JPH0611032B2 - Method for producing amorphous semiconductor thin film by plasma CVD method - Google Patents
Method for producing amorphous semiconductor thin film by plasma CVD methodInfo
- Publication number
- JPH0611032B2 JPH0611032B2 JP59185089A JP18508984A JPH0611032B2 JP H0611032 B2 JPH0611032 B2 JP H0611032B2 JP 59185089 A JP59185089 A JP 59185089A JP 18508984 A JP18508984 A JP 18508984A JP H0611032 B2 JPH0611032 B2 JP H0611032B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- thin film
- film
- amorphous semiconductor
- semiconductor thin
- 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
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [CVD]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/34—Deposited materials, e.g. layers
- H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
- H10P14/3404—Deposited materials, e.g. layers characterised by the chemical composition being Group IVA materials
- H10P14/3411—Silicon, silicon germanium or germanium
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- Light Receiving Elements (AREA)
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】 技術分野 本発明は、プラズマＣＶＤ法によるプラズマＣＶＤ法に
よる非晶質半導体薄膜の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an amorphous semiconductor thin film by a plasma CVD method using a plasma CVD method.
従来技術 近年、非晶質半導体、具体的にはアモルファスシリコン
ａ−Ｓｉが注目されており、このアモルファスシリコン
ａ−Ｓｉは等倍光センサー、太陽電池、薄膜トランジス
タＴＦＴ等のデバイスとして用いられる。これらのデバ
イスにおいてａ−Ｓｉ薄膜に要求される特性は、光導電
率σPが高いこと、光導電率と暗導電率との比σP／σD
が１０2以上であること、光応答速度が速いこと等であ
る。特に、等倍光センサーにあっては光応答速度が速い
ことが重要である。2. Description of the Related Art In recent years, attention has been paid to amorphous semiconductors, specifically, amorphous silicon a-Si, and the amorphous silicon a-Si is used as a device such as a 1 × photosensor, a solar cell, and a thin film transistor TFT. The characteristics required for the a-Si thin film in these devices are that the photoconductivity σ P is high, and the ratio of photoconductivity to dark conductivity σ P / σ D
Is 10 2 or more, and the photoresponse speed is fast. In particular, it is important for a 1 × photosensor to have a high photoresponse speed.
ここに、ａ−Ｓｉ薄膜の製造にプラスマＣＶＤ（化学気
相成長）法を用いるのが最も一般的であり、優れた光電
特性のａ−Ｓｉ膜の製造として次のような方法がとられ
ている。Here, the plasma CVD (chemical vapor deposition) method is most commonly used for manufacturing an a-Si thin film, and the following method is adopted for manufacturing an a-Si film having excellent photoelectric characteristics. There is.
まず、第一に、ＳｉＨ4ガス（１００％）を原料ガスと
して用い、成膜条件の最適化によりノンドープのａ−Ｓ
ｉで高特性の薄膜を得る方法である。この方法による場
合、光応答速度の速いものが得られるが、光導電率σP
が低く不充分である。First of all, SiH 4 gas (100%) is used as a source gas, and non-doped a-S
i is a method of obtaining a thin film having high characteristics. With this method, the one with a high photoresponse speed can be obtained, but the photoconductivity σ P
Is low and insufficient.
第二に、ａ−Ｓｉ膜中にＰＨ3を微量ドープさせること
により、特性の向上を図るようにしたものもある（文献
ＥＤ８３−１３２の「プレーナ型ａ−Ｓｉ２次元光セン
サ」参照）。この方法の場合、光導電率σPは充分であ
るが、光応答速度が遅く不充分である。Secondly, by lightly doped with PH 3 in the a-Si film, some of which was to improve the properties (see "planar a-Si2 dimensional photosensor" literature ED83-132). In this method, the photoconductivity σ P is sufficient, but the photoresponse speed is slow and insufficient.
