JPH04282871A - Thin film solar cell - Google Patents
Thin film solar cellInfo
- Publication number
- JPH04282871A JPH04282871A JP3045274A JP4527491A JPH04282871A JP H04282871 A JPH04282871 A JP H04282871A JP 3045274 A JP3045274 A JP 3045274A JP 4527491 A JP4527491 A JP 4527491A JP H04282871 A JPH04282871 A JP H04282871A
- Authority
- JP
- Japan
- Prior art keywords
- film
- thin film
- solar cell
- zinc
- oriented
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 44
- 239000010408 film Substances 0.000 claims abstract description 102
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000011787 zinc oxide Substances 0.000 claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 7
- 238000000992 sputter etching Methods 0.000 claims abstract description 7
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 4
- 229910052725 zinc Inorganic materials 0.000 claims 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 3
- 239000010949 copper Substances 0.000 claims 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052951 chalcopyrite Inorganic materials 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 30
- 239000000758 substrate Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- -1 argon ions Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance 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】本発明は太陽光等の光エネルギー
を、ＣｕＩｎＳｅ２ のようなカルコパイライト型化合
物を光電変換層とする半導体接合により電気エネルギー
に変換する薄膜太陽電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film solar cell that converts light energy such as sunlight into electrical energy by a semiconductor junction using a chalcopyrite type compound such as CuInSe2 as a photoelectric conversion layer.
【０００２】0002
【従来の技術】ＣｕＩｎＳｅ２ （ 以下ＣＩＳと略す
） は直接遷移型のバンド構造を有し、そのバンドギャ
ップが約１ｅＶであってシリコンの１．７ ｅＶより小
さいことから、太陽光スペクトルを長波長側まで有効に
活用できるため、高効率の太陽電池として期待されてい
る。またＣｕ／Ｉｎの組成比で伝導型が制御できるため
、ＰＮ接合形成が容易である。このような利点により、
現在活発な研究開発が行われている。[Prior Art] CuInSe2 (hereinafter abbreviated as CIS) has a direct transition type band structure, and its band gap is about 1 eV, which is smaller than silicon's 1.7 eV, so it shifts the solar spectrum to the long wavelength side. It is expected to be used as a highly efficient solar cell because it can be used effectively up to Furthermore, since the conductivity type can be controlled by the composition ratio of Cu/In, it is easy to form a PN junction. With these advantages,
Active research and development is currently underway.
【０００３】ＣＩＳを用いた太陽電池でよく知られてい
るのは、光入射側の窓層に、バンドギャップ２．４ ｅ
Ｖで、ＣＩＳとは格子の不整合が１％以下であるｎ型Ｃ
ｄＳを用いてｐ型ＣＩＳとヘテロ接合を形成したもので
ある。
このような薄膜太陽電池は図２に示すように、ガラス，
アルミナなどの基板１上にＭｏなどのオーム性接触用
の金属電極２を形成し、その上にｐ型ＣＩＳ膜３， ｎ
型ＣｄＳ膜４を順次積層し、さらにＺｎＯなどの透明電
極５を形成してなるものがあげられる。ＣＩＳ薄膜の形
成方法としては、Ｃｕ， Ｉｎ， Ｓｅを基板の一面上
の金属電極の上に各々層状に形成してその後に加熱して
形成する方法、セレン源としてセレン化水素 （ＳｅＨ
２） を用い、その雰囲気中でＣｕ， Ｉｎ積層膜を加
熱することにより作成する方法、あるいはこれらとは異
なり、各々の元素を含むソースより同時に蒸着， スパ
ッタリングを行って基板上にＣＩＳ膜形成を行う方法が
知られている。A well-known solar cell using CIS has a bandgap of 2.4 e in the window layer on the light incident side.
CIS is an n-type C with a lattice mismatch of 1% or less.
A heterojunction with p-type CIS is formed using dS. As shown in Figure 2, such thin-film solar cells are made of glass,
A metal electrode 2 such as Mo for ohmic contact is formed on a substrate 1 such as alumina, and a p-type CIS film 3, n
An example is one in which CdS type CdS films 4 are sequentially laminated and a transparent electrode 5 made of ZnO or the like is further formed. The CIS thin film can be formed by forming layers of Cu, In, and Se on a metal electrode on one surface of the substrate and then heating them, or by using hydrogen selenide (SeH) as a selenium source.
2) A method of forming a CIS film on a substrate by heating a stacked film of Cu and In in that atmosphere using There are known ways to do it.
