JP2011181658A - Oligomethyl arsine compound for amorphous semiconductor film, and film forming gas using the same - Google Patents

Oligomethyl arsine compound for amorphous semiconductor film, and film forming gas using the same Download PDF

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JP2011181658A
JP2011181658A JP2010044041A JP2010044041A JP2011181658A JP 2011181658 A JP2011181658 A JP 2011181658A JP 2010044041 A JP2010044041 A JP 2010044041A JP 2010044041 A JP2010044041 A JP 2010044041A JP 2011181658 A JP2011181658 A JP 2011181658A
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amorphous semiconductor
semiconductor film
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Toshihisa Ide
利久 井手
Tatsuya Irie
竜也 入江
Kenji Tanaka
健二 田仲
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Central Glass Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound which is chemically safe and easy to be transported in large quantities as a compound used for a pin-junction amorphous semiconductor film formed as a photoelectric conversion layer of a photovoltaic device. <P>SOLUTION: An oligomethyl arsine compound is used for the pin-junction amorphous semiconductor film formed as the photoelectric conversion layer of the photovoltaic device, and is represented by general formula (1) (CH<SB>3</SB>)nAsH<SB>3-n</SB>[wherein (n) represents an integer of 1 to 3]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は太陽電池などの光起電力装置の光電変換層の製造プロセスにおいて、ｐｉｎ接合の非晶質半導体膜の成膜に用いる化合物に関するものである   The present invention relates to a compound used for forming a pin junction amorphous semiconductor film in a process for producing a photoelectric conversion layer of a photovoltaic device such as a solar cell.

近年、クリーンなエネルギーとして、太陽光発電が注目されており、その中でも特に非晶質半導体を用いた太陽電池はコスト面において他の種類の太陽電池よりも有望であり、積極的な研究開発が進められている。   In recent years, solar power generation has attracted attention as a clean energy. Among them, solar cells using amorphous semiconductors are more promising than other types of solar cells in terms of cost, and are actively researched and developed. It is being advanced.

一般的に、非晶質半導体を用いる太陽電池はガラス基板上の上に、ＩＴＯ、ＳｎＯ２、などの透明電極、ｐ型、ｉ型、ｎ型の非晶質シリコン（ａ−ｓｉ）膜、Ａｇ、Ａｕなどの裏面電極を順に積層形成して構成されている。例えば、ａ−Ｓｉ膜は、ｐ型、ｉ型、ｎ型の各層を別々のプラズマＣＶＤ装置内で順次形成する、連続分離式にて作製されること（例えば、特許文献１）が知られている。 Generally, a solar cell using an amorphous semiconductor has a transparent electrode such as ITO or SnO 2 on a glass substrate, a p-type, i-type, or n-type amorphous silicon (a-si) film, A back electrode such as Ag and Au is laminated in order. For example, it is known that an a-Si film is produced by a continuous separation method in which p-type, i-type, and n-type layers are sequentially formed in separate plasma CVD apparatuses (for example, Patent Document 1). Yes.

特開昭６０−３１０８２号公報Japanese Patent Laid-Open No. 60-31082

一般的に、プラズマＣＶＤによりｎ型の非晶質半導体膜を得るために、５族の元素をドープするが、このドーピング原料として、アルシン（ＡｓＨ３）を用いる。しかし、ＡｓＨ３は沸点が−６２．５℃の気体であるため、大量に輸送をするためには高圧充填を行う必要がある。また、化学的に不安定であるため高濃度のＡｓＨ３を高圧充填して扱うことは安全性に問題が生じ、希釈して充填する必要がある。したがって、大量輸送が難しく、輸送コストが大きくなるという問題がある。このため、光起電力装置の光電変換層の製造プロセスのように大量のガス供給が必要なプロセスには不利である。また、ＡｓＨ３の許容濃度は０．００５％であり、極めて毒性が高いことから、設備上および取扱い上厳重な安全対策が必要不可欠となっている。 In general, in order to obtain an n-type amorphous semiconductor film by plasma CVD, a Group 5 element is doped. Arsine (AsH 3 ) is used as a doping material. However, AsH 3 is a gas having a boiling point of −62.5 ° C., high-pressure filling is necessary to transport a large amount. Further, since it is chemically unstable, handling with high concentration of AsH 3 under high pressure causes a problem in safety, and it is necessary to dilute and fill. Therefore, there is a problem that mass transportation is difficult and transportation cost is increased. For this reason, it is disadvantageous for a process that requires a large amount of gas supply, such as a manufacturing process of a photoelectric conversion layer of a photovoltaic device. Further, the allowable concentration of AsH 3 is 0.005%, which is extremely toxic. Therefore, strict safety measures are indispensable for facilities and handling.

