JPH04280477A - Manufacture of thin film solar cell - Google Patents
Manufacture of thin film solar cellInfo
- Publication number
- JPH04280477A JPH04280477A JP3042095A JP4209591A JPH04280477A JP H04280477 A JPH04280477 A JP H04280477A JP 3042095 A JP3042095 A JP 3042095A JP 4209591 A JP4209591 A JP 4209591A JP H04280477 A JPH04280477 A JP H04280477A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- thin film
- gallium
- metal electrode
- solar cell
- 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.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- 239000010408 film Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011669 selenium Substances 0.000 claims abstract description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052733 gallium Inorganic materials 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 20
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229920001021 polysulfide Polymers 0.000 claims description 6
- 239000005077 polysulfide Substances 0.000 claims description 6
- 150000008117 polysulfides Polymers 0.000 claims description 6
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 7
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910000807 Ga alloy Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PKLGPLDEALFDSB-UHFFFAOYSA-N [SeH-]=[Se].[In+3].[Cu+2].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se] Chemical compound [SeH-]=[Se].[In+3].[Cu+2].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se] PKLGPLDEALFDSB-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- LNGDVJCTPDAJRM-UHFFFAOYSA-N [SeH-]=[Se].[In+3].[Ag+].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se] Chemical compound [SeH-]=[Se].[In+3].[Ag+].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se] LNGDVJCTPDAJRM-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical group [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
- Y02E10/541—CuInSe2 material PV cells
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は金属電極上に形成された
Ｉ−ＩＩＩ −ＶＩ 族化合物半導体を用いた接合を有
する薄膜太陽電池の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a thin film solar cell having a junction using a group I-III-VI compound semiconductor formed on a metal electrode.
【０００２】0002
【従来の技術】Ｉ−ＩＩＩ −ＶＩ 族化合物半導体、
例えば銅インジウムダイセレナイド （ＣｕＩｎＳｅ２
），銅インジウムサルフアイド （ＣｕＩｎＳ２ ）
，銀インジウムダイセレナイド（ＡｇＩｎＳｅ２ ）
は光学バンドギャップが１．０ 〜１．８ｅＶ の範囲
にあり、バンドギャップ１．７ｅＶ のシリコンと異な
る光学バンドギャップを有するものが得られるため、そ
の利用が期待されている。近年、薄膜形成技術の進展に
より、薄膜太陽電池素子材料としてのこれらの物質は一
層注目されている。例えばＣｕＩｎＳｅ２ は、その光
学バンドギャップが約１ｅＶであって直接遷移形の帯構
造を持ち、ｐおよびｎ型の導電性を示す。また、バンド
ギャップ２．４ｅＶ のＣｄＳとは格子の不整合も１％
程度であり、従ってｎ型ＣｄＳを窓層材料として用いた
ｐ型ＣｕＩｎＳｅ２ のヘテロ接合を有する薄膜太陽電
池の開発が進められている。ＣｕＩｎＳｅ２ の薄膜層
を含むヘテロ接合薄膜太陽電池の金属電極とＣｕＩｎＳ
ｅ２ 薄膜層との接着性をガリウムを用いて改善して、
光起電力装置の製造工程における処理温度の上昇を可能
にすることは、特開平２−９４６６９ 号公報で公知で
ある。図２は上記公報に記載されている薄膜太陽電池の
一部の断面図で、厚さ１〜４ｍｍのガラス基板１上には
厚さ０．２ 〜２μｍのモリブデン （Ｍｏ） からな
る金属電極層２が形成される。半導体層は、ｐ型半導体
層として厚さ１〜３μｍのＣｕＩｎＳｅ２ 薄膜層４、
ｎ型半導体層として厚さ２５０ 〜５００ Åの硫化カ
ドミウム （ＣｄＳ） 薄膜層５および伝導性で広いバ
ンドギャップを有し、窓層としてのｎ型半導体層である
厚さ１．５ 〜３．５ μｍの酸化亜鉛 （ＺｎＯ）
薄膜層６からなる。金属電極層２とＣｕＩｎＳｅ２ 薄
膜層４との間には両層の接着性を向上させるため、ガリ
ウム （Ｇａ） を含む薄膜層３が形成される。層６の
上にはスパッタリング， 蒸着またはめっき法によりア
ルミニウム （Ａｌ） からなる金属電極層７が形成さ
れる。[Prior Art] Group I-III-VI compound semiconductors,
For example, copper indium di-selenide (CuInSe2
), copper indium sulfide (CuInS2)
, silver indium diselenide (AgInSe2)
has an optical band gap in the range of 1.0 to 1.8 eV, and is expected to be used because it provides a material with an optical band gap different from that of silicon, which has a band gap of 1.7 eV. In recent years, with the progress of thin film formation technology, these substances have attracted more attention as materials for thin film solar cell elements. For example, CuInSe2 has an optical bandgap of about 1 eV, has a direct transition type band structure, and exhibits p- and n-type conductivity. In addition, the lattice mismatch with CdS, which has a band gap of 2.4 eV, is 1%.
