JPH08195499A - Manufacture of chalcopyrite compound film - Google Patents
Manufacture of chalcopyrite compound filmInfo
- Publication number
- JPH08195499A JPH08195499A JP7003872A JP387295A JPH08195499A JP H08195499 A JPH08195499 A JP H08195499A JP 7003872 A JP7003872 A JP 7003872A JP 387295 A JP387295 A JP 387295A JP H08195499 A JPH08195499 A JP H08195499A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- group
- chalcogen
- elements
- film
- 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.)
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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
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- Physical Vapour Deposition (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、太陽電池等に用いられ
るカルコパイライト型化合物薄膜の製造方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a chalcopyrite type compound thin film used for solar cells and the like.
【０００２】[0002]
【従来の技術】カルコパイライト型化合物は、太陽電池
や発光素子等への応用が期待される材料である。特に、
ＣｕＩｎＳｅ2 、ＣｕＧａＳｅ2 、ＣｕＩｎＳ2 及びそ
れらの混晶化合物は、直接遷移型であるために光吸収係
数が大きく、またバンドギャップが太陽光スペクトルに
マッチしていることから、太陽電池材料としての応用が
期待されている。例えば、ＣｕＩｎＳｅ2 薄膜を少なく
とも表面が導電性を有する基板上に製造する方法とし
て、真空蒸着法、スパッタリング法、スプレー法、電着
法、カルコゲン化法などが知られている。これらの中
で、Ｃｕ／Ｉｎ積層膜、Ｃｕ−Ｉｎ合金膜またはＣｕ−
Ｉｎ−Ｓｅ混合膜（Ｓｅ量は化学量論比より少ない、つ
まりモル比でＳｅ／（Ｃｕ＋Ｉｎ）＜１）をＳｅ含有雰
囲気中で熱処理することによりＣｕＩｎＳｅ2 膜を形成
するセレン化法が、量産化にも適し、高変換効率が得ら
れていることから、最近注目されている（Ｊｐｎ．Ｊ．
Ａｐｐｌ．Ｐｈｙｓ．Ｖｏｌ．３２，Ｓｕｐｐｌ．３２
−３，ｐｐ．３５−４０（１９９３））。2. Description of the Related Art Chalcopyrite type compounds are materials expected to be applied to solar cells, light emitting devices and the like. In particular,
Since CuInSe 2 , CuGaSe 2 , CuInS 2 and their mixed crystal compounds are direct transition type, they have a large optical absorption coefficient and their band gaps match the solar spectrum, so they are applied as solar cell materials. Is expected. For example, as a method for producing a CuInSe 2 thin film on a substrate having at least a surface of conductivity, a vacuum vapor deposition method, a sputtering method, a spray method, an electrodeposition method, a chalcogenization method and the like are known. Among these, Cu / In laminated film, Cu-In alloy film or Cu-
The selenization method of forming a CuInSe 2 film by heat-treating an In-Se mixed film (the amount of Se is less than the stoichiometric ratio, that is, Se / (Cu + In) <1 in a molar ratio) in a Se-containing atmosphere is a mass production method. Since it is suitable for high efficiency and has high conversion efficiency (Jpn.J.
Appl. Phys. Vol. 32, Suppl. 32
-3, pp. 35-40 (1993)).
【０００３】しかし、セレン化法により作製されたＣｕ
ＩｎＳｅ2 膜には以下のような問題点がある。熱処理前
の膜としてＣｕ／Ｉｎ積層膜及びＣｕ−Ｉｎ合金膜を用
いた場合、熱処理によって結晶粒成長が顕著に起こり、
結晶性の高いＣｕＩｎＳｅ2薄膜が形成できるが、熱処
理の昇温中にＩｎの凝集が起こり、熱処理後の薄膜の表
面形態および面内組成が不均一になるという問題があっ
た。However, Cu produced by the selenization method
The InSe 2 film has the following problems. When a Cu / In laminated film and a Cu-In alloy film are used as the film before the heat treatment, the heat treatment causes remarkable grain growth,
Although a CuInSe 2 thin film with high crystallinity can be formed, there is a problem that In aggregates during the temperature rise of the heat treatment and the surface morphology and in-plane composition of the thin film after the heat treatment become non-uniform.
【０００４】一方、熱処理前の膜としてＣｕ−Ｉｎ−Ｓ
ｅ混合膜を用いた場合、Ｓｅ／（Ｃｕ＋Ｉｎ）比を大き
くすることにより、熱処理中のＩｎの凝集を抑制するこ
とができ、その結果、表面形態及び面内組成の均一なＣ
ｕＩｎＳｅ2 膜を形成することができるが、Ｓｅ／（Ｃ
ｕ＋Ｉｎ）比が大きくなるにつれて、熱処理後の薄膜の
結晶粒径が小さくなるという問題があった。つまり、均
一性と高結晶性とはトレードオフの関係にある。On the other hand, Cu-In-S is used as a film before heat treatment.
When an e-mixed film is used, by increasing the Se / (Cu + In) ratio, the aggregation of In during heat treatment can be suppressed, and as a result, C having a uniform surface morphology and in-plane composition can be obtained.
A uInSe 2 film can be formed, but Se / (C
There is a problem that the crystal grain size of the thin film after heat treatment becomes smaller as the (u + In) ratio becomes larger. That is, there is a trade-off between uniformity and high crystallinity.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、表面形態及
び面内組成の均一性が良好で、且つ結晶性の高いＣｕＩ
ｎＳｅ2 等のカルコパイライト型化合物薄膜の製造方法
及びそれを用いた薄膜太陽電池の製造方法を提供するこ
とを目的とする。DISCLOSURE OF THE INVENTION The present invention provides CuI which has good surface morphology and in-plane composition uniformity and high crystallinity.
An object of the present invention is to provide a method for producing a chalcopyrite type compound thin film such as nSe 2 and a method for producing a thin film solar cell using the thin film.
【０００６】[0006]
【課題を解決するための手段】かかる状況下において、
本発明者らは、上記課題を解決するために鋭意検討した
結果、まず基板上に、Ｃｕ／Ｉｎ比が１以上であるＣｕ
−Ｉｎ−Ｓｅ混合膜を形成して、次いで、Ｓｅ／（Ｃｕ
＋Ｉｎ）比が前記Ｃｕ−Ｉｎ−Ｓｅ混合膜より大きく、
Ｃｕ／Ｉｎ比が１より小さいＣｕ−Ｉｎ−Ｓｅ混合膜を
形成することにより得られた積層膜を、Ｓｅ含有雰囲気
中で熱処理することが、表面形態及び面内組成の均一性
が良好で、且つ結晶性の高いＣｕＩｎＳｅ2 薄膜を作製
することに有効であることを見いだし、本発明をなすに
至った。In such a situation,
As a result of diligent studies to solve the above problems, the present inventors first found that on the substrate, Cu having a Cu / In ratio of 1 or more was used.
