JP3095182B2 - Method for producing I-III-VI compound semiconductor thin film - Google Patents
Method for producing I-III-VI compound semiconductor thin filmInfo
- Publication number
- JP3095182B2 JP3095182B2 JP03124955A JP12495591A JP3095182B2 JP 3095182 B2 JP3095182 B2 JP 3095182B2 JP 03124955 A JP03124955 A JP 03124955A JP 12495591 A JP12495591 A JP 12495591A JP 3095182 B2 JP3095182 B2 JP 3095182B2
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- Prior art keywords
- film
- gas
- iii
- heat treatment
- producing
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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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、太陽電池やフォトセン
サ等の光起電力素子および光学素子として利用されるI-
III-VI族系化合物半導体薄膜の製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photovoltaic element such as a solar cell or a photo sensor and an optical element used as an optical element.
The present invention relates to a method for producing a group III-VI compound semiconductor thin film.
【０００２】[0002]
【従来の技術】従来、I-III-VI族系化合物半導体薄膜の
製造法として、以下に示すものが公知となっている。す
なわち、銅およびインジウム層を電気メッキにより順次
または同時に基板上に電着し、その後セレン含有ガス存
在下で熱処理してＣｕＩｎＳｅ2 を得る方法と、銅およ
びインジウムの層上に元素状セレンを蒸着し、その後不
活性ガス雰囲気中で熱処理する方法とが特開昭 61-2374
76に開示されている。また、成分元素の同時蒸着や金属
間化合物の蒸着といった真空蒸着による方法が特開昭 5
7-502196に開示されており、銅、インジウムおよびセレ
ンを順次蒸着し、セレン量を必要とされる化学量論比以
下にした状態で、セレンおよび硫黄含有ガス存在の下で
熱処理を行う方法が特開平1-231313に開示されている。
さらに、スプレーパイロシス法でセレン源および硫黄源
の溶液供給比率を逐次変更し、膜厚方向にＳｅとＳの濃
度分布を形成させる方法が特開平 2-73674に開示されて
いる。2. Description of the Related Art Hitherto, the following methods have been known as methods for producing I-III-VI group compound semiconductor thin films. That is, a method in which copper and indium layers are sequentially or simultaneously electrodeposited on a substrate by electroplating, and then heat-treated in the presence of a selenium-containing gas to obtain CuInSe 2 , and elemental selenium is deposited on the copper and indium layers. And then heat treatment in an inert gas atmosphere is disclosed in
76. Further, a method by vacuum deposition such as simultaneous deposition of component elements and deposition of an intermetallic compound is disclosed in
7-502196, a method of sequentially depositing copper, indium and selenium, and performing a heat treatment in the presence of a selenium and sulfur-containing gas in a state where the amount of selenium is equal to or less than a required stoichiometric ratio. It is disclosed in JP-A-1-231313.
Further, Japanese Patent Application Laid-Open No. 2-73674 discloses a method in which the solution supply ratios of a selenium source and a sulfur source are successively changed by a spray pyrolysis method to form a Se and S concentration distribution in a film thickness direction.
【０００３】上記のような方法によるとI-III-VI族系化
合物半導体の性能に大きく影響する組成比、特にＣｕお
よびＡｇなどのＩ族元素とＩｎおよびＧａなどの III族
元素との組成比は、これらを積層する際に膜厚を変える
ことにより制御されていた。しかしながら、Ｉｎおよび
Ｇａなどの III族元素は膜として堆積される際、基板面
に対して垂直方向に成長しやすいため縞状組織となりや
すく、膜表面を平滑にすることが困難であった。また、
たとえ平滑面が得られたとしても、ＩｎおよびＧａが金
属状態であると、ＳｅおよびＳ含有ガス雰囲気下におけ
る加熱処理の際、Ｃｕ2 ＳｅやＣｕ2Ｓなどの低温安定
型の中間生成物の生成が避けられなかった。このような
中間生成物は、高温熱処理を施しても完全には消失しな
いため、最終生成物を所望の単一化合物相にすることが
非常に困難となる。According to the above-described method, the composition ratio which greatly affects the performance of the I-III-VI group compound semiconductor, particularly the composition ratio of a group I element such as Cu and Ag and a group III element such as In and Ga. Has been controlled by changing the film thickness when laminating them. However, when a group III element such as In and Ga is deposited as a film, it tends to grow in a direction perpendicular to the substrate surface, so that it tends to form a stripe structure, and it is difficult to smooth the film surface. Also,
Even if a smooth surface is obtained, if In and Ga are in a metallic state, a low-temperature stable intermediate product such as Cu 2 Se or Cu 2 S during heat treatment in an atmosphere of a gas containing Se and S will be obtained. Generation was inevitable. Since such an intermediate product does not completely disappear even when subjected to a high-temperature heat treatment, it is very difficult to make the final product into a desired single compound phase.