【０００４】ＣｄＳ膜はＥＢ （エレクトロン・ビーム
） 蒸着法， スパッタ法， 浸漬法などで、ＺｎＯ膜
はスパッタ法でそれぞれ形成するのが一般的である。ま
た最近では、ＣｄＳ層４による光吸収ロスを極力低減す
るために、ＣｄＳ層の膜厚を１０００Å以下に薄くした
り、Ｃｄの一部をＺｎで置換して硫化亜鉛カドミウム
（ＣｄＺｎＳ） とすることにより光学ギャップを広げ
る （この時、同時に膜の電気抵抗は増加する） こと
が一般的になりつつある。この場合透明電極のＺｎＯ膜
がｎ＋ 層として一部ｎ膜の役割を担い、ＣｄＺｎＳ膜
はＺｎＯとＣＩＳの中間で両者の格子接合を取るための
バッファ層的な役割を担うことになる。[0004] CdS films are generally formed by EB (electron beam) evaporation, sputtering, dipping, etc., and ZnO films are generally formed by sputtering. Recently, in order to reduce the light absorption loss due to the CdS layer 4 as much as possible, the thickness of the CdS layer has been reduced to 1000 Å or less, and some of the Cd has been replaced with Zn to replace zinc cadmium sulfide.
(CdZnS) to widen the optical gap (at this time, the electrical resistance of the film increases at the same time) is becoming common. In this case, the ZnO film of the transparent electrode partially plays the role of an n film as an n+ layer, and the CdZnS film plays a role of a buffer layer between ZnO and CIS to form a lattice junction between the two.
【０００５】[0005]
【発明が解決しようとする課題】前記ＣＩＳ／ＣｄＺｎ
Ｓ／ＺｎＯ構造の薄膜太陽電池の高効率化を図るために
は、入射した太陽光を光電変換層であるＣＩＳ膜で有効
に吸収することが重要である。例えば他の薄膜太陽電池
であるアモルファス太陽電池においては、ガラス基板上
に主に熱ＣＶＤ法により形成するＳｎＯ２ からなる透
明電極の表面に形成条件の適正化によりテクスチャ化と
呼ばれる微細な凹凸をつけ、入射光を光電変換層に入射
する前に散乱させて太陽電池効率を高める技術がほぼ確
立している。ＣＩＳ太陽電池においても同様のテクスチ
ャ化により変換効率向上が期待できる。しかしながら、
ＣＩＳ太陽電池の場合には以下の点においてアモルファ
ス太陽電池の場合とは異なる。すなわち、ＣＩＳ太陽電
池はアモルファス太陽電池に比べて長波長光を利用する
が、材料的にＳｎＯ２ はＺｎＯに比べて長波長光の透
過率が劣るため、ＣＩＳ太陽電池では透明電極にＳｎＯ
２ ではなくＺｎＯを利用する必要がある。また、アモ
ルファス太陽電池においては、まず透明絶縁性基板上Ｓ
ｎＯ２ からなる透明電極を形成し、その上にアモルフ
ァスＳｉからなる光電変換層を形成するが、ＣＩＳ太陽
電池の場合には逆に基板上にＣＩＳ膜， ＣｄＺｎＳを
形成した後、その上に透明電極としてのＺｎＯ膜を形成
するプロセス順序となる。したがって、テクスチャ化Ｚ
ｎＯ膜を形成する場合に、下地であるＣｄＺｎＳとの接
触が電気的接触を含めて良好で、かつＣｄＺｎＳやＣＩ
Ｓに損傷を加えないことが必要である。[Problem to be solved by the invention] The CIS/CdZn
In order to improve the efficiency of a thin film solar cell having an S/ZnO structure, it is important that incident sunlight be effectively absorbed by a CIS film, which is a photoelectric conversion layer. For example, in an amorphous solar cell, which is another type of thin-film solar cell, fine irregularities called texturing are created by optimizing the formation conditions on the surface of a transparent electrode made of SnO2, which is formed mainly by thermal CVD on a glass substrate. The technology for increasing solar cell efficiency by scattering incident light before it enters the photoelectric conversion layer has almost been established. Similar texturing can also be expected to improve conversion efficiency in CIS solar cells. however,
CIS solar cells differ from amorphous solar cells in the following points. In other words, CIS solar cells use longer wavelength light than amorphous solar cells, but since SnO2 has a lower transmittance for long wavelength light than ZnO, CIS solar cells use SnO2 in the transparent electrode.
It is necessary to use ZnO instead of 2. In addition, in an amorphous solar cell, the S
A transparent electrode made of nO2 is formed, and a photoelectric conversion layer made of amorphous Si is formed on it, but in the case of a CIS solar cell, on the contrary, after forming a CIS film and CdZnS on a substrate, a transparent electrode is formed on it. This is the process order for forming a ZnO film. Therefore, texturing Z
When forming an nO film, the contact with the underlying CdZnS, including electrical contact, is good, and CdZnS and CI
It is necessary not to damage S.