-In-Se mixed film is formed, and then Se / (Cu
+ In) ratio is larger than that of the Cu-In-Se mixed film,
Heat treatment of a laminated film obtained by forming a Cu-In-Se mixed film having a Cu / In ratio of less than 1 in a Se-containing atmosphere provides good surface morphology and in-plane composition uniformity. Moreover, they have found that it is effective in producing a CuInSe 2 thin film having high crystallinity, and have completed the present invention.
【０００７】すなわち、本発明は以下の通りである。 １． 元素周期律表のＩｂ族元素、ＩＩＩｂ族元素及び
カルコゲン元素（Ｓ、Ｓｅ及びＴｅ）からなり、且つＩ
ｂ族元素／ＩＩＩｂ族元素≧１（モル比）である薄膜を
第１層（以下、第１カルコゲン元素含有層という。）と
して基板上に形成し、次いで、Ｉｂ族元素／ＩＩＩｂ族
元素＜１（モル比）で、且つカルコゲン元素／（Ｉｂ族
元素＋ＩＩＩｂ族元素）（モル比）が第１層のそれより
大きく１未満である薄膜を第２層（以下、第２カルコゲ
ン元素含有層という。）として第１層上に形成すること
により得られた薄膜を上記カルコゲン元素を含有する雰
囲気中で熱処理することを特徴とするカルコパイライト
型化合物薄膜の製造方法。 ２． カルコパイライト型化合物薄膜を用いる薄膜太陽
電池の製造方法において、該カルコパイライト型化合物
薄膜を、上記１の製造方法で製造することを特徴とする
薄膜太陽電池の製造方法。That is, the present invention is as follows. 1. Consists of Ib group element, IIIb group element and chalcogen element (S, Se and Te) of the periodic table of elements, and I
A thin film of group b element / group IIIb element ≧ 1 (molar ratio) is formed on a substrate as a first layer (hereinafter referred to as a first chalcogen element-containing layer), and then group Ib element / group IIIb element <1. A thin film having a (molar ratio) and a chalcogen element / (Ib group element + IIIb group element) (molar ratio) larger than that of the first layer and less than 1 is a second layer (hereinafter referred to as a second chalcogen element-containing layer). ), The thin film obtained by forming it on the first layer is heat-treated in an atmosphere containing the above chalcogen element, and a method for producing a chalcopyrite type compound thin film. 2. A method for producing a thin film solar cell using a chalcopyrite type compound thin film, comprising producing the chalcopyrite type compound thin film by the above-mentioned production method 1.
【０００８】本発明におけるカルコパイライト型化合物
薄膜の作製プロセスの一例を図１に示す。まず、膜厚
０．５〜２μｍのＭｏ等の導電性薄膜２が形成されたガ
ラスなどの基板１上に、元素周期律表ＩＩＩｂ族元素に
対するＩｂ族元素のモル比が１以上である第１カルコゲ
ン元素含有層３、元素周期律表ＩＩＩｂ族元素に対する
Ｉｂ族元素のモル比が１未満で、且つ元素周期律表Ｉｂ
族及びＩＩＩｂ族元素に対するカルコゲン元素のモル比
が、第１カルコゲン元素含有層のそれより大きく、１未
満である第２カルコゲン元素含有層４を順次形成したも
のを、上記カルコゲン元素を含有する雰囲気中で熱処理
することにより、カルコパイライト型化合物薄膜５を作
製する。本発明においてカルコゲン元素とはＳ、Ｓｅ及
びＴｅをいう。FIG. 1 shows an example of a process for producing a chalcopyrite type compound thin film according to the present invention. First, on a substrate 1 such as glass on which a conductive thin film 2 such as Mo having a film thickness of 0.5 to 2 μm is formed, the molar ratio of the group Ib element to the group IIIb element of the periodic table is 1 or more. The chalcogen element-containing layer 3, the molar ratio of the group Ib element to the group IIIb element of the periodic table of elements is less than 1, and the periodic table Ib
In the atmosphere containing the chalcogen element, the second chalcogen element-containing layer 4 in which the molar ratio of the chalcogen element to the group III and group IIIb elements is larger than that of the first chalcogen element-containing layer and is less than 1 is sequentially formed. Then, the chalcopyrite type compound thin film 5 is manufactured by heat treatment. In the present invention, the chalcogen element means S, Se and Te.
【０００９】また、本発明における薄膜太陽電池は図２
の構造を有する。図１に示したプロセスにより作製され
たカルコパイライト型化合物薄膜の上に、５〜１０００
ｎｍのＣｄＳ等のｎ型半導体層６、０．１〜２μｍのＺ
ｎＯ：Ａｌ等の透明電極層７を順次形成することによ
り、薄膜太陽電池は作製される。本発明におけるカルコ
パイライト化合物とは、Ｃｕ、Ａｇ等の元素周期律表Ｉ
ｂ族金属、Ａｌ、Ｇａ、Ｉｎ等の元素周期律表ＩＩＩｂ
族金属及びＳ、Ｓｅ、Ｔｅのカルコゲン元素からなり、
カルコパイライト（黄銅鉱）型構造をとる化合物を総称
したものである。これらの中でもＣｕＩｎＳ2 、ＡｇＩ
ｎＳ2 、ＣｕＩｎＳｅ2 、ＣｕＧａＳｅ2 、ＡｇＩｎＳ
ｅ2 、ＡｇＧａＳｅ2 、ＣｕＩｎＴｅ2 、ＣｕＧａＴｅ
2 、ＡｇＩｎＴｅ2 、ＡｇＧａＴｅ2 或いはそれらの固
溶体などが、適当なバンドギャップを持っており、薄膜
太陽電池用材料として好ましく、これらの中でも、Ｃｕ
ＩｎX Ｇａ1-X ＳｅY Ｓ1-Y なる化学式で表される化合
物がより好ましい。The thin film solar cell according to the present invention is shown in FIG.
