JP2975693B2 - Method for producing chalcopyrite-type compound thin film - Google Patents
Method for producing chalcopyrite-type compound thin filmInfo
- Publication number
- JP2975693B2 JP2975693B2 JP3013631A JP1363191A JP2975693B2 JP 2975693 B2 JP2975693 B2 JP 2975693B2 JP 3013631 A JP3013631 A JP 3013631A JP 1363191 A JP1363191 A JP 1363191A JP 2975693 B2 JP2975693 B2 JP 2975693B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- thin film
- substrate
- chalcopyrite
- type compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えばCdＳ膜との接合
よりなる薄膜太陽電池の材料として用いられる、ＸInＹ
2 なる化学式をもち、ＸがAgあるいはCuであり、ＹがSe
あるいはＳであるカルコパイライト型化合物薄膜の製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film solar cell comprising, for example, a junction with a CdS film.
Has 2 becomes formula, X is Ag or Cu, Y is Se
Alternatively, the present invention relates to a method for producing a chalcopyrite-type compound thin film of S.
【０００２】[0002]
【従来の技術】Ｉ−III −ＶI 2 族の組成をもつカルコ
パイライト型化合物、特にCuInSe2 , CuInSe, AgInＳ2
は、光学バンドギャップが1.0 〜1.8eV の範囲にあり、
バンドギャップ1.7 eVのシリコンと異なる光学バンドギ
ャップを有するものが得られるため、その利用が期待さ
れている。近年、薄膜形成技術の進展により、薄膜太陽
電池素子材料としてのこれらの物質は一層注目されてい
る。例えばCuInSe2 は、その光学バンドギャップが約１
eVであって直接遷移形の帯構造を持ち、ｐおよびｎ型の
導電性を示す。また、バンドギャップ2.4 eVのCdＳとは
格子の不整合も１％程度であり、従ってｎ型CdＳを窓層
材料として用いたｐ型CuInSe2 のヘテロ接合で高効率太
陽電池が得られる可能性があることから、近年その研
究, 開発が盛んに進められている。また、CuInＳ2 とCd
S とのヘテロ接合を用いた薄膜太陽電池も研究されてお
り、さらにバンドギャップの広いAgInSe2 , AgInＳも発
光素子用材料として注目されている。ここで、CuInSe2
を例にとりカルコパイライト系化合物薄膜の製造方法の
従来技術について説明する。一つの方法は、基板上にス
パッタリングによりCu, Inの順に積層し、セレン含有雰
囲気中で約 400℃に加熱してCuInSe2 薄膜を得る方法で
ある。以下この方法を気相セレン化方法と記す。あるい
は、基板上に蒸着あるいはスパッタリングによりCu, I
n, Seを積層し、不活性気体中で約 400℃に加熱処理す
ることによってCuInSe2 薄膜を得る方法もある。以下こ
の方法を固相セレン化方法と記す。両方法とも、大面積
化やインライン化が容易で工業上注目されている。その
インライン化の例として図２(a) 〜(f) に示されるよう
な気相セレン化方法を用いた特開昭62−20381 により公
知のCuInSe2 薄膜太陽電池の作成プロセスがある。すな
わち、ガラス板上にCr, Moをコートした基板１ (同図
(a))上に、ＤＣマグネトロンスパッタリング法により同
一真空中でCu膜２ (同図(b)), In膜３ (同図(c))を順次
室温で形成した後、Arで希釈されたSe, 例えば３％〜15
％Ｈ2 Seを含有するガス中にて400 ℃数時間加熱するこ
とにより、CuInSe2 薄膜４を形成する (同図(d))。そし
て、その上にｎ型CdＳ膜５ (同図(e))、ZnＯからなる透
明電極６ (同図(f))を順次積層する。 2. Description of the Related Art Chalcopyrite-type compounds having a composition of group I-III-VI 2 , especially CuInSe 2 , CuInSe, AgInS 2
Has an optical band gap in the range of 1.0 to 1.8 eV,
Since a material having an optical band gap different from that of silicon having a band gap of 1.7 eV can be obtained, its use is expected. In recent years, with the progress of thin film formation technology, these substances as thin film solar cell element materials have been receiving more attention. For example, CuInSe 2 has an optical band gap of about 1
It has an eV, direct transition band structure, and exhibits p-type and n-type conductivity. In addition, the lattice mismatch with CdS having a band gap of 2.4 eV is about 1%. Therefore, a high-efficiency solar cell may be obtained with a p-type CuInSe 2 heterojunction using n-type CdS as a window layer material. Therefore, research and development have been actively promoted in recent years. In addition, CuInS 2 and Cd
Thin-film solar cells using a heterojunction with S have also been studied, and AgInSe 2 and AgInS having a wide band gap have also attracted attention as materials for light emitting devices. Where CuInSe 2