Therefore, development of a thin film solar cell having a p-type CuInSe2 heterojunction using n-type CdS as the window layer material is progressing. Metal electrodes of heterojunction thin film solar cells containing thin film layers of CuInSe2 and CuInS
e2 Improving the adhesion with the thin film layer using gallium,
It is known from JP-A-2-94669 that it is possible to increase the processing temperature in the manufacturing process of photovoltaic devices. FIG. 2 is a cross-sectional view of a part of the thin film solar cell described in the above publication, in which a metal electrode layer made of molybdenum (Mo) with a thickness of 0.2 to 2 μm is placed on a glass substrate 1 with a thickness of 1 to 4 mm. 2 is formed. The semiconductor layer is a CuInSe2 thin film layer 4 with a thickness of 1 to 3 μm as a p-type semiconductor layer,
A cadmium sulfide (CdS) thin film layer 5 with a thickness of 250 to 500 Å as an n-type semiconductor layer and a 1.5 to 3.5 Å thick n-type semiconductor layer with conductivity and a wide bandgap as a window layer. μm zinc oxide (ZnO)
It consists of a thin film layer 6. A thin film layer 3 containing gallium (Ga) is formed between the metal electrode layer 2 and the CuInSe2 thin film layer 4 in order to improve the adhesion between both layers. A metal electrode layer 7 made of aluminum (Al) is formed on the layer 6 by sputtering, vapor deposition, or plating.
【０００３】ここで、ガリウム （Ｇａ） を含む薄膜
層３は、金属電極層２の上に１７原子％のガリウムを有
する銅ガリウム合金のマグネトロン・スパッタリングに
より、厚さ２０００〜３０００Åに形成される。またＣ
ｕＩｎＳｅ２ 薄膜層４は薄膜層３の上に、同じくマグ
ネトロン・スパッタリングによって厚さ３０００〜４０
００Åのインジウム（Ｉｎ） 薄膜層を形成した後、セ
レン （Ｓｅ） 雰囲気中で加熱するセレン化法によっ
て形成される。すなわち、窒素ガスで希釈された１２％
Ｈ２ Ｓｅを含む気体で満たされた加熱炉内で、金属電
極層２、ガリウムを含む層３およびインジウム （Ｉｎ
） 薄膜層が形成されたガラス基板１を、まず３００
℃で１５〜２０分間加熱し、次に４５０ ℃において３
０分間加熱することによってＣｕＩｎＳｅ２ 薄膜層４
を得る。このようにＣｕＩｎＳｅ２ は、セレン （Ｓ
ｅ） 雰囲気中で加熱によって薄膜層３の中の銅とイン
ジウムおよびセレンの相互拡散により生成する。Here, the thin film layer 3 containing gallium (Ga) is formed on the metal electrode layer 2 to a thickness of 2000 to 3000 Å by magnetron sputtering of a copper-gallium alloy containing 17 atomic percent gallium. Also C
The uInSe2 thin film layer 4 is deposited on the thin film layer 3 to a thickness of 3000 to 40 nm by magnetron sputtering.
It is formed by a selenization method in which an indium (In) thin film layer with a thickness of 0.00 Å is formed and then heated in a selenium (Se) atmosphere. i.e. 12% diluted with nitrogen gas
In a heating furnace filled with gas containing H2Se, a metal electrode layer 2, a layer 3 containing gallium, and an indium (In
) The glass substrate 1 on which the thin film layer was formed was first
℃ for 15-20 minutes, then at 450℃ for 3
CuInSe2 thin film layer 4 by heating for 0 min
get. In this way, CuInSe2 is selenium (S
e) Produced by mutual diffusion of copper, indium, and selenium in the thin film layer 3 by heating in an atmosphere.
