JPH11177112A - Photovoltaic device and its manufacture - Google Patents
Photovoltaic device and its manufactureInfo
- Publication number
- JPH11177112A JPH11177112A JP9356214A JP35621497A JPH11177112A JP H11177112 A JPH11177112 A JP H11177112A JP 9356214 A JP9356214 A JP 9356214A JP 35621497 A JP35621497 A JP 35621497A JP H11177112 A JPH11177112 A JP H11177112A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- photovoltaic device
- light absorbing
- group
- absorbing 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.)
- Pending
Links
Classifications
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｉ−ＩＩＩ−ＶＩ
2族化合物半導体を光吸収層とする光電変換効率の高い
光起電力装置及びその製造方法に関するものである。TECHNICAL FIELD The present invention relates to I-III-VI
The present invention relates to a photovoltaic device having a high photoelectric conversion efficiency using a group II compound semiconductor as a light absorbing layer and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】カルコパイライト構造を有するＩ−ＩＩ
Ｉ−ＶＩ2族化合物半導体を光吸収層とする光起電力装
置は、光吸収層が薄膜であっても高い光電変換効率を示
し、また光照射による効率の劣化等が少ないことから実
用化が期待されている。上記光吸収層を形成する方法と
しては、Ｉ−ＩＩＩ−ＶＩ2族化合物半導体を構成する
各元素を別々の蒸発源から同時に蒸発させて基板上で化
合物を得る多源同時蒸着法や化合物を構成する金属の積
層膜あるいは混合膜をカルコゲン元素を含む雰囲気中で
加熱する気相セレン化（硫化）法などが知られている。
特に後者は大面積に大量に製造できるため量産に適した
方法として注目されているが、作製パラメータの自由度
が小さいために基板との密着性、結晶構造、組織、導電
率など光吸収層として求められる膜特性の全てを良好な
ものとすることは困難であるという不具合があった。と
りわけ、結晶性の向上と基板との密着性の確保とはトレ
ードオフの関係にあることが知られており、これらを両
立させる技術が望まれていた。2. Description of the Related Art I-II having a chalcopyrite structure
A photovoltaic device using an I-VI Group 2 compound semiconductor as a light absorbing layer shows high photoelectric conversion efficiency even when the light absorbing layer is a thin film, and has little deterioration in efficiency due to light irradiation, so that it can be put to practical use. Expected. As a method of forming the light absorbing layer, there are a multi-source simultaneous vapor deposition method of simultaneously evaporating the respective elements constituting the I-III-VI Group 2 compound semiconductor from separate evaporation sources to obtain a compound on a substrate, and a method of forming the compound. Gaseous selenization (sulfide) method of heating a metal laminated film or mixed film in an atmosphere containing a chalcogen element is known.
In particular, the latter is attracting attention as a method suitable for mass production because it can be mass-produced in a large area, but because of the small degree of freedom of manufacturing parameters, it is used as a light absorbing layer such as adhesion to substrates, crystal structure, structure, conductivity There is a problem that it is difficult to improve all of the required film properties. In particular, it is known that there is a trade-off between the improvement in crystallinity and the securing of adhesion to a substrate, and a technique for achieving both is desired.
【０００３】このような技術として、特開平６−３１０
４７号公報には、カルコゲン元素を含む雰囲気中で熱処
理する前の薄膜中にＩ族およびＩＩＩ族元素以外に化学
量論組成より少ない量のカルコゲン元素を含有させるこ
とによって、熱処理後の膜の結晶性と基板との密着性を
向上させる方法が開示されている。しかしながら、この
ような方法では熱処理前の薄膜中のカルコゲン元素の含
有量の制御が難しく、量産にむかないという難点があ
る。また、基板との密着性も必ずしも実用上十分なレベ
ルには至っていないのが実状である。[0003] As such a technique, Japanese Patent Laid-Open Publication No.
No. 47 discloses that a thin film before heat treatment in an atmosphere containing a chalcogen element contains a chalcogen element in an amount smaller than the stoichiometric composition in addition to the group I and group III elements, thereby obtaining a crystal of the film after the heat treatment. A method for improving the properties and adhesion to a substrate is disclosed. However, in such a method, it is difficult to control the content of the chalcogen element in the thin film before the heat treatment, and there is a problem that the method is not suitable for mass production. Further, in reality, the adhesion to the substrate has not always reached a practically sufficient level.
【０００４】[0004]
【発明が解決しようとする課題】そこで本発明の課題は
このような問題点を解決し、光吸収層の結晶性が良好で
且つ基板との密着性に優れ、光電変換効率の高い光起電
力装置を提供することにある。また、本発明の課題は高
い光電変換効率を有する光起電力装置が低コストで得ら
れる製造方法を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve such a problem, and to provide a photovoltaic device having a light absorption layer having good crystallinity, excellent adhesion to a substrate, and high photoelectric conversion efficiency. It is to provide a device. Another object of the present invention is to provide a manufacturing method by which a photovoltaic device having high photoelectric conversion efficiency can be obtained at low cost.
【０００５】[0005]
【課題を解決するための手段】本発明によれば、第一
に、Ｉ−ＩＩＩ−ＶＩ2族化合物半導体からなる光吸収
層を有する光起電力装置において、光吸収層に接して光
の入射側と反対側に導電層を有し、少なくとも該導電層
と光吸収層との界面に、該導電層を構成する元素との間
で金属間化合物を形成する元素を有することを特徴とす
る光起電力装置が提供される。According to the present invention, in order to solve the problems], first, in the photovoltaic device having a light absorbing layer made of I-III-VI 2 group compound semiconductor, the incidence of light in contact with the light absorbing layer Having a conductive layer on the side opposite to the side, and at least at an interface between the conductive layer and the light absorbing layer, an element forming an intermetallic compound with an element constituting the conductive layer. An electromotive device is provided.
