JP2874149B2 - Method for manufacturing solar cell absorption layer - Google Patents
Method for manufacturing solar cell absorption layerInfo
- Publication number
- JP2874149B2 JP2874149B2 JP5258280A JP25828093A JP2874149B2 JP 2874149 B2 JP2874149 B2 JP 2874149B2 JP 5258280 A JP5258280 A JP 5258280A JP 25828093 A JP25828093 A JP 25828093A JP 2874149 B2 JP2874149 B2 JP 2874149B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- selenium
- indium
- solar cell
- layer
- 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
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
Description
【０００１】[0001]
【産業上の利用分野】本発明は周期律表の１Ｂ族、３Ｂ
族、及び６Ｂ族の元素からなる化合物半導体で形成され
た太陽電池吸収層の製造方法に関し、特に銅−インジウ
ム−セレン三元合金からなる太陽電池吸収層の製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a group 1B, 3B
The present invention relates to a method for manufacturing a solar cell absorption layer formed of a compound semiconductor composed of an element belonging to Group 6B and Group 6B, and more particularly to a method for manufacturing a solar cell absorption layer composed of a ternary copper-indium-selenium alloy.
【０００２】[0002]
【従来の技術】太陽電池は光エネルギーを電気エネルギ
ーに変換する装置であり、電気絶縁性基板上に、電極層
と光電変換性半導体からなる吸収層と光透過性電極層と
を順次積層して構成されるのが普通である。かかる光電
変換性半導体層としては、原子比率が１：１：２である
銅−インジウム−セレン三元合金の薄層が最も優れた光
電変換効率を示すものと考えられているが、これらの３
成分の比率を制御しながら合金薄層の厚さも制御するこ
とは必ずしも容易なことではなかった。2. Description of the Related Art A solar cell is a device for converting light energy into electric energy, and is formed by sequentially laminating an electrode layer, an absorption layer made of a photoelectric conversion semiconductor, and a light transmission electrode layer on an electrically insulating substrate. It is usually composed. As such a photoelectric conversion semiconductor layer, a thin layer of a ternary alloy of copper-indium-selenium having an atomic ratio of 1: 1: 2 is considered to exhibit the most excellent photoelectric conversion efficiency.
It was not always easy to control the thickness of the alloy thin layer while controlling the ratio of the components.
【０００３】すなわち、薄層を形成するのに広く用いら
れている蒸着法を利用して吸収層を製造しようとする
と、同時蒸着では銅、インジウム、セレンの比率を正確
に制御することが極めて困難であり、各成分をそれぞれ
順次に積層蒸着してから熱処理を加えて合金化する方法
では均一な合金化が必ずしも容易でなく、熱処理時に組
成の変動が起こり易い他、面積の広い吸収層を製造する
にはコストが高いという問題がある。また、電解めっき
法では銅やインジウム、あるいはこれらの合金を比較的
に低いコストで薄膜状に析出させることができるが、セ
レンの電着は容易でない。That is, when an absorption layer is to be manufactured by using a vapor deposition method widely used for forming a thin layer, it is extremely difficult to accurately control the ratio of copper, indium, and selenium by simultaneous vapor deposition. In a method in which each component is sequentially laminated and vapor-deposited and then heat-treated to form an alloy, uniform alloying is not always easy, and the composition tends to fluctuate during the heat-treatment, and an absorption layer having a large area is manufactured. There is a problem that the cost is high. Further, in the electrolytic plating method, copper, indium, or an alloy thereof can be deposited in a thin film at a relatively low cost, but electrodeposition of selenium is not easy.
【０００４】これに対して、セレンの微細粒子を分散懸
濁させた銅とインジウムとの合金電着浴を用いてセレン
粒子が分散含有された銅−インジウム合金層を形成し、
これを熱処理して銅−インジウム−セレン三元合金の吸
収層を製造する方法が提案されている（国際公開ＷＯ
９２／０５５８６号）。しかしながらこの方法において
電着物の組成を制御するには、電着浴のｐＨ、温度、金
属イオン濃度、電流密度、攪拌速度等の条件をバランス
させる必要がある。それでも銅とインジウムの組成だけ
であれば制御は比較的容易であるが、それに加えてセレ
ン粒子の含有量を制御することは容易でなく、従って性
能のよい太陽電池吸収層を安定して製造することは非常
に難しいことであった。On the other hand, a copper-indium alloy layer containing selenium particles dispersed therein is formed by using an electrodeposition bath of copper and indium in which fine particles of selenium are dispersed and suspended,
There has been proposed a method for producing an absorption layer of a ternary copper-indium-selenium alloy by heat-treating it (International publication WO
92/05586). However, in order to control the composition of the electrodeposit in this method, it is necessary to balance conditions such as the pH, temperature, metal ion concentration, current density, and stirring speed of the electrodeposition bath. Nevertheless, if the composition is only copper and indium, the control is relatively easy, but in addition, it is not easy to control the content of selenium particles. It was very difficult.