【０００６】本発明の目的は、上述の観点に立って有効
かつ簡便にＺｎＯ膜のテクスチャ化を図ることができる
実用的な薄膜太陽電池を提供することにある。[0006] An object of the present invention is to provide a practical thin film solar cell in which a ZnO film can be textured effectively and easily from the above-mentioned viewpoint.
【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、一方の面に金属電極が接触するカルコ
パイライト型結晶薄膜の他方の面側にその薄膜との間に
接合を形成する硫化亜鉛カドミウム薄膜および酸化亜鉛
膜を順に積層してなる薄膜太陽電池において、酸化亜鉛
膜が硫化亜鉛カドミウム薄膜に近い側の＜００２＞配向
膜と遠い側の＜１１０＞配向膜よりなるものとする。ま
た、酸化亜鉛膜が硫化亜鉛カドミウム薄膜に近い側の＜
００２＞配向膜と遠い側の＜１００＞配向膜よりなるも
のとする。あるいは、酸化亜鉛膜が＜００２＞配向膜で
ありかつ成膜後表面をスパッタエッチングすることによ
りテクスチャ化してなる膜であるものとする。さらに、
酸化亜鉛膜が表面をスパッタエッチングすることにより
テクスチャ化された＜００２＞配向膜を複数積層化され
てなるものであることも有効である。＜００２＞配向酸
化亜鉛膜は銅のＫα線を光源とするＸ線回折における＜
００２＞ピーク強度が＜１１０＞ピーク強度および＜１
００＞ピーク強度のそれぞれの１０倍以上であること、
＜１１０＞配向酸化亜鉛膜は銅のＫα線を光源とするＸ
線回折における＜１１０＞ピーク強度が＜００２＞ピー
ク強度の１０倍以上であること、また＜１００＞配向酸
化亜鉛膜は銅のＫα線を光源とするＸ線回折における＜
１００＞ピーク強度が＜００２＞ピーク強度の１０倍以
上であることが望ましい。[Means for Solving the Problems] In order to achieve the above object, the present invention provides a bond between the other surface of a chalcopyrite crystal thin film that is in contact with a metal electrode on one surface. A thin film solar cell formed by sequentially laminating a zinc cadmium sulfide thin film and a zinc oxide film, in which the zinc oxide film consists of a <002> oriented film on the side close to the zinc sulfide cadmium thin film and a <110> oriented film on the far side shall be. In addition, the zinc oxide film is located on the side closer to the zinc sulfide cadmium thin film.
002> alignment film and a <100> alignment film on the far side. Alternatively, it is assumed that the zinc oxide film is a <002> oriented film and that the surface is textured by sputter etching after film formation. moreover,
It is also effective that the zinc oxide film is formed by laminating a plurality of <002> orientation films whose surfaces are textured by sputter etching. <002> Oriented zinc oxide film has <
002> peak intensity is <110> peak intensity and <1
00> Each peak intensity is 10 times or more,
<110> Oriented zinc oxide film
The <110> peak intensity in line diffraction is 10 times or more than the <002> peak intensity, and the <100> oriented zinc oxide film has
It is desirable that the 100> peak intensity is 10 times or more the <002> peak intensity.
【０００８】[0008]
【作用】六方柱ＣｄＺｎＳは一般に強い＜００２＞配向
を示す。そして＜００２＞配向の六方柱ＺｎＯ膜はこれ
と良好な接触性を示すが、＜１１０＞もしくは＜１００
＞配向を有するＺｎＯ膜はＣｄＺｎＳとの接触性は劣る
。そこでＣｄＺｎＳ薄膜の上にまず接触性の良い＜００
２＞配向ＺｎＯ膜を形成する。しかし、この膜は鏡面性
を有し、テクスチャ度が低いので、その上にテクスチャ
度の高い＜１１０＞もしくは＜１００＞配向を有するＺ
ｎＯ膜を積層するか、あるいは表面をスパッタエッチン
グしてテクスチャ化する。[Operation] Hexagonal columnar CdZnS generally exhibits a strong <002> orientation. A hexagonal columnar ZnO film with <002> orientation shows good contact with this, but <110> or <100>
>A ZnO film having an orientation has poor contact with CdZnS. Therefore, on top of the CdZnS thin film, we first applied
2> Form an oriented ZnO film. However, since this film has specularity and low texture, Z
Either an nO film is laminated or the surface is textured by sputter etching.