【０００４】すなわち、上記従来の方法によると、最も
重要とされる組成制御性に問題があり、ミクロ的な成分
の偏析が発生しやすく、場合によってはI-III-VI族系カ
ルコパイライト相以外にＣｕ2 ＳｅやＣｕ2Ｓなどの中
間生成物の混在が避けられないという問題点があったの
である。That is, according to the above-mentioned conventional method, there is a problem in composition controllability, which is the most important, and micro-segregation of components tends to occur, and in some cases, other than the I-III-VI group chalcopyrite phase. In addition, there is a problem that intermediate products such as Cu 2 Se and Cu 2 S cannot be avoided.
【０００５】一方、上記のような中間生成物を生成させ
ずに、単一相の三元化合物を得るために、 200℃以上の
温度でＳｅおよびＳと反応させる方法、または 200℃以
下の温度においてはＮ2 などの不活性ガス雰囲気とし、
200℃以上の温度でＳｅおよびＳ含有ガスを導入すると
いった方法がとられていた。しかしながら、Ｉｎおよび
Ｇａは、その融点がそれぞれ 153℃および30℃と極めて
低く、しかも表面張力が大きいため、各元素の相互拡
散、すなわち硫化やセレン化が始まる前に凝集したりＩ
ｎおよびＧａの液相が生じてしまっていた。このよう
に、ＩｎおよびＧａが凝集したりＩｎやＧａの液相が存
在したりすると、その周辺部においてピンホールや膜剥
離が生じる原因となり、また、最終生成物である三元化
合物膜の表面状態は、ＩｎやＧａの表面状態をそのまま
再現するため、表面精度が悪く凹凸が多いという問題点
があった。On the other hand, in order to obtain a single-phase ternary compound without producing the above-mentioned intermediate product, a method of reacting with Se and S at a temperature of 200 ° C. or more, or a method of an inert gas atmosphere such as N 2 in,
A method of introducing Se and S-containing gas at a temperature of 200 ° C. or higher has been adopted. However, since In and Ga have extremely low melting points of 153 ° C. and 30 ° C., respectively, and a high surface tension, they can aggregate before the interdiffusion of each element, that is, before sulfuration or selenization starts, or I and Ga can be agglomerated.
A liquid phase of n and Ga had been generated. As described above, when In and Ga are aggregated or a liquid phase of In or Ga is present, pinholes or film peeling are caused in the peripheral portion thereof, and the surface of the ternary compound film as a final product is generated. Since the state reproduces the surface state of In or Ga as it is, there is a problem that surface accuracy is poor and there are many irregularities.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上述従来の
技術の問題点を解決し、組成制御性を向上させ、ミクロ
偏析がなく、しかも膜表面が平滑であるI-III-VI族系化
合物半導体膜の製造法を提供することを目的としてい
る。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, improves the composition controllability, has no micro-segregation, and has a smooth film surface. It is an object of the present invention to provide a method for manufacturing a compound semiconductor film.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、上記課題
を解決するため鋭意研究したところ、ＩｎおよびＧａの
一方または両方を酸化物膜としてＣｕおよびＡｇの一方
または両方の膜上に形成し、これをＳｅおよびＳの一方
または両方を含有する還元性ガス雰囲気下で熱処理する
ことによって、金属酸化物の還元と同金属のセレン化お
よび硫化とが同時に進行し、中間生成物の存在しない三
元化合物薄膜が得られることを見い出し、本発明を提供
することができた。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and found that one or both of In and Ga are formed as oxide films on one or both of Cu and Ag films. By subjecting this to a heat treatment in a reducing gas atmosphere containing one or both of Se and S, reduction of the metal oxide and selenization and sulfidation of the same metal proceed simultaneously, and no intermediate product is present. The inventors have found that a ternary compound thin film can be obtained, and have provided the present invention.