【０００６】第二に、上記第一に記載の光起電力装置に
おいて、導電層を構成する元素との間で金属間化合物を
形成する元素がダイヤモンド構造の結晶型を有すること
を特徴とする光起電力装置が提供される。Secondly, in the photovoltaic device according to the first aspect, the element forming the intermetallic compound with the element forming the conductive layer has a crystal structure of a diamond structure. An electromotive device is provided.
【０００７】第三に、上記第一または第二に記載の光起
電力装置において、導電層を構成する元素との間で金属
間化合物を形成する元素が白金族元素であることを特徴
とする光起電力装置が提供される。Third, in the photovoltaic device according to the first or second aspect, the element forming the intermetallic compound with the element constituting the conductive layer is a platinum group element. A photovoltaic device is provided.
【０００８】第四に、上記第一乃至第三のいずれかに記
載の光起電力装置において、光吸収層に接して光の入射
側に、光吸収層よりバンドギャップの大きい半導体材料
層を有することを特徴とする光起電力装置が提供され
る。Fourthly, in the photovoltaic device according to any one of the first to third aspects, a semiconductor material layer having a larger band gap than the light absorbing layer is provided on the light incident side in contact with the light absorbing layer. A photovoltaic device is provided.
【０００９】第五に、上記第四に記載の光起電力装置に
おいて、半導体材料層が光吸収層と接合を形成する層と
その層に接して光の入射側に形成された透明電極層から
なることを特徴とする光起電力装置が提供される。Fifth, in the photovoltaic device according to the fourth aspect, the semiconductor material layer comprises a layer forming a junction with the light absorbing layer and a transparent electrode layer formed on the light incident side in contact with the layer. A photovoltaic device is provided.
【００１０】第六に、上記第五に記載の光起電力装置に
おいて、光吸収層と接合を形成する層がＺｎＳ、ＺｎＳ
ｅ、ＺｎＯよりなる群から選ばれた少なくとも１種類を
含有して構成されていることを特徴とする光起電力装置
が提供される。Sixth, in the photovoltaic device according to the fifth aspect, the layer forming a junction with the light absorbing layer is made of ZnS or ZnS.
e, a photovoltaic device characterized by comprising at least one selected from the group consisting of ZnO.
【００１１】第七に、Ｉ−ＩＩＩ−ＶＩ2族化合物半導
体からなる光吸収層および光吸収層に接して光の入射側
と反対側に導電層を有し、少なくとも導電層と光吸収層
との界面に、導電層を構成する元素との間で金属間化合
物を形成する元素を有する光起電力装置の製造方法にお
いて、Ｉ族およびＩＩＩ族元素を含む層を少なくともＶ
Ｉ族元素を含む雰囲気中で加熱することによって光吸収
層を形成することを特徴とする光起電力装置の製造方法
が提供される。[0011] Seventh, has a conductive layer on the side opposite to the light incident side in contact with the light absorbing layer and a light absorbing layer made of I-III-VI 2 group compound semiconductor, and at least the conductive layer and the light absorbing layer At the interface of the photovoltaic device having an element forming an intermetallic compound with the element constituting the conductive layer, the layer containing the group I and group III elements is at least V
There is provided a method for manufacturing a photovoltaic device, wherein a light absorbing layer is formed by heating in an atmosphere containing a group I element.
【００１２】以下に本発明をさらに詳しく説明する。上
記第一に記載の光起電力装置は、Ｉ−ＩＩＩ−ＶＩ2族
化合物半導体からなる光吸収層を有する光起電力装置に
おいて、光吸収層に接して光の入射側と反対側に導電層
を有し、少なくとも該導電層と光吸収層との界面に、該
導電層を構成する元素との間で金属間化合物を形成する
元素を有することを特徴とするものである。ここで、導
電層とは導電層を設けた基板における導電層や導電性を
有する金属基板における光吸収層と接する表面を意味し
ている。Hereinafter, the present invention will be described in more detail. The photovoltaic device according to the first, in the photovoltaic device having a light absorbing layer made of I-III-VI 2 group compound semiconductor, the conductive layer on the side opposite to the light incident side in contact with the light absorbing layer And at least at an interface between the conductive layer and the light absorbing layer, an element which forms an intermetallic compound with an element constituting the conductive layer. Here, the conductive layer means a surface of the substrate provided with the conductive layer or a surface in contact with the light absorbing layer of a metal substrate having conductivity.
【００１３】Ｉ−ＩＩＩ−ＶＩ2族化合物半導体からな
る光吸収層を形成する際、ＩＩＩ族元素に対するＩ族元
素の原子数比を１より大きくする、すなわちＩ族元素リ
ッチな組成にすることによって結晶粒径が大きくなり、
良好な結晶性を有するとともにｐ型伝導を示す膜を得る
ことができ、このような膜は光吸収層として好適である
が、基板あるいは基板上に形成された導電層との密着性
に劣り、製造工程中に剥離する場合がある。[0013] When forming the light-absorbing layer comprising a I-III-VI 2 group compound semiconductor is larger than 1 atomic ratio of Group I element to the group III element, namely by the Group I element-rich composition The crystal grain size increases,
A film having good crystallinity and exhibiting p-type conductivity can be obtained. Such a film is suitable as a light absorption layer, but has poor adhesion to a substrate or a conductive layer formed over the substrate, Peeling may occur during the manufacturing process.
【００１４】本発明者らは、光吸収層と導電層との界面
に化学的な結合を導入することによって付着力を増大さ
せ、光吸収層と導電層との剥離を防止することができる
ことを見出した。すなわち、導電層と光吸収層との界面
に、導電層を構成する元素との間で金属間化合物を形成
する元素を含有させることによって、光吸収層の結晶性
が良好で且つ基板との密着性が優れていると共に高い光
電変換効率が得られることを見出した。The present inventors have found that by introducing a chemical bond at the interface between the light absorbing layer and the conductive layer, the adhesion can be increased and the separation between the light absorbing layer and the conductive layer can be prevented. I found it. In other words, the interface between the conductive layer and the light absorbing layer contains an element that forms an intermetallic compound with the element forming the conductive layer, so that the light absorbing layer has good crystallinity and adheres to the substrate. It has been found that excellent photoelectric conversion efficiency and high photoelectric conversion efficiency can be obtained.