【０００９】[0009]
【実施例】次に本発明を実施例に基づいて説明する。図
１に実施例の太陽電池の構造を模式的に示し、図２と共
通の部分には同一の符号が付されている。本構造は次の
ように形成される。ガラス基板１上にオーム性接触用と
してスパッタ法によりＭｏ膜２を１μｍの厚さで形成す
る。次に基板を３５０ 〜４５０ ℃に保持した状態で
、３個のるつぼ内に各々別々に保持したＣｕ，Ｉｎ，
Ｓｅの蒸発源から基板に三元素を同時に加熱蒸着してカ
ルコパイライト型ＣＩＳ薄膜３を１．５ μｍの厚さで
形成する。さらにこの上にＣｄＺｎＳ膜４をＥＢ蒸着法
により１０００Åの厚さで形成する。ＣｄＺｎＳ膜は＜
００２＞配向の強い六方柱結晶として成長する。ＺｎＯ
膜は一般に六方柱結晶として成長するが、製造方法，
製造条件により配向性を制御できること、並びに配向性
によりＺｎＯ膜の性質が異なることが実験の結果明らか
になってきた。すなわち、最も広い条件で生成する＜０
０２＞配向膜は、面が平滑な鏡面となり、基板に垂直な
方向、すなわち膜厚方向の抵抗率が水平な方向の抵抗率
に比べて小さい。一方＜１００＞および＜１１０＞配向
を有するＺｎＯ膜は、比較的限定された製造条件範囲内
でのみ生成し、表面はテクスチャ化を示し、基板に水平
な方向の抵抗率が垂直な方向の抵抗率に比べ小さい。本
実施例ではＺｎＯ膜を２層構造とし、ＣｄＺｎＳに接す
る第一層５に＜００２＞配向の強い鏡面膜、その上の第
二層６に＜１１０＞配向の強いテクスチャ膜を次のよう
な方法で各々１μｍの厚さで形成した。＜００２＞配向
の強い第一層５は、ここでは通常のスパッタ法で２００
℃で形成したが、その他の方法でも容易に得ることが
できる。一方、＜１１０＞配向の強い第二層は、図３に
構成を模式的に示す有機金属ＣＶＤ （ＭＯＣＶＤ）
装置により形成した。このＭＯＣＶＤ装置の反応室１１
内のヒータ１２を備えた基台１３に基板を置いて１５０
℃に加熱し、ジエチル亜鉛１４を収容したバブラ１５
と純水１６を収容したバブラ１７にアルゴンガス供給系
１８からアルゴンガスを吹き込むことにより、排気系１
９で真空排気された反応室１１にジエチル亜鉛と水を供
給して基板上の第一層５の上に第二層６を成膜した。得
られた２種類の膜５， ６の配向性は、ＣｕのＫα線を
光源とするＸ線回折により評価した。＜００２＞と＜１
１０＞のピーク強度比 （＜１１０＞ピーク強度／＜０
０２＞ピーク強度） の値は第一層で１０−２以下、第
二層では約５０であり、第一層５が＜００２＞配向、第
二層６が＜１１０＞配向が強いことが確認された。EXAMPLES Next, the present invention will be explained based on examples. FIG. 1 schematically shows the structure of a solar cell according to an example, and parts common to those in FIG. 2 are given the same reference numerals. This structure is formed as follows. A Mo film 2 with a thickness of 1 μm is formed on a glass substrate 1 by sputtering for ohmic contact. Next, with the substrate held at 350 to 450°C, Cu, In, and
A chalcopyrite type CIS thin film 3 with a thickness of 1.5 μm is formed by simultaneously heating and vapor-depositing three elements onto a substrate from a Se evaporation source. Furthermore, a CdZnS film 4 is formed thereon to a thickness of 1000 Å by EB evaporation. The CdZnS film is <
002>Grows as a strongly oriented hexagonal columnar crystal. ZnO
Films generally grow as hexagonal crystals, but the manufacturing method,
Experiments have revealed that the orientation can be controlled by controlling the manufacturing conditions and that the properties of the ZnO film differ depending on the orientation. In other words, <0 generated under the widest conditions
02> The alignment film has a smooth mirror surface, and the resistivity in the direction perpendicular to the substrate, that is, in the film thickness direction, is smaller than the resistivity in the horizontal direction. ZnO films with <100> and <110> orientations, on the other hand, are produced only within a relatively limited range of manufacturing conditions, exhibit textured surfaces, and exhibit a resistivity in the direction horizontal to the substrate that is higher than that in the direction perpendicular to the substrate. It is small compared to the rate. In this example, the ZnO film has a two-layer structure, and the first layer 5 in contact with CdZnS is a mirror film with a strong <002> orientation, and the second layer 6 above it is a textured film with a strong <110> orientation as follows. Each layer was formed to a thickness of 1 μm using a method. The first layer 5 with a strong <002> orientation is formed here by a normal sputtering method with a
Although it was formed at °C, it can also be easily obtained by other methods. On the other hand, the second layer with strong <110> orientation is formed by metal organic CVD (MOCVD) whose structure is schematically shown in FIG.