An example of a conventional method for producing a chalcopyrite-based compound thin film will be described. One method is to obtain a CuInSe 2 thin film by laminating Cu and In in this order on a substrate by sputtering and heating to about 400 ° C. in an atmosphere containing selenium. Hereinafter, this method is referred to as a gas-phase selenization method. Alternatively, Cu, I
There is also a method of obtaining a CuInSe 2 thin film by laminating n and Se and heating at about 400 ° C. in an inert gas. Hereinafter, this method is referred to as a solid-phase selenization method. Both methods are easy to increase in area and in-line, and have attracted industrial attention. As an example of the in-line conversion, there is a process for producing a CuInSe 2 thin-film solar cell known from Japanese Patent Application Laid-Open No. 62-20381 using a gas-phase selenization method as shown in FIGS. That is, a substrate 1 in which Cr and Mo are coated on a glass plate (see FIG.
(a)), a Cu film 2 (FIG. 2 (b)) and an In film 3 (FIG. 2 (c)) were sequentially formed at room temperature in the same vacuum by DC magnetron sputtering, and then diluted with Ar. Se, eg 3% ~ 15
By heating at 400 ° C. for several hours in a gas containing% H 2 Se, a CuInSe 2 thin film 4 is formed (FIG. 4D). Then, an n-type CdS film 5 (FIG. 9E) and a transparent electrode 6 made of ZnO (FIG. 9F) are sequentially stacked thereon.
【０００３】[0003]
【発明が解決しようとする課題】図２に示した気相セレ
ン化方法でも、また固相セレン化方法でも、蒸着法ある
いはスパッタリング法によってCu, In等の金属膜の形成
を行う場合、それぞれの膜が基板上に一様に形成される
必要がある。Cuについては室温で成膜を行っても均一に
膜が形成されるが、Inは融点が156.4 ℃と低いことか
ら、室温で成膜を行うと、成膜時の温度上昇により基板
上に円形の島状の膜厚の厚い部分が生じ、結果として形
成されるCuInSe2 膜は粒径の不揃いにより表面が凹凸に
なり、太陽電池にしたときの接合面が十分に形成でき
ず、短絡が大きくなり、またIn組成も不均一になるの
で、良好な太陽電池特性が得られないという問題があっ
た。これに対し、基板を液体窒素を用いて−173 ℃迄冷
却する方法がH.DittrichらによりProc. 9th E.C.Photov
oltaic Solar Energy Conf (Freiburg, 1989年) pp.163
〜166 に報告されている。しかし、蒸着装置あるいはス
パッタリング装置の基板支持体を液体窒素で冷却するこ
とは、液体窒素の使用量や構造上の点で問題があり、工
業化には適さない。In the vapor-phase selenization method shown in FIG. 2 and the solid-phase selenization method, when a metal film such as Cu or In is formed by a vapor deposition method or a sputtering method, the respective methods are described. The film needs to be formed uniformly on the substrate. Even if Cu is deposited at room temperature, a uniform film is formed. However, since In has a low melting point of 156.4 ° C, when deposited at room temperature, the temperature rises during deposition to form a circle on the substrate. The resulting CuInSe 2 film has an irregular surface due to uneven particle size, and the junction surface when formed into a solar cell cannot be formed sufficiently, resulting in a large short circuit. In addition, since the In composition becomes non-uniform, good solar cell characteristics cannot be obtained. On the other hand, a method of cooling a substrate to −173 ° C. using liquid nitrogen is described by H. Dittrich et al. In Proc. 9th ECPhotov.
oltaic Solar Energy Conf (Freiburg, 1989) pp.163
~ 166. However, cooling a substrate support of a vapor deposition apparatus or a sputtering apparatus with liquid nitrogen has problems in terms of the amount of liquid nitrogen used and its structure, and is not suitable for industrialization.
