JPH06120534A - Amorphous solar cell - Google Patents
Amorphous solar cellInfo
- Publication number
- JPH06120534A JPH06120534A JP4268614A JP26861492A JPH06120534A JP H06120534 A JPH06120534 A JP H06120534A JP 4268614 A JP4268614 A JP 4268614A JP 26861492 A JP26861492 A JP 26861492A JP H06120534 A JPH06120534 A JP H06120534A
- Authority
- JP
- Japan
- Prior art keywords
- tin oxide
- oxide film
- solar cell
- transparent electrode
- substrate
- 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
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は太陽電池を形成するため
の透明電極の構成を示した非晶質太陽電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous solar cell having a transparent electrode structure for forming a solar cell.
【０００２】[0002]
【従来の技術】一般に、透光性基板を用いるアモルファ
ス太陽電池は、その基板上に透明電極として熱ＣＶＤ法
により錫をド−プする酸化錫（ＳｎＯ2）などがよく知
られている。この熱ＣＶＤ法による製造方法は、５００
℃程度まで昇温した反応炉内に塩化錫及び酸素を原料と
するガスとフッ素あるいはトリフロロブロモメタン（Ｃ
Ｆ3Ｂｒ）、ジフロロクロメタン（ＣＨＣｌＦ2）等のフ
ロンガス中の１種類をド−ピングさせ、これら熱分解酸
化反応によって、基板上に付着させ形成されるものであ
る。2. Description of the Related Art In general, as an amorphous solar cell using a transparent substrate, tin oxide (SnO 2 ) which is doped with tin by a thermal CVD method as a transparent electrode on the substrate is well known. The manufacturing method by the thermal CVD method is 500
In the reaction furnace heated to about ℃, tin chloride and oxygen gas as raw materials and fluorine or trifluorobromomethane (C
F 3 Br), difluorochloromethane (CHClF 2 ), and the like are used to dope one kind of fluorocarbon gas, and these are pyrolyzed and oxidized to be deposited on the substrate.
【０００３】この熱ＣＶＤ法による透明電極の製造方法
で、上記フッ素のド−ピング量を一定にして酸化錫膜を
形成させると、図５に示したように透光性基板２１上に
同じ粒径の酸化錫膜２２が形成される。In this method of manufacturing a transparent electrode by the thermal CVD method, when a tin oxide film is formed with a constant fluorine doping amount, the same grains are formed on the transparent substrate 21 as shown in FIG. A tin oxide film 22 having a diameter is formed.
【０００４】また、上記したフロンガスのド−ピングと
して、図６に示したトリフロロブロモメタンを用いた酸
化錫膜２３の場合、図７に示すジフロロクロメタンの酸
化錫膜２４等の他のフロンガスを用いた場合と比べて結
晶粒径の大きな酸化錫膜が得ることができ、この膜の表
面はテクスチャ−化され、アモルファス太陽電池を形成
した時、入射光が適度に散乱されて光電変換層内に送ら
れ、発電量が増大される。In the case of the tin oxide film 23 using trifluorobromomethane shown in FIG. 6 as the above-mentioned fluorocarbon doping, other tin oxide film 24 of difluorochloromethane shown in FIG. It is possible to obtain a tin oxide film with a larger crystal grain size than when using CFC gas, the surface of this film is textured, and when an amorphous solar cell is formed, incident light is appropriately scattered and photoelectric conversion is performed. It is sent to the stratum and the amount of power generation is increased.
【０００５】一方、ジフロロクロメタンをド−ピングガ
スとして用いた場合はトリフロロブロモメタンを用いた
時よりも酸化錫膜の結晶粒径は小さくなることから、フ
ロンのド−ピング効率が良く、その表面はフラットなも
のになり、光入射の面積抵抗が低下するという利点があ
る。On the other hand, when difluorochloromethane is used as the doping gas, the crystal grain size of the tin oxide film is smaller than when trifluorobromomethane is used, so that the fluorocarbon doping efficiency is good, The surface becomes flat, and there is an advantage that the sheet resistance of light incidence is reduced.