It was formed by a device. Reaction chamber 11 of this MOCVD apparatus
Place the substrate on a base 13 equipped with a heater 12 inside
Bubbler 15 heated to ℃ and containing diethylzinc 14
By blowing argon gas from the argon gas supply system 18 into the bubbler 17 containing deionized water 16, the exhaust system 1
Diethyl zinc and water were supplied to the reaction chamber 11 which was evacuated in step 9 to form a second layer 6 on the first layer 5 on the substrate. The orientation of the two types of films 5 and 6 obtained was evaluated by X-ray diffraction using Cu Kα rays as a light source. <002> and <1
10> peak intensity ratio (<110> peak intensity/<0
02> peak intensity) is less than 10-2 in the first layer and approximately 50 in the second layer, confirming that the first layer 5 has a strong <002> orientation and the second layer 6 has a strong <110> orientation. It was done.
【００１０】次に、実施例２の太陽電池の形成方法につ
いて図４に基づいて説明する。ガラス基板１上にＭｏ膜
２， ＣＩＳ膜３， ＣｄＺｎＳ膜４を実施例１と全く
同様の方法によた形成する。次に、この上に実施例１と
同様、スパッタ法により＜００２＞配向の強いＺｎＯ膜
５を、この場合２．５ μｍの厚さで形成する。このま
まではＺｎＯ膜５の表面は前述した通り鏡面状態である
。この状態で基板を一対の電極の陰極側に置き、アルゴ
ンガスを用いてプラズマを発生させ、アルゴンイオンの
スパッタ効果で表面から約０．５ μｍの部分をスパッ
タエッチングする。スパッタエッチングされたＺｎＯ膜
５の表面７は、元の状態に比べてテクスチャ化した。さ
らにテクスチャ度を上げるためには必要に応じてＺｎＯ
膜５のスパッタによる形成と形成された膜表面のスパッ
タエッチングを交互に繰り返すことが有効である。Next, a method for forming the solar cell of Example 2 will be explained based on FIG. 4. A Mo film 2, a CIS film 3, and a CdZnS film 4 are formed on a glass substrate 1 in exactly the same manner as in Example 1. Next, as in Example 1, a ZnO film 5 having a strong <002> orientation is formed thereon by sputtering to a thickness of 2.5 μm in this case. In this state, the surface of the ZnO film 5 remains in a mirror-like state as described above. In this state, the substrate is placed on the cathode side of the pair of electrodes, plasma is generated using argon gas, and a portion approximately 0.5 μm from the surface is sputter-etched by the sputtering effect of argon ions. The sputter-etched surface 7 of the ZnO film 5 is textured compared to the original state. To further increase the degree of texture, use ZnO as necessary.
It is effective to alternately repeat forming the film 5 by sputtering and sputter etching the surface of the formed film.
【００１１】本発明の実施例１および実施例２のＣＩＳ
太陽電池を、下記の２種類の従来例の太陽電池と一緒に
ソーラシミュレータを用いて特性評価した。従来例１は
図２のように実施例のＺｎＯ膜のかわりに通常の＜００
２＞配向を有するＺｎＯ膜５を２μｍの厚さで付けた太
陽電池であり、従来例２は代わりに＜１１０＞配向を有
するＺｎＯ膜を２μｍの厚さで形成した太陽電池である
。特性を表１に示す。CIS of Example 1 and Example 2 of the present invention
The characteristics of the solar cell were evaluated using a solar simulator along with the following two types of conventional solar cells. As shown in FIG. 2, Conventional Example 1 uses a normal <00
This is a solar cell in which a ZnO film 5 having a <110> orientation is formed with a thickness of 2 μm, whereas Conventional Example 2 is a solar cell in which a ZnO film 5 having a <110> orientation is formed with a thickness of 2 μm instead. The characteristics are shown in Table 1.
【００１２】0012
【表１】[Table 1]
【００１３】表１からわかるように、実施例は従来例１
に比べ短絡電流密度ＪＳＣが向上し、従来例２に比べＶ
ＯＣ， ＦＦが優れる。これは、＜００２＞配向ＺｎＯ
膜は鏡面状であるため光の散乱が不十分であり、逆に＜
１１０＞配向が強いＺｎＯ膜はテクスチャ度が高く光を
充分散乱するためにＪＳＣは大きくなるが、＜００２＞
配向を示すＣｄＺｎＳ膜との接触が悪く、そのためＶＯ
Ｃ， ＦＦが低下するためと考えられる。As can be seen from Table 1, the embodiment is based on conventional example 1.