【０００４】本発明の目的は、上記の問題を解決し、表
面に凹凸のないＸInＹ2 化学式をもつ均一な特性のカル
コパイライト型化合物薄膜の工業化に適した製造方法を
提供することにある。An object of the present invention is to solve the above-mentioned problems and to provide a production method suitable for industrialization of a chalcopyrite-type compound thin film having a uniform characteristic having an XInY 2 chemical formula having no irregularities on the surface.
【０００５】[0005]
【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、ＸInＹ2 なる化学式をもち、ＸがAgあ
るいはCuであり、ＹがSeあるいはＳであるカルコパイラ
イト型化合物からなる薄膜を基板上にＸ元素およびInの
膜を積層後、Ｙ元素を含む雰囲気中で加熱して製造する
に際し、Inの成膜時に基板を−100 ℃ないし−20℃の温
度に保持するものとする。または、Inの成膜時に基板を
Inの融点以上で600 ℃以下の温度に保持するか、あるい
はＸ元素およびInの膜を積層後、基板をInの融点以上で
600 ℃以下の温度に加熱するものとする。さらに本発明
は、上記のカルコパイライト型化合物からなる薄膜を基
板上に、Ｘ元素, InおよびＹ元素の膜を積層後加熱して
製造するに際し、In成膜時に基板を−100 ℃ないし−20
℃の温度に保持するか、またはInの成膜時に基板をInの
融点以上で600 ℃以下の温度に保持するか、あるいは基
板上に、Ｘ元素, Inの膜を積層後、Ｙ元素の膜の積層前
に基板をInの融点以上で600 ℃以下の温度に加熱するも
のとする。According to the present invention, there is provided a chalcopyrite-type compound having a chemical formula of XInY 2 , wherein X is Ag or Cu, and Y is Se or S. When laminating a thin film on the substrate, laminating a film of X element and In, and then heating the film in an atmosphere containing Y element, the substrate should be kept at a temperature of -100 ° C to -20 ° C during the deposition of In. I do. Alternatively, the substrate can be
Keep the temperature above the melting point of In and 600 ° C or below, or after laminating the X element and In films,
Heat to a temperature of 600 ° C or less. Further, the present invention provides a method of manufacturing a thin film comprising the chalcopyrite-type compound by laminating a film of the X element, In and Y elements on a substrate and then heating the film.
℃, or the substrate is kept at a temperature higher than the melting point of In and 600 ° C. or less during the film formation of In, or a film of Y element after laminating a film of X element and In on the substrate. Before lamination, the substrate is heated to a temperature not lower than the melting point of In and not higher than 600 ° C.
【０００６】[0006]
【作用】室温で基板上にIn膜を形成した場合は島状Inの
寸法は２〜５μm にも達し、このようなIn膜を用いてカ
ルコパイライト型化合物の膜を製造した場合は、化合物
粒径も２〜５μm と大きくなる。基板温度を冷却してい
くと島状Inの寸法は次第に小さくなり、基板温度−20〜
−100 ℃の範囲で0.2 〜１μm 程度となる。−100 ℃よ
りさらに低温にすると島状Inの寸法はさらに小さくなる
が、冷却手段の問題から実用的でない。[Action] When an In film is formed on a substrate at room temperature, the size of the island-like In reaches 2 to 5 μm. When a film of a chalcopyrite-type compound is manufactured using such an In film, the compound particles are formed. The diameter also increases to 2 to 5 μm. As the substrate temperature is reduced, the size of the island-like In gradually decreases, and the substrate temperature decreases from -20 to
In the range of −100 ° C., it is about 0.2 to 1 μm. If the temperature is lower than −100 ° C., the size of the island-like In becomes smaller, but it is not practical due to the problem of cooling means.
【０００７】一方、In膜形成時の基板温度を、Inの融点
(156.4 ℃) 以上で600 ℃以下の温度に保持するか、あ
るいは、Ｘ膜およびIn膜を室温で積層した後、基板をIn
の融点 (156.4 ℃) 以上で600 ℃以下の温度に加熱する
ことにより、Inが溶融するために不均一だったIn膜が均
一化される。また、Ｘ元素との相互拡散が促進される。
このことによりＸ−In金属間化合物が完全に生成され、
In膜の不均一性を低減することが可能となり、これを用
いて作成したカルコパイライト型化合物薄膜の均一性の
向上がみられる。On the other hand, the substrate temperature at the time of forming the In film is set to the melting point of In.