【０００８】 すなわち本発明は、一般式（Ｃｕ1-xＡ
ｇx）（Ｉｎ1-yＧａy）（Ｓｅ1-zＳz）2（ただし、０≦
ｘ、ｙ、ｚ≦１）で表されるI−III−VI族系化合物から
なる半導体薄膜の製造法であって、ＣｕおよびＡｇの一
方または両方並びに酸化インジウムおよび酸化ガリウ
ム、好ましくはＩｎ2Ｏ3およびＧａ2Ｏ3の一方または両
方を個別にまたは同時に堆積した後、Ｓｅ源およびＳ源
の一方または両方を含有する還元性ガス雰囲気下で２０
０℃以上の温度で熱処理することを特徴とする上記I−I
II−VI族系化合物半導体薄膜の製造法を提供するもので
ある。That is, the present invention provides a compound represented by the general formula (Cu 1-x A
g x ) (In 1-y G ay ) (Se 1-z S z ) 2 (where 0 ≦
x, y, z ≦ 1) a method for producing a semiconductor thin film comprising a group I-III-VI compound represented by the formula (1), wherein one or both of Cu and Ag, indium oxide and gallium oxide, preferably In 2 O After depositing one or both of 3 and Ga 2 O 3 individually or simultaneously, the deposition is performed under a reducing gas atmosphere containing one or both of the Se source and the S source.
The above II, wherein the heat treatment is performed at a temperature of 0 ° C or more.
It is intended to provide a method for producing a II-VI group compound semiconductor thin film.
【０００９】本発明では、前記Ｓｅ源としてＨ2 Ｓｅガ
スおよびＳｅガスの一方または両方を用いることがで
き、また前記Ｓ源としてＨ2 ＳガスおよびＳガスの一方
または両方を用いることができ、さらに前記還元性ガス
としてＨ2 およびＣＯの一方または両方を用いることが
できる。In the present invention, one or both of H 2 Se gas and Se gas can be used as the Se source, and one or both of H 2 S gas and S gas can be used as the S source, Further, one or both of H 2 and CO can be used as the reducing gas.
【００１０】また、本発明におけるＣｕおよびＡｇの堆
積膜は、金属であっても酸化物であっても良く、また金
属と酸化物とが共存したものであっても良い。Further, the deposited film of Cu and Ag in the present invention may be a metal or an oxide, or may be a coexistence of a metal and an oxide.
【００１１】[0011]
【作用】本発明において、ＣｕおよびＡｇ膜を基板上に
堆積する方法として、通常行われている蒸着法、スパッ
タ法または電着法等を用いることができる。なお、これ
らの方法は、膜表面を平滑に形成したり膜厚の制御性に
優れることが工業的規模で確認されている。また、Ｃｕ
およびＡｇが酸化物であったり、または一部が酸化され
たものであっても、ＣｕおよびＡｇの含有量が既知であ
れば問題はない。これは、Ｉ族元素と III族元素との比
率が、後から堆積されるIII族元素の酸化物層の膜厚で
制御することが可能であり、しかもＩ族の金属であるＣ
ｕおよびＡｇの酸化物が III族の金属の酸化物であるＩ
ｎ2 Ｏ3 やＧａ2 Ｏ3 に比してはるかに還元されやすい
ためである。In the present invention, as a method for depositing a Cu and Ag film on a substrate, a commonly used vapor deposition method, sputtering method, electrodeposition method or the like can be used. It has been confirmed on an industrial scale that these methods form a film surface smoothly and have excellent controllability of the film thickness. Also, Cu
Even if Ag and Ag are oxides or partially oxidized, there is no problem as long as the contents of Cu and Ag are known. This is because the ratio between the group I element and the group III element can be controlled by the thickness of the oxide layer of the group III element which is deposited later, and the group I metal C
the oxides of u and Ag are oxides of Group III metals
This is because it is much more easily reduced than n 2 O 3 or Ga 2 O 3 .