It has the structure of. On the chalcopyrite type compound thin film produced by the process shown in FIG.
nm n-type semiconductor layer 6 such as CdS, 0.1 to 2 μm Z
A thin film solar cell is manufactured by sequentially forming the transparent electrode layer 7 of nO: Al or the like. The chalcopyrite compound in the present invention means the periodic table I of elements such as Cu and Ag.
Periodic Table IIIb of Group b metals, Al, Ga, In, etc.
Consisting of group metals and chalcogen elements such as S, Se and Te,
It is a generic term for compounds having a chalcopyrite (chalcopyrite) type structure. Among these, CuInS 2 and AgI
nS 2 , CuInSe 2 , CuGaSe 2 , AgInS
e 2 , AgGaSe 2 , CuInTe 2 , CuGaTe
2 , AgInTe 2 , AgGaTe 2 or their solid solutions have a suitable band gap and are preferable as a material for thin film solar cells. Among them, Cu is preferable.
A compound represented by the chemical formula In X Ga 1-X Se Y S 1-Y is more preferable.
【００１０】本発明において、熱処理前のカルコゲン元
素含有薄膜の形成方法としては、スパッタ法、真空蒸着
法、ＭＯＣＶＤ法、スプレー加熱法、電着法など多くの
方法が選択できる。その場合、熱処理前に、元素周期律
表ＩＩＩｂ族元素に対するＩｂ族元素のモル比が１以上
である第１カルコゲン元素含有層と元素周期律表ＩＩＩ
ｂ族元素に対するＩｂ族元素のモル比が１未満で、且つ
元素周期律表Ｉｂ族及びＩＩＩｂ族元素に対するカルコ
ゲン元素のモル比が第１カルコゲン元素含有層のそれよ
り大きく１未満であるカルコゲン元素含有層からなる積
層膜を形成する方法は、特に限定されるものではない
が、例えば、Ｉｂ族元素、ＩＩＩｂ族元素の金属ターゲ
ット及びカルコゲン元素を含有するスパッタガスを用い
たスパッタ法がある。Ｉｂ族元素、ＩＩＩｂ族元素のタ
ーゲットに印加するパワーおよびスパッタガス中のカル
コゲン元素濃度を調節してカルコゲン元素含有層を形成
し、その途中で、Ｉｂ族元素ターゲットへの印加パワー
を低減することにより（この際、ＩＩＩｂ族元素ターゲ
ットへの印加パワー、スパッタガス中のカルコゲン元素
濃度を同時に変化させることも可能）、所望の積層膜が
簡便に形成できる。In the present invention, as a method for forming the chalcogen element-containing thin film before heat treatment, many methods such as a sputtering method, a vacuum deposition method, a MOCVD method, a spray heating method and an electrodeposition method can be selected. In that case, before the heat treatment, the first chalcogen element-containing layer in which the molar ratio of the group Ib element to the group IIIb element of the periodic table is 1 or more, and the periodic table III of the element.
Containing a chalcogen element in which the molar ratio of the Ib group element to the b group element is less than 1, and the molar ratio of the chalcogen element to the Ib group and the IIIb group element of the periodic table of elements is larger than that of the first chalcogen element-containing layer and less than 1. The method of forming a laminated film of layers is not particularly limited, but for example, there is a sputtering method using a sputtering target containing a metal target of a group Ib element or a group IIIb element and a chalcogen element. By adjusting the power applied to the targets of the Ib group element and the IIIb group element and the chalcogen element concentration in the sputtering gas to form the chalcogen element-containing layer, the power applied to the Ib group element target is reduced in the middle thereof. (At this time, the power applied to the group IIIb element target and the chalcogen element concentration in the sputtering gas can be simultaneously changed), and a desired laminated film can be easily formed.
【００１１】本発明において、熱処理前の第１カルコゲ
ン元素含有層における、元素周期律表ＩＩＩｂ族元素に
対するＩｂ族元素のモル比は１以上であることが必要で
ある。この値が１未満であると、得られたカルコパイラ
イト型化合物薄膜の結晶性が不十分である。第１カルコ
ゲン元素含有層は、熱処理により形成されたカルコパイ
ライト型化合物薄膜の結晶粒径を増大させる。つまり結
晶成長促進層としての役割がある。熱処理前の膜の元素
周期律表ＩＩＩｂ族元素に対するＩｂ族元素のモル比が
大きい程、また（Ｉｂ族元素＋ＩＩＩｂ族元素）に対す
るカルコゲン元素のモル比が小さい程、熱処理による結
晶粒径増大の効果は大きい。しかし、ＩＩＩｂ族元素に
対するＩｂ族元素のモル比が大きすぎると、第２カルコ
ゲン元素含有層の各元素との混合が完全に行われ難く、
熱処理後のカルコパイライト型化合物薄膜の組成が深さ
方向で不均一となり易く好ましくない。（Ｉｂ族元素＋
ＩＩＩｂ族元素）に対するカルコゲン元素のモル比が小
さすぎると、Ｍｏ等の基板との密着性が悪くなるため剥
離し易くなり好ましくない。したがって、第１カルコゲ
ン元素含有層のＩＩＩｂ元素に対するＩｂ族元素のモル
比は、１．０５以上４未満であることが好ましく、１．
１以上２未満であることがより好ましい。また、カルコ
ゲン元素の含有量は、第２カルコゲン元素含有層のそれ
より小さく、且つ（Ｉｂ族元素＋ＩＩＩｂ族元素）に対
するカルコゲン元素のモル比が０．０２以上０．５未満
であることが好ましく、０．０５以上０．３未満である
ことがより好ましい。In the present invention, it is necessary that the molar ratio of the group Ib element to the group IIIb element of the periodic table in the first chalcogen element-containing layer before the heat treatment is 1 or more. When this value is less than 1, the crystallinity of the obtained chalcopyrite type compound thin film is insufficient. The first chalcogen element-containing layer increases the crystal grain size of the chalcopyrite type compound thin film formed by the heat treatment. That is, it has a role as a crystal growth promoting layer. The larger the molar ratio of the group Ib element to the group IIIb element of the film before heat treatment and the smaller the ratio of the chalcogen element to the group (Ib group element + IIIb group element) of the periodic table of the film, the effect of increasing the crystal grain size by the heat treatment Is big. However, if the molar ratio of the Ib group element to the IIIb group element is too large, it is difficult to completely mix the respective elements of the second chalcogen element-containing layer,
The composition of the chalcopyrite type compound thin film after heat treatment tends to be nonuniform in the depth direction, which is not preferable. (Group Ib element +
If the molar ratio of the chalcogen element to the (IIIb group element) is too small, the adhesion to the substrate such as Mo deteriorates and peeling easily occurs, which is not preferable. Therefore, the molar ratio of the group Ib element to the group IIIb element in the first chalcogen element-containing layer is preferably 1.05 or more and less than 4.
