JP3160974B2 - Solid solution thin film and method for producing the same - Google Patents
Solid solution thin film and method for producing the sameInfo
- Publication number
- JP3160974B2 JP3160974B2 JP32266891A JP32266891A JP3160974B2 JP 3160974 B2 JP3160974 B2 JP 3160974B2 JP 32266891 A JP32266891 A JP 32266891A JP 32266891 A JP32266891 A JP 32266891A JP 3160974 B2 JP3160974 B2 JP 3160974B2
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- JP
- Japan
- Prior art keywords
- mns
- cds
- solid solution
- thin film
- solution thin
- Prior art date
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/543—Solar cells from Group II-VI materials
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- Photovoltaic Devices (AREA)
- Light Receiving Elements (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は太陽電池の光透過窓層な
ど光電変換デバイスや光学デバイスなどに有用なＣdＳ
ーＭnＳ固溶体薄膜とそ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 CdS useful for a photoelectric conversion device or an optical device such as a light transmission window layer of a solar cell.
The present invention relates to a MnS solid solution thin film and a method for producing the same.
【０００２】[0002]
【従来の技術】近い将来、エネルギー供給が次第に困難
になることが予想され、太陽電池の高効率化、低コスト
化が大きな課題になってきた。なかでも、大面積化が容
易な薄膜系太陽電池は大幅な低コスト化が可能と見られ
そのエネルギー変換効率の向上が強く望まれている。2. Description of the Related Art In the near future, it is expected that energy supply will gradually become more difficult, and high efficiency and low cost of solar cells have become major issues. Above all, thin-film solar cells, which can be easily enlarged, can be significantly reduced in cost, and it is strongly desired to improve their energy conversion efficiency.
【０００３】この薄膜系太陽電池には化合物半導体（II
-VI族やI-III -VI2族）薄膜を用いたものが広く開発さ
れつつある。化合物半導体薄膜を用いた太陽電池の構成
は、バンドギャップが広くて光を透過する窓層としての
ｎ型ＣdＳ系半導体層とバンドギャップが狭くて光を吸
収する吸収層としてのｐ型のＣdＴe系あるいはＣuＩnＳ
e2系などの半導体層を積層したヘテロ接合が用いられ
る。A compound semiconductor (II)
(VI-VI and I-III-VI 2 ) thin films are being widely developed. The structure of a solar cell using a compound semiconductor thin film includes an n-type CdS-based semiconductor layer as a window layer having a wide band gap and transmitting light and a p-type CdTe-based as an absorption layer having a narrow band gap and absorbing light. Or CuInS
A heterojunction in which semiconductor layers such as an e 2 system are stacked is used.
【０００４】構成としては、例えばＩＴＯ（Ｉndium Ｔ
in Ｏxide）を設けたガラス基板上にｎ型ＣdＳ層を、次
いでｐ型ＣdＴe層を蒸着法で積層形成し、最後に金属電
極を設けて太陽電池とする。あるいは、ガラス基板上に
スクリーン印刷と焼成によってｎ型ＣdＳ層を、次いで
同様にスクリーン印刷と焼成によってｐ型ＣdＴe層を、
最後に金属あるいは炭素電極層を設けて太陽電池とす
る。As a configuration, for example, ITO (Indium T
An n-type CdS layer and then a p-type CdTe layer are formed on a glass substrate provided with in oxide) by vapor deposition, and finally a metal electrode is provided to complete a solar cell. Alternatively, an n-type CdS layer is formed on a glass substrate by screen printing and baking, and then a p-type CdTe layer is similarly formed by screen printing and baking.
Finally, a metal or carbon electrode layer is provided to complete a solar cell.