【００１２】一方、Ｉｎ2 Ｏ3 またはＧａ2 Ｏ3 を堆積
する場合においても、蒸着法、スパッタ法またはディッ
プコーティング法などのような化学的堆積法であれば問
題はない。これは、Ｉｎ2 Ｏ3 やＧａ2 Ｏ3 が、金属Ｉ
ｎやＧａよりも融点がはるかに高く、成膜性に優れてい
るためであり、Ｉｎ2 Ｏ3 にＳｎＯ2 を添加した透明導
電性ＩＴＯ膜は精度良く形成できることが良く知られて
いることからも明らかである。On the other hand, when depositing In 2 O 3 or Ga 2 O 3 , there is no problem if a chemical deposition method such as an evaporation method, a sputtering method, or a dip coating method is used. This is because In 2 O 3 or Ga 2 O 3 is a metal I
This is because the melting point is much higher than that of n or Ga, and the film formability is excellent, and it is well known that a transparent conductive ITO film obtained by adding SnO 2 to In 2 O 3 can be formed with high accuracy. Is also clear.
【００１３】 上記のようにして作製した積層膜は、Ｓ
およびＳｅの一方または両方を含有する還元性ガス雰囲
気下で熱処理が施される。その際、Ｉｎ2Ｏ3やＧａ2Ｏ3
は高温下でＳおよびＳｅガスを導入しても何等反応を示
さないため、Ｈ2等の還元性ガスと、ＳおよびＳｅの一
方または両方のガスとを共存させる必要がある。また、
熱処理温度は、２００℃未満では酸化物の還元反応が事
実上ほとんど進行しないため、２００℃以上に加熱する
必要がある。２００℃未満の熱処理温度で還元反応が進
行しないということは、中間生成物の生成がなく、単一
相の三元化合物を得やすいということである。The laminated film manufactured as described above has S
The heat treatment is performed in a reducing gas atmosphere containing one or both of Se and Se. At that time, In 2 O 3 or Ga 2 O 3
Does not show any reaction even when S and Se gases are introduced at a high temperature, it is necessary to coexist a reducing gas such as H 2 with one or both of S and Se. Also,
If the heat treatment temperature is lower than 200 ° C., the reduction reaction of the oxides hardly progresses, so that it is necessary to heat the heat treatment to 200 ° C. or higher. The fact that the reduction reaction does not proceed at a heat treatment temperature of less than 200 ° C. means that there is no generation of an intermediate product and a single-phase ternary compound is easily obtained.
【００１４】さらに、Ｉｎ2 Ｏ3 やＧａ2 Ｏ3 は熱的に
安定であって、 200℃程度の加熱では変質しない。その
ため、成膜時の表面状態が熱処理時の高温状態において
も保持され、得られる膜の表面に凹凸ができにくくな
る。したがって、成膜時の表面状態を保ちつつ、所望の
温度でのセレン化および硫化が可能となり、高品質三元
化合物薄膜を得ることができるのである。なお、セレン
化または硫化される温度に達するまでは、Ｎ2 ガスなど
の不活性ガス雰囲気下であっても問題はない。Further, In 2 O 3 and Ga 2 O 3 are thermally stable, and do not deteriorate when heated at about 200 ° C. Therefore, the surface state at the time of film formation is maintained even at the high temperature state at the time of heat treatment, and the surface of the obtained film is unlikely to have irregularities. Therefore, selenization and sulfurization at a desired temperature can be performed while maintaining the surface state at the time of film formation, and a high-quality ternary compound thin film can be obtained. It should be noted that there is no problem even under an inert gas atmosphere such as N 2 gas until the temperature at which selenization or sulfidation is reached.
【００１５】以下、実施例により本発明をさらに詳細に
説明する。しかし本発明の範囲は、以下の実施例により
制限されるものではない。Hereinafter, the present invention will be described in more detail by way of examples. However, the scope of the present invention is not limited by the following examples.
【００１６】[0016]
【実施例１】本実施例では、真空蒸着法によりコーニン
グ社の #7059ガラス基板上に膜厚が2000Ａ（オングスト
ローム）となるようにＣｕを積層し、この上に原子比が
Ｃｕ：Ｉｎ＝１：１、膜厚が5300Ａとなるように、スパ
ッタ法によってＩｎ2 Ｏ3 を積層した。なお、該スパッ
タ法におけるＩｎ2 Ｏ3 ターゲットは、Ｉｎ2 Ｏ3 粉末
を加圧成形した後、1400℃で焼結したものを用いた。ま
た、この積層膜の表面粗さ（Ｒａ）は約1000Ａであっ
た。EXAMPLE 1 In this example, Cu was laminated on a # 7059 glass substrate of Corning Co., Ltd. by a vacuum deposition method so as to have a film thickness of 2000 A (angstrom), and an atomic ratio of Cu: In = 1 on top of this. 1: In 2 O 3 was deposited by sputtering so that the film thickness became 5300A. As the In 2 O 3 target in the sputtering method, an In 2 O 3 powder obtained by pressing and molding at 1400 ° C. was used. The surface roughness (Ra) of the laminated film was about 1000A.