【０００６】[0006]
【発明が解決しようとする課題】ところが、上記したフ
ッ素及びフロンガスを絶えずド−ピングして透明電極を
形成する際、フッ素のド−プ量を増やしたり、あるいは
ジフロロクロメタンよりトリフロロブロモメタンを用い
た場合、結晶粒径が大きくなり、高テクスチャ−化にな
るので、入射光は散乱されて光電変換層内に送られ発電
電流が増大するものの、膜の抵抗の値が高くなるために
取り出せる電力量は低下すると共に、膜表面に鋭角的な
部分が生じて、非晶質半導体層からなる光電変換層への
積層に欠陥部分が生じ変換効率の低下を来す。However, when the transparent electrode is formed by continuously doping the above-mentioned fluorine and CFC gas, the doping amount of fluorine is increased or trifluorobromomethane is used rather than difluorochloromethane. In the case of using, since the crystal grain size becomes large and the texture becomes high, the incident light is scattered and sent to the photoelectric conversion layer to increase the generated current, but the resistance value of the film becomes high. The amount of electric power that can be taken out decreases, and at the same time, an acute angle portion is generated on the film surface, and a defective portion is generated in the stack of the amorphous semiconductor layer on the photoelectric conversion layer, resulting in a reduction in conversion efficiency.
【０００７】一方、フッ素のド−プ量を減らしたり、あ
るいはトリフロロブロモメタンよりジフロロクロメタン
を用いる場合には、結晶粒径が小さくなり、テクスチャ
−化されないので、抵抗値は低くなるが、光入射は光が
散乱されにくいために光電変換層内に送られても発電電
流の増大を見込めないといった問題点があった。On the other hand, when the doping amount of fluorine is reduced or when difluorochloromethane is used rather than trifluorobromomethane, the crystal grain size becomes small and it is not textured, but the resistance value becomes low. However, there is a problem in that it is not possible to expect an increase in the generated current even when the light is transmitted into the photoelectric conversion layer because the light is less likely to be scattered.
【０００８】[0008]
【課題を解決するための手段】本発明はこのような課題
を鑑みて、透明電極は、透光性基板表面上にフッ素をド
ープせずに熱ＣＶＤされた第１酸化錫膜と、第１酸化錫
膜上にフッ素をドープして熱ＣＶＤされた第２酸化錫膜
とによって構成されていると共にまた本発明の透明電極
は、透光性基板表面上にトリフロロブロモメタンをドー
プして熱ＣＶＤされた第１酸化錫膜と、第１酸化錫膜上
にジフロロクロメタンをドープして熱ＣＶＤされた第２
酸化錫膜とによって構成されている。In view of the above problems, the present invention provides a transparent electrode comprising a first tin oxide film which is thermally CVD-deposited on the surface of a transparent substrate without being doped with fluorine, and a first tin oxide film. The transparent electrode of the present invention is composed of a tin oxide film and a second tin oxide film which has been thermally CVD-doped with fluorine, and the transparent electrode of the present invention is formed by doping trifluorobromomethane on the surface of a transparent substrate and applying heat. The CVD first tin oxide film and the second tin oxide film thermally doped with difluorochloromethane on the first tin oxide film.
It is composed of a tin oxide film.
【０００９】[0009]
【作用】本発明によれば、結晶粒径の大きい高テクスチ
ャ−化された第１酸化錫膜を形成させた後、結晶粒径の
小さい第２の酸化錫膜を形成させるので、光はまず透光
性基板を通して、第１酸化錫膜へと進み、膜表面にて散
乱されて、さらに第２酸化錫膜へと進み光電変換層に入
射されることから、光を有効に利用でき、太陽電池の変
換効率を上げることができると共に、結晶粒径が大きい
膜上に結晶粒径の小さい膜を形成させるので、光電変換
層を膜上に容易に積層することができる。According to the present invention, since the first textured first tin oxide film having a large crystal grain size is formed and then the second tin oxide film having a small crystal grain size is formed, the light is first emitted. Through the light-transmitting substrate, the light travels to the first tin oxide film, is scattered on the film surface, and further travels to the second tin oxide film to enter the photoelectric conversion layer. Since the conversion efficiency of the battery can be increased and the film having a small crystal grain size is formed on the film having a large crystal grain size, the photoelectric conversion layer can be easily laminated on the film.