It is more preferably 1 or more and less than 2. The content of the chalcogen element is preferably smaller than that of the second chalcogen element-containing layer, and the molar ratio of the chalcogen element to (Ib group element + IIIb group element) is 0.02 or more and less than 0.5, It is more preferably 0.05 or more and less than 0.3.
【００１２】第２カルコゲン元素含有層は、ＩＩＩｂ族
元素の表面凝集を抑制する役割と、カルコパイライト型
化合物薄膜のＩＩＩｂ族元素に対するＩｂ族元素のモル
比が１付近になるようにするための組成調整の役割があ
る。積層膜全体の、ＩＩＩｂ族元素に対するＩｂ族元素
のモル比は、１から大きく外れると、熱処理後にカルコ
パイライト型化合物とともに、Ｉｂ族元素やＩＩＩｂ族
元素のカルコゲナイド等の異なる結晶相が混在しやすく
なることから、第２カルコゲン元素含有層のＩＩＩｂ族
元素に対するＩｂ族元素のモル比は、１未満であること
が必要であり、０．１以上０．９５未満であることが好
ましく、０．３以上０．９未満であることがより好まし
い。また、ＩＩＩｂ族元素の表面凝集を抑制するために
は（Ｉｂ族元素＋ＩＩＩｂ族元素）に対するカルコゲン
元素のモル比を大きくするほど効果が顕著である。しか
し、そのモル比が大きすぎると結晶粒径の増大は逆に抑
制されてしまう。したがって、（Ｉｂ族元素＋ＩＩＩｂ
族元素）に対するカルコゲン元素のモル比は１未満で、
第１カルコゲン元素含有層のそれより大きいことが必要
であり、０．０５以上０．９未満であることが好まし
く、０．１以上０．６未満であることがより好ましい。The second chalcogen element-containing layer has a role of suppressing the surface aggregation of the group IIIb element and a composition for keeping the molar ratio of the group Ib element to the group IIIb element of the chalcopyrite type compound thin film close to 1. It has a coordination role. If the molar ratio of the group Ib element to the group IIIb element deviates greatly from 1 in the entire laminated film, different crystal phases such as chalcogenide of the group Ib element or the group IIIb element tend to be mixed together with the chalcopyrite type compound after the heat treatment. Therefore, the molar ratio of the group Ib element to the group IIIb element in the second chalcogen element-containing layer needs to be less than 1, preferably 0.1 or more and less than 0.95, and 0.3 or more. More preferably, it is less than 0.9. Further, in order to suppress the surface aggregation of the IIIb group element, the effect becomes more remarkable as the molar ratio of the chalcogen element to (Ib group element + IIIb group element) is increased. However, if the molar ratio is too large, the increase in crystal grain size is suppressed. Therefore, (Ib group element + IIIb
The molar ratio of chalcogen element to (group element) is less than 1,
It is necessary to be larger than that of the first chalcogen element-containing layer, preferably 0.05 or more and less than 0.9, and more preferably 0.1 or more and less than 0.6.
【００１３】第１、第２カルコゲン元素含有層にはそれ
ぞれ上記のような役割があり、これらの積層膜を熱処理
前の膜として用いると、基板との密着性及び表面平坦性
を保持しながら、Ｉｂ−ＩＩＩｂ−カルコゲン元素混合
膜（Ｃｕ−Ｉｎ−Ｓｅ混合膜等）を用いる場合と比較し
て、より結晶性の良好な（結晶粒径の大きい）カルコパ
イライト型化合物薄膜の形成が可能となる。The first and second chalcogen element-containing layers have the respective roles as described above, and when these laminated films are used as the film before heat treatment, the adhesion with the substrate and the surface flatness are maintained, As compared with the case of using an Ib-IIIb-chalcogen element mixed film (Cu-In-Se mixed film or the like), it becomes possible to form a chalcopyrite type compound thin film having better crystallinity (large crystal grain size). .
【００１４】さらに、第１および第２カルコゲン元素含
有層からなる積層膜全体の、ＩＩＩｂ族元素に対するＩ
ｂ元素のモル比は、１から大きく外れると、熱処理後に
カルコパイライト型化合物とともにＩｂ族元素やＩＩＩ
ｂ族元素のカルコゲナイド等の異なる結晶相が混在しや
すくなり、太陽電池特性の低下の原因となることがある
ため、モル比が０．６〜１．５の範囲にあることが好ま
しく、０．７〜１．１の範囲にあることがより好まし
い。また、熱処理後に形成されたカルコパイライト型化
合物薄膜の膜厚が太陽電池に適した、約２〜３μｍの範
囲になれば、第１および第２カルコゲン元素含有層の膜
厚は特に限定はされないが、いずれかが極端に薄い場
合、結晶成長促進もしくは表面凝集抑制の効果が十分に
発生しないため、いずれの層とも０．０５〜２μｍの範
囲にあることが好ましく、０．１〜１．５μｍの範囲に
あることがより好ましい。Further, I for the IIIb group element in the entire laminated film including the first and second chalcogen element-containing layers
If the molar ratio of the b element deviates greatly from 1, after the heat treatment, along with the chalcopyrite type compound, the lb group element or III
Since different crystal phases such as chalcogenide of the b-group element are likely to coexist, which may cause deterioration of solar cell characteristics, the molar ratio is preferably in the range of 0.6 to 1.5. It is more preferably in the range of 7 to 1.1. Moreover, if the thickness of the chalcopyrite type compound thin film formed after the heat treatment is in the range of about 2 to 3 μm, which is suitable for the solar cell, the thickness of the first and second chalcogen element-containing layers is not particularly limited. When either of the layers is extremely thin, the effect of promoting crystal growth or suppressing the surface agglomeration does not sufficiently occur. Therefore, it is preferable that both layers have a thickness of 0.05 to 2 μm and a thickness of 0.1 to 1.5 μm. It is more preferable to be in the range.