【００１７】次に、該積層膜を反応管内に入れ、Ｎ2 ガ
ス雰囲気下、５℃/minの速度で 400℃まで昇温した。 4
00℃に達したところでＨ2 ＳおよびＨ2 Ｓｅを、流量モ
ル比がＨ2 Ｓ／（Ｈ2 Ｓｅ＋Ｈ2 Ｓ）＝0.9 となるよう
に導入し、２時間後、Ｎ2 ガスに切り替えて常温まで冷
却した。Next, the laminated film was placed in a reaction tube and heated to 400 ° C. at a rate of 5 ° C./min in an N 2 gas atmosphere. Four
The H 2 S and H 2 Se Upon reaching 00 ° C., the flow rate molar ratio was introduced so that the H 2 S / (H 2 Se + H 2 S) = 0.9, after 2 hours, is switched to N 2 gas ambient temperature Cooled down.
【００１８】上記のようにして得られた膜は灰黒色であ
り、ピンホールや剥離などの発生は認められなかった。
また、得られた膜の化学組成を調べたところ、Ｃｕ：Ｉ
ｎ：Ｓ：Ｓｅ＝ 24.4 : 25.2 : 4.7 : 45.7（原子％）
であり、ほぼ目標とする組成の膜を得ることができた。
さらに、得られた膜についてＸ線解析を行ったところ、
カルコパイライト単相であり他の異相の存在は認められ
なかった。なお、得られた膜の表面粗さ（Ｒａ）は約20
00Ａであり、熱処理前と比べてほとんど変化していなか
った。The film obtained as described above was gray-black, and no occurrence of pinholes or peeling was observed.
When the chemical composition of the obtained film was examined, it was found that Cu: I
n: S: Se = 24.4: 25.2: 4.7: 45.7 (atomic%)
Thus, a film having almost the target composition could be obtained.
Further, when an X-ray analysis was performed on the obtained film,
It was a chalcopyrite single phase, and no other heterophase was observed. The surface roughness (Ra) of the obtained film was about 20
00A, which was almost the same as before the heat treatment.
【００１９】[0019]
【実施例２】Ｉｎ2 Ｏ3 をＧａ2 Ｏ3 に置き換え、真空
蒸着法によりＧａ2 Ｏ3 を7300Ａの膜厚で積層したこと
以外は実施例１と同様にして膜を作製した。Replacing Example 2 In 2 O 3 to Ga 2 O 3, except that a laminate of Ga 2 O 3 with a thickness of 7300A was produced film in the same manner as in Example 1 by vacuum evaporation.
【００２０】得られた膜は灰黒色であり、ピンホールや
剥離などの発生は認められなかった。また、得られた膜
の化学組成は、Ｃｕ：Ｇａ：Ｓ：Ｓｅ＝ 23.8 : 25.2 :
5.0:46.0（原子％）であり、ほぼ目標とする組成の膜
を得ることができた。さらに、得られた膜についてＸ線
解析を行ったところ、カルコパイライト単相であり他の
異相の存在は認められなかった。なお、得られた膜の表
面粗さ（Ｒａ）は約2200Ａであり、熱処理前のＲａは約
1200Ａであり、ほとんど変化していなかった。The obtained film was gray-black, and no occurrence of pinholes or peeling was observed. The chemical composition of the obtained film was Cu: Ga: S: Se = 23.8: 25.2:
5.0: 46.0 (atomic%), and a film having almost the target composition could be obtained. Further, when the obtained film was analyzed by X-ray, it was a chalcopyrite single phase, and the presence of another hetero phase was not recognized. The surface roughness (Ra) of the obtained film was about 2200 A, and the Ra before the heat treatment was about 2200 A.
It was 1200 A, which was almost unchanged.
