JPS63155611A - Manufacture of semiconductor thin film - Google Patents
Manufacture of semiconductor thin filmInfo
- Publication number
- JPS63155611A JPS63155611A JP30230486A JP30230486A JPS63155611A JP S63155611 A JPS63155611 A JP S63155611A JP 30230486 A JP30230486 A JP 30230486A JP 30230486 A JP30230486 A JP 30230486A JP S63155611 A JPS63155611 A JP S63155611A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- reaction chamber
- semiconductor thin
- thin film
- mercury
- 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.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 14
- 239000010409 thin film Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 230000001678 irradiating effect Effects 0.000 claims abstract description 5
- 230000005855 radiation Effects 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052753 mercury Inorganic materials 0.000 abstract description 12
- 230000003287 optical effect Effects 0.000 abstract description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 230000005469 synchrotron radiation Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 2
- 231100000614 poison Toxicity 0.000 abstract 2
- 230000007096 poisonous effect Effects 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 6
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910007264 Si2H6 Inorganic materials 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明はアモルファスシリコン（ａ−３ｉ ）、アモル
ファスシリコンカーバイド（ａ−３ｉ１−ｘＣｘ）アモ
ルファスシリコンゲルマニウム（ａ−８ｉ１−ＸＧｅｘ
）、微結晶シリコン（ｕｃ−８ｔ）等の半導体薄膜の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field The present invention is applicable to amorphous silicon (a-3i), amorphous silicon carbide (a-3i1-xCx), amorphous silicon germanium (a-8i1-XGex)
), relates to a method for manufacturing semiconductor thin films such as microcrystalline silicon (UC-8T).
１１ｆｆ＋ 従来の技術
ａ −３ｉ、ａ−８ｉ１−ｘｃ”＋ａ−８ｉ１−ｘＧｅ
ｘ、、ｕｃ−３ｉ等の半導体薄膜はモノシラン（ＳｉＨ
リガス、ジシラン（Ｓｉ２Ｈ６）ガス、四フッ化シリコ
ン（ＳｉＦ４）ガス等を原料ガスとし、高周波グロブ放
電によるプラズマＣＶＤ法により形成することができる
。11ff+ Conventional technology a-3i, a-8i1-xc”+a-8i1-xGe
Semiconductor thin films such as x, uc-3i, etc. are made of monosilane (SiH
It can be formed by a plasma CVD method using high-frequency glob discharge, using a raw material gas such as silane gas, disilane (Si2H6) gas, or silicon tetrafluoride (SiF4) gas.
特に太陽電池や光センサ、更には電子写真の感光体ドラ
ム等の光デバイスに実用化されている上記λ−３ｉ等の
半導体薄膜の製造には、ＳｉＨ４ガスが他のガスに比し
て入手が容易で且つ安価である等の理由で最も使用され
ている。プラズマＣＶＤ法は、上記光デバイスの大面積
化要求も満足することができるために有効なプロセスで
ある。In particular, SiH4 gas is difficult to obtain compared to other gases in the production of semiconductor thin films such as the above-mentioned λ-3i, which are used in optical devices such as solar cells, optical sensors, and electrophotographic photoreceptor drums. It is the most used because it is easy and inexpensive. The plasma CVD method is an effective process because it can satisfy the above requirement for increasing the area of optical devices.
しかし乍ら、大面積化に有効なプラズマＣＶＤ法であっ
ても、形成されつつある半導体薄膜の膜面ばプラズマに
曝されるために、高速荷電粒子によるアタックを受け、
半導体薄膜の膜質を悪化させたり、界面特性を低下させ
るという問題点がある。However, even with the plasma CVD method, which is effective for increasing the area, the surface of the semiconductor thin film that is being formed is exposed to plasma, so it is attacked by high-speed charged particles.
There are problems in that the film quality of the semiconductor thin film is deteriorated and the interface properties are deteriorated.
Ｊａｐａｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉ
ｅｄ ｐｈｙｓｉｃｓＶＯｌ、２３． ｆｆ１２ 、２
月、１９８４年、ＰＰＬ９１−Ｌ９３に開示された紫外
線を輻射する光源の光エネルギによりＳｉ２Ｈ６の原料
ガスを直接分解する光ＣＶＤ法は上記高速荷電粒子によ
るプラズマダメージに対し極めて有効である。ところが
、斯る直接分解光ＣＶＤ法の場合、原料ガスとして３
ｉ ）（４ガスを用いてを当該ＳｉＨ４ガスは紫外線に
より直接分解されず、紫外線で分解可能なＳｉＨ４の高
次ガスである高価なＳｉ２Ｈ６ガスを使用しなければな
らない。Japanese Journal of Appli
ed physics VOl, 23. ff12,2
The photo-CVD method, which is disclosed in PPL91-L93 published in May, 1984, in which Si2H6 raw material gas is directly decomposed by the light energy of a light source that radiates ultraviolet rays, is extremely effective against plasma damage caused by the above-mentioned high-speed charged particles. However, in the case of such direct decomposition photoCVD method, 3
i) (Using 4 gases) The SiH4 gas is not directly decomposed by ultraviolet light, and expensive Si2H6 gas, which is a higher-order gas of SiH4 that can be decomposed by ultraviolet light, must be used.
