JP3208274B2 - Method for producing semiconductor thin film and plasma CVD apparatus used for the method - Google Patents
Method for producing semiconductor thin film and plasma CVD apparatus used for the methodInfo
- Publication number
- JP3208274B2 JP3208274B2 JP02908695A JP2908695A JP3208274B2 JP 3208274 B2 JP3208274 B2 JP 3208274B2 JP 02908695 A JP02908695 A JP 02908695A JP 2908695 A JP2908695 A JP 2908695A JP 3208274 B2 JP3208274 B2 JP 3208274B2
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- film
- thin film
- plasma cvd
- semiconductor thin
- plasma
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical Vapour Deposition (AREA)
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、電子産業における半導
体薄膜の製造方法及びそれに用いるプラズマＣＶＤ装置
に関するものであって、特に、太陽電池等の光半導体デ
バイスに最適な半導体薄膜の製造方法及びプラズマＣＶ
Ｄ装置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 semiconductor thin film in the electronics industry and a plasma CVD apparatus used for the same, and more particularly, to a method for producing a semiconductor thin film and a plasma suitable for an optical semiconductor device such as a solar cell. CV
It relates to the D device.
【０００２】[0002]
【従来の技術】今日、プラズマを用いた気相からの薄膜
形成方法は、金属膜、半導体膜、誘電体膜等の広範囲に
わたって用いられるようになってきた。特に、プラズマ
ＣＶＤ装置を用いて４族水素化合物をプラズマにして活
性種に分解して基板上に堆積させる、水素化アモルファ
スシリコン系薄膜（水素化アモルファスシリコン（ａ−
Ｓｉ：Ｈ）、水素化アモルファスシリコンカーボン（ａ
−ＳｉＣ：Ｈ）、水素化アモルファスシリコンゲルマニ
ウム（ａ−ＳｉＧｅ：Ｈ）等）は、半導体として最も重
要なｐｎ制御が報告されて以来、精力的な研究開発が行
われ、電卓などの民生用太陽電池や液晶表示デバイス、
感光ドラム、各種センサーの心臓部の半導体薄膜として
実用化されるに至っている。2. Description of the Related Art At present, a thin film forming method from a gas phase using plasma has been widely used for a metal film, a semiconductor film, a dielectric film and the like. In particular, a hydrogenated amorphous silicon-based thin film (hydrogenated amorphous silicon (a-
Si: H), hydrogenated amorphous silicon carbon (a
-SiC: H), hydrogenated amorphous silicon germanium (a-SiGe: H), etc. have been energetically researched and developed since the most important pn control as a semiconductor has been reported. Batteries and liquid crystal display devices,
It has been put to practical use as a semiconductor thin film at the heart of photosensitive drums and various sensors.
【０００３】このような半導体薄膜を用いたデバイスの
応用範囲をさらに広げ、マーケットを拡大していくため
には、高品質の膜を、高速かつ高歩留まりで成膜される
ことが望まれている。例えば、水素化アモルファスシリ
コン系薄膜を用いたアモルファス太陽電池について言え
ば、電卓などの民生用以外に大きな用途展開が期待され
る電力用の太陽電池として実用化されるためには、既存
の商用電力と競合できる低コスト化が不可欠である。本
発明者らのコスト分析によれば、水素化アモルファスシ
リコン系薄膜の成膜速度は、現状より一桁程度の高速
化、具体的には〜６００Å／分程度の高速成膜条件下で
高品質な膜を高歩留まりで堆積することが必要である。In order to further expand the application range of devices using such semiconductor thin films and to expand the market, it is desired that high-quality films be formed at high speed and with high yield. . For example, in the case of amorphous solar cells using hydrogenated amorphous silicon-based thin films, existing commercial power is required to be used as a solar cell for electric power, which is expected to be used in a wide range of applications other than consumer use such as calculators. It is indispensable to lower the cost to be able to compete with. According to the cost analysis of the present inventors, the deposition rate of the hydrogenated amorphous silicon-based thin film is higher by about one digit than the current state, specifically, high quality under high-speed deposition conditions of about 600 ° / min. It is necessary to deposit a high quality film at a high yield.