【００２１】[0021]
【実施例３】二元同時蒸着によりＩｎ2 Ｏ3 を約4800
Ａ、Ｇａ2 Ｏ3 を約 700Ａ積層したこと以外は実施例２
と同様にして膜を作製した。なお、本実施例において
は、Ｉｎ2 Ｏ3 とＧａ2 Ｏ3 とは、原子比でＧａ：Ｉｎ
＝ 0.1：0.9 を目標とした。[Embodiment 3] Approximately 4800 In 2 O 3 was deposited by binary simultaneous evaporation.
Example 2 except that A and Ga 2 O 3 were laminated at about 700A.
A film was produced in the same manner as described above. In this embodiment, In 2 O 3 and Ga 2 O 3 are Ga: In in atomic ratio.
= 0.1: 0.9.
【００２２】得られた膜は灰黒色であり、ピンホールや
剥離等の発生は認められなかった。また、得られた膜の
化学組成は、Ｃｕ：Ｉｎ：Ｇａ：Ｓ：Ｓｅ＝ 23.9 : 2
4.2 :2.3 : 4.8 : 44.8 （原子％）であり、ほぼ目標と
する組成の膜を得ることができた。さらに、得られた膜
についてＸ線解析を行ったところ、カルコパイライト単
相であり他の異相の存在は認められなかった。なお、得
られた膜の表面粗さ（Ｒａ）は約2700Ａであり、熱処理
前と比べてほとんど変化していなかった。The obtained film was gray black, and no occurrence of pinholes or peeling was observed. The chemical composition of the obtained film is Cu: In: Ga: S: Se = 23.9: 2
4.2: 2.3: 4.8: 44.8 (atomic%), and a film having almost the target composition could be obtained. Further, when the obtained film was analyzed by X-ray, it was a chalcopyrite single phase, and the presence of another hetero phase was not recognized. The surface roughness (Ra) of the obtained film was about 2700 A, which was almost unchanged from that before the heat treatment.
【００２３】[0023]
【比較例１】200℃で10時間の熱処理を行ったこと以外
は実施例１と同様にして膜を作製したところ、得られた
膜は熱処理前と外観上変化がなかった。得られた膜につ
いてＸ線解析を行ったところ、ＣｕとＩｎ2 Ｏ3 が認め
られただけで置換反応は起こっていなかった。Comparative Example 1 A film was prepared in the same manner as in Example 1 except that the heat treatment was performed at 200 ° C. for 10 hours. As a result, the appearance of the obtained film was unchanged from that before the heat treatment. When an X-ray analysis was performed on the obtained film, only substitution of Cu and In 2 O 3 was observed, but no substitution reaction occurred.
【００２４】[0024]
【比較例２】ＣｕおよびＩｎを真空蒸着法により順次積
層し、ＣｕおよびＩｎの膜厚をそれぞれ2000Ａおよび41
00Ａとしたこと以外は実施例１と同様にして膜を作製し
た。Comparative Example 2 Cu and In were sequentially laminated by a vacuum evaporation method, and the film thicknesses of Cu and In were set to 2,000 A and 41, respectively.
A film was prepared in the same manner as in Example 1 except that the film thickness was changed to 00A.
【００２５】得られた膜は灰黒色であったが、膜の所々
に剥離が認めらた。また、得られた膜の化学組成は、Ｃ
ｕ：Ｉｎ：Ｓ：Ｓｅ＝ 27.8 : 21.7 : 4.9 : 44.6 （原
子％）であり、目標とする組成から大きくずれていた。
さらに、得られた膜についてＸ線解析を行ったところ、
カルコパイライト相以外にＣｕＳまたはＣｕ2 Ｓと考え
られるピークが存在していた。なお、得られた膜の表面
粗さ（Ｒａ）は、熱処理前が4500Ａ、熱処理後が 18600
Ａであり、膜表面の凹凸が著しく大きくなっていた。Although the obtained film was gray-black, peeling was observed in some parts of the film. The chemical composition of the obtained film is C
u: In: S: Se = 27.8: 21.7: 4.9: 44.6 (atomic%), which greatly deviated from the target composition.
Further, when an X-ray analysis was performed on the obtained film,
In addition to the chalcopyrite phase, there was a peak considered to be CuS or Cu 2 S. The surface roughness (Ra) of the obtained film was 4500 A before heat treatment and 18600 A after heat treatment.
A, and the irregularities on the film surface were significantly large.