【０００５】ＣdＳの代わりにバンドギャップのより広
い半導体例えばＣdＳ-ＭnＳ固溶体薄膜を用いること
は、透過光量を増やし変換効率を上げることに大変有効
と考えられる。ＣdＳとＭnＳはＭnＳの組成比が５０モ
ル％以下の範囲でウルツ鉱型結晶構造の固溶体Ｃd1ーxＭ
nxＳ（０＜ｘ＜０.５）を形成することが高温での単結
晶育成や焼結体形成の結果から知られている（特公昭４
５ー３１１４４号公報、Ｍ. イケダ他, Ｊ．Ｐｈｙ
ｓ．Ｓｏｃ．Ｊｐｎ. ２５, ４５５（１９６８）)。It is considered that the use of a semiconductor having a wider band gap, for example, a CdS-MnS solid solution thin film instead of CdS is very effective in increasing the amount of transmitted light and increasing the conversion efficiency. Solid solution Cd 1 over x M wurtzite crystal structure CdS and MnS in the range compositional ratio below 50 mol% of MnS
n x S to form a (0 <x <0.5) is known from the result of single crystal growth and sintered formed at high temperature (JP-B 4
No. 5-31144, M. Ikeda et al. Phys
s. Soc. Jpn. 25, 455 (1968)).
【０００６】これらの方法ではＭｎＳの組成比が５０モ
ル％以上の範囲ではウルツ鉱型結晶構造の固溶体Ｃd0.5
Ｍn0.5Ｓと岩塩型結晶構造のＭｎＳとの混合物ができ
る。また、このＣdＳ-ＭnＳ固溶体薄膜の形成法として
は、２つの蒸発源からＣｄＳとＭｎＳを独立に蒸発させ
基板上に付着させて固溶体薄膜を形成する方法が考えら
れる。In these methods, when the composition ratio of MnS is in the range of 50 mol% or more, a solid solution Cd 0.5 having a wurtzite type crystal structure is used.
A mixture of Mn 0.5 S and MnS having a rock salt type crystal structure is obtained. As a method of forming the CdS-MnS solid solution thin film, a method of forming a solid solution thin film by independently evaporating CdS and MnS from two evaporation sources and attaching the CdS and MnS to a substrate is considered.
【０００７】[0007]
【発明が解決しようとする課題】この様に、バンドギャ
ップの広いＣdＳーＭnＳ固溶体を主体とする半導体薄膜
から成る窓層を形成するには作製上注意を要する。例え
ばＭnＳを抵抗加熱法で蒸着するとＭnＳが分解し、Ｍn
が残り易く固溶体膜が形成し難いので蒸着に工夫を必要
とする。またＭnＳの組成比を５０モル％以上のＣdＳー
ＭnＳ固溶体薄膜が実現できればより広いバンドギャッ
プにすることができる筈である。As described above, formation of a window layer composed of a semiconductor thin film mainly composed of a CdS-MnS solid solution having a wide band gap requires care in fabrication. For example, when MnS is deposited by a resistance heating method, MnS is decomposed and MnS is decomposed.
However, it is difficult for a solid solution film to be formed, so that a device is required for vapor deposition. Further, if a CdS-MnS solid solution thin film having a composition ratio of MnS of 50 mol% or more can be realized, a wider band gap should be achieved.
【０００８】[0008]
【課題を解決するための手段】本発明の固溶体薄膜の製
造方法は、 （１）基板上に、ＣdＳおよびＭnの２元を蒸着源とし
て、同時に蒸着することを特徴とするウルツ鉱型結晶構
造のＣdＳ-ＭnＳ固溶体薄膜の製造方法、 （２）基板上に、ＣdＳおよびＭnＳの２元を蒸着源とし
て、同時に蒸着する方法において、少なくともＭnＳは
電子ビーム蒸着法によって蒸着することを特徴とするウ
ルツ型結晶構造のＣdＳ-ＭnＳ固溶体薄膜の製造方法、 （３）基板上に、ＣdＳおよびＭnＳの固溶体あるいは混
合物をスパッタリング蒸着することを特徴とするウルツ
型結晶構造のＣdＳ-ＭnＳ固溶体薄膜の製造方法、であ
る。 The solid solution thin film of the present invention is produced.
The fabrication method is as follows: (1) On the substrate, CdS and Mn are used as the evaporation source.
Wurtzite-type crystal structure
The method of manufacturing concrete of CdS-MnS solid solution thin film (2) on a substrate, the 2 original CdS and MnS and the deposition source
In the method of simultaneously depositing, at least MnS is
Characterized by being deposited by an electron beam evaporation method.
A method for producing a CdS-MnS solid solution thin film having a Ruth-type crystal structure, (3) a solid solution or mixture of CdS and MnS on a substrate.
Wurtz characterized by sputtering deposition of the compound
A method for producing a CdS-MnS solid solution thin film having a type crystal structure.
You.