The short circuit current density JSC is improved compared to conventional example 2, and V
Excellent OC and FF. This is <002> oriented ZnO
Because the film is mirror-like, light scattering is insufficient;
A ZnO film with strong 110> orientation has a high degree of texture and scatters light sufficiently, resulting in a large JSC, but <002>
The contact with the CdZnS film showing orientation is poor, and therefore the VO
This is thought to be due to a decrease in C and FF.
【００１４】配向性の強さは、例えば前述したようにＣ
ｕのＫα線を光源とするＸ線回折のピーク強度を比較す
ることにより定量的に表すことができる。そこで実施例
１と同様の構造において第一層５および第二層６の配向
性、すなわちγ＝＜１１０＞ピーク強度／＜００２＞ピ
ーク強度と太陽電池特性の関係を調べると、第一層でγ
＜１０−１でかつ第二層でγ＞１０であれば表１に示し
た実施例の特性と同等であるが、第一層でγ＞１０−１
のときはＶＯＣ， ＦＦの低下が起こり、第二層でγ＜
１０の時はＪＳＣの低下が起こることがわかった。実施
例２の構造の太陽電池においても同様にＺｎＯ膜のγ値
は１０−１以下とする必要がある。The strength of the orientation is determined by, for example, C as mentioned above.
It can be expressed quantitatively by comparing the peak intensities of X-ray diffraction using Kα rays of u as a light source. Therefore, when we investigated the relationship between the orientation of the first layer 5 and the second layer 6, that is, γ = <110> peak intensity/<002> peak intensity, and the solar cell characteristics in the same structure as in Example 1, we found that the first layer γ
<10-1 and γ>10 in the second layer, the characteristics are equivalent to those of the example shown in Table 1, but if γ>10-1 in the first layer
When , VOC and FF decrease, and γ<
It was found that JSC decreases when the age is 10. Similarly, in the solar cell having the structure of Example 2, the γ value of the ZnO film must be 10 −1 or less.
【００１５】なお、実施例１では表面がテクスチャ化を
示すＺｎＯ膜として＜１１０＞配向膜を用いたが、＜１
００＞配向膜も＜１１０＞配向膜と全く同様の効果を持
つテクスチャ化ＺｎＯ膜として用いることができる。ま
た、以上の実施例ではカルコパイライト型結晶としてＣ
ＩＳを取り上げたが、ＣｄＺｎＳと光電変換のための接
合を形成する他のカルコパイライト型結晶も取り上げる
ことができる。In Example 1, a <110> oriented film was used as the ZnO film with a textured surface;
The 00> oriented film can also be used as a textured ZnO film having exactly the same effect as the <110> oriented film. In addition, in the above examples, C as a chalcopyrite crystal.
Although IS is discussed, other chalcopyrite-type crystals that form a junction for photoelectric conversion with CdZnS can also be discussed.
【００１６】[0016]
【発明の効果】本発明によれば、カルコパイライト型結
晶薄膜と接合を形成するＣｄＺｎＳ薄膜上の透明導電性
のＺｎＯ膜を、第一層を＜００２＞配向を有する膜、第
二層をテクスチャ度の強い＜１１０＞配向あるいは＜１
００＞配向を有する膜からなる２層構造にするか、＜０
０２＞配向を有する膜をスパッタエッチングしたテクス
チャ化したものを単層であるいは複数層積層して用いる
ことにより、＜００２＞配向ＺｎＯ膜のＣｄＺｎＳとの
接触が良いことを利用し、テクスチャ化を行うことが可
能となり、簡便な方法でカルコパイライト型結晶薄膜を
用いた太陽電池特性を向上させることができる。そして
、配向性は、Ｘ線回折におけるピーク強度を用いて有効
に定量的に規定することが可能である。According to the present invention, a transparent conductive ZnO film on a CdZnS thin film forming a junction with a chalcopyrite-type crystal thin film is formed by forming a first layer with a <002> orientation and a second layer with texture. Strong <110> orientation or <1
Either a two-layer structure consisting of a film with a 00> orientation or a <0
By using a textured sputter-etched film with 02> orientation as a single layer or in a stack of multiple layers, texturing is performed by taking advantage of the good contact of the <002> oriented ZnO film with CdZnS. This makes it possible to improve the characteristics of a solar cell using a chalcopyrite-type crystal thin film using a simple method. The orientation can be effectively and quantitatively defined using the peak intensity in X-ray diffraction.
【図１】本発明の一実施例のＣＩＳ太陽電池の断面図FIG. 1: Cross-sectional view of a CIS solar cell according to an embodiment of the present invention.