第三に、Ｎ2ガス又はＮＨ3ガスによってａ−Ｓｉ膜中に
Ｎドープさせることにより、特性の向上を図るようにし
たものもある（文献JAPANESE JOURNAL OF APPLIED PHYS
ICS VOL.21,No.8 AUGUST.1982 pp.L485-L487参照）。こ
の方法においては、太陽電池の窓材として広エネルギー
バンド材のものを目的とするものであり、光導電率σP
および光学的エネルギーバンドギャップEg optは向上す
るが、光応答速度の向上は図られていないものである。Thirdly, there is a structure in which the a-Si film is N-doped with N 2 gas or NH 3 gas to improve the characteristics (reference: JAPANESE JOURNAL OF APPLIED PHYS).
ICS VOL.21, No.8 AUGUST.1982 pp.L485-L487). In this method, the window material of the solar cell is a wide energy band material, and the photoconductivity σ P
And, the optical energy band gap Eg opt is improved, but the optical response speed is not improved.
目的 本発明は、このような点に鑑みなされたもので、光導電
率σPが高く、σP／σDの比が１０2以上あり、かつ、光
応答速度が速いａ−Ｓｉ膜を得ることができるプラズマ
ＣＶＤ法による非晶質半導体薄膜の製造方法を提供する
ことを目的とする。The present invention has been made in view of the above points, and provides an a-Si film having a high photoconductivity σ P , a σ P / σ D ratio of 10 2 or more, and a high photoresponse speed. It is an object of the present invention to provide a method for producing an amorphous semiconductor thin film by the plasma CVD method, which can be performed.
構成 本発明は、上記目的を達成するため、減圧された真空室
内に原料ガスを導入して高周波電力によるプラズマ中で
分解・反応させて基板上に非晶質半導体の薄膜を形成す
るプラズマＣＶＤ法による非晶質半導体薄膜の製造方法
において、原料ガスとしてＳｉＨ4ガス、ＮＨ3ガス、Ｈ
2ガスよりなる混合ガスを用いてＮＨ3ガスによって非晶
質半導体ａ−ＳｉにＮドープすることを特徴とするもの
である。Structure In order to achieve the above object, the present invention is a plasma CVD method for forming a thin film of an amorphous semiconductor on a substrate by introducing a source gas into a depressurized vacuum chamber and causing the gas to decompose and react in plasma by high frequency power. In the method for producing an amorphous semiconductor thin film according to the above method, SiH 4 gas, NH 3 gas, H
The amorphous semiconductor a-Si is N-doped with NH 3 gas using a mixed gas of 2 gases.
以下、本発明の一実施例を図面に基づいて説明する。本
発明はプラズマＣＶＤ法を採用するものであり、第１図
に示すように、平行平板型のプラズマＣＶＤ装置を例に
とり、その作用を説明する。まず、真空室１内に原料ガ
スをガス導入口２及びガス噴出孔３を介して導入させ、
基板側電極４と高周波側電極５との間に高周波電源６に
より高周波電圧を印加してプラズマ放電させる。このプ
ラズマ中で原料ガスを分解・反応させて、基板７上にａ
−Ｓｉ膜を成膜させるものである。なお、この成膜処理
中は余剰原料ガスを排気口８から除去させ、真空室１内
を所定圧力に維持させる。又、基板７はヒータ９によっ
て所定温度に加熱される。An embodiment of the present invention will be described below with reference to the drawings. The present invention employs the plasma CVD method, and as shown in FIG. 1, the operation of the parallel plate type plasma CVD apparatus will be described as an example. First, the raw material gas is introduced into the vacuum chamber 1 through the gas introduction port 2 and the gas ejection hole 3,
A high frequency power source 6 applies a high frequency voltage between the substrate side electrode 4 and the high frequency side electrode 5 to cause plasma discharge. The source gas is decomposed and reacted in this plasma, and a
-Si film is formed. During the film forming process, the excess source gas is removed from the exhaust port 8 to maintain the inside of the vacuum chamber 1 at a predetermined pressure. The substrate 7 is heated to a predetermined temperature by the heater 9.