【００１０】[0010]
【実施例】本発明による実施例を図面を用いて詳細に説
明する。図１は本発明による非晶質太陽電池の熱ＣＶＤ
装置の構成図である。１はフロンガスとしてトリフロロ
ブロモメタン（ＣＦ3Ｂｒ） 、２は酸素（Ｏ2） 、３、
５はキャリア窒素（Ｎ）、４は四塩化錫（ＳｎＣｌ4）
で、６は反応炉であり、この反応炉６内には透光性の基
板７を配置している。この装置において、反応炉６内
で、フッ素のド−プ量の増減により形成される透明電極
の製造方法を示す。まず、フロンガスであるトリフロロ
ブロモメタン１をド−プせずに基板７上に第１酸化錫膜
を形成させる。この酸化錫膜は四塩化錫４を０．６ｇ／
ｍｉｎ、酸素２を０．５ｌ／ｍｉｎを導入させ、５００
℃程度まで昇温した反応炉６内において５分間、熱分解
酸化反応によって、４０００Å程度に成長させ形成す
る。引き続き第２酸化錫膜として四塩化錫４を０．６ｇ
／ｍｉｎ、酸素２を０．５ｌ／ｍｉｎに対し、トリフロ
ロブロモメタン１を３ｌ／ｍｉｎを導入し、第１酸化錫
膜と同様に５００℃程度まで昇温した反応炉６内におい
て５分間２０００Å程度に成長させ積層形成する。この
ように形成させた２層の酸化錫膜の状態を図２に示す。
この図２に示すように透光性基板７上にフッ素をド−プ
しない結晶粒径の大きな第１酸化錫膜９が形成されてお
り、さらにこの膜９上にフッ素をド−プした結晶粒径の
小さな第２酸化錫膜１０が設けられている。そして図示
はされていないが、この第２酸化錫膜１０の表面に非晶
質シリコンからなる光電変換層並びに裏面電極としての
金属電極が形成される。Embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a thermal CVD of an amorphous solar cell according to the present invention.
It is a block diagram of an apparatus. 1 is trifluorobromomethane (CF 3 Br) as CFC gas, 2 is oxygen (O 2 ), 3,
5 is carrier nitrogen (N), 4 is tin tetrachloride (SnCl 4 ).
Reference numeral 6 is a reaction furnace, and a transparent substrate 7 is arranged in the reaction furnace 6. In this apparatus, a method for manufacturing a transparent electrode formed in the reaction furnace 6 by increasing / decreasing the amount of fluorine doping will be described. First, the first tin oxide film is formed on the substrate 7 without doping the fluorocarbon methane 1 which is a fluorocarbon gas. This tin oxide film contains 0.6 g of tin tetrachloride 4 /
min, oxygen 2 was introduced at 0.5 l / min, and 500
In the reaction furnace 6 heated to about 0 ° C., it is grown for 5 minutes by a thermal decomposition oxidation reaction to grow to about 4000 Å and formed. Then, 0.6 g of tin tetrachloride 4 as a second tin oxide film
/ Min, oxygen 2 at 0.5 l / min, trifluorobromomethane 1 at 3 l / min, and 2000 Å for 5 minutes in the reaction furnace 6 heated to about 500 ° C. like the first tin oxide film. It is grown to a certain degree and laminated. The state of the two-layer tin oxide film thus formed is shown in FIG.
As shown in FIG. 2, a first tin oxide film 9 having a large crystal grain size that does not dope fluorine is formed on the translucent substrate 7. Further, a film obtained by doping fluorine on this film 9 is formed. A second tin oxide film 10 having a small grain size is provided. Although not shown, a photoelectric conversion layer made of amorphous silicon and a metal electrode as a back electrode are formed on the surface of the second tin oxide film 10.
【００１１】透光性基板７側から入射された光は第１の
酸化錫膜９にて大きく散乱され、第２の酸化錫膜１０を
経由して光電変換層に到達し、光電変換に寄与する。Light incident from the transparent substrate 7 side is largely scattered by the first tin oxide film 9 and reaches the photoelectric conversion layer via the second tin oxide film 10 to contribute to photoelectric conversion. To do.
【００１２】図３は本発明の他の実施例を示しており、
フロンガスをトリフロロブロモメタン１及びジフロロク
ロメタン８を用いて透明電極を形成させるものであり、
上記第１実施例で用いた熱ＣＶＤ装置にフロングガスの
ド−ピングとしてジフロロクロメタン８をさらに設けて
いるものである。この装置において、上記同様のガス成
分については同一番号を付している。FIG. 3 shows another embodiment of the present invention,
CFC is used to form a transparent electrode by using trifluorobromomethane 1 and difluorochloromethane 8.
The thermal CVD apparatus used in the first embodiment is further provided with a difluorochloromethane 8 as a doping of the long gas. In this device, the same numbers are assigned to the same gas components as above.