【０００４】しかしながら、〜６００Å／分程度の高速
成膜条件を達成するために、プラズマＣＶＤ法で半導体
膜を成膜する場合に、供給する高周波電力を高めたり、
原料ガスの供給を増加させることにより、高速成膜が実
現できるが、パウダーの発生が多く、結局、低歩留まり
な膜しか得られなかった（以下「従来プラズマＣＶＤ法
１」という）。However, in order to achieve a high-speed film forming condition of about 600 ° / min, when a semiconductor film is formed by a plasma CVD method, the supplied high-frequency power may be increased,
By increasing the supply of the raw material gas, high-speed film formation can be realized, but powder is often generated and, as a result, only a film with a low yield was obtained (hereinafter, referred to as "conventional plasma CVD method 1").
【０００５】この問題点を解決するため、プラズマＣＶ
Ｄ法を用いたａ−Ｓｉ：Ｈ膜の高速成膜のために、高周
波発振回路に周期的にオン・オフを行う発振回路を組み
合わせ、図１（ａ）に示されるように、周期的オン・オ
フを行った変調高周波電源を励起電源に用いたプラズマ
ＣＶＤ法（Appl.Phys.Lett.53,(1988)1263、Appl.Phys.L
ett.57(1990)1616、応用物理第62巻第7号(1993)699）が
提案されている（以下「従来プラズマＣＶＤ法２」とい
う）。To solve this problem, a plasma CV
For high-speed deposition of an a-Si: H film using the D method, a high-frequency oscillation circuit is combined with an oscillation circuit that periodically turns on and off, and as shown in FIG. -Plasma CVD method using the modulated high-frequency power supply turned off as the excitation power supply (Appl. Phys. Lett. 53, (1988) 1263, Appl. Phys. L.
ett. 57 (1990) 1616, Applied Physics Vol. 62, No. 7, (1993) 699) (hereinafter referred to as "conventional plasma CVD method 2").
【０００６】従来プラズマＣＶＤ法２では、周期的オン
・オフの周波数１ｋＨｚ、デユーティ比５０％（従って
オン時間は５００μｓｅｃ）近傍の成膜条件で成膜速度
３００Å／分〜６００Å／分程度のａ−Ｓｉ：Ｈ膜を堆
積させた場合、従来プラズマＣＶＤ法１と比べて、反応
装置内には、いわゆるポリシランのパウダー発生が顕著
に抑さえられるという効果が認められている。反応装置
内に堆積されるパウダーは、装置メンテナンス頻度を増
加させるばかりではなく、このようなパウダーが基板に
付着すれば製品の歩留まりを低下させる。従って、高速
成膜でパウダー発生を抑制できる従来プラズマＣＶＤ法
２は生産ラインのスループット、及び歩留まりを高める
方法と言える。In the conventional plasma CVD method 2, a film is formed at a film forming rate of about 300 ° / min to about 600 ° / min under a film forming condition near a periodic on / off frequency of 1 kHz and a duty ratio of 50% (the on time is about 500 μsec). When a Si: H film is deposited, it is recognized that the effect of so-called polysilane powder generation is significantly suppressed in the reactor as compared with the conventional plasma CVD method 1. Powder deposited in the reactor not only increases equipment maintenance frequency, but also reduces product yield if such powder adheres to the substrate. Therefore, it can be said that the conventional plasma CVD method 2, which can suppress powder generation by high-speed film formation, is a method for improving the throughput and the yield of the production line.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、従来プ
ラズマＣＶＤ法２で得られるａ−Ｓｉ：Ｈ膜の膜構造を
赤外吸収スペクトルから本発明者が詳細に調べてみる
と、通常の〜６０Å／分程度の低速で堆積された高品質
なａ−Ｓｉ：Ｈ膜では、２０００ｃｍ- 1 付近のＳｉ−
Ｈ結合がほとんどであるのに対して、従来プラズマＣＶ
Ｄ法２の高速膜では〜２０９０ｃｍ- 1 付近のＳｉ−Ｈ
2 結合がＳｉ−Ｈ結合と同程度に存在することがわかっ
た。ａ−Ｓｉ：Ｈ膜中に含まれるＳｉ−Ｈ2 結合は、半
導体膜の光導電率、及び光導電率／暗導電率の比を低下
させ、ひいては光半導体デバイスの性能を低下させる。
従って、従来プラズマＣＶＤ法２によるａ−Ｓｉ：Ｈ膜
の成膜では、反応装置内でのパウダー発生を抑止しなが
ら高速成膜できるが、膜構造の変化に伴う光導電率、及
び光導電率／暗導電率の比の低下を招いてしまうという
大きな問題点があり、太陽電池等の光半導体デバイスの
半導体薄膜としては不適であった。However, when the present inventor examined the film structure of the a-Si: H film obtained by the conventional plasma CVD method 2 from the infrared absorption spectrum in detail, it was found that the film thickness was usually about 60 ° / deposited at a low speed of about minute high-quality a-Si: in H film, 2000 cm - 1 near Si-
Most of the H-coupling, whereas the conventional plasma CV
The fast film D Method 2 ~2090cm - 1 near Si-H
It was found that two bonds exist to the same extent as Si-H bonds. a-Si: H film Si-H 2 bonds contained in the optical conductivity of the semiconductor film, and reduce the ratio of the optical conductivity / dark conductivity, reducing the thus optical semiconductor device performance.