【００２６】[0026]
【発明の効果】本発明の開発により、ミクロ的な成分の
偏析の発生がなく、かつ膜表面の平滑なI-III-VI族系化
合物半導体膜を、組成の制御性良く製造することができ
るようになった。According to the development of the present invention, it is possible to produce an I-III-VI group compound semiconductor film having no microscopic segregation of components and having a smooth film surface with good controllability of the composition. It became so.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊藤 和人 東京都千代田区丸の内１丁目８番２号 同和鉱業株式会社内 (56)参考文献 特開 昭62−20381（ＪＰ，Ａ) 特開 平１−248627（ＪＰ，Ａ) 特開 平１−160060（ＪＰ，Ａ) 特開 平１−39076（ＪＰ，Ａ) 特開 平１−231313（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/203,21/363 C23C 14/58 H01L 31/04 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kazuto Ito 1-8-2 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd. (56) References JP-A-62-20381 (JP, A) JP-A Heihei 1-248627 (JP, A) JP-A-1-160060 (JP, A) JP-A-1-39076 (JP, A) JP-A-1-231313 (JP, A) (58) Fields investigated (Int. Cl. 7, DB name) H01L 21 / 203,21 / 363 C23C 14/58 H01L 31/04
Claims (4)
ａy）（Ｓｅ1-zＳz）2（ただし、０≦ｘ、ｙ、ｚ≦１）
で表されるI−III−VI族系化合物からなる半導体薄膜の
製造法であって、ＣｕおよびＡｇの一方または両方並び
に酸化インジウムおよび酸化ガリウムの一方または両方
を個別にまたは同時に堆積した後、Ｓｅ源およびＳ源の
一方または両方を含有する還元性ガス雰囲気下で２００
℃以上の温度で熱処理することを特徴とする上記I−III
−VI族系化合物半導体薄膜の製造法。[Claim 1] The general formula (Cu 1-x Ag x ) (In 1-y G
a y ) (Se 1 -z S z ) 2 (where 0 ≦ x, y, z ≦ 1)
A method for producing a semiconductor thin film comprising a group I-III-VI compound represented by the formula: wherein one or both of Cu and Ag and one or both of indium oxide and gallium oxide are deposited individually or simultaneously, source and S source
Under a reducing gas atmosphere containing one or both
The above I-III, wherein the heat treatment is performed at a temperature of not less than ℃.
-A method for producing a group VI compound semiconductor thin film.
ある請求項１記載の製造法。 2. When 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, and 0 <z <1.
The method according to claim 1.
れぞれＩｎ2Ｏ3およびＧａ2Ｏ3である請求項１または２
記載の製造法。Wherein indium oxide and gallium oxide are In 2 O 3 and Ga 2 O 3, respectively claim 1 or 2
Production method as described.
スの一方または両方であり、前記Ｓ源がＨ2Ｓガスおよ
びＳガスの一方または両方であり、前記還元性ガスがＨ
2およびＣＯの一方または両方である請求項１、２また
は３記載の製造法。4. The Se source is one or both of H 2 Se gas and Se gas, the S source is one or both of H 2 S gas and S gas, and the reducing gas is H gas.
Which is one or both of the 2 and CO according to claim 1, 2 or
Is the production method described in 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03124955A JP3095182B2 (en) | 1991-04-25 | 1991-04-25 | Method for producing I-III-VI compound semiconductor thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03124955A JP3095182B2 (en) | 1991-04-25 | 1991-04-25 | Method for producing I-III-VI compound semiconductor thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04326525A JPH04326525A (en) | 1992-11-16 |
| JP3095182B2 true JP3095182B2 (en) | 2000-10-03 |
Family
ID=14898355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03124955A Expired - Fee Related JP3095182B2 (en) | 1991-04-25 | 1991-04-25 | Method for producing I-III-VI compound semiconductor thin film |
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| Country | Link |
|---|---|
| JP (1) | JP3095182B2 (en) |
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| KR101389832B1 (en) * | 2012-11-09 | 2014-04-30 | 한국과학기술연구원 | Cigs or czts based film solar cells and method for preparing thereof |
| JP7068798B2 (en) * | 2017-10-26 | 2022-05-17 | 出光興産株式会社 | Manufacturing method of photoelectric conversion element |
| JP2021084838A (en) * | 2019-11-28 | 2021-06-03 | トヨタ自動車株式会社 | Method for producing semiconductor material |
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| JPH04326525A (en) | 1992-11-16 |
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