JPH0227824B2 - - Google Patents
Info
- Publication number
- JPH0227824B2 JPH0227824B2 JP56002067A JP206781A JPH0227824B2 JP H0227824 B2 JPH0227824 B2 JP H0227824B2 JP 56002067 A JP56002067 A JP 56002067A JP 206781 A JP206781 A JP 206781A JP H0227824 B2 JPH0227824 B2 JP H0227824B2
- Authority
- JP
- Japan
- Prior art keywords
- amorphous
- film
- hydrogen
- glow discharge
- amorphous silicon
- 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 - Lifetime
Links
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 11
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 33
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Light Receiving Elements (AREA)
Description
【発明の詳細な説明】
この発明はギヤツプステート密度の少ないアモ
ルフアス半導体膜の製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing an amorphous semiconductor film having a low gap state density.
アモルフアス半導体膜は、低価格太陽電池用材
料や薄膜トランジスタ材料として注目されてお
り、アモルフアス・シリコン膜やアモルフアス・
シリコン・ゲルマニウム膜が研究されている。ア
モルフアス半導体膜は、ダングリングボンドに起
因するギヤツプステート密度を可能な限り小さく
することが重要であり、種々の方法が考案されて
いる。その１つは、グロー放電法によつてシラン
（SiH4）を分解する方法である。この方法を用い
るとアモルフアス・シリコン膜中に水素が含ま
れ、水素によつてダングリングボンドが消去され
て、ギヤツプステート密度が減少する利点があ
る。しかし、この方法によると、シリコン膜中に
含まれる水素量は、ダングリングボンドを消去す
るのに必要な量の100倍程度になり、アモルフア
ス膜質の不安定性の原因になるといわれている。
この欠点を補うために次の方法がある。すなわ
ち、SiH4の熱分解法によりアモルフアス・シリ
コン膜を形成したのち、水素プラズマ中で400℃
程度の温度でアニールする方法である。この方法
によると、アモルフアス・シリコン膜の表面から
水素が膜中に浸入してダングリングボンドを消去
し、ギヤツプステート密度が減少する。この方法
によると、含まれる水素量はグロー放電法の場合
の1/10以下になり、アモルフアス膜質の不安定性
が除かれる利点がある。しかし、この方法では水
素が膜表面から主に拡散によつて浸入するため、
アモルフアス膜が厚くなるとアニール時間が長く
なる欠点がある。 Amorphous semiconductor films are attracting attention as materials for low-cost solar cells and thin film transistors, and include amorphous silicon films and amorphous silicon films.
Silicon-germanium films are being researched. In an amorphous semiconductor film, it is important to minimize the gap state density caused by dangling bonds, and various methods have been devised. One method is to decompose silane (SiH 4 ) using a glow discharge method. When this method is used, hydrogen is contained in the amorphous silicon film, and the hydrogen erases dangling bonds, which has the advantage of reducing the gap state density. However, according to this method, the amount of hydrogen contained in the silicon film is about 100 times the amount required to eliminate dangling bonds, which is said to cause instability of the amorphous film.
The following method is available to compensate for this drawback. That is, after forming an amorphous silicon film by thermal decomposition of SiH 4 , it was heated at 400°C in hydrogen plasma.
This is a method of annealing at a temperature of approximately According to this method, hydrogen permeates into the film from the surface of the amorphous silicon film, erases dangling bonds, and reduces the gap state density. According to this method, the amount of hydrogen contained is less than 1/10 of that in the glow discharge method, which has the advantage of eliminating instability of the amorphous film. However, in this method, hydrogen mainly enters from the membrane surface by diffusion, so
The disadvantage is that the thicker the amorphous film, the longer the annealing time.
本発明はこのような点に鑑みてなされたもの
で、グロー放電法で形成したアモルフアス半導体
膜を熱処理したのち、水素プラズマ中でアニール
することにより、短かいアニール時間で膜質の安
定したアモルフアス半導体膜を得ることができる
製法を提案するものである。 The present invention has been made in view of these points, and involves heat-treating an amorphous semiconductor film formed by a glow discharge method and then annealing it in hydrogen plasma, thereby producing an amorphous semiconductor film with stable film quality in a short annealing time. This paper proposes a manufacturing method that can obtain the following.