しかして、本実施例では、真空室１内に導入する原料ガ
スとしてＳｉＨ4ガス、ＮＨ3ガス、Ｈ2ガスよりなる混
合ガスを用いてＮＨ3ガスによってａ−Ｓｉ膜にＮドー
プするようにしたものである。Therefore, in the present embodiment, a mixed gas of SiH 4 gas, NH 3 gas, and H 2 gas is used as a source gas to be introduced into the vacuum chamber 1, and the a-Si film is N-doped with NH 3 gas. It was done.
このような混合ガスを原料ガスとして用いてａ−Ｓｉ膜
にＮドープすることにより、高い光導電率σPを有し、
σP／σDの比も高く、更に光応答速度の速い膜が得られ
たものである。By using such a mixed gas as a source gas and N-doping the a-Si film, a high photoconductivity σ P is obtained,
A film having a high σ P / σ D ratio and a high photoresponse speed was obtained.
次に、好ましい成膜条件を実験結果に基づき説明する。
まず、第２図はＳｉＨ4ガスの流量１０SCCM、Ｈ2ガスの
流量９０SCCMとし流量比ＳｉＨ4／Ｈ2を１／９≒０．１
１とした場合において流量比ＮＨ3／ＳｉＨ4を変化させ
た場合における光導電率σP、暗導電率σD及び光応答速
度Ｍ(5)の変化の様子を示すものである。なお、この測
定に用いたセルは幅／長さ＝５０で上層からＡｌ電極／
ａ−Ｓｉ膜／石英基板からなるものであり、波長５５５
nm、照度１００luxの照射光を照射することにより行な
ったものである。又、光応答速度につき、繰返し周期５
０msのパルス光を測定セルに照射した場合に最小出力を
Ｍ1、最大出力をＭ2とすると、Modulation ratio M(5)
は で定義されるものである。従って、Ｍ(5)の値が大きい
程、光応答特性が速いといえる。Next, preferable film forming conditions will be described based on experimental results.
First, in FIG. 2, the flow rate of SiH 4 gas is 10 SCCM and the flow rate of H 2 gas is 90 SCCM, and the flow rate ratio SiH 4 / H 2 is 1 / 9≈0.1.
When the flow rate ratio NH 3 / SiH 4 is changed to 1, the photoconductivity σ P , the dark conductivity σ D, and the photoresponse speed M (5) are changed. The cell used for this measurement had a width / length of 50 and the Al electrode /
It is composed of an a-Si film / quartz substrate and has a wavelength of 555.
The irradiation was performed by irradiating irradiation light having a wavelength of nm and an illuminance of 100 lux. In addition, the optical response speed has a repetition cycle of 5
If the minimum output is M 1 and the maximum output is M 2 when the measurement cell is irradiated with 0 ms pulsed light, Modulation ratio M (5)
Is Is defined in. Therefore, it can be said that the larger the value of M (5), the faster the light response characteristic.
この第２図に示す結果によれば、流量比ＮＨ3／ＳｉＨ4
がある程度小さい方がＭ(5)の値が大きいことがわか
る。具体的には、流量比ＮＨ3／ＳｉＨ4が５．０×１０
-5〜５．０×１０-4が適当であり、より好ましくは流量
比ＮＨ3／ＳｉＨ4が７．０×１０-5〜４．０×１０-4の
時に良好なる光応答特性が得られたものである。つま
り、Ｎ原子はｓ−Ｓｉ膜中では浅いドナー準位を形成す
るため膜内のＮ量が増えるに従って、σP、σDとも向上
するが、あまりＮＨ3の流量が増えてＮ原子のドープ濃
度が高くなると光応答速度Ｍ(5)が低下してしまうから
である。又、前述の流量比ＮＨ3／ＳｉＨ4＝５．０×１
０-5〜５．０×１０-4であれば、光導電率σPが高く、
σP／σDの比も１０2以上であることがわかる。次に、
流量比ＳｉＨ4／Ｈ2は０．１〜０．４（望ましくは、
０．１〜０．３）が適当である。このＨ2ガスの流量
は、ａ−Ｓｉ膜中のＨ濃度を制御するもので膜質を左右
し、流量比ＳｉＨ4／Ｈ2が小さすぎると膜中のＨ濃度が
高くなって−ＳｉＨ1の構造が多くなり特性が悪くな
り、逆に流量比ＳｉＨ4／Ｈ2が大きすぎると膜中のＨ濃
度が低くなってダングリングボンドが多くなり、やはり
特性が悪くなるからである。According to the results shown in FIG. 2, the flow rate ratio NH 3 / SiH 4
It can be seen that the value of M (5) is larger when is smaller to some extent. Specifically, the flow rate ratio NH 3 / SiH 4 is 5.0 × 10