本発明は、光起電力装置の光電変換層として成膜されるｐｉｎ接合の非晶質半導体膜に用いられる化合物で、特に、ＡｓＨ３ガスに代わる化学的に安全で、かつ大量輸送しやすいドーピング原料を提供することを目的としている。 The present invention is a compound used for an amorphous semiconductor film having a pin junction formed as a photoelectric conversion layer of a photovoltaic device. In particular, it is a chemically safe alternative to AsH 3 gas, and is easily doped in large quantities. The purpose is to provide raw materials.

このような状況に鑑み、本発明者らは、上記課題を解決すべく鋭意検討した結果、室温において液体であるオリゴメチルアルシン化合物が、ＡｓＨ３ガスに代わる化学的に安定で、かつ大量輸送しやすいドーピング原料となることを見出し、本発明に至った。 In view of such a situation, the present inventors have intensively studied to solve the above problems, and as a result, the oligomethylarsine compound, which is liquid at room temperature, is chemically stable and can be transported in large quantities instead of AsH 3 gas. As a result, the present invention has been found.

すなわち本発明は、光起電力装置の光電変換層として成膜されるｐｉｎ接合の非晶質半導体膜に用いられる、一般式（１）
（ＣＨ３）ｎＡｓＨ３−ｎ （１）
［式中、ｎは１〜３のいずれか一つの整数を表す］で表されるオリゴメチルアルシン化合物を提供するものである。さらには、ｎ型の該非晶質半導体膜を形成するためのドーピングガスとして用いられる、上記一般式（１）で表されるオリゴメチルアルシン化合物、また、ｎ型の該非晶質半導体膜を成膜するのに用いられる成膜ガスに、上記一般式（１）で表されるオリゴメチルアルシン化合物がドーピングガスとして０．０００１〜１０体積%の範囲内で混合されていることを特徴とする、ｎ型半導体となる非晶質半導体膜の成膜ガスを提供するものである。 That is, the present invention is a general formula (1) used for a pin junction amorphous semiconductor film formed as a photoelectric conversion layer of a photovoltaic device.
(CH 3 ) n AsH 3-n (1)
In the formula, n represents an oligomethylarsine compound represented by any one of 1 to 3. Furthermore, the oligomethylarsine compound represented by the general formula (1) used as a doping gas for forming the n-type amorphous semiconductor film, and the n-type amorphous semiconductor film are formed. The film-forming gas used for this is mixed with an oligomethylarsine compound represented by the above general formula (1) as a doping gas in a range of 0.0001 to 10% by volume, n A deposition gas for an amorphous semiconductor film to be a type semiconductor is provided.

本発明により、光起電力装置の光電変換層として成膜されるｐｉｎ接合の非晶質半導体膜に用いられる化合物として、化学的に安定な化合物を提供することができる。   According to the present invention, a chemically stable compound can be provided as a compound used for a pin junction amorphous semiconductor film formed as a photoelectric conversion layer of a photovoltaic device.

実施例に用いたプラズマＣＶＤの成膜装置の該略図である。1 is a schematic view of a plasma CVD film forming apparatus used in an example.

以下に本発明を詳細に説明する。   The present invention is described in detail below.