【０００５】[0005]
【発明が解決しようとする課題】かかる事情の下で、本
発明は原子比が所望の狭い範囲内に制御された銅−イン
ジウム−セレン三元合金の太陽電池吸収層を安定して製
造することができる改良方法を提供しようとするもので
ある。SUMMARY OF THE INVENTION Under such circumstances, the present invention aims to stably produce a solar cell absorption layer of a ternary copper-indium-selenium alloy whose atomic ratio is controlled within a desired narrow range. The purpose of the present invention is to provide an improved method that can achieve the above.
【０００６】[0006]
【課題を解決するための手段】本発明の太陽電池吸収層
の製造方法は、銅被覆セレン微粉末を分散懸濁させたイ
ンジウムメッキ浴を用いて該銅被覆セレン微粉末を分散
含有するインジウム電着層を導電性基板上に形成し、次
いで熱処理して該電着層を銅−インジウム−セレン三元
合金層に転換することを特徴とする。According to the present invention, there is provided a method for producing a solar cell absorbing layer, comprising the steps of: using an indium plating bath in which copper-coated selenium fine powder is dispersed and suspended; An electrodeposition layer is formed on a conductive substrate, and then heat-treated to convert the electrodeposition layer to a copper-indium-selenium ternary alloy layer.
【０００７】本発明の太陽電池吸収層の製造方法におい
て用いられる銅被覆セレン微粉末は、例えば特開昭５３
−１３０７０７号公報や特開昭５４−６７８５１号公報
に開示された方法を利用してセレン微粉末の表面に銅の
皮膜を形成することにより得ることができるが、特にこ
れらの方法に限定されるものではない。[0007] The copper-coated selenium fine powder used in the method for producing a solar cell absorption layer of the present invention is described in, for example,
Can be obtained by forming a copper film on the surface of selenium fine powder using the methods disclosed in JP-A-130707 and JP-A-54-67851, but are particularly limited to these methods. Not something.
【０００８】また銅被覆セレン微粉末を構成する銅とセ
レンとのモル比は特に限定されないが、例えば１：２と
したものが好ましく用いられる。またこのような組成の
銅被覆セレン微粉末を分散懸濁させたメッキ浴を用いて
インジウム電着層を形成するに当り、インジウムに対す
る銅のモル比が１：１に近くなるように銅被覆セレン微
粉末の同時電着量を調整することによって、銅：インジ
ウム：セレンのモル比が１：１：２に近い電着層を得る
ことができる。The molar ratio between copper and selenium constituting the copper-coated selenium fine powder is not particularly limited, but a molar ratio of, for example, 1: 2 is preferably used. Further, in forming an indium electrodeposited layer using a plating bath in which a copper-coated selenium fine powder having such a composition is dispersed and suspended, the copper-coated selenium is mixed so that the molar ratio of copper to indium becomes close to 1: 1. By adjusting the simultaneous electrodeposition amount of the fine powder, an electrodeposition layer having a molar ratio of copper: indium: selenium close to 1: 1: 2 can be obtained.
【０００９】[0009]
【作用】本発明の方法によって銅とインジウムとセレン
との組成を所望の範囲内に制御させることが容易とな
り、また電着層内の各成分の分布を均一なものとするこ
とができ、従って特性の揃った太陽電池吸収層を容易に
製造することができる。According to the method of the present invention, the composition of copper, indium and selenium can be easily controlled within a desired range, and the distribution of each component in the electrodeposition layer can be made uniform. A solar cell absorption layer having uniform characteristics can be easily manufactured.
【００１０】[0010]
（実施例１）インジウム１．０mol/l を含むシアン系電
着浴に、特開昭５４−６７８５１号の方法によって製造
した銅被覆セレン微粉末（銅：セレンのモル比が約１：
２であるもの）を３０g/l となるよう混合し、モリブデ
ン薄膜電極を表面に設けたガラス基板を陰極として電流
密度３A/dm2 で攪拌しながら１０分間電着を行なって、
厚さ１０μｍのインジウム電着層を有する積層板を得
た。この電着層を分析したところ、銅：インジウム：セ
レンのモル比が２４：２５：５１であることがわかっ
た。Example 1 A copper-coated selenium fine powder (copper: selenium having a molar ratio of about 1: 1) prepared by the method of JP-A-54-67851 was placed in a cyanic electrodeposition bath containing 1.0 mol / l of indium.
2) and electrodeposited for 10 minutes while stirring at a current density of 3 A / dm 2 using a glass substrate provided with a molybdenum thin film electrode on the surface as a cathode.
A laminate having a 10 μm-thick indium electrodeposited layer was obtained. Analysis of the electrodeposited layer revealed that the molar ratio of copper: indium: selenium was 24:25:51.
【００１１】次いでこの積層板をセレン粉末を入れたボ
ートと共に真空加熱炉中に装入し、１０-3Torrの真空と
した後に２００℃に１時間続いて４００℃に２時間熱処
理したところ、銅：インジウム：セレンの mol比が１：
１：２であってＰ型の結晶性のよい太陽電池吸収層が得
られた。Next, this laminate was put into a vacuum heating furnace together with a boat containing selenium powder, and a vacuum of 10 −3 Torr was applied. After that, the laminate was heat-treated at 200 ° C. for 1 hour, then at 400 ° C. for 2 hours. : Indium: Selenium mol ratio is 1:
1: 2, and a P-type solar cell absorption layer with good crystallinity was obtained.