グロー放電法で形成したアモルフアス・シリコ
ン膜中に含まれる水素の結合状態は、Si−Ｈ、Si
−H2、（Si−H2）ｎの３種類に大別される。ダン
グリングボンドを消去するためにはSi−Ｈが必要
であり、Si−H2や（Si−H2）ｎはアモルフアス
膜内にマイクロボイドを発生し、アモルフアス膜
質を不安定にさせる原因になつていると考えられ
ている。そのため、グロー放電法で形成したアモ
ルフアス・シリコン膜中に含まれるSi−H2や
（Si−H2）ｎを除去する必要がある。グロー放電
法で形成したアモルフアス・シリコン膜を加熱す
ると、加熱温度が350℃〜400℃の範囲と550℃〜
600℃の範囲で水素が膜から放出される。前者は
Si−H2および（Si−H2）ｎの分解によるもので
あり、後者はSi−Ｈの分解によるものである。そ
こで、グロー放電法で形成したアモルフアス膜を
先ず400℃〜550℃で加熱する。すると、Si−H2
や（Si−H2）ｎは分解してSiが発生するが、
Si元素の再配列によりSi−になる。アモルフアス
膜の表面近傍では水素の放出が盛んであるからSi
−の数は多いが、膜中ではSi−の数は少なくなつ
ている。この後、アモルフアス膜を水素プラズマ
中でアニールすると、水素によつてダングリング
ボンド（Si−）が消去される。この場合には、ア
モルフアス膜中にSi−Ｈの結合がかなり含まれて
いること、また、膜表面近傍にダングリングボン
ドが多く存在することから、アモルフアス膜が厚
い場合でもアニール時間が短くなる利点がある。
アニール時間を更に短くするためには、水素プラ
ズマに対してアモルフアス膜が負となるように外
部回路から電圧を印加した状態でアニールする方
法が考えられる。この場合には、電界の作用によ
りアモルフアス膜中での水素の拡散が促進される
ため、アニール時間が短くなる利点がある。 The bonding state of hydrogen contained in the amorphous silicon film formed by the glow discharge method is Si-H, Si
-H 2 and (Si-H 2 )n. Si-H is required to erase dangling bonds, and Si-H 2 and (Si-H 2 )n generate microvoids within the amorphous film, making the amorphous film unstable. It is believed that Therefore, it is necessary to remove Si-H 2 and (Si-H 2 )n contained in the amorphous silicon film formed by the glow discharge method. When an amorphous silicon film formed by the glow discharge method is heated, the heating temperature ranges from 350°C to 400°C and from 550°C to
Hydrogen is released from the membrane in the range of 600°C. The former is
This is due to the decomposition of Si- H2 and (Si- H2 )n, the latter being due to the decomposition of Si-H. Therefore, an amorphous film formed by a glow discharge method is first heated at 400°C to 550°C. Then, Si−H 2
(Si−H 2 )n decomposes and generates Si,
It becomes Si- due to rearrangement of Si elements. Since hydrogen is actively released near the surface of the amorphous amorphous film, Si
Although the number of - is large, the number of Si- is small in the film. Thereafter, when the amorphous film is annealed in hydrogen plasma, the dangling bonds (Si-) are erased by hydrogen. In this case, the amorphous amorphous film contains a considerable amount of Si-H bonds and there are many dangling bonds near the film surface, so the annealing time is short even if the amorphous film is thick. There is.
In order to further shorten the annealing time, a method can be considered in which annealing is performed while applying a voltage from an external circuit so that the amorphous film becomes negative with respect to hydrogen plasma. In this case, the effect of the electric field promotes the diffusion of hydrogen in the amorphous film, so there is an advantage that the annealing time is shortened.
以上述べたようにこの発明によれば、グロー放
電法で形成したアモルフアス半導体膜を400℃〜
550℃で熱処理したのち、水素プラズマ中で水素
プラズマに対してアモルフアス半導体膜が負とな
るような電圧を印加しながらアニールするので、
アニール時間を短かくすることができる。 As described above, according to the present invention, an amorphous semiconductor film formed by a glow discharge method can be
After heat treatment at 550℃, annealing is performed in hydrogen plasma while applying a voltage that makes the amorphous semiconductor film negative with respect to hydrogen plasma.
Annealing time can be shortened.
Claims (1)
ン膜を400℃乃至550℃の範囲内の温度で熱処理し
たのち、水素プラズマ中で水素プラズマに対して
アモルフアスシリコン膜が負となるように電圧を
印加しながらアニールすることを特徴とするアモ
ルフアス半導体膜の製造方法。1 After heat-treating the amorphous silicon film formed by the glow discharge method at a temperature within the range of 400°C to 550°C, a voltage is applied in hydrogen plasma so that the amorphous silicon film becomes negative with respect to the hydrogen plasma. 1. A method for producing an amorphous semiconductor film, characterized in that annealing is performed while the film is annealed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56002067A JPS57115823A (en) | 1981-01-12 | 1981-01-12 | Manufacture of amorphous semiconductor film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56002067A JPS57115823A (en) | 1981-01-12 | 1981-01-12 | Manufacture of amorphous semiconductor film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57115823A JPS57115823A (en) | 1982-07-19 |
| JPH0227824B2 true JPH0227824B2 (en) | 1990-06-20 |
Family
ID=11518993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56002067A Granted JPS57115823A (en) | 1981-01-12 | 1981-01-12 | Manufacture of amorphous semiconductor film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57115823A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05277848A (en) * | 1992-03-30 | 1993-10-26 | Nissan Shatai Co Ltd | Car body support device |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0264762B1 (en) * | 1986-10-24 | 1992-03-25 | Siemens Aktiengesellschaft | Method to passivate crystal defects in a hydrogen plasma |
| JP2723224B2 (en) * | 1987-05-15 | 1998-03-09 | 鐘淵化学工業株式会社 | Amorphous semiconductor and manufacturing method thereof |
| JPH088371B2 (en) * | 1993-03-10 | 1996-01-29 | 株式会社日立製作所 | Thin film solar cell and method of manufacturing the same |
| JP6732821B2 (en) | 2018-02-22 | 2020-07-29 | 株式会社東芝 | Method of manufacturing semiconductor device |
-
1981
- 1981-01-12 JP JP56002067A patent/JPS57115823A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05277848A (en) * | 1992-03-30 | 1993-10-26 | Nissan Shatai Co Ltd | Car body support device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57115823A (en) | 1982-07-19 |
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