本発明で用いられるオリゴメチルアルシン化合物は一般式（１）
（ＣＨ３）ｎＡｓＨ３−ｎ （１）
［式中、ｎは１〜３のいずれか一つの整数を表す］で表され、具体的には、トリメチルアルシン（Ａｓ（ＣＨ３）３）、ジメチルアルシン（（ＣＨ３）２ＡｓＨ）、メチルアルシン（（ＣＨ３）ＡｓＨ２）が挙げられる。この中で、（（ＣＨ３）２ＡｓＨは沸点２℃のガス状化合物であり、（ＣＨ３）ＡｓＨ２は沸点３６℃、Ａｓ（ＣＨ３）３は沸点５２℃である。このため室温（２５℃）以上の温度で液体であるＡｓ（ＣＨ３）３、（ＣＨ３）ＡｓＨ２が、安全面で特に好ましい化合物である。 The oligomethylarsine compound used in the present invention has the general formula (1)
(CH 3 ) n AsH 3-n (1)
[Wherein n represents an integer of 1 to 3], specifically, trimethylarsine (As (CH 3 ) 3 ), dimethylarsine ((CH 3 ) 2 AsH), methyl Arsine ((CH 3 ) AsH 2 ). Among them, ((CH 3 ) 2 AsH is a gaseous compound having a boiling point of 2 ° C., (CH 3 ) AsH 2 has a boiling point of 36 ° C., and As (CH 3 ) 3 has a boiling point of 52 ° C. Therefore, room temperature ( As (CH 3 ) 3 and (CH 3 ) AsH 2 which are liquids at a temperature of 25 ° C. or higher are particularly preferable compounds in terms of safety.

本発明の化合物のうち、Ａｓ（ＣＨ３）３は、例えばＩｎｏｒｇ．Ｃｈｅｍ．１９９０，２９，３５０２．に記載されるようにメチルグリニャール試薬とクロロジアルコキシアルシンを反応させる方法、(ＣＨ３)２ＡｓＨは、例えばＪ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９５４，７６，３８６．に記載されるようにジメチルクロロアルシンをＴＨＦ中ＬｉＡｌＨ４などの還元剤により水素化する方法、（ＣＨ３）ＡｓＨ２は、例えばＪ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９３７，５９，２０６８．に記載されるようにＫＡｓＨ２とＣＨ３Ｃｌを反応させる方法など、公知の方法で得ることができ、本発明は、該化合物を得る方法に限定されない。 Among the compounds of the present invention, As (CH 3 ) 3 is, for example, Inorg. Chem. 1990, 29, 3502. (CH 3 ) 2 AsH is a method of reacting a methyl Grignard reagent with chlorodialkoxyarsine as described in J. Am. Chem. Soc. 1954, 76, 386. A method of hydrogenating dimethylchloroarsine with a reducing agent such as LiAlH 4 in THF as described in (CH 3 ) AsH 2 is described, for example, in J. Am. Am. Chem. Soc. 1937, 59, 2068. And can be obtained by a known method such as a method of reacting KAsH 2 with CH 3 Cl, and the present invention is not limited to the method of obtaining the compound.

本発明の化合物は、プラズマＣＶＤ、熱ＣＶＤ、光ＣＶＤなどｐｉｎ接合の非晶質半導体膜を成膜する一般的な方法に用いることができる。   The compound of the present invention can be used in a general method for forming a pin junction amorphous semiconductor film such as plasma CVD, thermal CVD, and photo CVD.

