JP3095182B2 - Method for producing I-III-VI group compound semiconductor thin film - Google Patents
Method for producing I-III-VI group 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
- Authority
- JP
- Japan
- Prior art keywords
- film
- iii
- gas
- producing
- thin 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.)
- Expired - Fee Related
Links
- 150000001875 compounds Chemical class 0.000 title claims description 17
- 239000004065 semiconductor Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000010409 thin film Substances 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims description 17
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 10
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 7
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 description 50
- 239000011669 selenium Substances 0.000 description 24
- 239000010949 copper Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- 229910052738 indium Inorganic materials 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 13
- 229910052711 selenium Inorganic materials 0.000 description 13
- 239000012071 phase Substances 0.000 description 11
- 229910052733 gallium Inorganic materials 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 7
- 239000013067 intermediate product Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052951 chalcopyrite Inorganic materials 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
Landscapes
- Physical Vapour Deposition (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Photovoltaic Devices (AREA)
- Light Receiving Elements (AREA)
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。The present invention relates to an I-type photovoltaic element used as a solar cell, a photosensor, or an optical element.
This relates to a method for producing thin films of III-VI compound semiconductors.
【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。PRIOR ART The following methods have been known for producing thin films of I-III-VI group compound semiconductors: a method in which copper and indium layers are sequentially or simultaneously electroplated onto a substrate, followed by heat treatment in the presence of a selenium-containing gas to obtain CuInSe2 , and a method in which elemental selenium is evaporated onto a copper and indium layer, followed by heat treatment in an inert gas atmosphere, as disclosed in Japanese Patent Laid-Open Publication No. 61-2374.
76. A method using vacuum deposition such as simultaneous deposition of component elements or deposition of an intermetallic compound is disclosed in Japanese Patent Application Laid-Open No. 1975.
A method in which copper, indium and selenium are successively vapor-deposited, and the amount of selenium is adjusted to a required stoichiometric ratio or less, and then heat treatment is performed in the presence of selenium and a sulfur-containing gas is performed in the presence of a gas containing selenium.
Furthermore, Japanese Patent Laid-Open No. 2-73674 discloses a method in which the solution supply ratio of a selenium source and a sulfur source is successively changed in a spray pyrolysis method to form a concentration distribution of Se and S in the 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。[0003] According to the above-mentioned methods, the composition ratios that greatly affect the performance of I-III-VI compound semiconductors, particularly the composition ratios between group I elements such as Cu and Ag and group III elements such as In and Ga, are controlled by changing the film thickness when stacking these. However, when deposited as a film, group III elements such as In and Ga tend to grow perpendicular to the substrate surface, which tends to result in a striped structure, making it difficult to make the film surface smooth. In addition,
Even if a smooth surface was obtained, if In and Ga were in a metallic state, the generation of low-temperature stable intermediate products such as Cu2Se and Cu2S was unavoidable during heat treatment in a Se- and S-containing gas atmosphere. Since such intermediate products do not disappear completely even when high-temperature heat treatment is performed, it becomes very difficult to make the final product into the 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。[0004] In other words, the above-mentioned conventional methods have problems with composition controllability, which is considered to be the most important factor, and are prone to microscopic segregation of components. In some cases, there is a problem that the presence of intermediate products such as Cu 2 Se and Cu 2 S in addition to the I-III-VI group chalcopyrite phase is unavoidable.
【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 products, there is a method of reacting Se and S at a temperature of 200° C. or higher, or a method of reacting Se and S at a temperature of 200° C. or lower in an inert gas atmosphere such as N 2 ,
In the past, the method of introducing Se- and S-containing gases at temperatures of 200°C or higher was used. However, since the melting points of In and Ga are extremely low at 153°C and 30°C, respectively, and their surface tensions are large, the elements tend to aggregate before the mutual diffusion of the elements, i.e., before sulfurization or selenization, begins.
In this way, when In and Ga aggregate or when liquid phases of In and Ga exist, it causes pinholes and film peeling in the periphery, and also the surface state of the ternary compound film, which is the final product, reproduces the surface state of In and Ga as it is, so there is a problem that the surface precision 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 PRESENT INVETION The present invention aims to solve the above-mentioned problems of the prior art, and to provide a method for producing a I-III-VI compound semiconductor film which has improved composition controllability, is free of microsegregation, and has a smooth film surface.