【００１５】また、熱処理前の薄膜中におけるカルコゲ
ン元素は、非晶質の状態で存在していると熱処理による
結晶性向上効果が大きくなるため好ましい。例えば、Ｉ
ｂ族元素、ＩＩＩｂ族元素、カルコゲン元素からなる非
晶質である混合膜やＩｂ族元素、ＩＩＩｂ族元素からな
る結晶質とカルコゲン元素の非晶質とが混合している膜
などが挙げられる。Further, it is preferable that the chalcogen element in the thin film before the heat treatment exists in an amorphous state because the effect of improving the crystallinity by the heat treatment becomes large. For example, I
Examples thereof include an amorphous mixed film containing a b-group element, a IIIb-group element, and a chalcogen element, a film including a crystalline mixture of a Ib-group element and a IIIb-group element, and an amorphous chalcogen element.
【００１６】カルコゲン元素を含有するガス雰囲気中で
熱処理する場合のガスとしては、カルコゲン元素単体の
蒸気、カルコゲン元素の水素化物、炭化物、メチル化
物、エチル化物等があり、中でも水素化物は熱処理効果
が大きく現れ好ましい。カルコゲン元素を含有するガス
の濃度は特に限定されないが、０．０１〜１００ｍｏｌ
％が好ましく、より好ましくは０．１〜３０ｍｏｌ．％
である。希釈ガスとしては、アルゴン、ヘリウム、窒素
などの不活性ガスが用いられ、水素を添加しても同様な
効果が現れる。熱処理の温度については、３００℃以上
であることが好ましく、また、熱処理時間については
０．５時間以上が好ましい。Gases for heat treatment in a gas atmosphere containing a chalcogen element include vapor of a single chalcogen element, hydride of chalcogen element, carbide, methylated product, ethylated product, etc. Among them, hydride has a heat treatment effect. It appears large and is preferable. The concentration of the gas containing the chalcogen element is not particularly limited, but 0.01 to 100 mol
%, More preferably 0.1 to 30 mol. %
Is. An inert gas such as argon, helium, or nitrogen is used as the diluting gas, and similar effects can be obtained by adding hydrogen. The heat treatment temperature is preferably 300 ° C. or higher, and the heat treatment time is preferably 0.5 hour or longer.
【００１７】本発明の特徴は、基板上に元素周期律表Ｉ
ＩＩｂ族元素に対するＩｂ族元素のモル比が１以上であ
るカルコゲン元素含有層、元素周期律表ＩＩＩｂ族元素
に対するＩｂ族元素のモル比が１未満で、且つ元素周期
律表Ｉｂ族及びＩＩＩｂ族元素に対するカルコゲン元素
のモル比が前記カルコゲン元素含有層のそれより大きく
１未満であるカルコゲン元素含有層を順次積層し、それ
を上記カルコゲン元素を含有する雰囲気中で熱処理する
ことにより、薄膜の表面形態及び面内組成が均一であ
り、且つ結晶性の高いカルコパイライト型化合物薄膜を
形成できることである。The feature of the present invention is that the periodic table I of the element is provided on the substrate.
A chalcogen element-containing layer in which the molar ratio of the Ib group element to the IIb group element is 1 or more, the molar ratio of the Ib group element to the IIIb group element in the periodic table of elements is less than 1, and the Ib group and the IIIb group element in the periodic table of the elements The chalcogen element-containing layer having a molar ratio of the chalcogen element to the chalcogen element is larger than that of the chalcogen element-containing layer and less than 1, and then heat-treated in an atmosphere containing the chalcogen element to obtain a surface morphology of the thin film and That is, it is possible to form a chalcopyrite type compound thin film having a uniform in-plane composition and high crystallinity.
【００１８】[0018]
【実施例】以下に、この発明の実施例を具体的に説明す
る。EXAMPLES Examples of the present invention will be specifically described below.
【００１９】[0019]
【実施例１】Ｍｏをスパッタしたソーダライムガラス基
板上に、Ａｒ希釈５ｍｏｌ％Ｈ2 Ｓをスパッタガス、Ｃ
ｕおよびＩｎをターゲットとした２元同時スパッタ法に
よってＣｕ、Ｉｎ、Ｓからなる第１層を形成し、その上
にＣｕターゲットへの印加パワーを低くして連続してＣ
ｕ、Ｉｎ、Ｓからなる第２層を形成して膜厚１．８μｍ
の積層膜を作製した。なお、膜厚は（株）日本真空技術
製 ＤＥＫＴＡＫ１１Ａを用いて測定した。あらかじ
め、この第１層、第２層と同じスパッタ条件でそれぞれ
を別の基板上に形成しておいて、Ｃｕ、Ｉｎ、Ｓの組成
比をＥＰＭＡ（日本電子（株） ＪＣＸＡ−７３３）に
より測定したところ、それぞれ、５０ａｔ％、４０ａｔ
％、１０ａｔ％（Ｃｕ／Ｉｎ＝１．２５、Ｓ／（Ｃｕ＋
Ｉｎ）＝０．１１）、３５ａｔ％、４５ａｔ％、２０ａ
ｔ％（Ｃｕ／Ｉｎ＝０．７８、Ｓ／（Ｃｕ＋Ｉｎ）＝
０．２５）であった。次に、この薄膜を５ｍｏｌ．％の
Ｈ2 Ｓを含むＡｒガス雰囲気中５５０℃で３時間熱処理
を行った。熱処理後の薄膜の組成比をＥＰＭＡにより測
定したところ、Ｃｕ２５ａｔ％、Ｉｎ２５ａｔ％、Ｓ５
０ａｔ％であり、化学量論組成のＣｕＩｎＳ2 薄膜が形
成された。また、この薄膜の構造をＸ線回折にて解析し
たところ、ＣｕＩｎＳ2 の単一相であった。さらに、こ
の薄膜の表面をＳＥＭにより観察したところ、粒径２μ
ｍの均一なモルフォロジーであることが確認された。ま
た、基板との密着性は良好であった。Example 1 On a soda lime glass substrate sputtered with Mo, 5 mol% H 2 S diluted with Ar was used as sputter gas and C.
A first layer made of Cu, In, and S is formed by a binary co-sputtering method using u and In as targets, and the applied power to the Cu target is lowered on the first layer to continuously form C.
A second layer made of u, In, and S is formed to have a film thickness of 1.8 μm.