【０００９】また、本発明は、上記方法をとることによ
り、ＭnＳの組成比が５０モル％以上であるウルツ鉱型
結晶構造のＣdＳ-ＭnＳ固溶体薄膜が得られるものであ
る。 Further , the present invention provides a method according to the above method.
Wurtzite with a composition ratio of MnS of 50 mol% or more
A CdS-MnS solid solution thin film having a crystalline structure is obtained.
You.
【００１０】[0010]
【作用】本発明によれば、バンドギャップの広いＣdＳ
−ＭnＳ固溶体薄膜が得られ、本発明の製造方法によれ
ば、この固溶体薄膜を安価な蒸着装置で、例えばＣdＳ
とＭnの２源による同時蒸着によって容易に形成でき
る。しかもその固溶範囲を従来知られている範囲（０＜
ｘ＜０.５）よりはるかに広げることができる。またＩ
ｎなどの添加により低抵抗化が可能であり、太陽電池の
高効率化に有効である。According to the present invention, CdS having a wide band gap is used.
-MnS solid solution thin film is obtained, and according to the production method of the present invention, this solid solution thin film
And Mn can be easily formed by simultaneous vapor deposition using two sources. Moreover, the solid solution range is set to a conventionally known range (0 <
x <0.5). Also I
The resistance can be reduced by adding n or the like, which is effective for increasing the efficiency of the solar cell.
【００１１】[0011]
【実施例】以下、本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００１２】ガラス基板(コーニング社,＃７０５９）上
に基板温度１５０℃で、２つの蒸発源を用いてＣdＳと
Ｍnを同時に蒸発させ、ＣdＳとＭnＳのモル比を広範囲
に変えた厚さ約０.５μmのＣdＳーＭnＳ固溶体薄膜（Ｃ
ｄ1-xＭnxＳ）を形成した。これら薄膜のＸ線回折法で
の解析によると、図１に示すように広い固溶範囲（０＜
ｘ＜１）でＣｄＳと同じウルツ鉱型結晶構造を示し、従
来の既知の固溶範囲（０＜ｘ＜０.５）と異なる結果を
示した。CdS and Mn are simultaneously evaporated on a glass substrate (Corning Co., # 7059) at a substrate temperature of 150.degree. C. using two evaporation sources, and the thickness is about 0 in which the molar ratio of CdS to MnS is changed over a wide range. 0.5 µm CdS-MnS solid solution thin film (C
d 1-x Mn x S) was formed. According to X-ray diffraction analysis of these thin films, as shown in FIG. 1, a wide solid solution range (0 <
x <1) showed the same wurtzite-type crystal structure as CdS, showing a result different from the conventional known solid solution range (0 <x <0.5).
【００１３】従来は何れも高温（＞６００℃）の熱処理
によって得られた結晶あるいは焼結体であり、蒸着法
（基板温度Ｔｓ＝１００〜３００℃）で得られる薄膜と
は状態が異なるものと考えられる。分光透過率（Ｔr）
は図２に示す様にその吸収端波長はｘがある値（ｘ〜
０.１４）を越えると短波長側に移動し、バンドギャッ
プが広くなることが分かる。Conventionally, each is a crystal or a sintered body obtained by heat treatment at a high temperature (> 600 ° C.), and has a different state from a thin film obtained by a vapor deposition method (substrate temperature Ts = 100 to 300 ° C.). Conceivable. Spectral transmittance (T r )
As shown in FIG. 2, the absorption edge wavelength is x at a certain value (x to
It can be seen that when the ratio exceeds 0.14), the wavelength shifts to the shorter wavelength side and the band gap becomes wider.
【００１４】ただし、Ｔr＝０.３となる波長を吸収端波
長、これに相当するエネルギーをバンドギャップとす
る。これらの結果を表１に示す。これらの膜は何れもｎ
型の伝導特性を示し、そのままでも窓層として使える場
合が多いが、ｘが増大すると一般には電気伝導度σは小
さくなる。その場合はドナー不純物を添加する。例えば
これら膜の上にＩnを母体に対して１〜３モル％蒸着
し、Ｎ2ガス中２００〜４００℃でアニールし内部に拡
散添加する。これら膜は何れの組成でも１０-3〜１Ω -1
・cm-1の伝導度を示した。Where Tr= 0.3 absorption wavelength
Long, the energy corresponding to this is called the band gap.