【０００４】以上の製造工程において、ガリウムを含む
層３を設けることによって、モリブデン層とＣｕＩｎＳ
ｅ２ 薄膜層４との接着性が改善されると記されている
。すなわち、ガラス基板１の上のモリブデン金属層２と
その上のＣｕＩｎＳｅ２ 薄膜層４との接着が必ずしも
十分ではないときには、ＣｕＩｎＳｅ２ 薄膜層にしわ
， そりまたは剥離を生ずることがあるが、モリブデン
金属電極層２の近傍にガリウムが存在することにより接
着性が改善され、薄膜太陽電池の製造工程における処理
温度の上昇が可能となり、変換効率が向上する効果があ
る。In the above manufacturing process, by providing the layer 3 containing gallium, the molybdenum layer and CuInS
e2 It is described that the adhesion with the thin film layer 4 is improved. That is, when the adhesion between the molybdenum metal layer 2 on the glass substrate 1 and the CuInSe2 thin film layer 4 thereon is not necessarily sufficient, wrinkles, warping, or peeling may occur in the CuInSe2 thin film layer, but the molybdenum metal electrode layer The presence of gallium in the vicinity of 2 improves adhesion, makes it possible to increase the processing temperature in the manufacturing process of thin film solar cells, and has the effect of improving conversion efficiency.
【０００５】[0005]
【発明が解決しようとする課題】上記従来技術によれば
、モリブデン金属電極層上の近傍にガリウムを含む層を
設けることによって界面の接着性が向上する効果が得ら
れる。しかし従来技術ではスパッタリングによって形成
したガリウム， 銅を含む層およびインジウム薄膜層を
セレン雰囲気中で加熱することによりＣｕＩｎＳｅ２
薄膜層を得る。このため加熱履歴によってガリウムがＣ
ｕＩｎＳｅ２ 薄膜層内に拡散し、モリブデン金属電極
層上の界面および近傍におけるガリウム濃度が低下し、
剥離を生じない十分な接着を得ることができない欠点が
ある。According to the above-mentioned prior art, by providing a layer containing gallium in the vicinity of the molybdenum metal electrode layer, it is possible to obtain the effect of improving the adhesion of the interface. However, in the conventional technology, CuInSe2 is formed by heating a layer containing gallium and copper and an indium thin film layer formed by sputtering in a selenium atmosphere.
Obtain a thin film layer. Therefore, depending on the heating history, gallium becomes C
uInSe2 diffuses into the thin film layer, reducing the gallium concentration at and near the interface on the molybdenum metal electrode layer,
It has the disadvantage that it is not possible to obtain sufficient adhesion without peeling.
【０００６】本発明の目的は、金属電極との接着性改善
のためにＩ−ＩＩＩ −ＶＩ 化合物半導体層の金属電
極との近傍に入れられるガリウムの加熱による拡散を防
止して剥離を生じない健全な接着が行われる薄膜太陽電
池の製造方法を提供することにある。An object of the present invention is to prevent the diffusion of gallium, which is placed in the vicinity of the metal electrode of the I-III-VI compound semiconductor layer near the metal electrode, in order to improve the adhesion with the metal electrode, thereby preventing peeling. An object of the present invention is to provide a method for manufacturing a thin film solar cell in which adhesive bonding is performed.