(156.4 ° C) or higher and maintained at a temperature of 600 ° C or lower, or after laminating the X film and the In film at room temperature,
By heating to a temperature not lower than the melting point of (156.4 ° C.) and not higher than 600 ° C., the non-uniform In film due to the melting of In becomes uniform. Further, mutual diffusion with the X element is promoted.
This completely forms the X-In intermetallic compound,
The non-uniformity of the In film can be reduced, and the uniformity of the chalcopyrite-type compound thin film formed using the same can be improved.
【０００８】[0008]
【実施例】以下、図を引用して本発明の実施例について
説明する。図１(a) 〜(d) は気相セレン化法の工程であ
り、ガラス基板１ (同図(a))あるいは表面にMo層を被着
したガラス基板の上に蒸着法あるいはスパッタリング法
により3000Åの厚さのCu膜２を形成する (同図(b))。次
いで冷媒を用いて基板温度を−20〜−100 ℃に保ち、蒸
着法あるいはスパッタリング法で6600Åの厚さのIn膜３
を積層する (同図(c))。このIn膜の島状Inの寸法は0.2
〜１μｍであった。そのあと、例えば３〜15％のＨ2 Se
をArにより希釈したようなセレン含有雰囲気中で 400℃
で１時間加熱することによりCuInSe2 膜４を形成する
(同図(d))。あるいはCu膜２, In膜３積層後、基板を 35
0℃に加熱しジメチルセレン尿素水溶液を噴霧状にして
その表面に吹付けてCuInSe2 膜を形成してもよい。この
ようにして形成したｐ型CuInSe2膜の上に厚さ約0.5 μm
のｎ型CdS 膜を積層してｐｎ接合を形成した。このｐｎ
接合を用いた太陽電池では効率８〜10％が得られた。In
膜３の成膜時の基板温度を−100 ℃よりさらに低くした
場合、島状Inの寸法は0.2 μｍよりさらに小さくなる
が、太陽電池の特性では大きな改善はなかった。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the drawings. FIGS. 1 (a) to 1 (d) show a vapor-phase selenization process, which is performed by vapor deposition or sputtering on a glass substrate 1 (FIG. 1 (a)) or a glass substrate having a surface coated with a Mo layer. A Cu film 2 having a thickness of 3000 mm is formed (FIG. 2B). Then, the temperature of the substrate is kept at -20 to -100 ° C using a refrigerant, and the In film 3 having a thickness of 6600Å is formed by a vapor deposition method or a sputtering method.
Are laminated (FIG. (C)). The size of the island-like In of this In film is 0.2
１1 μm. Then, for example, 3-15% H 2 Se
400 ° C in a selenium-containing atmosphere such as diluted with Ar
To form CuInSe 2 film 4 by heating for 1 hour
(Figure (d)). Alternatively, after laminating Cu film 2 and In film 3,
The CuInSe 2 film may be formed by heating to 0 ° C. and spraying an aqueous solution of dimethyl selenium urea on the surface to spray. On the p-type CuInSe 2 film thus formed, a thickness of about 0.5 μm
Were stacked to form a pn junction. This pn
In the solar cell using the junction, an efficiency of 8 to 10% was obtained. In
When the substrate temperature at the time of forming the film 3 was further lowered below -100 ° C., the size of the island-like In became smaller than 0.2 μm, but there was no significant improvement in the characteristics of the solar cell.