一方、紫外線で直接分解することのできない３ｉＨ４ガ
スに対しては、第１４回薄膜・光面物理セミナー、第１
０５頁乃至第１１５頁に示された如く、反応室内に３ｉ
）（４ガスの原料ガスと共に水銀を導入し、水銀が紫外
線を吸収して励起され、斯る水銀がＳｉＨ４ガスと衝突
することにより分解する水銀増感反応が有力な手段とな
る。On the other hand, for 3iH4 gas which cannot be directly decomposed by ultraviolet rays, the 14th Thin Film and Optical Surface Physics Seminar,
3i in the reaction chamber as shown on pages 05 to 115.
) (Mercury sensitization reaction in which mercury is introduced together with the four raw material gases, the mercury absorbs ultraviolet rays and is excited, and the mercury decomposes by colliding with SiH4 gas is an effective method.
しかし、斯る水銀増感反応を利用した光ＣＶＤ法にあっ
ては、工業的に有利な５ｉＨ４ガスを原料ガスとして用
いることができるものの、増感剤として有毒物質である
水銀を使用しなければならない上に、水銀が膜中に混入
したり、真空系を汚染したりする。However, in the photoCVD method using such a mercury sensitization reaction, although 5iH4 gas, which is industrially advantageous, can be used as a raw material gas, it is necessary to use mercury, which is a toxic substance, as a sensitizer. In addition, mercury may enter the membrane or contaminate the vacuum system.
（ハ）発明が解決しようとする問題点
本発明製造方法は、上述のプラズマＣＶＤ法、直接分解
光ＣＶＤ法及び水銀増感光ＣＶＤ法が持つ、プラズマダ
メージ、３ｉ）（４ガスを使用できず工業的でない及び
増感剤として水銀を用いなければならないという問題点
を解決しようとするものである。(c) Problems to be Solved by the Invention The manufacturing method of the present invention is capable of reducing plasma damage caused by the above-mentioned plasma CVD, direct decomposition photoCVD, and mercury-sensitized photoCVD. This is an attempt to solve the problems that mercury is not a sensitizer and that mercury must be used as a sensitizer.
に）問題点を解決するための手段
本発明製造方法は上記問題点を解決すべく、減圧された
反応室内に原料ガスとしてＳｉＨ４ガスを導入し、該Ｓ
ｉＨ・１ガスに軟Ｘ線を照射して支持基板表面に半導体
薄膜を堆積せしめることを特徴とする１゜
（ホ）作用
上述の如く原料ガスとして５ｉ１４ガスを使用したにも
拘らず、該ＳｉＨ４ガスに軟Ｘ線を照射することによっ
て、水銀等の増感剤を用いることなく原料ガスである５
ｉＨ４ガスを直接分解し得る。B) Means for Solving the Problems In order to solve the above problems, the production method of the present invention introduces SiH4 gas as a raw material gas into the reaction chamber under reduced pressure, and
1°(e) action characterized by depositing a semiconductor thin film on the surface of a supporting substrate by irradiating iH.1 gas with soft X-rays. By irradiating the gas with soft X-rays, the raw material gas 5
iH4 gas can be decomposed directly.
（へ）実施例
第１図は本発明製造方法に用いられる反応装置の概略図
を示し、排気系（１）を介して減圧し得る反応室（２１
のほぼ中央に、堆積される半導体薄膜を支持するための
支持基板（３）を保持すべく図示していないヒータを内
蔵したサンプルホルダ（４）が設けられている。斯る反
応室（２）の側面には、上記支持基板（３）の堆積面に
近接して平行に波長７０〜１３０ｎｍの軟Ｘ線のビーム
を導入すべくシンクロトン八
放射装置のビームライン（５）が接続されており、その
途中には図示していない光学系が設けられ上記ジンクロ
ト−放射装置から出射したビームから任意の波長光を選
択する。減圧された反応室（２）内には支持基板（３）
の堆積面に対向して設けられた原料ガス導入口（６）か
ら少なくとも５ｉＨ４ガスを含む原料ガスが導入される
。(f) Example FIG. 1 shows a schematic diagram of a reaction apparatus used in the production method of the present invention, in which a reaction chamber (21
A sample holder (4) with a built-in heater (not shown) is provided approximately in the center of the sample holder (4) to hold a support substrate (3) for supporting the semiconductor thin film to be deposited. On the side of the reaction chamber (2), there is a beam line (of a synchrotron radiation device) for introducing a soft X-ray beam with a wavelength of 70 to 130 nm close to and parallel to the deposition surface of the support substrate (3). 5) is connected, and an optical system (not shown) is provided in the middle thereof to select light of an arbitrary wavelength from the beam emitted from the zinc chromatography radiator. A support substrate (3) is placed inside the reduced pressure reaction chamber (2).