Therefore, in the conventional method of forming an a-Si: H film by the plasma CVD method 2, high-speed film formation can be achieved while suppressing generation of powder in the reaction apparatus. There is a major problem that the ratio of the ratio of the dark / conductivity is reduced, and it is not suitable as a semiconductor thin film of an optical semiconductor device such as a solar cell.
【０００８】本発明の目的は、パウダー発生を抑止しな
がら高速成膜をした場合にも、太陽電池等の光半導体デ
バイスとして高品質な半導体薄膜の製造方法及びそれに
用いるＣＶＤ装置を提供することにある。An object of the present invention is to provide a method of manufacturing a high-quality semiconductor thin film as an optical semiconductor device such as a solar cell even when a high-speed film formation is performed while suppressing powder generation, and a CVD apparatus used therefor. is there.
【０００９】[0009]
【課題を解決するための手段】本発明の半導体薄膜の製
造方法は、高周波電力を周期的にオンオフさせて４族水
素化合物あるいはその誘導体をプラズマにして活性種に
分解し堆積させる半導体薄膜の製造方法であって、Ｓｉ
−Ｈ結合に対するＳｉ−Ｈ 2 結合の含有比が小さくなる
ように、上記オン時間は、［（プラズマ内の長寿命活性
種以外の活性種と反応する母ガスとの２次反応速度定
数）×（母ガス分子の数）］の逆数の時間以下に設定さ
れてなることを特徴とする。SUMMARY OF THE INVENTION A method of manufacturing a semiconductor thin film according to the present invention is a method of manufacturing a semiconductor thin film in which high-frequency power is periodically turned on and off to turn a group 4 hydrogen compound or its derivative into plasma to decompose and deposit active species. A method, comprising: Si
Content ratio of Si-H 2 bonds is small for -H bond
As described above, the on- time is set to be equal to or less than the reciprocal of [(second order reaction rate constant of mother gas reacting with active species other than long-lived active species in plasma) × (number of mother gas molecules)]. It is characterized by being done.
【００１０】さらに、本発明のプラズマＣＶＤ装置は、
上記半導体薄膜の製造方法に用いるプラズマＣＶＤ装置
であって、高周波電力の供給を行う高周波電力発生手段
と、高周波電力の供給の有無を時分割制御する手段とを
備えたことを特徴とする。Further, the plasma CVD apparatus of the present invention
A plasma CVD apparatus used in the manufacturing method of the semiconductor thin film, wherein a high frequency power generating means for supplying high-frequency power, further comprising: a means for dividing control when the presence or absence of the supply of the high-frequency power.
【００１１】[0011]
【作用】以上のように本発明は、プラズマ生成のエネル
ギー供給時間を、［（プラズマ内の長寿命活性種以外の
活性種と反応する母ガスとの２次反応速度定数）×（母
ガス分子の数）］の逆数の時間以下に設定したことによ
り、Ｓｉ−Ｈ結合に対するＳｉ−Ｈ2結合の含有比を小
とすることができた。この理由は以下のように考えられ
る。As described above, according to the present invention, the energy supply time for plasma generation is set to [(second order reaction rate constant with mother gas reacting with active species other than long-lived active species in plasma) × (base gas molecule) )], The content ratio of Si—H 2 bonds to Si—H bonds could be reduced. The reason is considered as follows.