-5 to 5.0 × 10 -4 is suitable, and more preferably, good photoresponse characteristics are obtained when the flow rate ratio NH 3 / SiH 4 is 7.0 × 10 -5 to 4.0 × 10 -4. It has been done. That is, since N atoms form a shallow donor level in the s-Si film, as the amount of N in the film increases, both σ P and σ D improve, but the flow rate of NH 3 increases too much to dope N atoms. This is because the photoresponse speed M (5) decreases as the concentration increases. In addition, the above flow rate ratio NH 3 / SiH 4 = 5.0 × 1
If 0 −5 to 5.0 × 10 −4 , the photoconductivity σ P is high,
It can be seen that the ratio of σ P / σ D is also 10 2 or more. next,
The flow ratio SiH 4 / H 2 is 0.1 to 0.4 (preferably,
0.1 to 0.3) is suitable. The flow rate of this H 2 gas controls the H concentration in the a-Si film and affects the film quality. If the flow rate ratio SiH 4 / H 2 is too small, the H concentration in the film becomes high and the -SiH 1 This is because the structure is increased and the characteristics are deteriorated. On the contrary, when the flow ratio SiH 4 / H 2 is too large, the H concentration in the film is lowered, the dangling bonds are increased, and the characteristics are deteriorated.
次に、高周波電源６（１３．５６ＭHz）の電力を変化さ
せた場合の膜特性についての実験結果を第３図に示す。
この結果によれば、高周波電力は３〜２０Ｗ（望ましく
は、３〜１０Ｗ）が適当であることがわかる。これは、
低パワーではＮＨ3ガスの分解が不充分でＮ原子が膜中
にドープされにくく、又、高パワーではＮＨ3ガスの分
解が促進されるもののプラズマによる膜へのダメージが
大きく膜質が悪くなるからである。Next, FIG. 3 shows the experimental results on the film characteristics when the power of the high frequency power source 6 (13.56 MHz) was changed.
According to this result, it is understood that the high frequency power is suitably 3 to 20 W (desirably, 3 to 10 W). this is,
At low power, the decomposition of NH 3 gas is insufficient and it is difficult to dope N atoms into the film. At high power, the decomposition of NH 3 gas is promoted, but the film is damaged greatly by the plasma and the film quality deteriorates. Is.
第４図は、基板温度を変化させた場合の膜特性について
の実験結果を示すものである。この結果によれば、暗導
電率σDが余り上昇しないように、基板温度を２００〜
３５０℃（望ましくは、２５０〜３００℃）とするのが
適当であることがわかる。FIG. 4 shows the experimental results on the film characteristics when the substrate temperature was changed. According to this result, the substrate temperature is set to 200 to 200 so that the dark conductivity σ D does not increase so much.
It is understood that it is suitable to set the temperature to 350 ° C. (desirably 250 to 300 ° C.).
第５図は、真空室１内の圧力を変化させた場合の膜特性
についての実験結果を示すものである。この結果によれ
ば、光導電率σPが余り低くならないように、圧力を
０．２〜５Torr（望ましくは、０．３〜０．７Torr）と
するのが適当である。FIG. 5 shows the experimental results on the film characteristics when the pressure in the vacuum chamber 1 was changed. According to this result, it is appropriate to set the pressure to 0.2 to 5 Torr (desirably 0.3 to 0.7 Torr) so that the photoconductivity σ P does not become too low.