【００１５】導電層を構成する元素としては高融点の遷
移金属が望ましく、ガラスなどの基板との密着性やコス
トを考慮するとＭｏ、Ｔｉなどが好適である。また、こ
れらの元素との間で金属間化合物を形成する元素として
は、Ａｌ、Ｇａ、Ｓｉ、Ｇｅ、Ｓｎ、Ｓｂ、Ｒｈ、Ｉ
ｒ、Ｐｄ、Ｐｔなどが例示できる。形成される金属間化
合物の多くはＡ−１５型結晶構造を有している。As the element constituting the conductive layer, a transition metal having a high melting point is desirable, and Mo, Ti, etc. are preferable in consideration of the adhesion to a substrate such as glass and the cost. Elements forming an intermetallic compound with these elements include Al, Ga, Si, Ge, Sn, Sb, Rh, and I.
r, Pd, Pt and the like can be exemplified. Many of the formed intermetallic compounds have an A-15 type crystal structure.
【００１６】上記第二に記載の光起電力装置は、導電層
を構成する元素との間で金属間化合物を形成する元素が
ダイヤモンド構造の結晶型を有することを特徴とするも
のである。ダイヤモンド構造はＩ−ＩＩＩ−ＶＩ2族化
合物の典型的な結晶型であるカルコパイライト構造に類
似であるため、光吸収層と導電層との界面に金属間化合
物の形成に寄与しなかった残存元素が単体で存在して
も、光吸収層との格子のマッチングが良好となり、光吸
収層の結晶性を損なうことがないのでより好ましい。そ
のような元素としては、Ｓｉ、Ｇｅ、Ｓｎなどが例示で
きる。[0016] The photovoltaic device according to the second aspect is characterized in that the element forming the intermetallic compound with the element forming the conductive layer has a crystal structure of a diamond structure. Typical for a similar chalcopyrite structure is crystalline, the remaining elements that did not contribute to the interface between the light-absorbing layer and the conductive layer to the formation of intermetallic compounds of the diamond structure I-III-VI 2 group compounds Is more preferable, because the lattice matching with the light absorbing layer becomes good and the crystallinity of the light absorbing layer is not impaired. Examples of such elements include Si, Ge, and Sn.
【００１７】上記第三に記載の光起電力装置は、導電層
を構成する元素との間で金属間化合物を形成する元素が
白金族元素であることを特徴とするものである。導電層
として好適なＭｏ、Ｔｉなどの元素はＩ−ＩＩＩ−ＶＩ
2族化合物半導体の薄膜の形成時に、比較的容易にＶＩ
族元素との化合物（セレン化物、硫化物）を形成しやす
く、そのような化合物層が界面に存在することによって
光吸収層と導電層とが層状剥離を引き起こす場合がある
が、金属間化合物を形成する元素が白金族元素の場合に
は、それらの元素はセレン化物や硫化物をほとんど形成
しないので、剥離の発生をよりよく防止することができ
る。そのような元素としては、Ｒｈ、Ｉｒ、Ｐｄ、Ｐｔ
などが例示できる。The photovoltaic device according to the third aspect is characterized in that the element forming the intermetallic compound with the element constituting the conductive layer is a platinum group element. Elements such as Mo and Ti suitable for the conductive layer are I-III-VI
When forming a group II compound semiconductor thin film, VI
Compounds with group elements (selenides, sulfides) are easily formed, and the presence of such a compound layer at the interface may cause delamination between the light absorbing layer and the conductive layer. When the element to be formed is a platinum group element, these elements hardly form selenide or sulfide, so that the occurrence of peeling can be better prevented. Such elements include Rh, Ir, Pd, Pt
And the like.
【００１８】上記第四に記載の光起電力装置は、さらに
光吸収層に接して該層より光入射側に、光吸収層よりバ
ンドギャップの大きい半導体材料層を設けたことを特徴
とするものである。このような半導体材料層を設けるこ
とにより、いわゆる窓効果によって、ホモ接合の場合に
比べて短波長感度が向上し、高い光電変換効率を得るこ
とができる。なお、この場合両者の伝導型を逆のものと
することは言うまでもない。The photovoltaic device according to the fourth aspect is characterized in that a semiconductor material layer having a larger band gap than the light absorbing layer is provided in contact with the light absorbing layer and on the light incident side of the layer. It is. By providing such a semiconductor material layer, the short-wavelength sensitivity is improved and a high photoelectric conversion efficiency can be obtained by a so-called window effect as compared with the case of the homojunction. In this case, it is needless to say that the conduction types of the two are reversed.
【００１９】上記第五に記載の光起電力装置は、光吸収
層よりバンドギャップの大きい半導体材料層が、光吸収
層と接合を形成する層とその層に接して光の入射側に形
成された透明電極層からなることを特徴とするものであ
る。これにより、理想的な接合界面の形成と表面再結合
の抑止が可能となり、光吸収層とそれに接する層の接合
特性が良好なものとなることによって高い光電変換効率
を得ることができる。In the photovoltaic device according to the fifth aspect, the semiconductor material layer having a larger band gap than the light absorption layer is formed on the light incident side in contact with the layer forming the junction with the light absorption layer. And a transparent electrode layer. Thereby, formation of an ideal bonding interface and suppression of surface recombination can be achieved, and high photoelectric conversion efficiency can be obtained by improving the bonding characteristics between the light absorbing layer and the layer in contact therewith.
【００２０】上記第六に記載の光起電力装置は、光吸収
層と接合を形成する層が、少なくともＺｎＳ、ＺｎＳ
ｅ、ＺｎＯよりなる群から選ばれた少なくとも１種類を
含有して構成されていることを特徴とするものである。
上記材料は、いずれもバンドギャップが２．６ｅＶ以上
と大きいため、大きな窓効果が期待でき、また適当な混
晶比を選ぶことによって、Ｉ−ＩＩＩ−ＶＩ2族化合物
半導体との格子不整合を小さくすることができるため、
良好な接合特性が得られる。さらには、従来用いられて
きたＣｄＳにおけるＣｄのような有害な物質を含まない
点でも望ましい。[0020] In the photovoltaic device according to the sixth aspect, the layer forming the junction with the light absorbing layer is formed of at least ZnS, ZnS.
e, and at least one selected from the group consisting of ZnO.