【００１２】モノシラン（ＳｉＨ4 ）ガスを原料ガスと
して用いたプラズマＣＶＤ法によるａ−Ｓｉ：Ｈ膜の成
膜を例にとって説明する。一般に、モノシランをプラズ
マ励起、分解すると、母ガスであるＳｉＨ4 から１次生
成物として、堆積するのに好適な主たる活性種のＳｉＨ
3 を含め、Ｓｉ，ＳｉＨ，ＳｉＨ2 などの活性種も生成
される。Ｓｉ，ＳｉＨ，ＳｉＨ2 ，ＳｉＨ3 の活性種
は、気相中で、桁違いに多い母ガスのＳｉＨ4 と２次反
応を起こす。An example of forming an a-Si: H film by a plasma CVD method using a monosilane (SiH 4 ) gas as a source gas will be described. In general, when monosilane is excited by plasma and decomposed, the main active species of SiH suitable for deposition as a primary product from the mother gas SiH 4 is SiH 4.
3 including, Si, SiH, active species such as SiH 2 also produced. The active species of Si, SiH, SiH 2 , and SiH 3 cause a secondary reaction with an extremely large number of mother gases, SiH 4 , in the gas phase.
【００１３】一方、ＳｉＨ，ＳｉＨ2 などの活性種の２
次反応過程を、もう少し詳しく調べてみると、その２次
反応速度定数は、およそ１０-1 2 ｃｍ3 ／ｓｅｃ程度
であるから、主たるＳｉＨ3 以外の活性種のＳｉＨやＳ
ｉＨ2 の寿命［＝（２次反応速度定数×ＳｉＨ4 分子の
数）- 1 ］は、２次反応速度定数を大まかに〜２×１０
-1 2 ｃｍ3 ／ｓｅｃとして、シランガスの反応圧力５
０ｍＴｏｒｒでは〜４００μｓｅｃ、さらに高い、例え
ば５００ｍＴｏｒｒという反応圧力であれば、その１０
分の１の〜４０μｓｅｃと計算され、主たるＳｉＨ3 の
寿命よりも短いと考えられる。[0013] On the other hand, SiH, of active species such as SiH 2 2
The following reaction process, when you look a bit more, the second-order rate constant, because it is approximately 10 -1 2 cm 3 / sec about, active species of SiH and other principal SiH 3 S
iH 2 life [= (number of second-order rate constants × SiH 4 molecules) - 1] is roughly to 2 × 10 The second-order rate constant
As -1 2 cm 3 / sec, the reaction pressure of the silane gas 5
At 0 mTorr, a reaction pressure of 400 μsec or higher, for example, 500 mTorr,
It is calculated to be 1/40 μsec, which is considered to be shorter than the life of the main SiH 3 .
【００１４】本発明は、プラズマ生成のエネルギーを間
欠的に供給することにより、４族水素化合物をプラズマ
にして活性種に分解し基板上に堆積させるものにおい
て、２次反応過程を抑止するため、上記のように活性種
のＳｉＨやＳｉＨ2 の寿命の時間を目安にして、それ以
下のエネルギー供給時間に設定するものである。According to the present invention, in order to intermittently supply the energy of plasma generation to convert a group 4 hydrogen compound into plasma to decompose into active species and deposit it on a substrate, a secondary reaction process is suppressed. As described above, the energy supply time is set to be shorter than the lifetime of the active species SiH or SiH 2 .
【００１５】[0015]
（実施例１）本実施例は、４族水素化合物の原料ガスと
してモノシランを用いて太陽電池用の半導体薄膜である
ａ−Ｓｉ：Ｈ膜を成膜した場合である。なお、原料ガス
として、４族水素化合物の誘導体であるＳｉＨ2Ｆ2，Ｓ
ｉＨＦ3，ＳｉＨ2Ｃｌ2を用いることもできる。(Embodiment 1) In this embodiment, an a-Si: H film, which is a semiconductor thin film for a solar cell, is formed using monosilane as a source gas of a Group 4 hydrogen compound. In addition, SiH 2 F 2 , S, which is a derivative of a Group 4 hydrogen compound, is used as a source gas.
iHF 3 and SiH 2 Cl 2 can also be used.
【００１６】図２に、本実施例に用いたプラズマＣＶＤ
装置の模式図を示す。このプラズマＣＶＤ装置は、いわ
ゆる容量結合型のプラズマＣＶＤ装置で、反応室１のカ
ソード電極２に高周波電源３と変調用電源４とがマッチ
ング回路５を介して接続され、基板６を固定した対極の
アノード電極７との間でプラズマ８を発生させる構造で
ある。ここで、基板６は、赤外吸収スペクトルを評価す
るため結晶シリコンウエハーである。FIG. 2 shows the plasma CVD used in this embodiment.