A laminated film of The film thickness was measured using DEKTAK11A manufactured by Nippon Vacuum Technology Co., Ltd. The first and second layers were formed on different substrates under the same sputtering conditions in advance, and the composition ratios of Cu, In, and S were measured by EPMA (JCXA-733, JEOL Ltd.). As a result, 50at% and 40at respectively
%, 10 at% (Cu / In = 1.25, S / (Cu +
In) = 0.11), 35at%, 45at%, 20a
t% (Cu / In = 0.78, S / (Cu + In) =
0.25). Next, this thin film was treated with 5 mol. Heat treatment was performed at 550 ° C. for 3 hours in an Ar gas atmosphere containing H 2 S in an amount of 3%. When the composition ratio of the thin film after the heat treatment was measured by EPMA, it was found that Cu25at%, In25at%, S5
A CuInS 2 thin film having a stoichiometric composition of 0 at% was formed. When the structure of this thin film was analyzed by X-ray diffraction, it was a single phase of CuInS 2 . Furthermore, when the surface of this thin film was observed by SEM, the particle size was 2 μm.
It was confirmed that the m had a uniform morphology. Also, the adhesion to the substrate was good.
【００２０】１μｍのＭｏをスパッタ成膜したソーダラ
イムガラス基板上に、上記の方法により３μｍのＣｕＩ
ｎＳ2 薄膜を形成した。さらにその上に、５０ｎｍのＣ
ｄＳ薄膜を溶液成長法により、１．５μｍのＺｎＯ：Ａ
ｌ薄膜（ＡｌドープＺｎＯ）をスパッタにより順次形成
することにより、図２と同じ構造の薄膜太陽電池を作製
した。この太陽電池素子にＡＭ１．５の光を照射したと
ころ、変換効率は９．８％であった。On a soda-lime glass substrate on which 1 μm of Mo was sputter-deposited, CuI of 3 μm was formed by the above method.
An nS 2 thin film was formed. On top of that, C of 50 nm
The dS thin film was formed by a solution growth method to obtain ZnO: A of 1.5 μm.
A thin film solar cell having the same structure as that shown in FIG. 2 was produced by sequentially forming a thin film (Al-doped ZnO) by sputtering. When this solar cell element was irradiated with light of AM1.5, the conversion efficiency was 9.8%.
【００２１】[0021]
【比較例１】Ｍｏをスパッタしたソーダライムガラス基
板上に、Ａｒ希釈１０ｍｏｌ％Ｈ2Ｓをスパッタガス、
ＣｕおよびＩｎをターゲットとした２元同時スパッタ法
によってＣｕ、Ｉｎ、Ｓからなる薄膜を形成した。この
薄膜のＣｕ、Ｉｎ、Ｓの組成比をＥＰＭＡ（日本電子
（株） ＪＣＸＡ−７３３）により測定したところ、そ
れぞれ、３７ａｔ％、３７ａｔ％、２６ａｔ％（Ｃｕ／
Ｉｎ＝１．００、Ｓ／（Ｃｕ＋Ｉｎ）＝０．３５）であ
った。次に、この薄膜を５ｍｏｌ．％のＨ2 Ｓを含むＡ
ｒガス雰囲気中５５０℃で３時間熱処理を行った。熱処
理後の薄膜の組成比をＥＰＭＡにより測定したところ、
Ｃｕ２５ａｔ％、Ｉｎ２５ａｔ％、Ｓ５０ａｔ％であ
り、化学量論組成のＣｕＩｎＳ2 薄膜が形成された。ま
た、この薄膜の構造をＸ線回折にて解析したところ、Ｃ
ｕＩｎＳ2 の単一相であった。さらに、この薄膜の表面
をＳＥＭにより観察したところ、粒径１μｍの均一なモ
ルフォロジーであることが確認された。また、基板との
密着性は良好であった。Comparative Example 1 Ar-diluted 10 mol% H 2 S was sputtered on a soda-lime glass substrate sputtered with Mo,
A thin film made of Cu, In, and S was formed by a binary co-sputtering method targeting Cu and In. The composition ratio of Cu, In, and S of this thin film was measured by EPMA (JCXA-733, JEOL Ltd.), and 37 at%, 37 at%, and 26 at% (Cu /
In = 1.00 and S / (Cu + In) = 0.35). Next, this thin film was treated with 5 mol. % Containing 2 % H 2 S
Heat treatment was performed at 550 ° C. for 3 hours in an r gas atmosphere. When the composition ratio of the thin film after heat treatment was measured by EPMA,
Cu25at%, In25at%, and S50at%, and a CuInS 2 thin film having a stoichiometric composition was formed. Further, when the structure of this thin film was analyzed by X-ray diffraction, C
It was a single phase of uInS 2 . Further, when the surface of this thin film was observed by SEM, it was confirmed that the thin film had a uniform morphology with a particle size of 1 μm. Also, the adhesion to the substrate was good.
【００２２】１μｍのＭｏをスパッタ成膜したソーダラ
イムガラス基板上に、上記の方法により３μｍのＣｕＩ
ｎＳ2 薄膜を形成した。さらにその上に、５０ｎｍのＣ
ｄＳ薄膜を溶液成長法により、１．５μｍのＺｎＯ：Ａ
ｌ薄膜（ＡｌドープＺｎＯ）をスパッタにより順次形成
することにより、図２と同じ構造の薄膜太陽電池を作製
した。この太陽電池素子にＡＭ１．５の光を照射したと
ころ、変換効率は６．８％であった。On a soda-lime glass substrate on which 1 μm of Mo was sputter-deposited, CuI of 3 μm was formed by the above method.
An nS 2 thin film was formed. On top of that, C of 50 nm
The dS thin film was formed by a solution growth method to obtain ZnO: A of 1.5 μm.
A thin film solar cell having the same structure as that shown in FIG. 2 was produced by sequentially forming a thin film (Al-doped ZnO) by sputtering. When this solar cell element was irradiated with light of AM1.5, the conversion efficiency was 6.8%.