【０００７】[0007]
【課題を解決するための手段】上記の目的を達成するた
めに、本発明は、Ｉ−ＩＩＩ −ＶＩ 族化合物半導体
層の金属電極層に近い側にガリウムを含む層が介在する
薄膜太陽電池の製造方法において、金属電極層上にガリ
ウムを含む層を形成したのち、その層の表面に硫黄被膜
を被着し、次いでその被膜の上に加熱処理を含む工程に
よりＩ−ＩＩＩ −ＶＩ 族化合物半導体層を形成する
ものとする。
そしてＩ−ＩＩＩ −ＶＩ 族化合物が銅インジウムダ
イセレナイド （ＣｕＩｎＳｅ２ ） であって、金属
電極層上に銅ガリウム層を形成し、その銅ガリウム層の
表面に硫黄を含む溶液を接触させて硫黄被膜を形成し、
次いでその被膜の上に少なくともインジウム層を積層し
、セレンを含む雰囲気中で加熱してＣｕＩｎＳｅ２ 層
を形成することが効果的である。さらに、表面に硫黄被
膜を被着した銅ガリウム層の上にインジウム層のほかに
銅層を積層することも有効である。また、硫黄を含む溶
液が多硫化アンモニウム溶液であることも有効である。[Means for Solving the Problems] In order to achieve the above object, the present invention provides a thin film solar cell in which a layer containing gallium is interposed on the side of the I-III-VI compound semiconductor layer near the metal electrode layer. In the manufacturing method, a layer containing gallium is formed on a metal electrode layer, a sulfur film is deposited on the surface of the layer, and then a group I-III-VI compound semiconductor is formed by a step including heat treatment on the film. shall form a layer. The I-III-VI group compound is copper indium di-selenide (CuInSe2), and a copper gallium layer is formed on the metal electrode layer, and a sulfur film is formed by contacting the surface of the copper gallium layer with a solution containing sulfur. form,
Next, it is effective to stack at least an indium layer on the film and heat it in an atmosphere containing selenium to form a CuInSe2 layer. Furthermore, it is also effective to laminate a copper layer in addition to the indium layer on the copper gallium layer whose surface is coated with a sulfur film. It is also effective that the sulfur-containing solution is an ammonium polysulfide solution.
【０００８】[0008]
【作用】ガリウムを含む層を形成したのち、その表面に
硫黄 （Ｓ）被膜を被着するため、ガリウムを含む層の
表面に硫黄の数原子層からなる薄い被膜が形成される。
硫黄被膜の存在により、後工程の加熱処理によるガリウ
ムの拡散が防止され、金属電極層上の界面および近傍に
ガリウムが残存するため、剥離を生じない十分な接着を
得ることができる。[Operation] After forming a layer containing gallium, a sulfur (S) film is applied to its surface, so a thin film consisting of several atomic layers of sulfur is formed on the surface of the layer containing gallium. The presence of the sulfur film prevents gallium from diffusing during the heat treatment in the post-process, and gallium remains at and near the interface on the metal electrode layer, making it possible to obtain sufficient adhesion without peeling.
【０００９】[0009]
【実施例】図１は本発明の一実施例により製造されたＣ
ｕＩｎＳｅ２ 薄膜層を用いたヘテロ接合を含む太陽電
池の一部の断面を示し、図２と共通の部分には同一の符
号が付されている。図において、厚さ１ｍｍのガラス基
板１上には厚さ２μｍのモリブデン （Ｍｏ） からな
る金属電極層２が形成される。その上に形成された半導
体層は、ｐ型半導体層の厚さ２μｍのＣｕＩｎＳｅ２
薄膜層４、ｎ型半導体層の厚さ４００ Åの硫化カドミ
ウム （ＣｄＳ） 薄膜層５および電極層を兼ねる窓層
としてのｎ型半導体層である厚さ３μｍの酸化亜鉛 （
ＺｎＯ） 薄膜層６からなる。ＺｎＯ層６の上にはアル
ミニウム （Ａｌ） からなる条状金属電極層７が形成
されている。金属電極層２とＣｕＩｎＳｅ２ 薄膜層４
との間には、銅−ガリウムからなる厚さ３０００Åの薄
膜層３および硫黄被膜８が形成されている。[Example] Figure 1 shows a C manufactured according to an embodiment of the present invention.
2 shows a cross section of a part of a solar cell including a heterojunction using a uInSe2 thin film layer, and parts common to FIG. 2 are given the same reference numerals. In the figure, a metal electrode layer 2 made of molybdenum (Mo) with a thickness of 2 μm is formed on a glass substrate 1 with a thickness of 1 mm. The semiconductor layer formed thereon is a p-type semiconductor layer of CuInSe2 with a thickness of 2 μm.
Cadmium sulfide (CdS) with a thickness of 400 Å as the thin film layer 4 and the n-type semiconductor layer; Zinc oxide with a thickness of 3 μm as the n-type semiconductor layer as the thin film layer 5 and the window layer that also serves as the electrode layer.