【０００９】図３は、本発明の別の実施例によって製造
されるCuInSe2 薄膜を用いた薄膜太陽電池の作成プロセ
スを示すものであり、図２におけると同様にMo等の金属
膜をコートしたガラス基板１上に、蒸着法あるいはスパ
ッタリング法によりCu膜２およびIn膜３を順次形成した
後 (同図(a),(b),(c))、Arなどの不活性気体中で基板を
Inの融点 (156.4 ℃) から600 ℃までの温度に加熱し、
Cu−In金属間化合物層40を生成する (同図(d))。もしく
は、蒸着法あるいはスパッタリング法によりCu膜２を形
成した後、In膜３を形成する際の基板をInの融点(156.4
℃) から600℃の温度に保持することにより、Cu−In金
属間化合物40を生成する (同図(d))。そのCu−In金属間
化合物40をArなどの不活性気体で希釈されたSe, 例えば
３％〜18％Ｈ2 Seを含有するガス中にて400 ℃, １時間
加熱することにより、CuInSe2薄膜４を形成する (同図
(e))。あるいは、Cu−In金属間化合物層40の表面にスプ
レー法等により噴霧状Se含有溶液あるいはSe蒸気を吹き
つけてCuInSe2 薄膜４を形成する。本方法において、基
板上に形成されるIn膜３の島状寸法と基板温度との関係
と、そのあと図２(e),(f) と同様の図３(f),(g) の工程
を経て作成した太陽電池の特性結果とについて、従来技
術であるCu膜２, In膜３を室温で形成した場合との比較
検討を行った。図４の実線７は島状Inの寸法を示し、室
温でIn膜３を形成した場合の島状の寸法は２〜５μｍに
も達し、このとき形成されるCuInSe 2 膜４の粒径も２〜
５μｍの大きなものが形成され、CuInSe2膜４の表面の
凹凸も大きく、太陽電池にしたとき界面が十分に形成で
きずショートが大きく特性はでなかった。基板温度を上
げていくと、In膜３の島状寸法は次第に減少し、Inの融
点 (156.4 ℃) 以上ではCu, Inの金属間化合物40が生成
され、粒径が0.2 〜１μｍ程度となり、これを用いた太
陽電池では、図４の破線８に示すように変換効率８〜10
％が得られた。FIG. 3 is a perspective view of another embodiment of the present invention.
CuInSeTwoProcess for making thin-film solar cells using thin films
And metal such as Mo as in FIG.
On a glass substrate 1 coated with a film, a vapor deposition method or a spa
Cu film 2 and In film 3 were sequentially formed by the sputtering method.
Later ((a), (b), (c) in the same figure), the substrate is placed in an inert gas such as Ar.
Heat from the melting point of In (156.4 ° C) to 600 ° C,
A Cu-In intermetallic compound layer 40 is generated (FIG. 4D). If
Forms the Cu film 2 by vapor deposition or sputtering.
After the formation, the substrate for forming the In film 3 is heated to the melting point of In (156.4
(° C) to 600 ° C.
An intergeneric compound 40 is produced (FIG. 4D). The Cu-In metal
Compound 40 diluted Se with an inert gas such as Ar, for example
3% -18% HTwo400 ° C, 1 hour in gas containing Se
By heating, CuInSeTwoForm a thin film 4 (see FIG.
(e)). Alternatively, the surface of the Cu-In intermetallic compound layer 40 is
Spraying Se-containing solution or Se vapor by laser method
Put on CuInSeTwoA thin film 4 is formed. In this method,
Relationship between island size of In film 3 formed on plate and substrate temperature
3 (f) and (g) similar to FIGS. 2 (e) and (f).
Of the characteristics of the solar cell created through
Comparison with the case of forming Cu film 2 and In film 3 at room temperature
Study was carried out. The solid line 7 in FIG.
The size of the island when the In film 3 is formed at a temperature is 2 to 5 μm.
The CuInSe formed at this time TwoThe particle size of the film 4 is 2 to
A 5 μm large one is formed and CuInSeTwoOf the surface of membrane 4
The unevenness is large, and the interface is sufficiently formed
Flaw short was large and characteristics were not obtained. Increase substrate temperature
As the thickness increases, the island-like dimensions of the In film 3 gradually decrease, and
Above the point (156.4 ° C), Cu and In intermetallic compounds 40 are formed.
And the particle size becomes about 0.2 to 1 μm.
In the positive battery, as shown by a broken line 8 in FIG.
%was gotten.
【００１０】600 ℃以上では、島状寸法はより小さくな
るが、太陽電池の特性では大きな改善がなく、またガラ
ス基板の耐熱性などから600 ℃が限界と考えられた。そ
して、Cu膜２, In膜３を積層したのち加熱処理する方法
においても、熱処理温度とIn膜表面粒径および太陽電池
変換効率との間に同様な関係が得られた。At 600 ° C. or higher, the island size becomes smaller, but there is no significant improvement in the characteristics of the solar cell, and 600 ° C. is considered to be the limit due to the heat resistance of the glass substrate and the like. In the method of stacking the Cu film 2 and the In film 3 and then performing the heat treatment, the same relationship was obtained between the heat treatment temperature, the In film surface grain size, and the solar cell conversion efficiency.
【００１１】図５(a) 〜(e) は固相セレン化法の工程で
あり、図１〜図３と共通の部分には同一の符号が付され
ており、同図(a) 〜(c) は図１(a) 〜(c) について述べ
たと同様に行われる。すなわち、In膜３成膜時の基板温
度は本発明により−20〜−100 ℃に保持される。次い
で、In膜３の上に厚さ1.5 μm 以上のSe膜９を蒸着法あ
るいはスパッタリング法で形成する (同図(d))。このあ
と、ArあるいはＮ2 等の不活性気体中で約400 ℃に加熱
処理することによってCuInSe2薄膜４を得る (同図
(e))。このCuInSe2 膜を用いて作製した太陽電池でも上
記と同様の特性を得た。FIGS. 5 (a) to 5 (e) show the steps of the solid-phase selenization method, and the same parts as those in FIGS. 1 to 3 are denoted by the same reference numerals. c) is performed in the same manner as described with reference to FIGS. 1 (a) to 1 (c). That is, the substrate temperature during the formation of the In film 3 is maintained at -20 to -100 ° C according to the present invention. Next, a Se film 9 having a thickness of 1.5 μm or more is formed on the In film 3 by a vapor deposition method or a sputtering method (FIG. 4D). Thereafter, a CuInSe 2 thin film 4 is obtained by performing a heat treatment at about 400 ° C. in an inert gas such as Ar or N 2 (FIG.
(e)). The same characteristics as described above were obtained in a solar cell manufactured using this CuInSe 2 film.
【００１２】同様な改善結果は、固相セレン化法のIn膜
３成膜時の基板温度を156.4 〜600℃に保持した場合、
あるいはCu膜２, In膜３積層後図５(d) のSe膜９成膜前
に156.4 〜600 ℃に加熱した場合にも得ることができ
た。A similar improvement result is obtained when the substrate temperature during the formation of the In film 3 by the solid-phase selenization method is maintained at 156.4 to 600 ° C.
Alternatively, it can be obtained even when the film is heated to 156.4 to 600 ° C. after laminating the Cu film 2 and the In film 3 and before forming the Se film 9 in FIG.
【００１３】このほか、Ag, In積層のセレン化によるAg
InSe2 薄膜の形成、あるいはCu, In積層, Ag, In積層の
硫黄化によるCuInＳ2 , AgInＳ2 薄膜の形成の場合に
も、−20〜−100 ℃あるいは156.4 〜600 ℃の基板上に
成膜したIn膜を用いることにより、もしくはCu, In積
層, Ag, In積層後156.4 〜600 ℃に加熱することにより
均一性の良好なカルコパイライト型化合物薄膜を得るこ
とができた。[0013] In addition, Ag, In
In case of forming InSe 2 thin film or CuInS 2 , AgInS 2 thin film by sulfurization of Cu, In laminated, Ag, In laminated, film formation on substrate at -20 to -100 ℃ or 156.4 to 600 ℃ A chalcopyrite-type compound thin film with good uniformity could be obtained by using the In film thus obtained or by heating the layer to 156.4 to 600 ° C. after stacking the Cu and In layers and the Ag and In layers.
【００１４】[0014]
【発明の効果】本発明によれば、基板上のＸ金属膜上へ
のIn膜成膜時に生ずる島状Inの寸法を、In膜成膜時の基
板温度を冷媒の使用で容易に得られる−100 〜−20℃に
することによって小さくするか、もしくはＸ金属膜上へ
のIn成膜時の基板温度をInの融点 (156.4 ℃) ないし60
0 ℃で加熱するかあるいはＸ膜, In膜を順次積層した
後、156.4 〜600 ℃で加熱処理することによってＸ−In
の金属間化合物を生成してInの不均一性を改善すること
により、均一なIn膜を形成することによってＸInＹ 2 の
化学式をもつカルコパイライト型化合物の薄膜を全面均
一な特性で製造することが可能になった。特にこれによ
り得られるCuInSe2 膜を用いてCdＳ膜との接合を形成す
ることにより、太陽光スペクトルを長波長側まで活用で
きる太陽電池の特性を向上させることができた。According to the present invention, an X metal film on a substrate is
The size of the island-like In generated when the In film is formed
Plate temperature to -100 to -20 ° C, which can be easily obtained by using refrigerant
To make it smaller, or onto the X metal film
The substrate temperature at the time of In film formation was changed from In melting point (156.4 ° C) to 60
Heated at 0 ℃ or laminated X film and In film sequentially
After that, heat treatment at 156.4 to 600 ° C.
Of intermetallic compounds to improve In heterogeneity
XInY by forming a uniform In film Twoof
A thin film of chalcopyrite-type compound having the chemical formula
It has become possible to manufacture with uniform characteristics. Especially
CuInSe obtainedTwoForming junction with CdS film using film
By utilizing the solar spectrum to the long wavelength side
It was possible to improve the characteristics of the solar cell.
【図１】本発明の一実施例の気相セレン化法によるCuIn
Se2膜製造工程を(a) 〜(d) の順に示す断面図FIG. 1 shows CuIn by vapor phase selenization according to one embodiment of the present invention.
Sectional view showing the Se 2 film manufacturing process in the order of (a) to (d)
【図２】公知のCuInSe2 薄膜太陽電池の製造プロセスを
(a) 〜(f) の順に示す断面図FIG. 2 shows a manufacturing process of a known CuInSe 2 thin film solar cell.
Sectional views shown in the order of (a) to (f)
【図３】本発明の異なる実施例の気相セレン化法による
CuInSe2薄膜を用いた太陽電池の製造プロセスを(a) 〜
(g) の順に示す断面図FIG. 3 shows a gas-phase selenization method according to another embodiment of the present invention.
The manufacturing process of a solar cell using the CuInSe 2 thin film (a) ~
Sectional view shown in (g) order
【図４】In成膜時の基板温度とIn膜表面粒径およびCuIn
Se2 薄膜太陽電池の変換効率との関係線図FIG. 4 shows substrate temperature, In film surface grain size, and CuIn during In film formation.
Relational diagram between the conversion efficiency of the Se 2 thin film solar cell
【図５】本発明の一実施例の固相セレン化法によるCuIn
Se2 薄膜製造工程を(a) 〜(e)の順に示す断面図FIG. 5 shows CuIn by solid-phase selenization according to one embodiment of the present invention.
Sectional view showing the Se 2 thin film manufacturing process in the order of (a) to (e)
１ ガラス基板 ２ Cu膜 ３ In膜 ４ CuInSe2 金属間化合物層 ５ CdＳ膜 ９ Se膜Reference Signs List 1 glass substrate 2 Cu film 3 In film 4 CuInSe 2 intermetallic compound layer 5 CdS film 9 Se film
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01L 21/36 H01L 21/365 H01L 31/04 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 6 , DB name) H01L 21/36 H01L 21/365 H01L 31/04
Claims (6)
いは銅であり、Ｙがセレンあるいは硫黄であるカルコパ
イライト型化合物からなる薄膜を基板上にＸ元素および
インジウムの膜を積層後、Ｙ元素を含む雰囲気中で加熱
して製造するに際し、インジウムの成膜時に基板を−１
００℃ないし−２０℃の温度に保持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 a chalcopyrite-type compound having a chemical formula of XInY 2 , wherein X is silver or copper, and Y is selenium or sulfur. During the production by heating in an atmosphere containing
A method for producing a chalcopyrite-type compound thin film, which is maintained at a temperature of from 00 ° C to -20 ° C.
いは銅であり、Ｙがセレンあるいは硫黄であるカルコパ
イライト型化合物からなる薄膜を基板上にＸ元素および
インジウムの膜を積層後、Ｙ元素を含む雰囲気中で加熱
して製造するに際し、インジウムの成膜時に基板をイン
ジウムの融点以上で６００℃以下の温度に保持すること
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. A thin film made of a chalcopyrite-type compound having a chemical formula of XInY 2 , wherein X is silver or copper, and Y is selenium or sulfur. A method of producing a chalcopyrite-type compound thin film, wherein the substrate is kept at a temperature of not less than the melting point of indium and not more than 600 ° C. during the formation of indium during heating in an atmosphere containing.
いは銅であり、Ｙがセレンあるいは硫黄であるカルコパ
イライト型化合物からなる薄膜を基板上にＸ元素および
インジウムの膜を積層後、Ｙ元素を含む雰囲気中で加熱
して製造するに際し、基板上にＸ元素およびインジウム
の膜を積層後、Ｙ元素を含む雰囲気中で加熱する前に、
該Ｙ元素を含む雰囲気中での加熱とは別個に、基板をイ
ンジウムの融点以上で６００℃以下の温度に加熱するこ
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。3. A thin film comprising a chalcopyrite type compound having a chemical formula of XInY 2 , wherein X is silver or copper, and Y is selenium or sulfur, a film of X element and indium is laminated on a substrate, When manufacturing by heating in an atmosphere containing Y, after laminating a film of X element and indium on the substrate, before heating in an atmosphere containing Y element,
A method for producing a chalcopyrite-type compound thin film, comprising heating a substrate to a temperature of not less than the melting point of indium and not more than 600 ° C. separately from the heating in an atmosphere containing the Y element.
いは銅であり、Ｙがセレンあるいは硫黄であるカルコパ
イライト型化合物からなる薄膜を基板上に、Ｘ元素、イ
ンジウムおよびＹ元素の膜を積層後加熱して製造するに
際し、インジウムの成膜時に基板を−１００℃ないし−
２０℃の温度に保持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。4. A thin film of a chalcopyrite type compound having a chemical formula of XInY 2 , wherein X is silver or copper and Y is selenium or sulfur, and a film of X element, indium and Y element is laminated on a substrate. When manufacturing by heating after heating, the substrate is kept at -100 ° C.
A method for producing a chalcopyrite-type compound thin film, wherein the temperature is maintained at 20 ° C.
いは銅であり、Ｙがセレンあるいは硫黄であるカルコパ
イライト型化合物からなる薄膜を基板上に、Ｘ元素、イ
ンジウムおよびＹ元素の膜を積層後加熱して製造するに
際し、インジウムの成膜時に基板をインジウムの融点以
上で６００℃以下の温度に保持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。5. A thin film comprising a chalcopyrite-type compound having a chemical formula of XInY 2 , wherein X is silver or copper and Y is selenium or sulfur, and a film of X element, indium and Y element is laminated on a substrate. A method for producing a chalcopyrite-type compound thin film, wherein the substrate is kept at a temperature of not less than the melting point of indium and not more than 600 ° C. during indium film formation in the production by post-heating.
いは銅であり、Ｙがセレンあるいは硫黄であるカルコパ
イライト型化合物からなる薄膜を基板上に、Ｘ元素、イ
ンジウムおよびＹ元素の膜を積層後加熱して製造するに
際し、基板上にＸ元素およびインジウムの膜を積層後、
Ｙ元素の膜の積層前に基板をインジウムの融点以上で６
００℃以下の温度に加熱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。6. A thin film comprising a chalcopyrite type compound having a chemical formula of XInY 2 , wherein X is silver or copper and Y is selenium or sulfur, and a film of X element, indium and Y element is laminated on the substrate. When manufacturing by post-heating, after laminating a film of element X and indium on the substrate,
Before laminating the film of the Y element, the substrate is heated at a temperature not lower than the melting point of indium.
A method for producing a chalcopyrite-type compound thin film, comprising heating to a temperature of 00 ° C. or lower.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-233045 | 1990-09-03 | ||
| JP23304590 | 1990-09-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04212430A JPH04212430A (en) | 1992-08-04 |
| JP2975693B2 true JP2975693B2 (en) | 1999-11-10 |
Family
ID=16948940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3013631A Expired - Fee Related JP2975693B2 (en) | 1990-09-03 | 1991-02-05 | Method for producing chalcopyrite-type compound thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2975693B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3064701B2 (en) * | 1992-10-30 | 2000-07-12 | 松下電器産業株式会社 | Method for producing chalcopyrite-type compound thin film |
| JPH07254723A (en) * | 1994-03-16 | 1995-10-03 | Yazaki Corp | Production of thin film solar cell |
| JP3777280B2 (en) * | 1999-09-07 | 2006-05-24 | 新光電気工業株式会社 | Method for producing compound semiconductor solar cell |
| JP5259178B2 (en) * | 2004-03-15 | 2013-08-07 | ソロパワー、インコーポレイテッド | Method and apparatus for depositing a thin layer of semiconductor for solar cell manufacture |
| JP2006196798A (en) * | 2005-01-17 | 2006-07-27 | Matsushita Electric Ind Co Ltd | Method of inspecting thin film solar cell |
| WO2014095503A1 (en) | 2012-12-20 | 2014-06-26 | Saint-Gobain Glass France | Method for producing a compound semiconductor, and thin-film solar cell |
-
1991
- 1991-02-05 JP JP3013631A patent/JP2975693B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04212430A (en) | 1992-08-04 |
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