非晶質半導体としては、ａ−Ｓｉ、ａ−ＳｉＧｅ、ａ−ＳｉＮ、ａ−ＳｉＣ、ａ−ＳｉＯ２などが挙げられる。Ｓｉ源としては、モノシラン（ＳｉＨ４）など、ａ−ＳｉＧｅのＧｅ源としては、モノゲルマン（ＧｅＨ４）など、ａ−ＳｉＮのＮ源としては、アンモニア、窒素など、ａ−ＳｉＣのＣ源としては、エタン、プロパンなどの低級アルカン、ａ−ＳｉＯのＯ源としては、酸素などのガスが非晶質半導体膜の成膜に用いられる。またこの際、モノシラン、モノゲルマンなどは希釈された状態で成膜装置内に供給され、キャリアガスとして水素、ヘリウム、窒素などが用いられる
特に本発明の化合物は、非晶質半導体の成膜時のドーピング原料として用いることが有効である。また、ドーピング原料として用いる場合、本発明の化合物を０．０００１〜１０体積％の範囲内で混合させた成膜ガスを用いることが好ましい。０．０００１体積％未満ではドーピング濃度が低濃度すぎてｎ型としての機能が低下し、１０体積％超では、半導体膜を形成する材料が低濃度すぎて半導体としての機能が低下する虞がある。 Examples of the amorphous semiconductor include a-Si, a-SiGe, a-SiN, a-SiC, and a-SiO 2 . As a Si source, monosilane (SiH 4 ), etc. As a-SiGe Ge source, as monogermane (GeH 4 ), etc. As a-SiN N source, as ammonia, nitrogen, etc. As a C source of a-SiC In this case, a lower alkane such as ethane or propane, or a gas such as oxygen is used for forming an amorphous semiconductor film as an O source of a-SiO. At this time, monosilane, monogermane, etc. are supplied into the film forming apparatus in a diluted state, and hydrogen, helium, nitrogen, etc. are used as a carrier gas. Particularly, the compound of the present invention is used for forming an amorphous semiconductor. It is effective to use it as a doping material. Moreover, when using as a doping raw material, it is preferable to use the film-forming gas which mixed the compound of this invention in 0.0001-10 volume%. If it is less than 0.0001% by volume, the doping concentration is too low and the function as an n-type is reduced. If it exceeds 10% by volume, the material forming the semiconductor film is too low and the function as a semiconductor may be reduced. .

以下、実施例および比較例を挙げ、本発明をより具体的に詳細に説明するが、本発明は以下の実施例に限定されるものではない。   Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.

磁製カップの上にろ紙を置き、Ｉｎｏｒｇ．Ｃｈｅｍ．１９９０，２９，３５０２．に記載されている方法を用いて得られたＡｓ（ＣＨ３）３を注射器で０．５ｍＬ滴下し、その様子を観察した。５分後においても、ろ紙が燃えた形跡も焦げた形跡も観測されなかった。この実験を繰り返し３回実施したが同様の結果となった。このことから、自然発火性はないものと考えられる。 Place the filter paper on the porcelain cup and place it in Inorg. Chem. 1990, 29, 3502. As (CH 3 ) 3 obtained by using the method described in 1 ), 0.5 mL was dropped with a syringe, and the state was observed. Even after 5 minutes, no evidence of burning or scorching of the filter paper was observed. This experiment was repeated three times with similar results. From this, it is considered that there is no spontaneous ignition.

磁製カップの上にろ紙を置きＪ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９５４，７６，３８６．に記載されている方法を用いて得られた（ＣＨ３）２ＡｓＨを注射器で０．５ｍＬ滴下し、その様子を観察した。５分後においても、ろ紙が燃えた形跡も焦げた形跡も観測されなかった。この実験を繰り返し３回実施したが同様の結果となった。このことから、自然発火性はないものと考えられる。 Place the filter paper on the porcelain cup. Am. Chem. Soc. 1954, 76, 386. 0.5 mL of (CH 3 ) 2 AsH obtained using the method described in 1 ) was dropped with a syringe, and the state was observed. Even after 5 minutes, no evidence of burning or scorching of the filter paper was observed. This experiment was repeated three times with similar results. From this, it is considered that there is no spontaneous ignition.