(ZnO) thin film layer 6. A strip metal electrode layer 7 made of aluminum (Al) is formed on the ZnO layer 6. Metal electrode layer 2 and CuInSe2 thin film layer 4
A thin film layer 3 made of copper-gallium having a thickness of 3000 Å and a sulfur coating 8 are formed between the two.
【００１０】このような構造の構成には、まず、スパッ
タリングによりモリブデン電極層２を形成したのち、１
７原子％のガリウムを有する銅ガリウム合金のスパッタ
リングによって銅−ガリウムからなる薄膜層３を形成す
る。続いて、多硫化アンモニウム溶液に浸漬し、５０℃
にて３時間放置して薄膜層３の表面に硫黄被膜８を形成
する。ここで、多硫化アンモニウムは化学式（（ＮＨ４
） ２ Ｓｘ ， ｘ＞１） で表すことのできる硫
黄過剰の硫化アンモニウムである。この多硫化アンモニ
ウム溶液への浸漬により、銅ガリウム層３の表面には約
１０ｎｍの厚さの硫黄を主成分とする被膜８が形成され
る。オージエ電子分光分析によれば、硫黄被膜は多硫化
アンモニウム中の硫黄が銅ガリウム表面に吸着されて硫
黄の数原子層からなる薄膜として残存していることが認
められた。To construct such a structure, first, a molybdenum electrode layer 2 is formed by sputtering, and then a molybdenum electrode layer 2 is formed by sputtering.
A thin copper-gallium layer 3 is formed by sputtering a copper-gallium alloy with 7 atomic percent gallium. Subsequently, it was immersed in an ammonium polysulfide solution and heated to 50°C.
A sulfur film 8 is formed on the surface of the thin film layer 3 by leaving it for 3 hours. Here, ammonium polysulfide has the chemical formula ((NH4
) 2 Sx , x>1) It is ammonium sulfide with excess sulfur. By immersion in this ammonium polysulfide solution, a coating 8 containing sulfur as a main component and having a thickness of about 10 nm is formed on the surface of the copper gallium layer 3. According to Auger electron spectroscopy, it was confirmed that the sulfur film in the ammonium polysulfide was adsorbed onto the copper gallium surface and remained as a thin film consisting of several atomic layers of sulfur.
【００１１】再び、スパッタリングによって厚さ２００
０Åの銅 （Ｃｕ） 薄膜層、厚さ４４００Åのインジ
ウム （Ｉｎ） 薄膜層を連続的に形成し、セレン化法
によってＣｕＩｎＳｅ２ 薄膜層４を形成する。セレン
化法として、１２％Ｈ２ Ｓｅを含む窒素ガスで満たさ
れた加熱炉内で、薄膜層が形成されたガラス基板１を５
００ ℃で３０分間加熱することによってＣｕＩｎＳｅ
２ 薄膜層を得る。最後にスパッタリングおよびパター
ニングにより、アルミニウム電極層７を形成する。[0011] Again, a thickness of 200 mm was obtained by sputtering.
A copper (Cu) thin film layer with a thickness of 0 Å and an indium (In) thin film layer with a thickness of 4400 Å are successively formed, and a CuInSe2 thin film layer 4 is formed by a selenization method. In the selenization method, a glass substrate 1 on which a thin film layer has been formed is heated in a heating furnace filled with nitrogen gas containing 12% H2Se.
CuInSe by heating at 00 °C for 30 min
2 Obtain a thin film layer. Finally, an aluminum electrode layer 7 is formed by sputtering and patterning.
【００１２】以上の製造方法により得たモリブデン層２
上の銅ガリウム層３およびＣｕＩｎＳｅ２薄膜層４につ
いてのオージエ分析では、ガリウムは銅−ガリウム層３
のみに検出され、ＣｕＩｎＳｅ２ 薄膜層４内には検出
されなかった。
これは、銅ガリウム層３上の硫黄被膜８の存在により、
ガリウムのＣｕＩｎＳｅ２ 薄膜層４への拡散が防止さ
れていることを示す。Molybdenum layer 2 obtained by the above manufacturing method
Auger analysis for the top copper-gallium layer 3 and the CuInSe2 thin film layer 4 shows that gallium is
It was detected only in the CuInSe2 thin film layer 4. This is due to the presence of the sulfur film 8 on the copper gallium layer 3.
This shows that diffusion of gallium into the CuInSe2 thin film layer 4 is prevented.