You. Table 1 shows the results. Each of these films has n
When it shows the conduction characteristics of the mold and can be used as a window layer as it is
In general, the electrical conductivity σ decreases as x increases.
It will be cheap. In that case, a donor impurity is added. For example
On these films, In is vapor-deposited by 1 to 3 mol% with respect to the base material.
Then NTwoAnneal at 200-400 ° C in gas and expand inside
Add powder. These films have a composition of 10-3~ 1Ω -1
·cm-1Showed the conductivity.
【００１５】[0015]
【表１】 [Table 1]
【００１６】この様に、従来のＣdＳ膜に比べて短波長
域まで分光透過率が大である上に、電気伝導度も高い。
ＣdＳとＭnＳの他の組成比のＣdＳ-ＭnＳ固溶体を用い
ても、またＩnの代わりにＡlやＧaを用いても同様の効
果が得られる。この固溶体薄膜はＣdＳとＭnＳの同時蒸
着でＭnＳを電子ビーム法で蒸着しても、あるいはＣdＳ
−ＭnＳの固溶体や混合物をスパッタリング法で蒸着し
ても得ることができる。As described above, as compared with the conventional CdS film, the spectral transmittance is high even in a short wavelength region and the electric conductivity is high.
Similar effects can be obtained by using a CdS-MnS solid solution having another composition ratio of CdS and MnS, or by using Al or Ga instead of In. This solid solution thin film can be obtained by depositing MnS by an electron beam method by simultaneous deposition of CdS and MnS, or
It can also be obtained by depositing a solid solution or mixture of -MnS by a sputtering method.
【００１７】ところで、ＭｎＳの組成比が５０モル％以
上のＣdＳ-ＭnＳ固溶体は従来合成出来ていなかった組
成であり、本発明の方法により始めて実現できたもので
ある。また、（表１）から分かるようにＭｎＳの組成比
が１０モル％以下では太陽電池の窓層として用いた場合
効果がなく、さらに特公昭４５ー３１１４４号公報に示
すようにＭｎＳの組成比が０.１モル％以下では光導電
体の応答速度を速くする効果は得られない。Meanwhile, a CdS-MnS solid solution having a composition ratio of MnS of 50 mol% or more is a composition which could not be synthesized conventionally, and can be realized only by the method of the present invention. Further, as can be seen from Table 1, when the composition ratio of MnS is 10 mol% or less, there is no effect when used as a window layer of a solar cell, and as shown in JP-B-45-31144, the composition ratio of MnS is reduced. If it is less than 0.1 mol%, the effect of increasing the response speed of the photoconductor cannot be obtained.
【００１８】[0018]
【発明の効果】本発明によれば、太陽電池の変換効率向
上に有効なバンドギャップの広い、低抵抗のＣdＳ-Ｍn
Ｓ固溶体薄膜を提供できる。また、本発明の製造方法に
よれば、上記ＣdＳ-ＭnＳ固溶体薄膜を安価な装置を用
いて容易に形成することが可能となる。このＣdＳ-Ｍn
Ｓ固溶体薄膜は太陽電池の変換効率向上とコストダウン
に有効であり、また他の光電変換デバイス、光学デバイ
スなどへの応用を可能にする。According to the present invention, a low-resistance CdS-Mn having a wide band gap and effective for improving the conversion efficiency of a solar cell.
An S solid solution thin film can be provided. Further, according to the manufacturing method of the present invention, the CdS-MnS solid solution thin film can be easily formed by using an inexpensive apparatus. This CdS-Mn
The S solid solution thin film is effective for improving the conversion efficiency and cost of the solar cell, and enables application to other photoelectric conversion devices and optical devices.
【図１】本発明の実施例におけるＣdＳ-ＭnＳ固溶体薄
膜の組成と格子定数を示す図FIG. 1 is a diagram showing the composition and lattice constant of a CdS—MnS solid solution thin film according to an example of the present invention.
【図２】本発明の実施例におけるＣdＳ-ＭnＳ固溶体薄
膜の分光透過率を示すグラフFIG. 2 is a graph showing the spectral transmittance of a CdS—MnS solid solution thin film according to an example of the present invention.