【００２３】[0023]
【比較例２】Ａｒをスパッタガスとして用いたこと以外
は比較例１と同様にして、Ｃｕ、Ｉｎからなる薄膜を形
成した。この薄膜のＣｕ、Ｉｎの組成比をＥＰＭＡ（日
本電子（株） ＪＣＸＡ−７３３）により測定したとこ
ろ、それぞれ５０ａｔ％、５０ａｔ％（Ｃｕ／Ｉｎ：
１．００）であった。次に、この薄膜を５ｍｏｌ．％の
Ｈ2 Ｓを含むＡｒガス雰囲気中５５０℃で３時間熱処理
を行った。熱処理後の薄膜の組成比をＥＰＭＡにより測
定したところ、Ｃｕ２５ａｔ％、Ｉｎ２５ａｔ％、Ｓ５
０ａｔ％であり、化学量論組成のＣｕＩｎＳ2 薄膜が形
成された。また、この薄膜の構造をＸ線回折にて解析し
たところ、ＣｕＩｎＳ2 の単一相であった。さらに、こ
の薄膜の表面をＳＥＭにより観察したところ、粒径が
０．３〜２．０μｍと粒径の大きな結晶が存在するが、
不均一なモルフォロジーであった。また、基板との密着
性は悪く剥離し易かった。実施例１と同様に作製した太
陽電池素子にＡＭ１．５の光を照射したところ、変換効
率は３．２％であった。Comparative Example 2 A thin film made of Cu and In was formed in the same manner as in Comparative Example 1 except that Ar was used as the sputtering gas. When the composition ratio of Cu and In of this thin film was measured by EPMA (JCXA-733, JEOL Ltd.), it was 50 at% and 50 at% (Cu / In:
It was 1.00). Next, this thin film was treated with 5 mol. Heat treatment was performed at 550 ° C. for 3 hours in an Ar gas atmosphere containing H 2 S in an amount of 3%. When the composition ratio of the thin film after the heat treatment was measured by EPMA, it was found that Cu25at%, In25at%, S5
A CuInS 2 thin film having a stoichiometric composition of 0 at% was formed. When the structure of this thin film was analyzed by X-ray diffraction, it was a single phase of CuInS 2 . Furthermore, when the surface of this thin film was observed by SEM, crystals with a large grain size of 0.3 to 2.0 μm existed.
The morphology was non-uniform. In addition, the adhesion to the substrate was poor and peeling was easy. When the solar cell element manufactured in the same manner as in Example 1 was irradiated with light of AM1.5, the conversion efficiency was 3.2%.
【００２４】[0024]
【実施例２】Ｍｏをスパッタしたソーダライムガラス基
板上に、Ｃｕ、Ｉｎ、Ｓｅを蒸発源とした真空同時蒸着
法により、Ｃｕ、Ｉｎ、Ｓｅからなる第１層を形成し、
その上にＣｕの蒸発量を低く、Ｓｅの蒸発量を高くし
て、連続してＣｕ、Ｉｎ、Ｓｅからなる第２層を形成し
て膜厚２．０μｍの積層膜を作製した。なお、膜厚は
（株）日本真空技術製 ＤＥＫＴＡＫ１１Ａを用いて測
定した。この第１層、第２層と同じ蒸着条件でそれぞれ
を別の基板上に形成しておいて、Ｃｕ、Ｉｎ、Ｓｅの組
成比をＥＰＭＡ（日本電子（株） ＪＣＸＡ−７３３）
により測定したところ、それぞれ、４８ａｔ％、３２ａ
ｔ％、２０ａｔ％（Ｃｕ／Ｉｎ＝１．５０、Ｓｅ／（Ｃ
ｕ＋Ｉｎ）＝０．２５）、２５ａｔ％、４０ａｔ％、３
５ａｔ％（Ｃｕ／Ｉｎ＝０．６３、Ｓｅ／（Ｃｕ＋Ｉ
ｎ）＝０．５４）であった。次に、この薄膜を真空中に
おいてＳｅ蒸気を当てながら５００℃で２時間熱処理を
行った。熱処理後の薄膜の組成比をＥＰＭＡにより測定
したところ、Ｃｕ２５ａｔ％、Ｉｎ２５ａｔ％、Ｓｅ５
０ａｔ％であり、化学量論組成のＣｕＩｎＳｅ2 薄膜が
形成された。また、この薄膜の構造をＸ線回折にて解析
したところ、ＣｕＩｎＳｅ 2 の単一相であった。さら
に、この薄膜の表面をＳＥＭにより観察したところ、粒
径２μｍの均一なモルフォロジーであることが確認され
た。また、基板との密着性は良好であった。上記の方法
により作製したＣｕＩｎＳｅ2 薄膜をＣｕＩｎＳ2 薄膜
の代わりに用いて実施例１と同様な構造の太陽電池素子
を作製し、これにＡＭ１．５の光を照射したところ、変
換効率は１４．８％であった。Example 2 Mo-sputtered soda lime glass substrate
Vacuum simultaneous vapor deposition using Cu, In, and Se as evaporation sources on the plate
Forming a first layer of Cu, In, and Se by
On top of that, lower the evaporation of Cu and increase the evaporation of Se.
To continuously form a second layer of Cu, In, and Se.
As a result, a laminated film having a film thickness of 2.0 μm was produced. The film thickness is
Measured using DEKTAK 11A manufactured by Nippon Vacuum Technology Co., Ltd.
Decided Under the same vapor deposition conditions as the first and second layers,
Is formed on another substrate, and a set of Cu, In and Se is formed.
The composition ratio is EPMA (JEOL Ltd. JCXA-733)
When measured by, respectively, 48at%, 32a
t%, 20 at% (Cu / In = 1.50, Se / (C
u + In) = 0.25), 25 at%, 40 at%, 3
5 at% (Cu / In = 0.63, Se / (Cu + I
n) = 0.54). Next, put this thin film in a vacuum.
Heat treatment at 500 ° C for 2 hours while applying Se vapor.
went. Measure composition ratio of thin film after heat treatment by EPMA
After that, Cu25at%, In25at%, Se5
CuInSe having a stoichiometric composition of 0 at%2Thin film
Been formed. In addition, the structure of this thin film is analyzed by X-ray diffraction.
After that, CuInSe 2It was a single phase of. Further
When the surface of this thin film was observed by SEM,
It was confirmed that the morphology was uniform with a diameter of 2 μm.
Was. Also, the adhesion to the substrate was good. Method above
CuInSe produced by2CuInS thin film2Thin film
A solar cell element having the same structure as in Example 1
Was manufactured and irradiated with AM1.5 light,
The conversion efficiency was 14.8%.