1 shows a schematic view of the device. This plasma CVD apparatus is a so-called capacitively-coupled plasma CVD apparatus in which a high-frequency power supply 3 and a modulation power supply 4 are connected to a cathode electrode 2 of a reaction chamber 1 via a matching circuit 5 and a counter electrode to which a substrate 6 is fixed. This is a structure in which plasma 8 is generated between the anode 8 and the anode 8. Here, the substrate 6 is a crystalline silicon wafer for evaluating an infrared absorption spectrum.
【００１７】このプラズマＣＶＤ装置を用いて、流量コ
ントローラを通して５００ｓｃｃｍのシランガスを反応
室１に導入し（導入口は図示せず）、一定割合で排気し
て、反応室１内の圧力０．６２Ｔｏｒｒとし、高周波電
源３の発振周波数は２７．１２ＭＨｚで、この高周波電
力に直流的にオン・オフを一定周期で繰り返す変調用電
源４の低周波電力を重ね合わせ、図１（ｂ）に示すよう
に、２７．１２ＭＨｚの高周波電力を周期的にオン・オ
フする変調高周波電力を発生させ、マッチング回路５を
通してカソード電極２に供給し、アノード電極７との間
でプラズマ８を発生させ、シランプラズマを両電極間に
発生させることによって、基板６上にａ−Ｓｉ：Ｈ膜を
堆積させた。本実施例では、高周波電力を完全にオフに
せずとも、プラズマ生成のオン・オフを行うができれば
よい。なお、基板温度は２７０℃とした。Using this plasma CVD apparatus, a silane gas of 500 sccm is introduced into the reaction chamber 1 through a flow rate controller (the inlet is not shown), and the silane gas is exhausted at a constant rate to make the pressure in the reaction chamber 1 0.62 Torr. The oscillation frequency of the high-frequency power source 3 is 27.12 MHz, and the high-frequency power is superimposed on the low-frequency power of the modulation power source 4 which repeats DC on and off at a constant cycle, as shown in FIG. A modulated high-frequency power for periodically turning on and off a high-frequency power of 27.12 MHz is generated, supplied to the cathode electrode 2 through the matching circuit 5, and a plasma 8 is generated between the anode electrode 7 and the silane plasma. An a-Si: H film was deposited on the substrate 6 by causing the film to be generated in between. In this embodiment, it is sufficient that the plasma generation can be turned on and off without completely turning off the high frequency power. Note that the substrate temperature was 270 ° C.
【００１８】図３に、上記成膜条件で、変調高周波の１
周期のオン時間を、オフ時間は５０μｓｅｃと固定して
５μｓｅｃから１００μｓｅｃまで変えた時に得られた
膜の赤外吸収スペクトルから解析したＳｉ−Ｈ結合及び
Ｓｉ−Ｈ2 結合の結合水素量の原子％の結果を示す。上
記成膜条件の中で、成膜速度は約６００Å／分となるよ
うに高周波電力のパワーを２００Ｗから１ｋＷまで調整
した。図３から、明らかなように、膜中のＳｉ−Ｈ2 結
合は、オン時間〜５０μｓｅｃ以下から減少し始め、５
μｓｅｃでは、Ｓｉ−Ｈ結合に対するＳｉ−Ｈ2 結合の
含有比が〜１０％程度まで低下している。これは、通常
の成膜速度が約６０Å／分程度の低速膜と、濃度及び含
有比で同等の高品質な膜であり、光導電率、及び光導電
率／暗導電率の比の優れた膜が得られた。なお、Ｓｉ−
Ｈ結合に対するＳｉ−Ｈ2 結合の含有比は２０％以下で
あれば、太陽電池としては実用上問題がない。FIG. 3 shows that the modulated high frequency 1
The period of on-time, off-time 50μsec and fixed to atoms bonded hydrogen content of the infrared Si-H bonds was analyzed from the absorption spectrum and Si-H 2 bonds of the resulting film when changing to 100μsec from 5 .mu.sec% The result is shown. Under the above film forming conditions, the power of the high frequency power was adjusted from 200 W to 1 kW so that the film forming rate was about 600 ° / min. As is clear from FIG. 3, the Si—H 2 bond in the film starts to decrease from the on-time of 50 μsec or less.
