that the internal space of the hollow electrode opens toward the counter electrode. A thin film forming apparatus characterized in that an introduction port for a compound gas is opened toward the internal space of the hollow electrode, and a film-forming substrate support exists on the side of the hollow electrode opposite to the counter electrode.
る請求項１記載の薄膜生成装置。2. The thin film forming apparatus according to claim 1, wherein the substrate support on which the film is to be formed has the same potential as the hollow electrode.
化合物ガス導入管に連通し、対向電極の中空電極側の面
に分散して貫通孔が明けられた請求項１あるいは２記載
の薄膜生成装置。3. The counter electrode according to claim 1, wherein the counter electrode has a cavity therein, and the cavity communicates with the compound gas introducing pipe, and the through hole is formed by being dispersed on the surface of the counter electrode on the hollow electrode side. Thin film generator.
た複数個の角筒状電極よりなる請求項１ないし３のいず
れかに記載の薄膜生成装置。4. The thin film forming apparatus according to claim 1, wherein the hollow electrode comprises a plurality of rectangular cylindrical electrodes which are bonded to each other with their side surfaces in close contact with each other.
質の熱源体が介在する請求項１ないし４のいずれかに記
載の薄膜生成装置。5. The thin-film generation apparatus according to claim 1, wherein a porous heat source is interposed between the hollow electrode and the substrate support.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17839893A JP3144165B2 (en) | 1993-01-22 | 1993-07-20 | Thin film generator |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-8671 | 1993-01-22 | ||
| JP867193 | 1993-01-22 | ||
| JP17839893A JP3144165B2 (en) | 1993-01-22 | 1993-07-20 | Thin film generator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06275547A JPH06275547A (en) | 1994-09-30 |
| JP3144165B2 true JP3144165B2 (en) | 2001-03-12 |
Family
ID=26343229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17839893A Expired - Fee Related JP3144165B2 (en) | 1993-01-22 | 1993-07-20 | Thin film generator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3144165B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5386037A (en) * | 1994-06-20 | 1995-01-31 | General Electric Company | Trisstannoxanes useful for polymerizing macrocyclic poly(alkylene dicarboxylate) oligomers |
| DE19755902C1 (en) * | 1997-12-08 | 1999-05-12 | Fraunhofer Ges Forschung | Plasma surface treatment process involves hollow cathode self-cleaning |
| US6369157B1 (en) | 2000-01-21 | 2002-04-09 | Cyclics Corporation | Blend material including macrocyclic polyester oligomers and processes for polymerizing the same |
| US7767781B2 (en) | 2000-09-01 | 2010-08-03 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
| DE502006003016D1 (en) * | 2005-05-04 | 2009-04-16 | Oerlikon Trading Ag | PLASMA AMPLIFIER FOR PLASMA TREATMENT PLANT |
| JP5116999B2 (en) * | 2006-06-27 | 2013-01-09 | 株式会社ピュアロンジャパン | Plasma generator |
-
1993
- 1993-07-20 JP JP17839893A patent/JP3144165B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06275547A (en) | 1994-09-30 |
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