Each of the above materials has a large band gap of 2.6 eV or more, so that a large window effect can be expected. Also, by selecting an appropriate mixed crystal ratio, the lattice mismatch with the I-III-VI group 2 compound semiconductor can be reduced. Because it can be smaller,
Good joining characteristics are obtained. Furthermore, it is desirable in that it does not contain harmful substances such as Cd in CdS that has been conventionally used.
【００２１】上記第七に記載の光起電力装置の製造方法
は、少なくともＩ族およびＩＩＩ族元素を含む層を、少
なくともＶＩ族元素を含む雰囲気中で加熱することによ
って光吸収層を形成することを特徴とするものである。
光吸収層をこのようにして形成することにより、良好な
結晶性と基板（基板上の導電層）との密着性を確保しな
がら光吸収層を大面積で大量に製造することができ、光
起電力装置の製造コストを低減することができる。In the method of manufacturing a photovoltaic device according to the seventh aspect, the light absorbing layer is formed by heating a layer containing at least a group I element and a group III element in an atmosphere containing at least a group VI element. It is characterized by the following.
By forming the light-absorbing layer in this manner, the light-absorbing layer can be mass-produced in a large area while ensuring good crystallinity and adhesion to the substrate (conductive layer on the substrate). The manufacturing cost of the electromotive device can be reduced.
【００２２】[0022]
【発明の実施の形態】以下に、本発明の実施の形態を図
面に基づいて説明する。図１は本発明の光起電力装置の
一例を模式的に示す断面図であり、導電層を設けた基板
や導電性を有する金属基板などの基板１、導電層を構成
する元素との間で金属間化合物を形成する元素を含む層
２、Ｉ−ＩＩＩ−ＶＩ2族化合物半導体からなる光吸収
層３、光吸収層３と逆の伝導型である光吸収層と接合を
形成する層４および透明電極層５から構成されている。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing an example of the photovoltaic device of the present invention. FIG. 1 shows a substrate 1 such as a substrate provided with a conductive layer or a conductive metal substrate, and an element constituting the conductive layer. layer 2, I-III-VI 2 group compound light absorbing layer 3 made of a semiconductor containing an element which forms an intermetallic compound layer 4 to form a junction with the light absorption layer is a light-absorbing layer 3 and the opposite conductivity type and It is composed of a transparent electrode layer 5.
【００２３】導電層はＭｏ、Ｔｉなどを真空蒸着法、ス
パッタリング法等により膜厚０．５〜５μｍに堆積して
形成される。導電層を構成する元素との間で金属間化合
物を形成する元素を含む層２は導電層上にＡｌ、Ｇａ、
Ｓｉ、Ｇｅ、Ｓｎ、Ｓｂ、Ｒｈ、Ｉｒ、Ｐｄ、Ｐｔなど
を真空蒸着法、スパッタリング法等により膜厚１〜５０
０ｎｍに堆積した後、３００〜６００℃の熱処理（Ｉ−
ＩＩＩ−ＶＩ2族化合物半導体からなる光吸収層３を形
成する過程での熱処理で兼ねてもよい）を施すことによ
り形成することができる。The conductive layer is formed by depositing Mo, Ti, or the like to a thickness of 0.5 to 5 μm by a vacuum deposition method, a sputtering method, or the like. The layer 2 containing an element that forms an intermetallic compound with the element that forms the conductive layer has Al, Ga,
Si, Ge, Sn, Sb, Rh, Ir, Pd, Pt, etc. are formed to a thickness of 1 to 50 by a vacuum deposition method, a sputtering method, or the like.
0 nm, and then heat-treated at 300 to 600 ° C. (I-
Heat treatment in the process of forming the light absorption layer 3 made of a III-VI Group 2 compound semiconductor).
【００２４】Ｉ−ＩＩＩ−ＶＩ2化合物半導体からなる
光吸収層３を構成する元素は、Ｉ族元素としてＣｕ、Ａ
ｇ、ＩＩＩ族元素としてＩｎ、Ｇａ、Ａｌ、ＶＩ族元素
としてＳｅ、Ｓ、の各々から１種類または２種を選択す
ることが望ましい。各元素は、Ｉ−ＩＩＩ−ＶＩ2化合
物半導体のバンドギャップを太陽光スペクトルに対する
量子効率が大きくなるような値（概ね１〜２ｅＶ）に設
定するように選択することが好ましい。また、Ｉ−ＩＩ
Ｉ−ＶＩ2族化合物半導体からなる光吸収層３は、ＩＩ
Ｉ族元素に対するＩ族元素の原子数比を０．９５〜１．
９５とし、伝導型をｐ型とするのが好ましい。Elements constituting the light absorbing layer 3 made of an I-III-VI 2 compound semiconductor include Cu and A as Group I elements.
It is desirable to select one or two of In, Ga, Al as a group III element and Se, S as a group VI element. It is preferable that each element is selected so that the band gap of the I-III-VI 2 compound semiconductor is set to a value (about 1 to 2 eV) at which the quantum efficiency with respect to the solar spectrum increases. In addition, I-II
The light absorbing layer 3 made of an I-VI group 2 compound semiconductor is composed of II
The atomic ratio of the group I element to the group I element is 0.95 to 1.
Preferably, the conductivity type is 95 and the conductivity type is p-type.