【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。[0011] The present inventors have conducted extensive research to solve the above problems and have discovered that by forming an oxide film of either or both of In and Ga on either or both of Cu and Ag films and then heat treating this in an atmosphere of a reducing gas containing either or both of Se and S, the reduction of the metal oxide and the selenization and sulfurization of the same metal proceed simultaneously, resulting in a ternary compound thin film free of intermediate products, thereby making it possible to provide 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 Ga y ) (Se 1-z S z ) 2 (0≦
The present invention relates to a method for producing a semiconductor thin film made of a group I-III-VI compound represented by the formula (x, y, z≦1), the method comprising the steps of depositing one or both of Cu and Ag, and one or both of indium oxide and gallium oxide, preferably In 2 O 3 and Ga 2 O 3 , separately or simultaneously, and then subjecting the resulting semiconductor thin film to a reducing gas atmosphere containing one or both of a Se source and a S source for 20 minutes.
The above-mentioned I-I is characterized by being heat-treated at a temperature of 0° C. or higher.
A method for producing II-VI compound semiconductor thin films is provided.
【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, one or both of H 2 S gas and S gas can be used as the S source, and 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。In the present invention, the deposited films of Cu and Ag may be either metal or oxide, or may be a mixture of metal and 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, the Cu and Ag films can be deposited on the substrate by the commonly used deposition method, sputtering method, electrodeposition method, etc. It has been confirmed on an industrial scale that these methods are capable of forming a smooth film surface and have excellent controllability of film thickness.
Even if Cu 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 of Group I elements to Group III elements can be controlled by the thickness of the oxide layer of the Group III elements that is deposited later, and the Group I metal, Cu, is not affected by the thickness of the oxide layer.
The oxides of u and Ag are oxides of metals of Group III.
This is because it is much easier to reduce than n 2 O 3 and 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 In 2 O 3 or Ga 2 O 3 is deposited, there is no problem if it is deposited by a chemical deposition method such as vapor deposition, sputtering, or dip coating. This is because In 2 O 3 and Ga 2 O 3 are metal I
This is because it has a much higher melting point than In or Ga and has excellent film-forming properties, and this is also evident from the fact that it is well known that a transparent conductive ITO film made by adding SnO2 to In2O3 can be formed with high precision.
【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 prepared as described above is S
The heat treatment is performed in a reducing gas atmosphere containing either or both of In 2 O 3 and Ga 2 O 3
Since no reaction occurs when S and Se gases are introduced at high temperatures, it is necessary to make a reducing gas such as H2 coexist with either or both of S and Se gases.
The heat treatment temperature must be 200° C. or higher because the reduction reaction of the oxides does not proceed substantially at temperatures below 200° C. The fact that the reduction reaction does not proceed at a heat treatment temperature below 200° C. means that no intermediate products are produced and it is easy to obtain a single-phase ternary compound.
【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。Furthermore, In 2 O 3 and Ga 2 O 3 are thermally stable and do not change when heated to about 200°C. Therefore, the surface condition at the time of film formation is maintained even at high temperatures during heat treatment, and the surface of the resulting film is less likely to become uneven. Therefore, selenization and sulfurization can be performed at the desired temperature while maintaining the surface condition at the time of film formation, and a high-quality ternary compound thin film can be obtained. Note that there is no problem if the film is formed in an inert gas atmosphere such as N 2 gas until the temperature at which the film is selenized or sulfurized 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。The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to 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 Corning # 7059 glass substrate by vacuum deposition to a thickness of 2000 A (angstroms), and In2O3 was laminated on top of this by sputtering to an atomic ratio of Cu:In = 1:1 and a thickness of 5300 A. The In2O3 target used in the sputtering method was made by compressing In2O3 powder and sintering it at 1400°C. The surface roughness (Ra) of this laminated film was about 1000 A.
【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.
When the temperature reached 00° C., H 2 S and H 2 Se were introduced so that the molar flow rate was H 2 S/(H 2 Se+H 2 S)=0.9, and after 2 hours, the gas was switched to N 2 gas and the mixture was cooled to room temperature.
【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 in color, and no pinholes or peeling was observed.
In addition, the chemical composition of the obtained film was examined and found to be Cu:I
n:S:Se= 24.4: 25.2: 4.7: 45.7 (atomic %)
Thus, a film with nearly the target composition could be obtained.