効果 本発明は、上述したようにＳｉＨ4ガス、ＮＨ3ガス、Ｈ
2ガスよりなる所定流量比の混合ガスを原料ガスとして
用いることにより、ａ−Ｓｉ膜にＮドープするようにし
たので、光導電率σPが高くてσP／σDの比が１０2以上
の特性の膜であって、光応答特性の速いものを得ること
ができ、よって、良好なる特性の等倍光センサー等のデ
バイスを作ることができるものである。Effect The present invention, as described above, uses SiH 4 gas, NH 3 gas, H
Since the a-Si film is N-doped by using a mixed gas of two gases at a predetermined flow rate ratio as the source gas, the photoconductivity σ P is high and the ratio σ P / σ D is 10 2 or more. It is possible to obtain a film having the above characteristic and a fast photoresponse characteristic, and thus it is possible to manufacture a device such as a 1 × photosensor having excellent characteristics.
図面は本発明の一実施例を示すもので、第１図はプラズ
マＣＶＤ装置の概略側面図、第２図ないし第５図は実験
結果を示す特性図である。The drawings show one embodiment of the present invention. FIG. 1 is a schematic side view of a plasma CVD apparatus, and FIGS. 2 to 5 are characteristic diagrams showing experimental results.
Claims (1)
高周波電力によるプラズマ中で分解・反応させて基板上
に非晶質半導体の薄膜を形成するプラズマＣＶＤ法によ
る非晶質半導体薄膜の製造方法において、原料ガスとし
てＳｉＨ4ガス、ＮＨ3ガス、Ｈ2ガスよりなり、ＮＨ3／
ＳｉＨ4流量比が5.0×10-5〜5.0×10-4なる混合ガスを
用い、高周波電力1.0〜4.0Ｗ、基板温度250〜300℃、圧
力0.4〜２Torrなる条件でＮＨ3ガスによって非晶質半導
体ａ−ＳｉにＮドープすることを特徴とするプラズマＣ
ＶＤ法による非晶質半導体薄膜の製造方法。1. An amorphous semiconductor thin film formed by a plasma CVD method, wherein a raw material gas is introduced into a depressurized vacuum chamber and decomposed and reacted in plasma with high frequency power to form an amorphous semiconductor thin film on a substrate. In the manufacturing method, SiH 4 gas, NH 3 gas, and H 2 gas are used as raw material gas, and NH 3 /
Amorphous with NH 3 gas under the conditions that SiH 4 flow rate ratio is 5.0 × 10 −5 to 5.0 × 10 −4 , high frequency power is 1.0 to 4.0 W, substrate temperature is 250 to 300 ° C., and pressure is 0.4 to 2 Torr. Plasma C characterized in that semiconductor a-Si is N-doped
A method for manufacturing an amorphous semiconductor thin film by the VD method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59185089A JPH0611032B2 (en) | 1984-09-04 | 1984-09-04 | Method for producing amorphous semiconductor thin film by plasma CVD method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59185089A JPH0611032B2 (en) | 1984-09-04 | 1984-09-04 | Method for producing amorphous semiconductor thin film by plasma CVD method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6163022A JPS6163022A (en) | 1986-04-01 |
| JPH0611032B2 true JPH0611032B2 (en) | 1994-02-09 |
Family
ID=16164639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59185089A Expired - Lifetime JPH0611032B2 (en) | 1984-09-04 | 1984-09-04 | Method for producing amorphous semiconductor thin film by plasma CVD method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611032B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0962437A (en) * | 1995-08-23 | 1997-03-07 | Nec Corp | Computer input device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5778546A (en) * | 1980-11-05 | 1982-05-17 | Stanley Electric Co Ltd | Production of photoconductive silicon layer |
| JPS58115018A (en) * | 1981-12-26 | 1983-07-08 | Sharp Corp | Electrophotographic photosensitive material |
| JPS5957909A (en) * | 1982-09-29 | 1984-04-03 | Mitsui Toatsu Chem Inc | Formation of amorphous silicon film |
| JPS5957908A (en) * | 1982-09-29 | 1984-04-03 | Mitsui Toatsu Chem Inc | Formation of amorphous silicon film |
-
1984
- 1984-09-04 JP JP59185089A patent/JPH0611032B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0962437A (en) * | 1995-08-23 | 1997-03-07 | Nec Corp | Computer input device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6163022A (en) | 1986-04-01 |
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