真空引きした１ＬのＳＵＳ製シリンダーにＪ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９３７，５９，２０６８．に記載されている方法を用いて得られた（ＣＨ３）ＡｓＨ２を室温で入れ、その後空気を所定量入れ、全体で１０００ｔｏｒｒとなるようにした。その後室温で圧力変化の様子を観察した。空気の濃度０〜１００％のいずれの場合においても５分後における圧力変動は観測されなかった。このことから、自然発火性はないものと考えられる。 To a 1 L SUS cylinder evacuated, J. Am. Chem. Soc. 1937, 59, 2068. (CH 3 ) AsH 2 obtained by using the method described in 1 ) was introduced at room temperature, and then a predetermined amount of air was introduced so that the total amount was 1000 torr. Thereafter, the pressure change was observed at room temperature. No pressure fluctuation was observed after 5 minutes in any case of air concentration 0-100%. From this, it is considered that there is no spontaneous ignition.

図１は、本実施例に用いたプラズマＣＶＤの成膜装置の概略図である。上部放電電極２ａ、及び温度制御手段を備えた電極ヒータ１２を内蔵した下部放電電極２ｂが対向して配置されている。下部放電電極２ｂ上には成膜対象のガラス基板３が載置されている。真空チャンバ１には高周波電源４により、１３．５６ＭＨｚの高周波電圧が印加される。また、真空チャンバ１には排気システム５が接続されており、その内部が真空状態に維持されている。そして、上部放電電極２ａ、下部放電電極２ｂ間に真空放電が生じてプラズマが発生するようになっている。   FIG. 1 is a schematic view of a plasma CVD film forming apparatus used in this embodiment. An upper discharge electrode 2a and a lower discharge electrode 2b incorporating an electrode heater 12 having a temperature control means are arranged to face each other. A glass substrate 3 to be deposited is placed on the lower discharge electrode 2b. A high frequency voltage of 13.56 MHz is applied to the vacuum chamber 1 by a high frequency power source 4. Further, an exhaust system 5 is connected to the vacuum chamber 1, and the inside thereof is maintained in a vacuum state. A vacuum discharge is generated between the upper discharge electrode 2a and the lower discharge electrode 2b to generate plasma.

真空チャンバ１は、配管９を介してＳｉＨ４ボンベ６及びＩｎｏｒｇ．Ｃｈｅｍ．１９９０，２９，３５０２．に記載されている方法を用いて得られたＡｓ（ＣＨ３）３を充填したボンベ７に連結されている。配管９の中途にはＳｉＨ４のガス流量を制御するマスフローコントローラ８ａとＡｓ（ＣＨ３）３のガス量を制御するマスフローコントローラ８ｂとが設けられている。Ａｓ（ＣＨ３）３ボンベ７の周囲にはＡｓ（ＣＨ３）３を気化するためのヒータ１０が設置され、５０℃に加温されている。また、配管９には、その内部を加温するためのコイルヒータ１１が巻きつけられている。なお、１０ＭＰａ以上の高圧充填されたＡｓＨ３とは異なり、Ａｓ（ＣＨ３）３は室温で２６５ｔｏｒｒ程度の蒸気圧をもつ液体であるため、５０℃におけるボンベ内圧力は略０．１ＭＰａである。 The vacuum chamber 1 is connected to the SiH 4 cylinder 6 and the Inorg. Chem. 1990, 29, 3502. The cylinder 7 filled with As (CH 3 ) 3 obtained by using the method described in the above. In the middle of the pipe 9, a mass flow controller 8a for controlling the gas flow rate of SiH 4 and a mass flow controller 8b for controlling the gas amount of As (CH 3 ) 3 are provided. A heater 10 for vaporizing As (CH 3 ) 3 is installed around the As (CH 3 ) 3 cylinder 7 and heated to 50 ° C. A coil heater 11 is wound around the pipe 9 to heat the inside. Unlike AsH 3 filled with a high pressure of 10 MPa or more, As (CH 3 ) 3 is a liquid having a vapor pressure of about 265 torr at room temperature, and the pressure inside the cylinder at 50 ° C. is about 0.1 MPa.