Furthermore, when the obtained film was subjected to X-ray analysis,
The film was a single phase of chalcopyrite, and no other phases were observed. The surface roughness (Ra) of the film was approximately 20
00A, which was almost unchanged from 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。Example 2 A film was prepared in the same manner as in Example 1, except that In 2 O 3 was replaced with Ga 2 O 3 and Ga 2 O 3 was laminated to a thickness of 7300 Å by vacuum deposition.
【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 film obtained was gray-black, and no pinholes or peeling was observed. The chemical composition of the film obtained was Cu:Ga:S:Se=23.8:25.2:
5.0:46.0 (atomic %), a film with almost the target composition was obtained. Furthermore, X-ray analysis of the obtained film revealed that it was a single phase of chalcopyrite and no other phases were present. The surface roughness (Ra) of the obtained film was about 2200A, and the Ra before heat treatment was about
It was 1200A and had hardly changed at all.
【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。[Example 3] In2O3 was deposited at about 4800
A, Ga2O3 was laminated to about 700A .
In this example, the atomic ratio of In 2 O 3 to Ga 2 O 3 was Ga:In
The target ratio was 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 film obtained was gray-black, and no pinholes or peeling was observed. The chemical composition of the film obtained was Cu:In:Ga:S:Se=23.9:2.
The composition of the film was 4.2:2.3:4.8:44.8 (atomic percent), which is almost the target composition. Furthermore, X-ray analysis of the film showed that it was a single phase of chalcopyrite, with no other phases present. The surface roughness (Ra) of the film was approximately 2700A, which was almost unchanged from 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 heat treatment was performed at 200° C. for 10 hours. The appearance of the film obtained was unchanged from that before heat treatment. X-ray analysis of the film obtained revealed that only Cu and In 2 O 3 were found, and no substitution reaction had 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 laminated in sequence by vacuum deposition to thicknesses of 2000 Å and 41 Å, respectively.
A membrane was prepared in the same manner as in Example 1, except that the thickness was 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。The film obtained was gray-black in color, but peeling was observed in places. The chemical composition of the film obtained was C
The composition ratio of u:In:S:Se was 27.8:21.7:4.9:44.6 (atomic percent), which was significantly different from the target composition.
Furthermore, when the obtained film was subjected to X-ray analysis,
In addition to the chalcopyrite phase, there were peaks thought to be due to CuS or Cu 2 S. The surface roughness (Ra) of the obtained film was 4500A before heat treatment and 18600A after heat treatment.
A, and the unevenness of the film surface was significantly increased.
【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。As a result of the development of the present invention, it has become possible to manufacture I-III-VI compound semiconductor films that are free from microscopic component segregation and have a smooth film surface with good composition control.
───────────────────────────────────────────────────── 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 ─────────────────────────────────────────────────────────── Continued from the front page (72) Inventor Kazuto Ito 1-8-2 Marunouchi Chiyoda-ku, Tokyo Dowa Mining Co., Ltd. (56) References JP 62-20381 (JP, A) JP 1-248627 (JP, A) JP 1-160060 (JP, A) JP 1-39076 (JP, A) JP 1-231313 (JP, A) (58) Field surveyed (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] General formula (Cu 1-x Ag x ) (In 1-y G
a y ) (Se 1-z S z ) 2 (0≦x, y, z≦1)
The present invention relates to a method for producing a semiconductor thin film made of a group I-III-VI compound represented by the formula:
200 under a reducing gas atmosphere containing either or both
The above-mentioned I-III is characterized in that it is heat-treated at a temperature of .degree. C. or higher.
- A method for manufacturing thin films of Group VI compound semiconductors.
ある請求項１記載の製造法。 Claim 2: 0≦x≦1, 0≦y≦1, 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。3. The method according to claim 1 or 2, wherein the indium oxide and the gallium oxide are In 2 O 3 and Ga 2 O 3, respectively.
The manufacturing method 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 method according to claim 1, wherein 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
2 and / or CO.
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 group 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 group 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 group compound semiconductor thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3095182B2 (en) |
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| JP5710368B2 (en) * | 2011-05-06 | 2015-04-30 | 株式会社東芝 | Photoelectric conversion element and solar cell |
| 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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- 1991-04-25 JP JP03124955A patent/JP3095182B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH04326525A (en) | 1992-11-16 |
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