In μsec, the content ratio of the Si—H 2 bond to the Si—H bond is reduced to about 10%. This is a high-quality film equivalent in concentration and content ratio to a low-speed film having a normal film formation rate of about 60 ° / min, and has excellent photoconductivity and a ratio of photoconductivity / dark conductivity. A film was obtained. In addition, Si-
If the content ratio of Si—H 2 bonds to H bonds is 20% or less, there is no practical problem as a solar cell.
【００１９】本実施例の成膜条件でＳｉ−Ｈ2 結合の含
有比を小とするオン時間幅の時間スケールは、式［２次
反応速度定数×ＳｉＨ4 分子の数］- 1 から〜３０μｓ
ｅｃ以下となり、本実施例で膜の高品質化が見られた５
０μｓｅｃ以下と良く符合していることが分かる。The time scale of the on time width and a small content ratio of SiH 2 bonds in the film formation conditions of this embodiment, equation [the number of second-order rate constants × SiH 4 molecules] - 1 from ~30μs
ec or less, and a high quality film was observed in this example.
It can be seen that the values match well with 0 μsec or less.
【００２０】従って、本発明の製造方法及びプラズマＣ
ＶＤ装置を用いれば、成膜速度約６００Å／分という従
来より一桁早い成膜速度で高品質なａ−Ｓｉ：Ｈ膜が得
られた。なお、本実施例では反応室内にパウダー発生が
ほとんど見られなかった。Therefore, the manufacturing method of the present invention and the plasma C
When a VD apparatus was used, a high-quality a-Si: H film was obtained at a film formation rate of about 600 ° / min, which is an order of magnitude faster than the conventional one. In this example, almost no powder was generated in the reaction chamber.
【００２１】（実施例２）実施例１よりもさらに高速化
を図るために、モノシランガスの流量を実施例１の倍の
１０００ｓｃｃｍとした。それ以外のプラズマＣＶＤ装
置、及び成膜条件は、特に断らない限り、実施例１と同
じである。本実施例では、成膜速度は約１３００Å／分
と、実施例１の倍の高速化を達成することができた。(Embodiment 2) The flow rate of the monosilane gas was set to 1000 sccm which is twice as large as that of the embodiment 1 in order to achieve a higher speed than in the embodiment 1. The other plasma CVD apparatus and film forming conditions are the same as in Example 1 unless otherwise specified. In this embodiment, the film formation rate was about 1300 ° / min, which was twice as fast as that of the first embodiment.
【００２２】図４に、変調高周波の１周期のオン時間
を、オフ時間は５０μｓｅｃと固定して１０μｓｅｃか
ら１００μｓｅｃまで変えた時に得られた膜の赤外吸収
スペクトルから解析したＳｉ−Ｈ結合及びＳｉ−Ｈ2 結
合の結合水素量の原子％の結果を示す。成膜条件の中
で、成膜速度は約１３００Å／分となるように高周波電
力のパワーを４００Ｗから１．５ｋＷまで調整した。本
実施例でも、オン時間が〜５０μｓｅｃ以下からＳｉ−
Ｈ2 結合が減少し始め、高品質な膜が得られている。FIG. 4 shows the Si—H bond and Si analyzed from the infrared absorption spectrum of the film obtained when the ON time of one cycle of the modulated high frequency was fixed at 50 μsec and the OFF time was changed from 10 μsec to 100 μsec. The results are shown in terms of atomic% of the amount of hydrogen bonded to -H 2 bonds. Under the film forming conditions, the power of the high frequency power was adjusted from 400 W to 1.5 kW so that the film forming speed was about 1300 ° / min. Also in the present embodiment, the on-time is reduced from 50 μsec or less to Si-
H 2 bonds begin to decrease and a high quality film is obtained.
【００２３】また、本実施例の成膜条件でＳｉ−Ｈ2 結
合の含有比を小とするオン時間幅の時間スケールは、反
応ガス圧力が実施例１と同じ０．６５Ｔｏｒｒであるの
で、実施例１と同じ〜３０μｓｅｃとなり、本実施例で
も膜の高品質化が見られた５０μｓｅｃ以下と良く符合
していると言える。The time scale of the on-time width for reducing the Si—H 2 bond content ratio under the film forming conditions of the present embodiment is 0.65 Torr, which is the same as that of the first embodiment. It is the same as that of Example 1 up to 30 μsec, and it can be said that also in this example, it is well matched to 50 μsec or less at which high quality of the film was observed.