次に動作について説明する。真空チャンバ１内の下部放電電極２ｂ上に載置されているガラス基板３を電極ヒータ１２により２００℃に加熱する。排気システム５により真空チャンバ１内を略１Ｐａの真空状態に維持し、高周波電源４により１３．５６ＭＨｚの高周波電圧を出力３０Ｗで印加する。一方、ＳｉＨ４ボンベ６からマスフローコントローラ８ａにてその流量を制御したＳｉＨ４ガスをコイルヒータ１１への通電により内部を５０℃程度に維持した配管９を介して真空チャンバ１内に導入する。また、ヒータ１０にて５０℃に加温して気化させたボンベ７内のＡｓ（ＣＨ３）３を、マスフローコントローラ８ｂにてその流量を制御し、配管９を介して真空チャンバ１内に導入する。ＳｉＨ４ガスとＡｓ（ＣＨ３）３ガスの導入量は各マスフローコントローラ８ａおよび８ｂを用いて、トータルガス流量を１０ｓｃｃｍ、導入されるトータルガス中のＡｓ（ＣＨ３）３ガスのガス混合率を０．１体積％に調節し、０．８ｎｍ／ｓ程度の蒸着速度にて成膜する。このときの真空チャンバ１内を圧力１０Ｐａに維持されている。このようにしてガラス基板３上に膜厚１０００Åの膜が得られた。得られた膜に対しＳＩＭＳ測定を実施した結果、３×１０１９ａｔｏｍｓ／ｃｍ３のＡｓがドーピングされており、ＡｓＨ３を用いた場合と同等の濃度であった。 Next, the operation will be described. The glass substrate 3 placed on the lower discharge electrode 2 b in the vacuum chamber 1 is heated to 200 ° C. by the electrode heater 12. The inside of the vacuum chamber 1 is maintained in a vacuum state of about 1 Pa by the exhaust system 5, and a high frequency voltage of 13.56 MHz is applied by the high frequency power source 4 at an output of 30 W. On the other hand, it is introduced into the vacuum chamber 1 through the pipe 9 that maintained internal to about 50 ° C. The SiH 4 gas controlling the flow rate from the SiH 4 gas cylinder 6 by a mass flow controller 8a by energizing the coil heater 11. Further, As (CH 3 ) 3 in the cylinder 7 heated to 50 ° C. by the heater 10 and vaporized is introduced into the vacuum chamber 1 through the pipe 9 while controlling the flow rate by the mass flow controller 8b. To do. The amount of SiH 4 gas and As (CH 3 ) 3 gas introduced was determined using the mass flow controllers 8a and 8b, the total gas flow rate was 10 sccm, and the gas mixing ratio of As (CH 3 ) 3 gas in the total gas introduced The film is formed at a deposition rate of about 0.8 nm / s by adjusting to 0.1% by volume. The inside of the vacuum chamber 1 at this time is maintained at a pressure of 10 Pa. In this way, a film having a thickness of 1000 mm was obtained on the glass substrate 3. As a result of performing SIMS measurement on the obtained film, 3 × 10 19 atoms / cm 3 of As was doped, and the concentration was the same as when AsH 3 was used.

Ａｓ(ＣＨ３)３を、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９５４，７６，３８６．に記載されている方法を用いて得られた（ＣＨ３）２ＡｓＨに代えた以外は、実施例４と同じように成膜し、Ａｓが実施例４と同様の濃度でドーピングされた膜が得られた。 The As (CH 3) 3, J . Am. Chem. Soc. 1954, 76, 386. A film was formed in the same manner as in Example 4 except that (CH 3 ) 2 AsH obtained by using the method described in 1) was used, and a film doped with As at the same concentration as in Example 4 was obtained. Obtained.