ｘ ＭnＳの組成比（Ｃd1-xＭnxＳ） ａ ウルツ鉱型結晶構造の格子定数（ａ軸） ｃ ウルツ鉱型結晶構造の格子定数（ｃ軸） λ 波長 Ｔr 透過率The composition ratio of x MnS (Cd 1-x Mn x S) a wurtzite lattice constant of the crystal structure (a-axis) c lattice constant a wurtzite type crystal structure (c-axis) lambda wave T r transmittance
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平尾 孝 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 昭57−95676（ＪＰ，Ａ) 特開 昭61−106499（ＪＰ，Ａ) Ｓｅｍｉｃｏｎｄｕｃｔｏｒｓ ａｎ ｄ Ｍａｔｅｒｉａｌｓ，Ｃｈａｐｔｅ ｒ １（ｐｐ．１−33），Ｗ．Ｇｉｒｉ ａｔ ａｔ ａｌ．，1988，Ａｃａｄｅ ｍｉｃ Ｐｒｅｓｓ Ｉｎｃ. (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 31/00 - 31/119 H01L 21/365 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Hirao 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-57-95676 (JP, A) JP-A-61- 106499 (JP, A) Semiconductors and Materials, Chapter 1 (pp. 1-33); Giri at at al. , 1988, Academic Press Inc. (58) Fields investigated (Int. Cl. 7 , DB name) H01L 31/00-31/119 H01L 21/365
Claims (4)
源として、同時に蒸着することを特徴とするウルツ鉱型
結晶構造のＣdＳ-ＭnＳ固溶体薄膜の製造方法。1. Binary deposition of CdS and Mn on a substrate
Wurtzite type characterized by simultaneous evaporation as a source
A method for producing a CdS-MnS solid solution thin film having a crystal structure .
着源として、同時に蒸着する方法において、少なくとも
ＭnＳは電子ビーム蒸着法によって蒸着することを特徴
とするウルツ鉱型結晶構造のＣdＳ-ＭnＳ固溶体薄膜の
製造方法。2. The method according to claim 1, wherein a binary of CdS and MnS is vaporized on the substrate.
A method for producing a CdS-MnS solid solution thin film having a wurtzite crystal structure , wherein at least MnS is deposited by an electron beam evaporation method in a simultaneous deposition method as a deposition source .
るいは混合物をスパッタリング蒸着することを特徴とす
るウルツ鉱型結晶構造のＣdＳ-ＭnＳ固溶体薄膜の製造
方法。3. A method for producing a CdS-MnS solid solution thin film having a wurtzite crystal structure, wherein a solid solution or a mixture of CdS and MnS is deposited by sputtering on a substrate.
よって作られるＣｄＳ−ＭｎＳの固溶体薄膜であって、
ＭnＳの組成比が５０モル％以上であることを特徴とす
るウルツ鉱型結晶構造のＣdＳ-ＭnＳ固溶体薄膜。 4. The method according to claim 1, wherein
It is a solid solution thin film of CdS-MnS thus produced,
The composition ratio of MnS is 50 mol% or more.
CdS-MnS solid solution thin film with wurtzite crystal structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32266891A JP3160974B2 (en) | 1991-12-06 | 1991-12-06 | Solid solution thin film and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32266891A JP3160974B2 (en) | 1991-12-06 | 1991-12-06 | Solid solution thin film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05160424A JPH05160424A (en) | 1993-06-25 |
| JP3160974B2 true JP3160974B2 (en) | 2001-04-25 |
Family
ID=18146275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32266891A Expired - Fee Related JP3160974B2 (en) | 1991-12-06 | 1991-12-06 | Solid solution thin film and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3160974B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111905761A (en) * | 2020-07-29 | 2020-11-10 | 广西科技师范学院 | Mn (manganese)1Cd3S4Method for preparing photocatalyst |
-
1991
- 1991-12-06 JP JP32266891A patent/JP3160974B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Ｓｅｍｉｃｏｎｄｕｃｔｏｒｓ ａｎｄ Ｍａｔｅｒｉａｌｓ，Ｃｈａｐｔｅｒ １（ｐｐ．１−３３），Ｗ．Ｇｉｒｉａｔ ａｔ ａｌ．，１９８８，Ａｃａｄｅｍｉｃ Ｐｒｅｓｓ Ｉｎｃ． |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05160424A (en) | 1993-06-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |