JPH06310747A - Formation of chalcopyrite thin film and fabrication of thin film solar cell - Google Patents
Formation of chalcopyrite thin film and fabrication of thin film solar cellInfo
- Publication number
- JPH06310747A JPH06310747A JP5097900A JP9790093A JPH06310747A JP H06310747 A JPH06310747 A JP H06310747A JP 5097900 A JP5097900 A JP 5097900A JP 9790093 A JP9790093 A JP 9790093A JP H06310747 A JPH06310747 A JP H06310747A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- chalcopyrite
- heat treatment
- solar cell
- chalcogen element
- 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.)
- Withdrawn
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
-
- 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
Landscapes
- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、カルコパイライト型化
合物の薄膜の形成方法及び薄膜太陽電池の製造方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a thin film of chalcopyrite type compound and a method for manufacturing a thin film solar cell.
【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ている材料である。従
来、カルコパイライト型化合物の薄膜（以下、カルコパ
イライト薄膜と記す。）を非晶質基板、非晶質薄膜ある
いは金属薄膜上に形成する場合は、カルコパイライト型
化合物そのものを蒸発源として蒸着させる真空蒸着法、
カルコパイライト型化合物そのものをターゲットとして
用いるスパッタリング法、カルコパイライト型化合物の
成分元素を別々に蒸着させる多元の真空蒸着法、カルコ
パイライト型化合物の成分元素を別々にターゲットとし
て用いるマルチスパッタリング法、あるいは構成金属の
積層薄膜、例えばＣｕ−Ｉｎ薄膜のカルコゲナイト化等
のプロセスによって形成している。2. Description of the Related Art Chalcopyrite type compounds are materials that are expected to be applied to solar cells, light emitting devices and the like. Conventionally, when a thin film of a chalcopyrite compound (hereinafter referred to as a chalcopyrite thin film) is formed on an amorphous substrate, an amorphous thin film, or a metal thin film, a vacuum for vaporizing the chalcopyrite compound itself as an evaporation source. Evaporation method,
A sputtering method using the chalcopyrite type compound itself as a target, a multi-source vacuum deposition method in which the constituent elements of the chalcopyrite type compound are separately deposited, a multi-sputtering method using the constituent elements of the chalcopyrite type compound as separate targets, or a constituent metal Is formed by a process such as chalcogenization of a laminated thin film of, for example, a Cu—In thin film.
【０００３】しかしながら、カルコパイライト型化合物
そのものを蒸発源あるいはターゲットとして用いる場
合、カルコゲン元素の離脱による組成ずれがおこりやす
い。成分元素を別々に蒸着、スパッタする場合は、個々
の元素の蒸着速度の厳密な制御が難しい等の問題が生じ
る。また、構成金属の積層薄膜をカルコゲナイト化する
場合、形成した薄膜の基板に対する密着性が悪かった
り、形状の異なる結晶粒が混在しやすい等の問題があっ
た。However, when the chalcopyrite type compound itself is used as an evaporation source or a target, a composition shift due to the release of the chalcogen element is likely to occur. When the component elements are separately vapor-deposited and sputtered, there arises a problem that it is difficult to strictly control the vapor deposition rate of each element. In addition, when the laminated thin films of the constituent metals are chalcogenized, there are problems that the formed thin films have poor adhesion to the substrate, and that crystal grains having different shapes are easily mixed.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、基板に対す
る密着性が良好で、カルコゲン元素の欠乏がなく、組成
の制御された高結晶性のカルコパイライト薄膜の形成方
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 is directed to a method for forming a highly crystalline chalcopyrite thin film having good adhesion to a substrate, no chalcogen element deficiency and a controlled composition, and a thin film solar using the same. An object is to provide a method for manufacturing a battery.
【０００５】[0005]
【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、カルコパイライト薄膜中の成分金属元素
とカルコゲン元素との組成比と、膜の結晶性との関係に
ついて鋭意検討した結果、カルコゲン元素の組成比が、
化学量論組成（カルコゲン元素／金属元素のモル比１）
よりやや小さな薄膜を、そのカルコゲン元素を含有する
ガス雰囲気中で熱処理することにより、膜中にカルコゲ
ン元素が取り込まれて化学量論組成に近づくと共に、結
晶粒が大きく成長し、高結晶性のカルコパイライト薄膜
を形成することができ、しかも、このようなカルコパイ
ライト薄膜を用いて作製した薄膜太陽電池は、従来の方
法で作製したものに比べ、良好な特性を示すことをみい
だし、本発明をなすに至った。[Means for Solving the Problems] Under such circumstances,
The present inventors, as a result of diligent examination of the relationship between the composition ratio of the component metal element and the chalcogen element in the chalcopyrite thin film and the crystallinity of the film, the composition ratio of the chalcogen element,
Stoichiometric composition (molar ratio of chalcogen element / metal element 1)
By heat-treating a slightly smaller thin film in a gas atmosphere containing the chalcogen element, the chalcogen element is incorporated into the film and the stoichiometric composition is approached. It has been found that a pyrite thin film can be formed, and that a thin-film solar cell produced using such a chalcopyrite thin film exhibits better characteristics than those produced by a conventional method. It came to eggplant.
【０００６】すなわち、本発明は以下のとおりである。 １） 元素周期律表Ｉｂ族及びＩＩＩｂ族金属並びにカ
ルコゲン元素からなり、熱処理後にカルコパイライト型
構造を採りうる薄膜を、上記カルコゲン元素を含有する
ガス雰囲気中で熱処理するカルコパイライト型化合物の
薄膜の形成方法において、熱処理前の上記薄膜中の元素
周期律表Ｉｂ族及びＩＩＩｂ族金属に対するカルコゲン
元素のモル比が、０．２以上１未満であることを特徴と
するカルコパイライト型化合物の薄膜の形成方法。 ２） 上記１記載のカルコパイライト型化合物の薄膜の
形成方法によって得られたカルコパイライト型化合物の
薄膜を用いることを特徴とする薄膜太陽電池の製造法。That is, the present invention is as follows. 1) Formation of a thin film of a chalcopyrite type compound, which is a thin film made of a metal of Group Ib and Group IIIb of the Periodic Table of Elements and a chalcogen element and having a chalcopyrite type structure after heat treatment in a gas atmosphere containing the chalcogen element. A method for forming a thin film of a chalcopyrite-type compound, characterized in that the molar ratio of the chalcogen element to the metal of group Ib and group IIIb of the periodic table in the thin film before heat treatment is 0.2 or more and less than 1. . 2) A method for producing a thin-film solar cell, which comprises using a thin film of a chalcopyrite-type compound obtained by the method for forming a thin film of a chalcopyrite-type compound as described in 1 above.
【０００７】本発明におけるカルコパイライト型化合物
とは、Ｃｕ，Ａｇ等の元素周期律表Ｉｂ族金属及びＡ
ｌ，Ｇａ，Ｉｎ等の元素周期律表ＩＩＩｂ族金属並びに
Ｓ，Ｓｅ，Ｔｅ等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。本発明において、熱処理前の薄膜の形成方法と
しては、スパッタ蒸着法、抵抗加熱蒸着法、電子線ビー
ム蒸着法、ＭＢＥ、ＭＯＣＶＤ、ＡＬＥ、スプレー加熱
分解法、無電解メッキ法等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Ｉｂ族及びＩＩＩｂ
族金属に対するカルコゲン元素のモル比が０．２以上１
未満であるような薄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、形成しようとするカルコパ
イライト型化合物の粉末又は成分金属元素各々のカルコ
ゲナイド化合物の混合粉末を、アルゴン等の不活性雰囲
気中で熱処理した粉末を原料として、スパッタ蒸着ある
いは抵抗加熱蒸着を行う方法及び成分金属元素とカルコ
ゲン元素を別々にとばす多源同時蒸着において、各元素
の蒸発速度をコントロールする方法等がある。The chalcopyrite type compound in the present invention means a metal of Group Ib of the periodic table of elements such as Cu and Ag and A.
It is a general term for compounds having a chalcopyrite (chalcopyrite) type structure, which is composed of a group IIIb metal of the periodic table of elements such as l, Ga and In and a chalcogen element such as S, Se and Te. In the present invention, as a method for forming a thin film before heat treatment, many methods such as a sputter deposition method, a resistance heating deposition method, an electron beam deposition method, MBE, MOCVD, ALE, a spray heating decomposition method, and an electroless plating method are selected. it can. In that case, before the heat treatment, Group Ib and IIIb of the periodic table of the elements are used.
Molar ratio of chalcogen element to group metal is 0.2 or more 1
The method for forming a thin film having a thickness less than that is not particularly limited, but, for example, a powder of a chalcopyrite type compound to be formed or a mixed powder of chalcogenide compounds of each of the component metal elements is mixed with argon or the like. There are a method of performing sputter vapor deposition or resistance heating vapor deposition using a powder heat-treated in an active atmosphere, and a method of controlling the evaporation rate of each element in multisource simultaneous vapor deposition in which component metal elements and chalcogen elements are separately skipped.
【０００８】熱処理前の薄膜中の元素周期律表Ｉｂ族金
属とＩＩＩｂ族金属のモル比は、熱処理後にカルコパイ
ライト型構造をとりうれば特に限定されるものではない
が、ＩＩＩｂ族金属に対するＩｂ族金属のモル比が、例
えば３以上と１よりも非常に大きかったり、０．３以下
と非常に小さかったりすると、熱処理後にカルコパイラ
イト型化合物とともにＩｂ族金属やＩＩＩｂ族金属のカ
ルコゲナイドが混在するようになり好ましくない。The molar ratio of the group Ib metal to the group IIIb metal of the periodic table in the thin film before the heat treatment is not particularly limited as long as it has a chalcopyrite type structure after the heat treatment, but is not limited to the group Ib group to the group Ib metal. If the molar ratio of the metal is, for example, 3 or more, which is much larger than 1, or 0.3 or less, which is very small, the chalcogenide of the Ib group metal or the IIIb group metal may be mixed together with the chalcopyrite compound after the heat treatment. It is not preferable.
【０００９】また本発明においては、熱処理前の薄膜
の、カルコゲン元素を除く成分金属元素である元素周期
律表Ｉｂ族及びＩＩＩｂ族金属に対するカルコゲン元素
のモル比が、０．２以上１未満であることが必要であ
り、好ましくは０．３以上０．９以下である。１以上で
あると、熱処理による結晶性向上効果が著しく小さくな
る。一方、モル比が０．２より小さいと、熱処理した膜
が、中にボイドを有する密着性の低いものになる。Further, in the present invention, the molar ratio of the chalcogen element to the metal of group Ib and IIIb of the periodic table, which is a component metal element excluding the chalcogen element, of the thin film before heat treatment is 0.2 or more and less than 1. It is necessary, and preferably 0.3 or more and 0.9 or less. When it is 1 or more, the effect of improving the crystallinity by the heat treatment is significantly reduced. On the other hand, when the molar ratio is less than 0.2, the heat-treated film has voids inside and low adhesion.
【００１０】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、窒素等
の不活性ガスが用いられる。熱処理の温度については、
このガスによる結晶性向上効果を得るためには、熱処理
前の膜成長時の基板温度より高いことが必要であり、３
００℃以上であることが好ましい。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 element of chalcogen, a hydride of a chalcogen element, a carbide, a methylated product, an ethylated product, etc. Among them, a 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
% Is preferable, and more preferably 0.1 to 30 mol%. As the diluting gas, an inert gas such as argon, helium or nitrogen is used. For the temperature of heat treatment,
In order to obtain the effect of improving the crystallinity by this gas, it is necessary that the temperature is higher than the substrate temperature during the film growth before the heat treatment.
It is preferably 00 ° C. or higher. The heat treatment time is preferably 0.5 hours or more.
【００１１】カルコパイライト化合物には、多くの種類
があるが、それらのうち、ＣｕＩｎＳ2 ，ＣｕＩｎＳｅ
2 ，ＣｕＩｎＴｅ2 ，ＣｕＧａＳｅ2 ，ＣｕＧａＴ
ｅ2 ，ＡｇＩｎＳ2 ，ＡｇＩｎＳｅ2 ，ＡｇＩｎＴ
ｅ2 ，ＡｇＧａＳｅ2 ，ＡｇＧａＴｅ 2 或いはそれらの
固溶体等が、適当なバンドギャップを持っており、薄膜
太陽電池用の材料として好ましい。There are many types of chalcopyrite compounds.
There are, among them, CuInS2, CuInSe
2, CuInTe2, CuGaSe2, CuGaT
e2, AgInS2, AgInSe2, AgInT
e2, AgGaSe2, AgGaTe 2Or those
The solid solution has an appropriate band gap,
Preferred as a material for solar cells.
【００１２】本発明の特徴は、カルコパイライト薄膜を
形成するに際し、熱処理前の薄膜中のカルコゲン元素を
除く成分金属元素に対するカルコゲン元素のモル比が
０．２以上１未満になっていることであり、構成するカ
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、化学量論組成に近づくと共に、結晶粒が著しく成長
して高結晶性のカルコパイライト薄膜を形成でき、か
つ、このようなカルコパイライト薄膜を用いて作製した
薄膜太陽電池が良好な特性を示すということである。A characteristic of the present invention is that, when forming a chalcopyrite thin film, the molar ratio of the chalcogen element to the component metal element excluding the chalcogen element in the thin film before the heat treatment is 0.2 or more and less than 1. By performing heat treatment in an atmosphere containing the constituent chalcogen element, it becomes possible to form a highly crystalline chalcopyrite thin film due to the crystal grains growing significantly while approaching the stoichiometric composition. It means that the thin-film solar cell produced by using has excellent characteristics.
【００１３】[0013]
【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.
【００１４】[0014]
【実施例１】Ｃｕ2 Ｓ粉末とＩｎ2 Ｓ3 粉末をモル比
１：１で混合後、Ａｒ雰囲気中８５０℃で４時間焼成し
た。この粉末より作製したターゲットを用いて、スパッ
タリング法により、基板温度２５０℃でＣｕ，Ｉｎ，Ｓ
からなる薄膜を形成した。この薄膜の組成比をＥＰＭＡ
により測定したところ、Ｃｕ２８ａｔ％、Ｉｎ２８ａｔ
％、Ｓ４４ａｔ％（Ｃｕ／Ｉｎ：１．０、Ｓ／（Ｃｕ＋
Ｉｎ）：０．７９）であった。Example 1 Cu 2 S powder and In 2 S 3 powder were mixed at a molar ratio of 1: 1 and then calcined in an Ar atmosphere at 850 ° C. for 4 hours. By using a target produced from this powder, Cu, In, S at a substrate temperature of 250 ° C. by a sputtering method.
Was formed. The composition ratio of this thin film is EPMA
Measured by Cu28at%, In28at
%, S44 at% (Cu / In: 1.0, S / (Cu +
In): 0.79).
【００１５】次に、この薄膜を５ｍｏｌ％のＨ2 Ｓを含
むＡｒガス雰囲気中７００℃で３時間熱処理を行った。
熱処理後の薄膜の組成比をＥＰＭＡ（日本電子（株）製
ＪＣＸＡ−７３３）により測定したところ、Ｃｕ２５
ａｔ％、Ｉｎ２５ａｔ％、Ｓ５０ａｔ％であり、化学量
論組成のＣｕＩｎＳ2 薄膜が形成されたことがわかる。
また、図１は、熱処理後の薄膜のＸ線回折スペクトル
（（株）リガク製 ＲＵ−２００を使用した。）である
が、このスペクトルからもカルコパイライト型構造を有
するＣｕＩｎＳ2 薄膜であることが確認できる。尚、Ｃ
ｕＩｎＳ2 （１１２）面のピークの半値幅は０．２４度
であった。Next, this thin film was heat-treated at 700 ° C. for 3 hours in an Ar gas atmosphere containing 5 mol% of H 2 S.
The composition ratio of the thin film after the heat treatment was measured by EPMA (JCXA-733 manufactured by JEOL Ltd.).
At%, In25 at%, and S50 at%, it can be seen that a CuInS 2 thin film having a stoichiometric composition was formed.
In addition, FIG. 1 shows an X-ray diffraction spectrum (using RU-200 manufactured by Rigaku Corporation) of the thin film after the heat treatment. From this spectrum, it can be seen that the thin film is a CuInS 2 thin film having a chalcopyrite type structure. I can confirm. Incidentally, C
The full width at half maximum of the peak of the uInS 2 (112) plane was 0.24 degrees.
【００１６】図２は、上記の方法により作製したＣｕＩ
ｎＳ2 薄膜を用いた太陽電池の１例である。金属薄膜２
上の所定領域に、本発明の方法により、組成比がＣｕ／
Ｉｎ＝１のＣｕＩｎＳ2 薄膜３を形成する。その上に、
ヘテロｐ−ｎ接合を形成するために、ＣｄＳ薄膜４を形
成する。その上の所定領域に、上部透明電極５を形成す
る。このようにして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４．５％であった。FIG. 2 shows CuI prepared by the above method.
It is an example of a solar cell using an nS 2 thin film. Metal thin film 2
By the method of the present invention, the composition ratio Cu / Cu /
A CuInS 2 thin film 3 with In = 1 is formed. in addition,
A CdS thin film 4 is formed to form a hetero pn junction. The upper transparent electrode 5 is formed in a predetermined region above the upper transparent electrode 5. AM1.5 is applied to the solar cell element thus manufactured.
When irradiated with light, the conversion efficiency was 4.5%.
【００１７】[0017]
【比較例１】混合粉末の焼成雰囲気が１０ｍｏｌ％のＨ
2 Ｓを含むＡｒガスであること以外は、実施例１と同様
にして、ＣｕＩｎＳ2 薄膜及び太陽電池素子を作製し
た。熱処理前後の薄膜の組成比は、いずれもＣｕ２４．
５ａｔ％，Ｉｎ２４．５ａｔ％，Ｓ５１ａｔ％（Ｃｕ／
Ｉｎ：１．０、Ｓ／（Ｃｕ＋Ｉｎ）：１．０４）であ
り、熱処理による組成の変化はみられなかった。図３
は、熱処理後の薄膜のＸ線回折スペクトルであるが、カ
ルコパイライト型構造に特有の（１０３）面ピークがみ
られない。また、実施例１に比べて、ピーク強度が低い
上に、ＣｕＩｎＳ2 （１１２）面ピークの半値幅が０．
４８度と大きく、結晶性が劣っていることがわかる。さ
らに、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１．５％であった。[Comparative Example 1] The firing atmosphere of the mixed powder was 10 mol% of H 2.
A CuInS 2 thin film and a solar cell element were produced in the same manner as in Example 1 except that Ar gas containing 2 S was used. The composition ratio of the thin film before and after the heat treatment was Cu24.
5at%, In24.5at%, S51at% (Cu /
In: 1.0, S / (Cu + In): 1.04), and no change in composition due to heat treatment was observed. Figure 3
Is an X-ray diffraction spectrum of the thin film after heat treatment, but no (103) plane peak peculiar to the chalcopyrite type structure is observed. In addition, the peak intensity is lower than that of Example 1, and the half width of the CuInS 2 (112) plane peak is less than 0.
It is as large as 48 degrees, which shows that the crystallinity is inferior. Further, when the manufactured solar cell element was irradiated with light of AM1.5, the conversion efficiency was 1.5%.
【００１８】[0018]
【実施例２】Ｃｕ，Ｉｎ，Ｓｅの３つの蒸発源より、温
度２５０℃の基板上に、同時に蒸着し、Ｃｕ−Ｉｎ−Ｓ
ｅからなる薄膜を形成した。この際、各蒸発源の温度を
コントロールすることにより、膜中のＣｕとＩｎのモル
比が１で、ＣｕとＩｎに対するＳｅのモル比が１より小
さくなるようにした。この薄膜の組成比をＥＰＭＡによ
り測定したところ、Ｃｕ３３ａｔ％，Ｉｎ３３ａｔ％，
Ｓｅ３４ａｔ％（Ｃｕ／Ｉｎ：１．０，Ｓｅ／（Ｃｕ＋
Ｉｎ）：０．５２）であった。次に、この薄膜を、１０
ｍｏｌ％のＳｅ蒸気を含むＮ2 ガス中６００℃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ＣｕＩｎＳ
ｅ2 薄膜が形成されたことがわかる。又、熱処理後の薄
膜のＸ線回折スペクトルにおけるＣｕＩｎＳｅ2 （１１
２）面のピークの半値幅は０．２５度であった。Example 2 Cu-In-S was simultaneously vapor-deposited on a substrate at a temperature of 250 ° C. from three evaporation sources of Cu, In and Se.
A thin film of e was formed. At this time, the temperature of each evaporation source was controlled so that the molar ratio of Cu and In in the film was 1 and the molar ratio of Se to Cu and In was smaller than 1. When the composition ratio of this thin film was measured by EPMA, Cu33at%, In33at%,
Se34 at% (Cu / In: 1.0, Se / (Cu +
In): 0.52). Next, this thin film is
Heat treatment was performed at 600 ° C. for 2 hours in N 2 gas containing mol% Se vapor. When the composition ratio of the thin film after the heat treatment was measured by EPMA, Cu25at%, In25at
%, Se50 at%, stoichiometric composition CuInS
It can be seen that the e 2 thin film was formed. In addition, CuInSe 2 (11
The half width of the peak on the 2) plane was 0.25 degree.
【００１９】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
様の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６．５％であった。CuInSe 2 produced by the above method
A solar cell element having the same structure as in Example 1 was prepared by using the thin film instead of the CuInS 2 thin film, and irradiated with light of AM1.5, the conversion efficiency was 6.5%.
【００２０】[0020]
【比較例２】Ｃｕ，Ｉｎ，Ｓｅ各蒸発源の温度をコント
ロールすることにより、膜中のＣｕとＩｎのモル比が１
で、ＣｕとＩｎに対するＳｅのモル比が１より大きくな
るようにしたこと以外は、実施例２と同様にしてＣｕＩ
ｎＳｅ2 薄膜及び太陽電池素子を作製した。熱処理前後
の薄膜の組成比は、いずれもＣｕ２４．２ａｔ％，Ｉｎ
２４．２ａｔ％，Ｓｅ５１．６ａｔ％（Ｃｕ／Ｉｎ：
１．０、Ｓｅ／（Ｃｕ＋Ｉｎ）：１．０７）であり、熱
処理による組成の変化はみられなかった。熱処理後の薄
膜のＸ線回折スペクトルにおけるＣｕＩｎＳｅ2 （１１
２）面のピークの半値幅は０．４８度であった。また、
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３．５％であった。Comparative Example 2 By controlling the temperature of each evaporation source of Cu, In, and Se, the molar ratio of Cu and In in the film is 1
In the same manner as in Example 2, except that the molar ratio of Se to Cu and In was set to be greater than 1, CuI
An nSe 2 thin film and a solar cell element were produced. The composition ratios of the thin film before and after the heat treatment were Cu 24.2 at% and In
24.2 at%, Se51.6 at% (Cu / In:
1.0, Se / (Cu + In): 1.07), and no change in composition due to heat treatment was observed. CuInSe 2 (11 in the X-ray diffraction spectrum of the thin film after heat treatment
The half width of the peak on the 2) plane was 0.48 degrees. Also,
When the manufactured solar cell element was irradiated with light of AM1.5, the conversion efficiency was 3.5%.
【００２１】[0021]
【比較例３】Ｃｕ，Ｉｎ，Ｓｅ各蒸発源の温度をコント
ロールすることにより、膜中のＣｕとＩｎのモル比が
１、ＣｕとＩｎに対するＳｅのモル比が０．１になるよ
うにしたこと以外は、実施例２と同様にしてＣｕＩｎＳ
ｅ2 薄膜及び太陽電池素子を作製した。熱処理後の薄膜
の組成比をＥＰＭＡにより測定したところ、Ｃｕ２５ａ
ｔ％，Ｉｎ２５ａｔ％，Ｓｅ５０ａｔ％であり、Ｘ線回
折スペクトルにおけるＣｕＩｎＳｅ2 （１１２）面のピ
ークの半値幅は０．２６度であった。ただし、ＳＥＭに
より表面を観察すると、明かに異相とわかる針状結晶が
混在しており、加えて、熱処理後の薄膜には部分的に剥
離がみられた。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 3 By controlling the temperature of each evaporation source of Cu, In and Se, the molar ratio of Cu and In in the film was set to 1 and the molar ratio of Se to Cu and In was set to 0.1. Except for the above, CuInS was prepared in the same manner as in Example 2.
An e 2 thin film and a solar cell element were produced. When the composition ratio of the thin film after heat treatment was measured by EPMA, it was found that Cu25a
t%, In25 at% and Se50 at%, and the half width of the peak of the CuInSe 2 (112) plane in the X-ray diffraction spectrum was 0.26 degrees. However, when the surface was observed by SEM, needle-like crystals clearly showing different phases were mixed, and in addition, partial peeling was observed in the thin film after the heat treatment. When the manufactured solar cell element was irradiated with light of AM 1.5, the conversion efficiency was 3.2%.
【００２２】[0022]
【発明の効果】本発明によれば、基板に対する密着性が
良好で、化学量論組成を有する高結晶性のカルコパイラ
イト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 highly crystalline chalcopyrite thin film having good adhesion to a substrate and having a stoichiometric composition can be formed, and a thin film solar cell produced using this thin film is Shows good properties.
【図１】実施例１における、熱処理後の薄膜のＸ線回折
スペクトルである。FIG. 1 is an X-ray diffraction spectrum of a thin film after heat treatment in Example 1.
【図２】本発明によるカルコパイライト薄膜を用いた太
陽電池の素子構造の１例である。FIG. 2 is an example of an element structure of a solar cell using the chalcopyrite thin film according to the present invention.
【図３】比較例１における、熱処理後の薄膜のＸ線回折
スペクトルである。FIG. 3 is an X-ray diffraction spectrum of a thin film after heat treatment in Comparative Example 1.
１ ガラス基板 ２ 金属電極 ３ ＣｕＩｎＳ2 薄膜 ４ ＣｄＳ薄膜 ５ 透明電極1 glass substrate 2 metal electrode 3 CuInS 2 thin film 4 CdS thin film 5 transparent electrode
Claims (2)
並びにカルコゲン元素からなり、熱処理後にカルコパイ
ライト型構造を採りうる薄膜を、上記カルコゲン元素を
含有するガス雰囲気中で熱処理するカルコパイライト型
化合物の薄膜の形成方法において、熱処理前の上記薄膜
中の元素周期律表Ｉｂ族及びＩＩＩｂ族金属に対するカ
ルコゲン元素のモル比が、０．２以上１未満であること
を特徴とするカルコパイライト型化合物の薄膜の形成方
法。1. A chalcopyrite-type compound obtained by heat-treating, in a gas atmosphere containing the chalcogen element, a thin film made of a metal of Group Ib and Group IIIb of the Periodic Table of Elements and a chalcogen element and having a chalcopyrite-type structure after the heat treatment. In the method for forming a thin film, the molar ratio of the chalcogen element to the Group Ib and Group IIIb metals of the periodic table in the thin film before heat treatment is 0.2 or more and less than 1 and is a thin film of a chalcopyrite type compound. Forming method.
物の薄膜の形成方法によって得られたカルコパイライト
型化合物の薄膜を用いることを特徴とする薄膜太陽電池
の製造法。2. A method for producing a thin film solar cell, which comprises using a thin film of a chalcopyrite type compound obtained by the method of forming a thin film of a chalcopyrite type compound according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5097900A JPH06310747A (en) | 1993-04-23 | 1993-04-23 | Formation of chalcopyrite thin film and fabrication of thin film solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5097900A JPH06310747A (en) | 1993-04-23 | 1993-04-23 | Formation of chalcopyrite thin film and fabrication of thin film solar cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06310747A true JPH06310747A (en) | 1994-11-04 |
Family
ID=14204618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5097900A Withdrawn JPH06310747A (en) | 1993-04-23 | 1993-04-23 | Formation of chalcopyrite thin film and fabrication of thin film solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06310747A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012151432A (en) * | 2010-06-28 | 2012-08-09 | Kyocera Corp | Photoelectric conversion element and photoelectric conversion device, and method of manufacturing photoelectric conversion element |
| JP2013224487A (en) * | 2012-03-19 | 2013-10-31 | Mitsubishi Materials Corp | Sputtering target for forming compound thin film, and method for producing the same |
-
1993
- 1993-04-23 JP JP5097900A patent/JPH06310747A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012151432A (en) * | 2010-06-28 | 2012-08-09 | Kyocera Corp | Photoelectric conversion element and photoelectric conversion device, and method of manufacturing photoelectric conversion element |
| JP2013224487A (en) * | 2012-03-19 | 2013-10-31 | Mitsubishi Materials Corp | Sputtering target for forming compound thin film, and method for producing the same |
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