Ａｓ(ＣＨ３)３を、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９３７，５９，２０６８．に記載されている方法を用いて得られた（ＣＨ３）ＡｓＨ２に代え、ヒータ１０およびヒータ１１をはずした以外は、実施例４と同じように成膜し、Ａｓが実施例４と同様の濃度でドーピングされた膜が得られた。 The As (CH 3) 3, J . Am. Chem. Soc. 1937, 59, 2068. A film was formed in the same manner as in Example 4 except that the heater 10 and the heater 11 were removed in place of (CH 3 ) AsH 2 obtained by using the method described in 1 ), and As was the same as in Example 4. A film doped with a concentration of

なお、上述の実施例では、成膜方法としてプラズマＣＶＤ法を用いたが、公知の光ＣＶＤ法またはマイクロＣＶＤ法等を用いても同様の効果が得られた。   In the above-described embodiment, the plasma CVD method is used as the film forming method, but the same effect can be obtained by using a known photo-CVD method or micro-CVD method.

１・・・真空チャンバ
２ａ・・・上部放電電極
２ｂ・・・下部放電電極
３・・・ガラス基板
４・・・高周波電源
５・・・排気システム
６・・・ＳｉＨ４ボンベ
７・・・ボンベ
８ａ、８ｂ・・・マスフローコントローラ
９・・・配管
１０・・・ヒータ
１１・・・コイルヒータ
１２・・・電極ヒータ
DESCRIPTION OF SYMBOLS 1 ... Vacuum chamber 2a ... Upper discharge electrode 2b ... Lower discharge electrode 3 ... Glass substrate 4 ... High frequency power supply 5 ... Exhaust system 6 ... SiH 4 cylinder 7 ... Cylinder 8a, 8b ... mass flow controller 9 ... pipe 10 ... heater 11 ... coil heater 12 ... electrode heater

Claims (3)

光起電力装置の光電変換層として成膜されるｐｉｎ接合の非晶質半導体膜に用いられる、一般式（１）
（ＣＨ３）ｎＡｓＨ３−ｎ （１）
［式中、ｎは１〜３のいずれか一つの整数を表す。］で表されるオリゴメチルアルシン化合物。 General formula (1) used for a pin junction amorphous semiconductor film formed as a photoelectric conversion layer of a photovoltaic device
(CH 3 ) nAsH 3-n (1)
[Wherein n represents any one integer of 1 to 3. ] The oligomethylarsine compound represented by this. ｎ型の該非晶質半導体膜を形成するためのドーピングガスとして用いられる、請求項１に記載のオリゴメチルアルシン化合物。 The oligomethylarsine compound according to claim 1, which is used as a doping gas for forming the n-type amorphous semiconductor film. ｎ型の該非晶質半導体膜を成膜するのに用いられる成膜ガスに、請求項１に記載のオリゴメチルアルシン化合物がドーピングガスとして０．０００１〜１０体積％の範囲内で混合されていることを特徴とする、ｎ型半導体となる非晶質半導体膜の成膜ガス。
The oligomethylarsine compound according to claim 1 is mixed as a doping gas in a range of 0.0001 to 10% by volume in a film forming gas used to form the n-type amorphous semiconductor film. A film forming gas for an amorphous semiconductor film to be an n-type semiconductor.
JP2010044041A 2010-03-01 2010-03-01 Oligomethyl arsine compound for amorphous semiconductor film, and film forming gas using the same Pending JP2011181658A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05102502A (en) * 1991-10-09 1993-04-23 Mitsui Toatsu Chem Inc Amorphous solar cell
JPH07297138A (en) * 1994-04-22 1995-11-10 Mitsui Toatsu Chem Inc Method for depositing thin film of crystalline semiconductor
JP2000012465A (en) * 1998-06-22 2000-01-14 Sharp Corp Formation of silicon film and manufacture of solar battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05102502A (en) * 1991-10-09 1993-04-23 Mitsui Toatsu Chem Inc Amorphous solar cell
JPH07297138A (en) * 1994-04-22 1995-11-10 Mitsui Toatsu Chem Inc Method for depositing thin film of crystalline semiconductor
JP2000012465A (en) * 1998-06-22 2000-01-14 Sharp Corp Formation of silicon film and manufacture of solar battery

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