【００２４】以上の実施例ではオフ時間は５０μｓｅｃ
と固定したが、オフ時間は、１μｓｅｃから１００００
μｓｅｃまでの範囲であればよく、望ましくは、１０μ
ｓｅｃから１００μｓｅｃまでの範囲であればよい。さ
らに、上記実施例では、オン時間とオフ時間の割合は一
定であるが、必ずしも一定でなくてもよく、上記オン時
間とオフ時間の範囲内であれば、成膜中にその割合を変
化させてもよい。In the above embodiment, the off time is 50 μsec.
But the off-time is from 1 μsec to 10000
μsec and preferably 10 μsec.
The time may be in the range from sec to 100 μsec. Further, in the above embodiment, the ratio between the on-time and the off-time is constant. However, the ratio is not necessarily constant. If the ratio is within the range between the on-time and the off-time, the ratio is changed during film formation. You may.
【００２５】また、以上の実施例では、水素化アモルフ
ァスシリコンａ−Ｓｉ：Ｈ膜を例にとって説明してきた
が、４族水素化合物を原料ガスとして作成される、狭バ
ンドギャップのａ−ＳｉＧｅ：Ｈ膜あるいは広バンドギ
ャップのａ−ＳｉＣ：Ｈ膜などのアモルファスシリコン
系合金膜の同種元素同士の高速、高品質化にも、本発明
が有効である。In the above embodiment, the hydrogenated amorphous silicon a-Si: H film has been described as an example. However, a narrow band gap a-SiGe: H formed using a Group 4 hydrogen compound as a source gas. The present invention is also effective in increasing the speed and quality of the same kind of elements of an amorphous silicon alloy film such as a film or an a-SiC: H film having a wide band gap.
【００２６】なお、本実施例は、太陽電池等の光半導体
デバイスに最適であるが、光が動作上関与しないＴＦＴ
等の半導体デバイス全般にも適用できる。Although this embodiment is most suitable for an optical semiconductor device such as a solar cell, a TFT in which light is not involved in the operation.
The present invention can be applied to semiconductor devices in general.
【００２７】[0027]
【発明の効果】本発明によれば、水素化アモルファス薄
膜を高速で堆積した場合にも、光導電率、及び光導電率
／暗導電率の比に優れた高品質な半導体薄膜が高歩留ま
りで得られ、太陽電池、感光ドラム、各種光センサー等
の光半導体デバイス及びＴＦＴ等の半導体デバイス全般
の半導体薄膜として適用できる。According to the present invention, even when a hydrogenated amorphous thin film is deposited at a high speed, a high-quality semiconductor thin film having excellent photoconductivity and a ratio of photoconductivity / dark conductivity can be obtained at a high yield. It can be obtained as a semiconductor thin film for semiconductor devices such as solar cells, photosensitive drums, various optical sensors, and semiconductor devices such as TFTs.
【００２８】その結果、高スループットで生産すること
が可能となり、低コストで高性能の半導体デバイスを提
供できるようになる。As a result, high-throughput production becomes possible, and a low-cost, high-performance semiconductor device can be provided.
【図１】（ａ）従来の、高周波電力を周期的にオン・オ
フした変調高周波電力の模式図である。 （ｂ）本発明の、高周波電力を周期的にオン・オフした
変調高周波電力の模式図である。FIG. 1A is a schematic diagram of a conventional modulated high-frequency power in which high-frequency power is periodically turned on and off. FIG. 4B is a schematic diagram of modulated high-frequency power obtained by periodically turning on and off high-frequency power according to the present invention.
【図２】本実施例に用いたプラズマＣＶＤ装置の模式図
である。FIG. 2 is a schematic view of a plasma CVD apparatus used in the present embodiment.
【図３】実施例１の実験結果を示す図である。FIG. 3 is a view showing experimental results of Example 1.
【図４】実施例２の実験結果を示す図である。FIG. 4 is a diagram showing experimental results of Example 2.