【００２５】Ｉ−ＩＩＩ−ＶＩ2化合物半導体からなる
光吸収層３の形成方法としては、多源同時蒸着法、気相
セレン化（硫化）法などが採用される。多源同時蒸着法
は、上記のようにして選ばれたＩ族、ＩＩＩ族およびＶ
Ｉ族元素を別々の蒸発源から同時に蒸発させて、上方に
設置された基板（３００〜５００℃に加熱）上で所望の
組成の化合物を得る方法であり、各元素の蒸発速度を厳
密にコントロールすることが必要である。As a method for forming the light absorbing layer 3 made of an I-III-VI 2 compound semiconductor, a multi-source simultaneous vapor deposition method, a gaseous selenization (sulfide) method, or the like is employed. The multi-source co-evaporation method uses Group I, Group III and V selected as described above.
A method of simultaneously evaporating Group I elements from separate evaporation sources to obtain a compound having a desired composition on a substrate (heated to 300 to 500 ° C.) placed above, and strictly controlling the evaporation rate of each element. It is necessary to.
【００２６】気相セレン化（硫化）法は、Ｉ族およびＩ
ＩＩ族元素からなる積層膜あるいは混合膜を真空蒸着
法、スパッタリング法などで基板上に形成した後、Ｓｅ
あるいはＳを含む雰囲気、例えば不活性ガスで希釈した
Ｈ2ＳｅあるいはＨ2Ｓガス中で４００〜６００℃に加熱
して化合物を得る方法であり、この方法は光吸収層の大
面積化、量産化が容易である点から好ましい。Ｉ−ＩＩ
Ｉ−ＶＩ2族化合物半導体からなる光吸収層３の膜厚と
しては、０．５〜５μｍが適切である。The gas-phase selenization (sulphidation) method is based on group I and I
After forming a laminated film or a mixed film comprising a group II element on a substrate by a vacuum evaporation method, a sputtering method, or the like, Se
Alternatively, the compound is obtained by heating to 400 to 600 ° C. in an atmosphere containing S, for example, H 2 Se or H 2 S gas diluted with an inert gas. It is preferable because the conversion is easy. I-II
The appropriate thickness of the light absorption layer 3 made of an I-VI group 2 compound semiconductor is 0.5 to 5 μm.
【００２７】Ｉ−ＩＩＩ−ＶＩ2族化合物半導体からな
る光吸収層に接して該層より光入射側に設けられる半導
体材料層（光吸収層と逆の伝導型である半導体材料層）
の材料としては、Ｉ−ＩＩＩ−ＶＩ2族化合物半導体と
同一の化合物半導体を用いること（ホモ接合）もできる
が、それよりバンドギャップの大きい半導体を用いるこ
とが、窓効果によって短波長領域の光をより多く光吸収
層に取り込むことができる点、すなわち短波長感度を向
上させる点から望ましい。さらには、半導体材料層を光
吸収層と接合を形成する層（例えば光吸収層と逆の伝導
型であるｎ型半導体層）４とその上の透明電極層（例え
ば縮退したｎ型半導体層）５の積層として形成すること
が、接合特性を良好とする点から望ましい。A semiconductor material layer (a semiconductor material layer having a conductivity type opposite to that of the light absorption layer) provided in contact with the light absorption layer made of the I-III-VI Group 2 compound semiconductor and on the light incident side of the layer.
As a material for the compound (I), the same compound semiconductor as the group I-III-VI group 2 compound semiconductor can be used (homojunction), but a semiconductor having a larger band gap can be used because of the window effect. From the light absorbing layer, that is, the short wavelength sensitivity is improved. Further, a layer (for example, an n-type semiconductor layer having a conductivity type opposite to that of the light-absorbing layer) 4 that forms a junction between the semiconductor material layer and the light-absorbing layer and a transparent electrode layer (for example, a degenerated n-type semiconductor layer) thereon It is desirable to form them as a laminate of 5 from the viewpoint of improving the bonding characteristics.
【００２８】光吸収層と接合を形成する層４は、例えば
溶液成長法、ＭＯＣＶＤ法等により、ＺｎＳｅ、Ｚｎ
Ｓ、ＺｎＯまたはこれらの混晶を膜厚１０〜２００ｎｍ
に堆積して形成し、透明電極層５は、例えばスパッタリ
ング法、イオンプレーティング法、真空蒸着法、ＭＯＣ
ＶＤ法等によりＩＴＯ、ＺｎＯ：Ａｌ等を膜厚０．１〜
２μｍに堆積して形成することができる。The layer 4 which forms a junction with the light absorbing layer is made of, for example, ZnSe, Zn
S, ZnO or a mixed crystal of these with a film thickness of 10 to 200 nm
The transparent electrode layer 5 is formed by, for example, sputtering, ion plating, vacuum evaporation, MOC
ITO, ZnO: Al, etc., with a film thickness of 0.1 to
It can be formed by depositing 2 μm.
【００２９】[0029]
【実施例】以下に本発明を実施例により説明する。 実施例１ 図１に示す構成の光起電力装置を図２に示す工程で以下
のようにして作製した。まず、ガラス基板１１上に導電
層として、スパッタリング法により膜厚１μｍのＭｏ薄
膜１２を堆積し導電層付き基板１とした。この導電層上
に真空蒸着法でＳｎ薄膜２１、Ｃｕ薄膜６１およびＩｎ
薄膜６２をそれぞれ膜厚３０ｎｍ、３５０ｎｍおよび５
５０ｎｍで堆積しプリカーサ層６とした。これを石英管
炉内に設置し、ＡｒまたはＮ2ガス中で５００℃まで昇
温した後、Ｈ2Ｓガスを希釈量１０％の割合にして４時
間流して硫化を行った。硫化後さらにＡｒまたはＮ2ガ
スを流しながら５００℃に１時間保持したのち冷却し
た。このようにして、導電層との界面にＭｏとの間で金
属間化合物を形成する元素Ｓｎを含む層２を有するＩ−
ＩＩＩ−ＶＩ2族化合物半導体（ＣｕＩｎＳ2）からなる
光吸収層３１を形成した。EXAMPLES The present invention will be described below with reference to examples. Example 1 A photovoltaic device having the configuration shown in FIG. 1 was manufactured in the process shown in FIG. 2 as follows. First, a Mo thin film 12 having a thickness of 1 μm was deposited as a conductive layer on a glass substrate 11 by a sputtering method to obtain a substrate 1 with a conductive layer. On this conductive layer, Sn thin film 21, Cu thin film 61 and In thin film were formed by vacuum evaporation.