【００１３】この装置において、まず第１酸化錫膜とし
て四塩化錫４を０．６ｇ／ｍｉｎ、酸素２を０．５ｌ／
ｍｉｎを導入させ、このガスに対しトリフロロブロモメ
タン１を３ｌ／ｍｉｎ導入する。５００℃程度まで昇温
した反応炉６内において５分間、熱分解反応によって、
４０００Å程度に成長した酸化錫膜を形成させる。さら
に、引き続き第２酸化錫膜として四塩化錫４を０．６ｇ
／ｍｉｎ、酸素２を０．５ｌ／ｍｉｎに対し、トリフロ
ロブロモメタン１の導入を止め、替わりにジフロロクロ
メタン８を０．２ｌ／ｍｉｎを導入し、５００℃程度ま
で昇温した反応炉６内において５分間２０００Å程度に
成長した酸化錫膜を積層形成する。このように形成させ
た酸化錫膜を図４に示す。この図４に示すように透光性
基板７上にトリリフロロブロモメタン１をド−プした結
晶粒径の大きな第１酸化錫膜１１が形成されており、さ
らにこの膜１１上にジフロロクロメタン８をド−プした
結晶粒径の小さな第２酸化錫膜１２が設けられている。
そして図示はされていないが、この第２酸化錫膜１２の
表面に非晶質シリコンからなる光電変換層並びに裏面電
極としての金属電極が形成される。透光性基板７側から
入射された光は第１の酸化錫膜１１にて大きく散乱さ
れ、第２の酸化錫膜１２を経由して光電変換層に到達
し、光電変換に寄与する。In this apparatus, first, tin tetrachloride 4 was used as a first tin oxide film at 0.6 g / min and oxygen 2 was used at 0.5 l / min.
min is introduced, and trifluorobromomethane 1 is introduced into this gas at 3 l / min. In the reaction furnace 6 heated up to about 500 ° C. for 5 minutes, by the thermal decomposition reaction,
A tin oxide film grown to about 4000 Å is formed. Furthermore, 0.6 g of tin tetrachloride 4 is continuously used as a second tin oxide film.
/ Min, oxygen 2 at 0.5 l / min, introduction of trifluorobromomethane 1 was stopped, difluorochloromethane 8 at 0.2 l / min was introduced instead, and the reaction furnace was heated to about 500 ° C. In 6, a tin oxide film grown to about 2000 Å is laminated for 5 minutes. The tin oxide film thus formed is shown in FIG. As shown in FIG. 4, a first tin oxide film 11 having a large crystal grain size and doped with trilifluorobromomethane 1 is formed on a transparent substrate 7, and a difluorochrome film is further formed on this film 11. A second tin oxide film 12 having a small crystal grain size doped with methane 8 is provided.
Although not shown, a photoelectric conversion layer made of amorphous silicon and a metal electrode as a back electrode are formed on the surface of the second tin oxide film 12. Light incident from the transparent substrate 7 side is largely scattered by the first tin oxide film 11, reaches the photoelectric conversion layer via the second tin oxide film 12, and contributes to photoelectric conversion.
【００１４】[0014]
【発明の効果】本発明太陽電池に用いられる透明電極
は、透光性基板表面上にフッ素をドープせずに熱ＣＶＤ
された第１酸化錫膜と、該第１酸化錫膜上にフッ素をド
ープして熱ＣＶＤされた第２酸化錫膜とによって構成さ
れており、さらに、本発明では透明電極は、透光性基板
表面上にトリフロロブロモメタンをドープして熱ＣＶＤ
された第１酸化錫膜と、該第１酸化錫膜上にジフロロク
ロメタンをドープして熱ＣＶＤされた第２酸化錫膜とに
よって構成されているので、透光性基板から入射された
光は結晶粒径が大きな第１酸化錫膜で大きく散乱させら
れた後、第２酸化錫膜を経て光電変換層に導入されて発
電に寄与すると同時に、その発電電力は主として抵抗値
の低い第２酸化錫膜を経由して効率よく発電電力として
取り出される。The transparent electrode used in the solar cell of the present invention is formed by thermal CVD without doping fluorine on the surface of the transparent substrate.
And a second tin oxide film which is obtained by doping fluorine on the first tin oxide film and thermally CVD is performed. Further, in the present invention, the transparent electrode is transparent. Doped with trifluorobromomethane on the substrate surface and thermal CVD
Since the first tin oxide film is formed by heat treatment and the second tin oxide film is formed by thermal CVD of the first tin oxide film on which difluorochloromethane is doped, the light is emitted from the transparent substrate. The light is largely scattered by the first tin oxide film having a large crystal grain size, and then is introduced into the photoelectric conversion layer through the second tin oxide film to contribute to power generation, and at the same time, the generated power is mainly low in resistance. Efficiently extracted as generated power via the tin dioxide film.
【００１５】また、光電変換層は結晶粒径の小さな第２
酸化錫膜上に形成されるので、積層の際の欠陥の発生が
なく、良好な成膜性を示す。Further, the photoelectric conversion layer has a second crystal grain size of small second.
Since it is formed on the tin oxide film, defects are not generated during lamination and good film formation is exhibited.