【００２５】[0025]
【比較例３】Ｍｏをスパッタしたソーダライムガラス基
板上に、Ｃｕ、Ｉｎ、Ｓｅを蒸発源とした真空同時蒸着
法により、Ｃｕ、Ｉｎ、Ｓｅからなる薄膜を形成した。
この薄膜のＣｕ、Ｉｎ、Ｓｅの組成比をＥＰＭＡ（日本
電子（株） ＪＣＸＡ−７３３）により測定したとこ
ろ、それぞれ、３５ａｔ％、３５ａｔ％、３０ａｔ％
（Ｃｕ／Ｉｎ＝１．００、Ｓｅ／（Ｃｕ＋Ｉｎ）＝０．
４３）であった。 次に、この薄膜を真空中においてＳ
ｅ蒸気を当てながら５００℃で２時間熱処理を行った。
熱処理後の薄膜の組成比をＥＰＭＡにより測定したとこ
ろ、Ｃｕ２５ａｔ％、Ｉｎ２５ａｔ％、Ｓｅ５０ａｔ％
であり、化学量論組成のＣｕＩｎＳｅ2 薄膜が形成され
た。また、この薄膜の構造をＸ線回折にて解析したとこ
ろ、ＣｕＩｎＳｅ2 の単一相であった。さらに、この薄
膜の表面をＳＥＭにより観察したところ、粒径が１μｍ
と均一なモルフォロジーであった。また、基板との密着
性は良好であった。実施例２と同様に作製した太陽電池
素子にＡＭ１．５の光を照射したところ、変換効率は１
１．０％であった。Comparative Example 3 A thin film of Cu, In and Se was formed on a soda lime glass substrate sputtered with Mo by a vacuum co-evaporation method using Cu, In and Se as evaporation sources.
The composition ratios of Cu, In, and Se of this thin film were measured by EPMA (JCXA-733, JEOL Ltd.), and were 35 at%, 35 at%, and 30 at%, respectively.
(Cu / In = 1.00, Se / (Cu + In) = 0.
43). Next, this thin film is subjected to S in vacuum.
e Heat treatment was performed at 500 ° C. for 2 hours while applying steam.
When the composition ratio of the thin film after heat treatment was measured by EPMA, Cu25at%, In25at%, Se50at%
And a CuInSe 2 thin film having a stoichiometric composition was formed. When the structure of this thin film was analyzed by X-ray diffraction, it was a single phase of CuInSe 2 . Furthermore, when the surface of this thin film was observed by SEM, the particle size was 1 μm.
And had a uniform morphology. Also, the adhesion to the substrate was good. When the solar cell element manufactured in the same manner as in Example 2 was irradiated with light of AM1.5, the conversion efficiency was 1
It was 1.0%.
【００２６】[0026]
【発明の効果】本発明によれば、表面形態及び面内組成
が均一であり、且つ結晶性の高いカルコパイライト型化
合物薄膜を形成することができ、この薄膜を用いて作製
した薄膜太陽電池は良好な特性を示す。According to the present invention, a chalcopyrite type compound thin film having a uniform surface morphology and in-plane composition and high crystallinity can be formed, and a thin film solar cell manufactured using this thin film is Shows good properties.
【図１】本発明によるカルコパイライト型化合物薄膜の
作製プロセスの一例を示す。FIG. 1 shows an example of a process for producing a chalcopyrite type compound thin film according to the present invention.
【図２】本発明によるカルコパイライト型化合物薄膜を
用いた太陽電池の素子構造の１例を示す断面図である。FIG. 2 is a sectional view showing an example of an element structure of a solar cell using a chalcopyrite type compound thin film according to the present invention.
１ 基板 ２ 導電性薄膜 ３ 第１カルコゲン元素含有層 ４ 第２カルコゲン元素含有層 ５ カルコパイライト型化合物薄膜 ６ ｎ型半導体層 ７ 透明電極層 DESCRIPTION OF SYMBOLS 1 Substrate 2 Conductive thin film 3 First chalcogen element-containing layer 4 Second chalcogen element-containing layer 5 Chalcopyrite type compound thin film 6 n-type semiconductor layer 7 Transparent electrode layer
Claims (2)
元素及びカルコゲン元素（Ｓ、Ｓｅ及びＴｅ）からな
り、且つＩｂ族元素／ＩＩＩｂ族元素≧１（モル比）で
ある薄膜を第１層として基板上に形成し、次いで、Ｉｂ
族元素／ＩＩＩｂ族元素＜１（モル比）で、且つカルコ
ゲン元素／（Ｉｂ族元素＋ＩＩＩｂ族元素）（モル比）
が第１層のそれより大きく１未満である薄膜を第２層と
して第１層上に形成することにより得られた薄膜を上記
カルコゲン元素を含有する雰囲気中で熱処理することを
特徴とするカルコパイライト型化合物薄膜の製造方法。1. A thin film comprising an Ib group element, a IIIb group element and a chalcogen element (S, Se and Te) of the Periodic Table of Elements, wherein Ib group element / IIIb group element ≧ 1 (molar ratio). Formed on the substrate as a layer, then Ib
Group element / IIIb group element <1 (molar ratio) and chalcogen element / (Ib group element + IIIb group element) (molar ratio)
A thin film obtained by forming a thin film having a value of greater than that of the first layer and less than 1 as a second layer on the first layer, and heat treating the thin film in an atmosphere containing the chalcogen element. Method for producing thin type compound thin film.
薄膜太陽電池の製造方法において、該カルコパイライト
型化合物薄膜を、請求項１記載の製造方法で製造するこ
とを特徴とする薄膜太陽電池の製造方法。2. A method of manufacturing a thin-film solar cell using a chalcopyrite type compound thin film, wherein the chalcopyrite type compound thin film is manufactured by the manufacturing method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7003872A JPH08195499A (en) | 1995-01-13 | 1995-01-13 | Manufacture of chalcopyrite compound film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7003872A JPH08195499A (en) | 1995-01-13 | 1995-01-13 | Manufacture of chalcopyrite compound film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08195499A true JPH08195499A (en) | 1996-07-30 |
Family
ID=11569287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7003872A Withdrawn JPH08195499A (en) | 1995-01-13 | 1995-01-13 | Manufacture of chalcopyrite compound film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08195499A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001148489A (en) * | 1999-09-07 | 2001-05-29 | Shinko Electric Ind Co Ltd | Manufacturing method for compound semiconductor solar battery |
| JP2011176204A (en) * | 2010-02-25 | 2011-09-08 | Kyocera Corp | Method of manufacturing semiconductor layer, and method of manufacturing photoelectric conversion device |
| JP2012222006A (en) * | 2011-04-04 | 2012-11-12 | Tdk Corp | Solar cell, and manufacturing method of solar cell |
-
1995
- 1995-01-13 JP JP7003872A patent/JPH08195499A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001148489A (en) * | 1999-09-07 | 2001-05-29 | Shinko Electric Ind Co Ltd | Manufacturing method for compound semiconductor solar battery |
| JP2011176204A (en) * | 2010-02-25 | 2011-09-08 | Kyocera Corp | Method of manufacturing semiconductor layer, and method of manufacturing photoelectric conversion device |
| JP2012222006A (en) * | 2011-04-04 | 2012-11-12 | Tdk Corp | Solar cell, and manufacturing method of solar cell |
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