【００１３】また以上の製造方法を用いて得た薄膜太陽
電池において、ＣｕＩｎＳｅ２ 薄膜に、しわ， 剥離
等はみられなかった。セレン化工程での５００ ℃加熱
によっても剥離が生じないことは、本実施例でのＣｕＩ
ｎＳｅ２ 薄膜とモリブデン層との接着が良いことを示
す。そして、ＣｕＩｎＳｅ２ は、セレン化工程で銅，
インジウムおよびセレンの相互拡散により生成するか
ら、より高い温度で加熱できることは、短時間で良質な
膜を得ることを可能とし、太陽電池特性の改善および製
造時間の短縮をはかり得ることを意味する。[0013] Furthermore, in the thin film solar cell obtained using the above manufacturing method, no wrinkles, peeling, etc. were observed in the CuInSe2 thin film. The fact that peeling does not occur even when heated at 500 °C in the selenization process indicates that CuI in this example
This shows that the adhesion between the nSe2 thin film and the molybdenum layer is good. Then, CuInSe2 is made from copper during the selenization process.
Since it is produced by interdiffusion of indium and selenium, the ability to heat it at higher temperatures means that it is possible to obtain a high-quality film in a short time, improving solar cell characteristics and shortening manufacturing time.
【００１４】本実施例により得た薄膜太陽電池は、従来
技術による太陽電池と比べ、約５％の変換効率の向上を
示した。これは主として解放電圧 （ＶＯＣ） の増大
、すなわち従来技術での約０．４３ボルトから約０．４
８ボルトへ増大したことによるもので、接着性が向上し
、セレン化工程での加熱処理温度を高くすることができ
たことによるものである。The thin film solar cell obtained in this example showed an improvement in conversion efficiency of about 5% compared to the solar cell according to the prior art. This is primarily due to an increase in open circuit voltage (VOC), from about 0.43 volts in the prior art to about 0.4 volts.
This is due to the increase to 8 volts, improved adhesiveness, and the ability to increase the heat treatment temperature in the selenization process.
【００１５】上記の実施例ではガリウムと銅の合金を用
い、さらに純銅の層も形成したが、銅ガリウム層の厚さ
を厚くしてそこからＣｕＩｎＳｅ２ の形成に十分な銅
を供給することができれば、純銅薄膜層を形成しないで
インジウム薄膜層のみを積層してもよい。また、ガリウ
ムを含む層に銅ばかりでなくインジウムを含ませてもよ
い。なお、本発明はＣｕＩｎＳｅ２ を用いた薄膜太陽
電池に限定されず、一面に金属電極が接するＩ−ＩＩＩ
−ＶＩ 化合物半導体薄膜層を有する薄膜太陽電池に
実施することができる。In the above embodiment, an alloy of gallium and copper was used, and a layer of pure copper was also formed, but if the thickness of the copper gallium layer could be increased and enough copper could be supplied from there to form CuInSe2, it would be possible to Alternatively, only an indium thin film layer may be laminated without forming a pure copper thin film layer. Furthermore, the layer containing gallium may contain not only copper but also indium. Note that the present invention is not limited to thin-film solar cells using CuInSe2, but is applicable to I-III solar cells in which a metal electrode is in contact with one surface.
-VI It can be implemented in a thin film solar cell having a compound semiconductor thin film layer.
【００１６】[0016]
【発明の効果】本発明によれば、金属電極上にガリウム
を含む層を設け、その層の上に硫黄被膜を形成したのち
、Ｉ−ＩＩＩ −ＶＩ 族化合物半導体薄膜層を積層す
ることにより、後工程における加熱処理の際にガリウム
の半導体薄膜層への拡散が防止され、金属電極層との界
面近傍におけるガリウム含有による半導体薄膜層の接着
性改善の効果を維持することができた。従って、例えば
ＣｕＩｎＳｅ２ 薄膜を得るためのセレン化の加熱処理
温度を金属電極層との剥離を生ずることなく５００ ℃
にあげることができ、短時間でセレン化ができるように
なるなど、良質のＩ−ＩＩＩ −ＶＩ 族化合物半導体
薄膜層を得ることが可能となった。このため薄膜太陽電
池の変換効率が向上した。According to the present invention, a layer containing gallium is provided on a metal electrode, a sulfur film is formed on the layer, and then a group I-III-VI compound semiconductor thin film layer is laminated. Diffusion of gallium into the semiconductor thin film layer was prevented during the heat treatment in the post-process, and the effect of improving the adhesion of the semiconductor thin film layer due to the inclusion of gallium near the interface with the metal electrode layer could be maintained. Therefore, for example, the heat treatment temperature for selenization to obtain a CuInSe2 thin film can be adjusted to 500 °C without peeling from the metal electrode layer.