【
図２】従来のＣＩＳ太陽電池の断面図[
Figure 2: Cross-sectional view of a conventional CIS solar cell
【図３】図１に示
した太陽電池の製作に用いられるＭＯＣＶＤ装置の断面
図[Figure 3] Cross-sectional view of MOCVD equipment used to manufacture the solar cell shown in Figure 1
【図４】本発明の異なる実施例のＣＩＳ太陽電池の断面
図FIG. 4 is a cross-sectional view of a CIS solar cell according to different embodiments of the present invention.
１ ガラス基板 ２ Ｍｏ膜 ３ ＣＩＳ膜 ４ ＣｄＺｎＳ膜 ５ ＜００２＞配向ＺｎＯ膜 ６ ＜１１０＞配向ＺｎＯ膜 ５１ テクスチャ化面 1 Glass substrate 2 Mo film 3 CIS membrane 4 CdZnS film 5 <002> oriented ZnO film 6 <110> oriented ZnO film 51 Textured surface
Claims (7)
ライト型結晶薄膜の他方の面側にその薄膜と接合を形成
する硫化亜鉛カドミウム薄膜および酸化亜鉛膜を順に積
層してなるものにおいて、酸化亜鉛膜が硫化亜鉛カドミ
ウム膜に近い側の＜００２＞配向膜と遠い側の＜１１０
＞配向膜よりなることを特徴とする薄膜太陽電池。Claim 1: A chalcopyrite-type crystal thin film in contact with a metal electrode on one surface, and a zinc cadmium sulfide thin film and a zinc oxide film that form a bond with the thin film on the other side of the thin film, in which oxidized The <002> oriented film on the side where the zinc film is close to the zinc sulfide cadmium film and the <110> oriented film on the far side
>A thin film solar cell characterized by comprising an alignment film.
ライト型結晶薄膜の他方の面側にその薄膜と接合を形成
する硫化亜鉛カドミウム薄膜および酸化亜鉛膜を順に積
層してなるものにおいて、酸化亜鉛膜が硫化亜鉛カドミ
ウム薄膜に近い側の＜００２＞配向膜と遠い側の＜１０
０＞配向膜よりなることを特徴とする薄膜太陽電池。2. A chalcopyrite-type crystal thin film in contact with a metal electrode on one surface, and a zinc cadmium sulfide thin film and a zinc oxide film that form a bond with the thin film on the other side of the thin film, in which oxidized The <002> oriented film on the side where the zinc film is close to the zinc cadmium sulfide thin film and the <10> oriented film on the far side
A thin film solar cell comprising a 0> alignment film.
ライト型結晶薄膜の他方の面側にその薄膜と接合を形成
する硫化亜鉛カドミウム薄膜および酸化亜鉛膜を順に積
層してなるものにおいて、酸化亜鉛膜が＜００２＞配向
膜でありかつ成膜後表面をスパッタエッチングすること
によりテクスチャ化してなる膜であることを特徴とする
薄膜太陽電池。3. A chalcopyrite-type crystal thin film in contact with a metal electrode on one surface, and a zinc cadmium sulfide thin film and a zinc oxide film that form a bond with the thin film on the other side of the thin film, in which oxidized A thin film solar cell characterized in that the zinc film is a <002> oriented film and is textured by sputter etching the surface after film formation.
ライト型結晶薄膜の他方の面側にその薄膜と接合を形成
する硫化亜鉛カドミウム薄膜および酸化亜鉛膜を順に積
層してなるものにおいて、酸化亜鉛膜が表面をスパッタ
エッチングすることによりテクスチャ化された＜００２
＞配向膜を複数積層化されてなるものであることを特徴
とする薄膜太陽電池。4. A chalcopyrite-type crystal thin film in contact with a metal electrode on one surface, and a zinc cadmium sulfide thin film and a zinc oxide film that form a bond with the thin film on the other side of the thin film, in which oxidized The zinc film was textured by sputter etching the surface <002
>A thin film solar cell characterized by being formed by laminating a plurality of alignment films.
において、＜００２＞配向酸化亜鉛膜は銅のＫα線を光
源とするＸ線回折における＜００２＞ピーク強度が＜１
１０＞ピーク強度および＜１００＞ピーク強度のそれぞ
れの１０倍以上である薄膜太陽電池。5. In the method according to claim 1, 2, 3, or 4, the <002> oriented zinc oxide film has a <002> peak intensity of <1 in X-ray diffraction using copper Kα rays as a light source.
A thin film solar cell having 10 times or more of each of the 10> peak intensity and the <100> peak intensity.
配向酸化亜鉛膜は銅のＫα線を光源とするＸ線回折にお
ける＜１１０＞ピーク強度が＜００２＞ピーク強度の１
０倍以上である薄膜太陽電池。Claim 6: The product according to claim 1, wherein <110>
The oriented zinc oxide film has a <110> peak intensity of 1 of the <002> peak intensity in X-ray diffraction using copper Kα rays as a light source.