【００１２】[0012]
【発明の効果】本発明の太陽電池吸収層の製造方法によ
れば、操作条件の制御が容易な分散電着方法を利用して
銅：インジウム：セレンの原子組成が所望の範囲内にあ
って結晶性のよい太陽電池吸収層を生産性よく製造する
ことができ、経済的効果が大きい。According to the method of manufacturing a solar cell absorption layer of the present invention, the atomic composition of copper: indium: selenium is within a desired range by using a dispersion electrodeposition method in which operating conditions are easily controlled. A solar cell absorption layer having good crystallinity can be manufactured with high productivity, and the economic effect is great.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01L 31/04 C01B 19/00 C23C 20/00 ＪＩＣＳＴファイル（ＪＯＩＳ)──────────────────────────────────────────────────続 き Continuation of the front page (58) Fields surveyed (Int. Cl. 6 , DB name) H01L 31/04 C01B 19/00 C23C 20/00 JICST file (JOIS)
Claims (1)
ンジウムメッキ浴を用いて該銅被覆セレン微粉末を分散
含有するインジウム電着層を導電性基板上に形成し、次
いで熱処理して該電着層を銅−インジウム−セレン三元
合金層に転換することを特徴とする太陽電池吸収層の製
造方法。1. An indium electrodeposition layer containing a copper-coated selenium fine powder dispersed therein is formed on a conductive substrate using an indium plating bath in which the copper-coated selenium fine powder is dispersed and suspended, and then heat-treated. A method for producing a solar cell absorption layer, comprising converting an electrodeposition layer to a copper-indium-selenium ternary alloy layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5258280A JP2874149B2 (en) | 1993-10-15 | 1993-10-15 | Method for manufacturing solar cell absorption layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5258280A JP2874149B2 (en) | 1993-10-15 | 1993-10-15 | Method for manufacturing solar cell absorption layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07115213A JPH07115213A (en) | 1995-05-02 |
| JP2874149B2 true JP2874149B2 (en) | 1999-03-24 |
Family
ID=17318058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5258280A Expired - Lifetime JP2874149B2 (en) | 1993-10-15 | 1993-10-15 | Method for manufacturing solar cell absorption layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2874149B2 (en) |
-
1993
- 1993-10-15 JP JP5258280A patent/JP2874149B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07115213A (en) | 1995-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2806469B2 (en) | Method for manufacturing solar cell absorption layer | |
| US7297868B2 (en) | Preparation of CIGS-based solar cells using a buffered electrodeposition bath | |
| JP3513154B2 (en) | Solar cell having chalcopyrite absorption layer | |
| US5137835A (en) | Method for manufacturing a chalcopyrite solar cell | |
| US7582506B2 (en) | Precursor containing copper indium and gallium for selenide (sulfide) compound formation | |
| US5275714A (en) | Method of producing an absorber layer for solar cells with the aid of electrodeposition | |
| EP0021774B1 (en) | Photovoltaic cells and a method of making such cells | |
| KR19990071500A (en) | A method for manufacturing a precursor film of CUXLNYGAZSEN (X = 0-2, Y = 0-2, Z = 0-2, N = 0-3) by electrodeposition to produce a high efficiency solar cell | |
| WO1990015445A1 (en) | Improved group i-iii-vi2 semiconductor films for solar cell application | |
| US3492167A (en) | Photovoltaic cell and method of making the same | |
| US20110284078A1 (en) | Method of forming cadmium telluride thin film | |
| US20040131792A1 (en) | Electroless deposition of cu-in-ga-se film | |
| US8409418B2 (en) | Enhanced plating chemistries and methods for preparation of group IBIIIAVIA thin film solar cell absorbers | |
| JPH10135501A (en) | Semiconductor device, its manufacture and solar cell | |
| US20120288986A1 (en) | Electroplating method for depositing continuous thin layers of indium or gallium rich materials | |
| JP2874149B2 (en) | Method for manufacturing solar cell absorption layer | |
| JP2940782B2 (en) | Method for manufacturing solar cell absorption layer | |
| JPH09321326A (en) | Manufacturing cis thin film solar cell and forming copper-indium-selenium alloy | |
| JP2974107B2 (en) | Method for manufacturing solar cell absorption layer | |
| Rastogi et al. | Improvements in stoichiometry and stability of p‐Cu x S in thin‐film CdS solar cells | |
| WO1998048079A1 (en) | Preparation of copper-indium-gallium-diselenide precursor films by electrodeposition for fabricating high efficiency solar cells | |
| JPH09148602A (en) | Cis type solar battery and its manufacture | |
| JPH08120479A (en) | Plating and production of solar cell | |
| JP2920903B2 (en) | Manufacturing method of thin film solar cell | |
| JPH0794765A (en) | Method of fabrication of solar cell absorption layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19981208 |