The thin film 62 is formed to a thickness of 30 nm, 350 nm and
The precursor layer 6 was deposited at a thickness of 50 nm. This was placed in a quartz tube furnace, heated to 500 ° C. in Ar or N 2 gas, and then sulfurized by flowing H 2 S gas at a dilution of 10% for 4 hours. After sulfurization, the mixture was kept at 500 ° C. for 1 hour while flowing Ar or N 2 gas, and then cooled. Thus, the I- layer having the layer 2 containing the element Sn forming an intermetallic compound with Mo at the interface with the conductive layer is obtained.
A light absorbing layer 31 made of a III-VI group 2 compound semiconductor (CuInS 2 ) was formed.
【００３０】ついで、光吸収層３１の上に、ＭＯＣＶＤ
法でＺｎＳ−ＺｎＯ混晶体膜を膜厚１００ｎｍで堆積し
光吸収層と接合を形成する層（ｎ型半導体層）４とし
た。次に、スパッタリング法で膜厚４００ｎｍのＩＴＯ
薄膜を堆積し透明電極層５を形成し光起電力装置を得
た。上記光起電力装置の製造工程中、膜剥離等の欠陥の
発生は全く見られなかった。この光起電力装置の光電変
換効率は、９．５％（ＡＭ１．５、１００ｍＷ／ｃ
ｍ2）であった。Next, on the light absorbing layer 31, MOCVD
A ZnS-ZnO mixed crystal film was deposited to a thickness of 100 nm by a method to form a layer (n-type semiconductor layer) 4 which forms a junction with the light absorbing layer. Next, a 400 nm-thick ITO film was formed by sputtering.
A transparent electrode layer 5 was formed by depositing a thin film to obtain a photovoltaic device. During the manufacturing process of the photovoltaic device, no generation of defects such as film peeling was observed at all. The photoelectric conversion efficiency of this photovoltaic device is 9.5% (AM 1.5, 100 mW / c).
m 2 ).
【００３１】比較例１ Ｓｎ薄膜２１を堆積しないこと以外は実施例１と同様に
して光起電力装置を作製したところ、硫化後にＣｕＩｎ
Ｓ2薄膜に部分的な剥離がみられた。この光起電力装置
の光電変換効率は、６．７％（ＡＭ１．５、１００ｍＷ
／ｃｍ2）であった。Comparative Example 1 A photovoltaic device was manufactured in the same manner as in Example 1 except that the Sn thin film 21 was not deposited.
Partial peeling was observed in the S 2 thin film. The photoelectric conversion efficiency of this photovoltaic device is 6.7% (AM 1.5, 100 mW).
/ Cm 2 ).
【００３２】実施例２ 図１に示す構成の光起電力装置を図２に示す工程で以下
のようにして作製した。まず、ガラス基板１１上に導電
層として、スパッタリング法により膜厚１μｍのＭｏ薄
膜１２を堆積し導電層付き基板１とした。この導電層上
に真空蒸着法でＧｅ薄膜２１、Ｃｕ薄膜６１およびＩｎ
薄膜６２をそれぞれ膜厚５０ｎｍ、３５０ｎｍおよび５
５０ｎｍで堆積しプリカーサ層６とした。これを石英管
炉内に設置し、ＡｒまたはＮ2ガス中で５００℃まで昇
温した後、Ｈ2Ｓｅガスを希釈量１０％の割合にして２
時間流してセレン化を行った。セレン化後さらにＡｒま
たはＮ2ガスを流しながら５００℃に１時間保持したの
ち冷却した。このようにして、導電層との界面にＭｏと
の間で金属間化合物を形成する元素Ｇｅを含む層２を有
するＩ−ＩＩＩ−ＶＩ2族化合物半導体（ＣｕＩｎＳ
ｅ2）からなる光吸収層３１を形成した。Example 2 A photovoltaic device having the structure shown in FIG. 1 was manufactured in the process shown in FIG. 2 as follows. First, a Mo thin film 12 having a thickness of 1 μm was deposited as a conductive layer on a glass substrate 11 by a sputtering method to obtain a substrate 1 with a conductive layer. The Ge thin film 21, the Cu thin film 61 and the In thin film were formed on the conductive layer by a vacuum evaporation method.
The thin film 62 is formed to a thickness of 50 nm, 350 nm and
The precursor layer 6 was deposited at a thickness of 50 nm. This was placed in a quartz tube furnace, heated to 500 ° C. in Ar or N 2 gas, and diluted with H 2 Se gas at a rate of 10%.
Selenization was performed by flowing over time. After selenization, the mixture was kept at 500 ° C. for 1 hour while flowing Ar or N 2 gas, and then cooled. In this manner, an I-III-VI group 2 compound semiconductor (CuInS) having the layer 2 containing the element Ge that forms an intermetallic compound with Mo at the interface with the conductive layer
e 2 ) was formed.
【００３３】ついで、光吸収層３１の上に、ＭＯＣＶＤ
法でＺｎＳｅ−ＺｎＯ混晶体膜を膜厚１００ｎｍで堆積
し光吸収層と接合を形成する層（ｎ型半導体層）４とし
た。次に、スパッタリング法で膜厚４００ｎｍのＩＴＯ
薄膜を堆積し透明電極層５を形成し光起電力装置を得
た。上記光起電力装置の製造工程中、膜剥離等の欠陥の
発生は全く見られなかった。この光起電力装置の光電変
換効率は、１０．４％（ＡＭ１．５、１００ｍＷ／ｃｍ
2）であった。Next, on the light absorbing layer 31, MOCVD is performed.
A ZnSe-ZnO mixed crystal film was deposited to a thickness of 100 nm by a method to form a layer (n-type semiconductor layer) 4 which forms a junction with the light absorbing layer. Next, a 400 nm-thick ITO film was formed by sputtering.