A thin film solar cell that is 0 times or more.
配向酸化亜鉛膜は銅のＫα線を光源とするＸ線回折にお
ける＜１００＞ピーク強度が＜００２＞ピーク強度の１
０倍以上である薄膜太陽電池。Claim 7: In the product according to claim 2, <100>
The oriented zinc oxide film has a <100> peak intensity of 1 of the <002> peak intensity in X-ray diffraction using copper Kα rays as a light source.
A thin film solar cell that is 0 times or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3045274A JPH04282871A (en) | 1991-03-12 | 1991-03-12 | Thin film solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3045274A JPH04282871A (en) | 1991-03-12 | 1991-03-12 | Thin film solar cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04282871A true JPH04282871A (en) | 1992-10-07 |
Family
ID=12714735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3045274A Pending JPH04282871A (en) | 1991-03-12 | 1991-03-12 | Thin film solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04282871A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500690B1 (en) | 1999-10-27 | 2002-12-31 | Kaneka Corporation | Method of producing a thin-film photovoltaic device |
| JP2004311704A (en) * | 2003-04-07 | 2004-11-04 | Kanegafuchi Chem Ind Co Ltd | Substrate for thin film photoelectric converter and thin film photoelectric converter using the same |
| JP2005277339A (en) * | 2004-03-26 | 2005-10-06 | Ricoh Co Ltd | Vertical transistor and light emitting device |
| JP2007027566A (en) * | 2005-07-20 | 2007-02-01 | Ricoh Co Ltd | Vertical transistor and light emitting element |
| WO2009110092A1 (en) * | 2008-03-07 | 2009-09-11 | 昭和シェル石油株式会社 | Laminated structuer of cis-type solar battery and integrated structure |
| JP2014093370A (en) * | 2012-11-01 | 2014-05-19 | Toyota Central R&D Labs Inc | Photoelectric element |
| JP2016026413A (en) * | 2009-02-18 | 2016-02-12 | クアルコム，インコーポレイテッド | Photovoltaic cell and method of manufacturing the same |
| JP2016521016A (en) * | 2013-06-17 | 2016-07-14 | ジョン，ヨン−クォン | Solar cell and manufacturing method thereof |
| WO2017126150A1 (en) * | 2016-01-19 | 2017-07-27 | 国立研究開発法人物質・材料研究機構 | ROLLING BODY ZnO-COATING METHOD, ROLLING BODY WITH ZnO-COATING, AND BEARING INCORPORATING SAME |
-
1991
- 1991-03-12 JP JP3045274A patent/JPH04282871A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500690B1 (en) | 1999-10-27 | 2002-12-31 | Kaneka Corporation | Method of producing a thin-film photovoltaic device |
| JP2004311704A (en) * | 2003-04-07 | 2004-11-04 | Kanegafuchi Chem Ind Co Ltd | Substrate for thin film photoelectric converter and thin film photoelectric converter using the same |
| JP2005277339A (en) * | 2004-03-26 | 2005-10-06 | Ricoh Co Ltd | Vertical transistor and light emitting device |
| JP2007027566A (en) * | 2005-07-20 | 2007-02-01 | Ricoh Co Ltd | Vertical transistor and light emitting element |
| WO2009110092A1 (en) * | 2008-03-07 | 2009-09-11 | 昭和シェル石油株式会社 | Laminated structuer of cis-type solar battery and integrated structure |
| JP2016026413A (en) * | 2009-02-18 | 2016-02-12 | クアルコム，インコーポレイテッド | Photovoltaic cell and method of manufacturing the same |
| JP2014093370A (en) * | 2012-11-01 | 2014-05-19 | Toyota Central R&D Labs Inc | Photoelectric element |
| JP2016521016A (en) * | 2013-06-17 | 2016-07-14 | ジョン，ヨン−クォン | Solar cell and manufacturing method thereof |
| WO2017126150A1 (en) * | 2016-01-19 | 2017-07-27 | 国立研究開発法人物質・材料研究機構 | ROLLING BODY ZnO-COATING METHOD, ROLLING BODY WITH ZnO-COATING, AND BEARING INCORPORATING SAME |
| JPWO2017126150A1 (en) * | 2016-01-19 | 2018-11-15 | 国立研究開発法人物質・材料研究機構 | Method of ZnO coating on rotator and rotator having ZnO coating and bearing incorporating the same |
| US10495146B2 (en) | 2016-01-19 | 2019-12-03 | National Institute For Materials Science | ZnO coating method for rolling body, rolling body with ZnO coating, and bearing incorporating same |
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