１ 反応室 ２ カソード電極 ３ 高周波電源 ４ 変調用電源 ５ マッチング回路 ６ 基板 ７ アノード電極 DESCRIPTION OF SYMBOLS 1 Reaction chamber 2 Cathode electrode 3 High frequency power supply 4 Modulation power supply 5 Matching circuit 6 Substrate 7 Anode electrode
───────────────────────────────────────────────────── フロントページの続き (72)発明者 富田 孝司 大阪府大阪市阿倍野区長池町22番22号 シャープ株式会社内 (56)参考文献 特開 平５−156451（ＪＰ，Ａ) 特開 平５−217908（ＪＰ，Ａ) 特開 平６−291045（ＪＰ，Ａ) 特開 平７−37818（ＪＰ，Ａ) 特開 昭64−73620（ＪＰ，Ａ) 特開 平６−291048（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/205 C23C 16/50 H01L 31/04 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Koji Tomita 22-22 Nagaikecho, Abeno-ku, Osaka-shi, Osaka Inside Sharp Corporation (56) References JP-A-5-156451 (JP, A) JP-A-5-205 217908 (JP, A) JP-A-6-291045 (JP, A) JP-A-7-37818 (JP, A) JP-A 64-73620 (JP, A) JP-A-6-291048 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) H01L 21/205 C23C 16/50 H01L 31/04
Claims (2)
族水素化合物あるいはその誘導体をプラズマにして活性
種に分解し堆積させる半導体薄膜の製造方法であって、Ｓｉ−Ｈ結合に対するＳｉ−Ｈ 2 結合の含有比が小さく
なるように、上記オン 時間は、［（プラズマ内の長寿命
活性種以外の活性種と反応する母ガスとの２次反応速度
定数）×（母ガス分子の数）］の逆数の時間以下に設定
されてなることを特徴とする半導体薄膜の製造方法。1. A high frequency power is periodically turned on and off by
A method for producing a semiconductor thin film in which an aromatic hydrogen compound or a derivative thereof is decomposed into active species by plasma and deposited, wherein the content ratio of Si—H 2 bonds to Si—H bonds is small.
The ON time is set to be equal to or less than the reciprocal of [(second order reaction rate constant of mother gas reacting with active species other than long-lived active species in plasma) × (number of mother gas molecules)]. A method of manufacturing a semiconductor thin film, wherein the method is set.
に用いるプラズマＣＶＤ装置であって、高周波電力 の供給を行う高周波電力発生手段と、高周波
電力の供給の有無を時分割制御する手段とを備えたこと
を特徴とするプラズマＣＶＤ装置。2. A plasma CVD apparatus used in the method for manufacturing a semiconductor thin film according to claim 1, a high frequency power generating means for supplying high-frequency power, frequency
Means for time-divisionally controlling whether power is supplied or not, a plasma CVD apparatus.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02908695A JP3208274B2 (en) | 1995-02-17 | 1995-02-17 | Method for producing semiconductor thin film and plasma CVD apparatus used for the method |
| US08/601,990 US5618758A (en) | 1995-02-17 | 1996-02-15 | Method for forming a thin semiconductor film and a plasma CVD apparatus to be used in the method |
| DE69633754T DE69633754T2 (en) | 1995-02-17 | 1996-02-16 | Manufacturing method for a thin semiconductor film |
| EP96301052A EP0727826B1 (en) | 1995-02-17 | 1996-02-16 | A method for forming a thin semiconductor film |
| US08/783,283 US6009828A (en) | 1995-02-17 | 1997-01-10 | Method for forming a thin semiconductor film and a plasma CVD apparatus to be used in the method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02908695A JP3208274B2 (en) | 1995-02-17 | 1995-02-17 | Method for producing semiconductor thin film and plasma CVD apparatus used for the method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08222520A JPH08222520A (en) | 1996-08-30 |
| JP3208274B2 true JP3208274B2 (en) | 2001-09-10 |
Family
ID=12266547
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|---|---|---|---|
| JP02908695A Expired - Fee Related JP3208274B2 (en) | 1995-02-17 | 1995-02-17 | Method for producing semiconductor thin film and plasma CVD apparatus used for the method |
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| Country | Link |
|---|---|
| JP (1) | JP3208274B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008004813A (en) * | 2006-06-23 | 2008-01-10 | Sharp Corp | Silicon-based thin film photoelectric conversion element and manufacturing method and manufacturing apparatus therefor |
| JP4761322B2 (en) * | 2009-04-30 | 2011-08-31 | シャープ株式会社 | Method for forming semiconductor film and method for manufacturing photoelectric conversion device |
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1995
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