A source gas containing at least 5iH4 gas is introduced from a source gas inlet (6) provided opposite the deposition surface of the substrate.
而して、反応室（２）内に例えは単結晶半導体基板、ガ
ラス基板、５ｎ０２或いはＩＴＯをコートした導電性ガ
ラス基板、金属基板等から選択使用された支持基板（３
＋を配置し、反応室（２）をクローズして排気系（１）
を稼動させて１０ ＴＯｒｒ以下に減圧する。In the reaction chamber (2), a support substrate (3) selected from a single crystal semiconductor substrate, a glass substrate, a conductive glass substrate coated with 5N02 or ITO, a metal substrate, etc. is placed in the reaction chamber (2).
+, close the reaction chamber (2), and open the exhaust system (1).
The pressure is reduced to below 10 Torr.
支持基板（３）を約２００〜３００℃に保持しつつＳｉ
Ｈ４ガスを原料ガス尋人口（５１から反応室（２）内に
導入し斯るガス圧を０．１〜ＩＴｏｒｒに調整する。こ
の状態で２．５０ ｅ Ｖ電子蓄積リングのシンクロト
ロン放射装置を出射したビームの内、ビームライン（５
）及びその途中の光学系により・５−選択された波長約
７１３ｎｍの軟Ｘ線を反応室（２１内に導入する。Si
H4 gas is introduced into the reaction chamber (2) from the raw material gas pressure port (51) and the gas pressure is adjusted to 0.1 to ITorr.In this state, the synchrotron radiation device with the 2.50 eV electron storage ring is Among the emitted beams, the beam line (5
) and an optical system in the middle of the process to introduce soft X-rays with a selected wavelength of about 713 nm into the reaction chamber (21).
導入する軟Ｘ線の強度は７オトン数にして１０ 〜１０
個（蓄積電流１００ｍＡのとき）であり、この条件
のＦでａ−３ｉが１．５〜２ Ａ／Ｓｅｃ （７）成膜
速度で支持基板（３）の堆積面に堆積した。The intensity of the soft X-rays introduced is 10 to 10 in terms of 7 otons.
(at a storage current of 100 mA), and a-3i was deposited on the deposition surface of the supporting substrate (3) at a film formation rate of 1.5 to 2 A/Sec (7) under these conditions.
ｆト）発明の効果
本発明製造方法は以上の説明から明らかな如く、原料ガ
スとして５ｉＨ４ガスを使用したにも拘らず、該５ｉＨ
４ガスに軟Ｘ線を照射することによって、直接分解する
ことができるので、有毒物質である水銀等の増感剤を用
いる必要がなく斯る増感剤が膜中に混入したり、真空系
を汚染したりすることもない。しかも、支持基板表面は
プラズマＣＶＤ法のようにプラズマに曝されず、従って
原料ガスとして入手が容易で安価なＳｉＨ４ガスを使用
してもプラズマダメージのない良質な半導体薄膜を得る
ことかできる。g) Effects of the invention As is clear from the above explanation, the production method of the present invention, despite using 5iH4 gas as the raw material gas,
4 gases can be directly decomposed by irradiating them with soft X-rays, so there is no need to use sensitizers such as mercury, which is a toxic substance. It will not contaminate the water. Furthermore, the surface of the supporting substrate is not exposed to plasma as in the plasma CVD method, so even if SiH4 gas, which is easily available and inexpensive, is used as a raw material gas, a high quality semiconductor thin film without plasma damage can be obtained.
第１図は本発明製造方法に用いられる製造装置の概略図
であって、（２）は反応室、（３）は支持基板、（５）
はビームライン、（６）は原料ガス導入口、を夫々示し
ている。FIG. 1 is a schematic diagram of the manufacturing apparatus used in the manufacturing method of the present invention, in which (2) is a reaction chamber, (3) is a support substrate, and (5) is a reaction chamber.
(6) indicates the beam line, and (6) indicates the source gas inlet.
Claims (1)
（ＳｉＨ＿４）ガスを導入し、該モノシランガスに軟Ｘ
線を照射して支持基板表面に半導体薄膜を堆積せしめる
ことを特徴とした半導体薄膜の製造方法。(1) Monosilane (SiH_4) gas is introduced as a raw material gas into the reaction chamber under reduced pressure, and the monosilane gas is
1. A method for producing a semiconductor thin film, comprising depositing a semiconductor thin film on the surface of a support substrate by irradiating the semiconductor thin film with radiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30230486A JPS63155611A (en) | 1986-12-18 | 1986-12-18 | Manufacture of semiconductor thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30230486A JPS63155611A (en) | 1986-12-18 | 1986-12-18 | Manufacture of semiconductor thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63155611A true JPS63155611A (en) | 1988-06-28 |
Family
ID=17907358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30230486A Pending JPS63155611A (en) | 1986-12-18 | 1986-12-18 | Manufacture of semiconductor thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63155611A (en) |
-
1986
- 1986-12-18 JP JP30230486A patent/JPS63155611A/en active Pending
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