【図１】本発明による非晶質太陽電池を形成する際に用
いる熱ＣＶＤ装置の構成図である。FIG. 1 is a configuration diagram of a thermal CVD apparatus used when forming an amorphous solar cell according to the present invention.
【図２】本発明による非晶質太陽電池に用いる透明電極
の断面図である。FIG. 2 is a cross-sectional view of a transparent electrode used in an amorphous solar cell according to the present invention.
【図３】本発明による非晶質太陽電池を形成する際の他
の実施例の熱ＣＶＤ装置の構成図である。FIG. 3 is a configuration diagram of a thermal CVD apparatus according to another embodiment when forming an amorphous solar cell according to the present invention.
【図４】本発明による非晶質太陽電池の他の実施例の透
明電極の断面図である。FIG. 4 is a cross-sectional view of a transparent electrode of another embodiment of the amorphous solar cell according to the present invention.
【図５】従来の非晶質太陽電池に用いられる透明電極の
断面図である。FIG. 5 is a cross-sectional view of a transparent electrode used in a conventional amorphous solar cell.
【図６】従来の非晶質太陽電池に用いられる透明電極の
断面図である。FIG. 6 is a cross-sectional view of a transparent electrode used in a conventional amorphous solar cell.
【図７】従来の非晶質太陽電池に用いられる透明電極の
断面図である。FIG. 7 is a cross-sectional view of a transparent electrode used in a conventional amorphous solar cell.
１ トリフロロブロモメタン ４ 四塩化錫 ７ 基板 ８ ジフロロクロメタン 1 Trifluorobromomethane 4 Tin tetrachloride 7 Substrate 8 Difluorochloromethane
Claims (2)
た透明電極と、該電極上に積層された非晶質半導体から
成る光電変換層と、該光電変換層上に設けられた金属電
極と、から成る非晶質太陽電池において、上記透明電極
は、透光性基板表面上にフッ素をドープせずに熱ＣＶＤ
された第１酸化錫膜と、該第１酸化錫膜上にフッ素をド
ープして熱ＣＶＤされた第２酸化錫膜とによって構成さ
れていることを特徴とした非晶質太陽電池。1. A transparent substrate, a transparent electrode formed on the surface of the substrate, a photoelectric conversion layer made of an amorphous semiconductor laminated on the electrode, and provided on the photoelectric conversion layer. In an amorphous solar cell including a metal electrode, the transparent electrode is formed by thermal CVD without doping fluorine on the surface of the transparent substrate.
And a second tin oxide film formed by thermal CVD of the first tin oxide film on which fluorine is doped.
た透明電極と、該電極上に積層された非晶質半導体から
成る光電変換層と、該光電変換層上に設けられた金属電
極と、から成る非晶質太陽電池において、上記透明電極
は、透光性基板表面上にトリフロロブロモメタンをドー
プして熱ＣＶＤされた第１酸化錫膜と、該第１酸化錫膜
上にジフロロクロメタンをドープして熱ＣＶＤされた第
２酸化錫膜とによって構成されていることを特徴とした
非晶質太陽電池。2. A transparent substrate, a transparent electrode formed on the surface of the substrate, a photoelectric conversion layer made of an amorphous semiconductor laminated on the electrode, and provided on the photoelectric conversion layer. In an amorphous solar cell including a metal electrode, the transparent electrode comprises a first tin oxide film thermally doped with trifluorobromomethane on the surface of a transparent substrate, and the first tin oxide film. An amorphous solar cell comprising a second tin oxide film doped with difluorochloromethane and thermally CVD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4268614A JPH06120534A (en) | 1992-10-07 | 1992-10-07 | Amorphous solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4268614A JPH06120534A (en) | 1992-10-07 | 1992-10-07 | Amorphous solar cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06120534A true JPH06120534A (en) | 1994-04-28 |
Family
ID=17460994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4268614A Pending JPH06120534A (en) | 1992-10-07 | 1992-10-07 | Amorphous solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06120534A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011013719A1 (en) * | 2009-07-29 | 2011-02-03 | 旭硝子株式会社 | Transparent conductive substrate for solar cell, and solar cell |
| KR101382884B1 (en) * | 2012-09-12 | 2014-04-09 | 엘지이노텍 주식회사 | Solar cell and method of fabricating the same |
-
1992
- 1992-10-07 JP JP4268614A patent/JPH06120534A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011013719A1 (en) * | 2009-07-29 | 2011-02-03 | 旭硝子株式会社 | Transparent conductive substrate for solar cell, and solar cell |
| KR101382884B1 (en) * | 2012-09-12 | 2014-04-09 | 엘지이노텍 주식회사 | Solar cell and method of fabricating the same |
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