A transparent electrode layer 5 was formed by depositing a thin film to obtain a photovoltaic device. During the manufacturing process of the photovoltaic device, no generation of defects such as film peeling was observed at all. The photoelectric conversion efficiency of this photovoltaic device is 10.4% (AM 1.5, 100 mW / cm
2 ).
【００３４】比較例２ Ｇｅ薄膜２１を堆積しないこと以外は実施例２と同様に
して光起電力装置を作製したところ、セレン化後にＣｕ
ＩｎＳｅ2薄膜に部分的な剥離がみられた。この光起電
力装置の光電変換効率は、８．６％（ＡＭ１．５、１０
０ｍＷ／ｃｍ2）であった。Comparative Example 2 A photovoltaic device was manufactured in the same manner as in Example 2 except that the Ge thin film 21 was not deposited.
Partial peeling was observed in the InSe 2 thin film. The photoelectric conversion efficiency of this photovoltaic device is 8.6% (AM 1.5, 10
0 mW / cm 2 ).
【００３５】実施例３ 図１に示す構成の光起電力装置を図３に示す工程で以下
のようにして作製した。まず、ガラス基板１１上に導電
層として、スパッタリング法により膜厚２μｍのＴｉ薄
膜１３を堆積し導電層付き基板１とし、この導電層上に
スパッタリング法で膜厚１００ｎｍのＰｔ薄膜２２を堆
積した。この上にスパッタリング法でＣｕ−Ｇａ薄膜６
３およびＩｎ薄膜６２をそれぞれ膜厚４００ｎｍおよび
５５０ｎｍで堆積しプリカーサ層６とした。これを石英
管炉内に設置し、ＡｒまたはＮ2ガス中で５５０℃まで
昇温した後、Ｈ2Ｓｅガスを希釈量１０％の割合にして
２時間流してセレン化を行った。セレン化後さらにＡｒ
またはＮ2ガスを流しながら５００℃に１時間保持した
のち冷却した。このようにして、導電層との界面にＴｉ
との間で金属間化合物を形成する元素Ｐｔを含む層２を
有するＩ−ＩＩＩ−ＶＩ2族化合物半導体〔Ｃｕ（Ｉ
ｎ，Ｇａ）Ｓｅ2〕からなる光吸収層３２を形成した。Example 3 A photovoltaic device having the structure shown in FIG. 1 was manufactured in the process shown in FIG. 3 as follows. First, a 2 μm-thick Ti thin film 13 was deposited as a conductive layer on a glass substrate 11 by a sputtering method to form a substrate 1 with a conductive layer, and a 100 nm-thick Pt thin film 22 was deposited on the conductive layer by a sputtering method. A Cu—Ga thin film 6 is formed thereon by sputtering.
3 and In thin film 62 were deposited to a thickness of 400 nm and 550 nm, respectively, to form a precursor layer 6. This was placed in a quartz tube furnace, heated to 550 ° C. in Ar or N 2 gas, and then selenized by flowing H 2 Se gas at a dilution of 10% for 2 hours. After selenization, Ar
Alternatively, the mixture was kept at 500 ° C. for 1 hour while flowing N 2 gas, and then cooled. In this way, the interface with the conductive layer
I-III-VI group 2 compound semiconductor having a layer 2 containing an element Pt which forms an intermetallic compound with [Cu (I
n, Ga) Se 2 ] was formed.
【００３６】ついで、光吸収層３２の上に、ＭＯＣＶＤ
法でＺｎＳｅ−ＺｎＯ混晶体膜を膜厚５０ｎｍで堆積し
光吸収層と接合を形成する層（ｎ型半導体層）４とし
た。次に、スパッタリング法で膜厚４００ｎｍのＩＴＯ
薄膜を堆積し透明電極層５を形成し光起電力装置を得
た。上記光起電力装置の製造工程中、膜剥離等の欠陥の
発生は全く見られなかった。この光起電力装置の光電変
換効率は、１１．０％（ＡＭ１．５、１００ｍＷ／ｃｍ
2）であった。Then, MOCVD is applied on the light absorbing layer 32.
A ZnSe-ZnO mixed crystal film was deposited to a thickness of 50 nm by a method to form a layer (n-type semiconductor layer) 4 which forms a junction with the light absorbing layer. Next, a 400 nm-thick ITO film was formed by sputtering.
A transparent electrode layer 5 was formed by depositing a thin film to obtain a photovoltaic device. During the manufacturing process of the photovoltaic device, no generation of defects such as film peeling was observed at all. The photoelectric conversion efficiency of this photovoltaic device is 11.0% (AM 1.5, 100 mW / cm
2 ).
【００３７】比較例３ Ｐｔ薄膜２２を堆積しないこと以外は実施例３と同様に
して光起電力装置を作製したところ、セレン化後にＣｕ
（Ｉｎ，Ｇａ）Ｓｅ2薄膜に部分的な剥離がみられた。
この光起電力装置の光電変換効率は、９．０％（ＡＭ
１．５、１００ｍＷ／ｃｍ2）であった。Comparative Example 3 A photovoltaic device was produced in the same manner as in Example 3 except that the Pt thin film 22 was not deposited.
Partial peeling was observed in the (In, Ga) Se 2 thin film.
The photoelectric conversion efficiency of this photovoltaic device is 9.0% (AM
1.5, 100 mW / cm 2 ).
【００３８】[0038]
【発明の効果】請求項１乃至３の光起電力装置によれ
ば、光吸収層の結晶性が良好で且つ基板との密着性が優
れていると共に高い光電変換効率が得られる。請求項４
の光起電力装置によれば、短波長感度が向上し、高い光
電変換効率が得られる。請求項５の光起電力装置によれ
ば、光吸収層とそれに接する層の接合特性が良好とな
り、さらに高い光電変換効率が得られる。According to the photovoltaic devices of the first to third aspects, the crystallinity of the light absorbing layer is good, the adhesion to the substrate is excellent, and a high photoelectric conversion efficiency can be obtained. Claim 4
According to this photovoltaic device, the short-wavelength sensitivity is improved, and a high photoelectric conversion efficiency can be obtained. According to the photovoltaic device of the fifth aspect, the junction characteristics between the light absorbing layer and the layer in contact with the light absorbing layer are improved, and higher photoelectric conversion efficiency can be obtained.