It has become possible to obtain a high-quality I-III-VI compound semiconductor thin film layer, such as by being able to perform selenization in a short time. This has improved the conversion efficiency of thin-film solar cells.
【図１】本発明の一実施例による薄膜太陽電池の一部断
面図FIG. 1 is a partial cross-sectional view of a thin film solar cell according to an embodiment of the present invention.
【図２】従来の薄膜太陽電池の一部断面図[Figure 2] Partial cross-sectional view of a conventional thin-film solar cell
１ ガラス基板 ２ 金属電極層 ３ 銅ガリウム薄膜層 ４ ＣｕＩｎＳｅ２ 薄膜層 ５ ＣｄＳ薄膜層 ６ ＺｎＯ薄膜層 ７ Ａｌ層 ８ 硫黄被膜 1 Glass substrate 2 Metal electrode layer 3 Copper gallium thin film layer 4 CuInSe2 thin film layer 5 CdS thin film layer 6 ZnO thin film layer 7 Al layer 8 Sulfur coating
Claims (4)
金属電極層に近い側にガリウムを含む層が介在する薄膜
太陽電池の製造方法において、金属電極層上にガリウム
を含む層を形成したのち、その層の表面に硫黄被膜を被
着し、次いでその被膜の上に加熱処理を含む工程により
Ｉ−ＩＩＩ −ＶＩ 族化合物半導体層を形成すること
を特徴とする薄膜太陽電池の製造方法。Claim 1: A method for manufacturing a thin-film solar cell in which a layer containing gallium is interposed on the side of a group I-III-VI compound semiconductor layer close to a metal electrode layer, in which the layer containing gallium is formed on the metal electrode layer; A method for producing a thin film solar cell, comprising: depositing a sulfur film on the surface of the layer, and then forming a group I-III-VI compound semiconductor layer on the film by a step including heat treatment.
ウムダイセレナイドであり、金属電極層上に銅ガリウム
層を形成し、その銅ガリウム層の表面に硫黄を含む溶液
を接触させて硫黄被膜を形成し、次いでその被膜の上に
少なくともインジウム層を積層したのち、セレンを含む
雰囲気中で加熱して銅インジウムダセイセレナイド層を
形成する請求項１記載の薄膜太陽電池の製造方法。2. The I-III-VI group compound is copper indium diselenide, and a copper gallium layer is formed on the metal electrode layer, and a sulfur coating is formed by contacting the surface of the copper gallium layer with a solution containing sulfur. 2. The method of manufacturing a thin-film solar cell according to claim 1, wherein at least an indium layer is laminated on the film, and then heated in an atmosphere containing selenium to form a copper indium selenide layer.
上にインジウム層のほかに銅層を積層する請求項２記載
の薄膜太陽電池の製造方法。3. The method for manufacturing a thin film solar cell according to claim 2, wherein a copper layer is laminated in addition to the indium layer on the copper gallium layer having a sulfur coating on its surface.
である請求項２あるいは３記載の薄膜太陽電池の製造方
法。4. The method for producing a thin film solar cell according to claim 2 or 3, wherein the sulfur-containing solution is an ammonium polysulfide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3042095A JP2815719B2 (en) | 1991-03-08 | 1991-03-08 | Manufacturing method of thin film solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3042095A JP2815719B2 (en) | 1991-03-08 | 1991-03-08 | Manufacturing method of thin film solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04280477A true JPH04280477A (en) | 1992-10-06 |
| JP2815719B2 JP2815719B2 (en) | 1998-10-27 |
Family
ID=12626444
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|---|---|---|---|
| JP3042095A Expired - Fee Related JP2815719B2 (en) | 1991-03-08 | 1991-03-08 | Manufacturing method of thin film solar cell |
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| Country | Link |
|---|---|
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|---|---|
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