【００３９】請求項６の光起電力装置によれば、光吸収
層とそれに接する層の接合特性がより良好となり、高い
光電変換効率が得られると共に有害物質を含まないた
め、安全性の高い光起電力装置が得られる。請求項７の
光起電力装置の製造方法によれば、光吸収層の結晶性お
よび基板との密着性を確保しながら大面積を有する均一
な光吸収層を大量に製造することができ、光起電力装置
の製造コストを低減することができる。According to the photovoltaic device of the sixth aspect, the junction characteristics between the light absorbing layer and the layer in contact with the light absorbing layer are improved, and a high photoelectric conversion efficiency is obtained and no harmful substances are contained. An electromotive device is obtained. According to the method for manufacturing a photovoltaic device of claim 7, a large amount of a uniform light absorbing layer having a large area can be manufactured while securing the crystallinity of the light absorbing layer and the adhesion to the substrate. The manufacturing cost of the electromotive device can be reduced.
【図１】本発明の光起電力装置の一例を模式的に示す断
面図である。FIG. 1 is a cross-sectional view schematically showing one example of a photovoltaic device of the present invention.
【図２】本発明の光起電力装置の製造工程の一例を模式
的に示す説明図である。FIG. 2 is an explanatory view schematically showing one example of a manufacturing process of the photovoltaic device of the present invention.
【図３】本発明の光起電力装置の製造工程の他の例を模
式的に示す説明図である。FIG. 3 is an explanatory view schematically showing another example of the manufacturing process of the photovoltaic device of the present invention.
１ 基板 ２ 導電層を構成する元素との間で金属間化合物を形成
する元素を含む層 ３ Ｉ−ＩＩＩ−ＶＩ2族化合物半導体からなる光吸収
層 ４ 光吸収層と接合を形成する層 ５ 透明電極層DESCRIPTION OF SYMBOLS 1 Substrate 2 Layer containing the element which forms an intermetallic compound with the element which comprises a conductive layer 3 Light absorption layer which consists of a II-III-VI group 2 compound semiconductor 4 Layer which forms a junction with a light absorption layer 5 Transparency Electrode layer
Claims (7)
なる光吸収層を有する光起電力装置において、光吸収層
に接して光の入射側と反対側に導電層を有し、少なくと
も該導電層と光吸収層との界面に、該導電層を構成する
元素との間で金属間化合物を形成する元素を有すること
を特徴とする光起電力装置。1. A photovoltaic device having a light absorbing layer made of I-III-VI 2 group compound semiconductor, has a conductive layer on the side opposite to the light incident side in contact with the light absorbing layer, at least the conductive A photovoltaic device comprising, at an interface between a layer and a light absorbing layer, an element which forms an intermetallic compound with an element constituting the conductive layer.
合物を形成する元素がダイヤモンド構造の結晶型を有す
ることを特徴とする請求項１記載の光起電力装置。2. The photovoltaic device according to claim 1, wherein the element forming the intermetallic compound with the element forming the conductive layer has a crystal structure of a diamond structure.
合物を形成する元素が白金族元素であることを特徴とす
る請求項１または２記載の光起電力装置。3. The photovoltaic device according to claim 1, wherein the element forming the intermetallic compound with the element forming the conductive layer is a platinum group element.
層よりバンドギャップの大きい半導体材料層を有するこ
とを特徴とする請求項１、２または３記載の光起電力装
置。4. The photovoltaic device according to claim 1, further comprising a semiconductor material layer having a larger band gap than the light absorbing layer on a light incident side in contact with the light absorbing layer.
る層とその層に接して光の入射側に形成された透明電極
層からなることを特徴とする請求項４記載の光起電力装
置。5. The photovoltaic device according to claim 4, wherein the semiconductor material layer comprises a layer forming a junction with the light absorbing layer and a transparent electrode layer formed on the light incident side in contact with the layer. apparatus.
ＺｎＳｅ、ＺｎＯよりなる群から選ばれた少なくとも１
種類を含有して構成されていることを特徴とする請求項
５記載の光起電力装置。6. A layer forming a junction with the light absorbing layer is ZnS,
At least one selected from the group consisting of ZnSe and ZnO
The photovoltaic device according to claim 5, wherein the photovoltaic device is configured to contain a type.
なる光吸収層および光吸収層に接して光の入射側と反対
側に導電層を有し、少なくとも導電層と光吸収層との界
面に、導電層を構成する元素との間で金属間化合物を形
成する元素を有する光起電力装置の製造方法において、
Ｉ族およびＩＩＩ族元素を含む層を少なくともＶＩ族元
素を含む雰囲気中で加熱することによって光吸収層を形
成することを特徴とする光起電力装置の製造方法。7. I-III-VI 2 group compound light-absorbing layer comprising a semiconductor and in contact with the light absorbing layer has a conductive layer on the side opposite to the incident side of light, the interface between at least the conductive layer and the light absorbing layer In a method for manufacturing a photovoltaic device having an element that forms an intermetallic compound with an element constituting a conductive layer,
A method for manufacturing a photovoltaic device, comprising forming a light absorbing layer by heating a layer containing Group I and Group III elements in an atmosphere containing at least Group VI elements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9356214A JPH11177112A (en) | 1997-12-09 | 1997-12-09 | Photovoltaic device and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9356214A JPH11177112A (en) | 1997-12-09 | 1997-12-09 | Photovoltaic device and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11177112A true JPH11177112A (en) | 1999-07-02 |
Family
ID=18447913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9356214A Pending JPH11177112A (en) | 1997-12-09 | 1997-12-09 | Photovoltaic device and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11177112A (en) |
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