JPH05291139A - Manufacture of solid solution thin film and manufacture of solar cell - Google Patents
Manufacture of solid solution thin film and manufacture of solar cellInfo
- Publication number
- JPH05291139A JPH05291139A JP4094004A JP9400492A JPH05291139A JP H05291139 A JPH05291139 A JP H05291139A JP 4094004 A JP4094004 A JP 4094004A JP 9400492 A JP9400492 A JP 9400492A JP H05291139 A JPH05291139 A JP H05291139A
- Authority
- JP
- Japan
- Prior art keywords
- cds
- thin film
- solid solution
- solar cell
- zns
- 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.)
- Granted
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
- Y02E10/543—Solar cells from Group II-VI materials
Landscapes
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Photovoltaic Devices (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
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や
エレクトロルミネッセンス用発光体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ＺnＳ固溶体薄
膜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 producing a CdS-ZnS solid solution thin film useful for photoelectric conversion devices, optical devices and the like such as light transmitting window layers of solar cells and light emitting layers for electroluminescence.
【０００２】[0002]
【従来の技術】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なのでそのエネルギー変換効率の
向上が強く望まれている。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ＣdＴe系あるいはＣu
ＩnＳe2系などのｐ型の半導体層を積層したヘテロ接合
などが用いられる。構成としては、例えばＩＴＯ（Ｉnd
ium Ｔin 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。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-ＺnＳ固溶体薄膜を用いることが、透
過光量を増やし変換効率を上げることに大変有効である
ことが知られている。2. Description of the Related Art A thin-film solar cell whose area can be easily made large can be significantly reduced in cost, and therefore it is strongly desired to improve its energy conversion efficiency. For this thin film solar cell, a compound semiconductor (II-VI group or I-III-VI 2 group) thin film is being widely developed. A solar cell using a compound semiconductor thin film has an n-type CdS-based semiconductor layer as a window layer that has a wide bandgap and transmits light, and a CdTe-based or Cu as an absorption layer that has a narrow bandgap and absorbs light.
A heterojunction in which p-type semiconductor layers such as InSe 2 series are laminated is used. As a configuration, for example, ITO (Ind
An n-type CdS layer and then a p-type CdTe layer are laminated on the glass substrate provided with (ium tin oxide) by a vapor deposition method, and finally a metal electrode is provided to form a solar cell. Alternatively, an n-type CdS layer is formed on a glass substrate by screen printing and firing,
Then, p-type CdTe is similarly subjected to screen printing and firing.
The layer is finally provided with a metal or carbon electrode layer to form a solar cell. It is known that the use of a semiconductor having a wider band gap such as a CdS-ZnS solid solution thin film instead of CdS is very effective in increasing the amount of transmitted light and increasing the conversion efficiency.
【０００３】ＣdＳ-ＺnＳ固溶体薄膜の形成法として
は、２つの蒸発源からＣdＳとＺnＳを独立に蒸発させる
か、ＣdＳとＺnＳの混合物あるいは固溶体をスパッタ法
で蒸発させ基板上に付着させて固溶体薄膜を形成する方
法などがある。例えば、前者の場合ＣdＳとＺnＳを別々
の蒸発源から同時に蒸発させそれぞれの蒸発レートを調
節して、１００℃以下に保った例えばガラス基板上に所
望の組成比のＣdＳーＺnＳ固溶体薄膜を形成することが
できる。As a method for forming a CdS-ZnS solid solution thin film, CdS and ZnS are independently evaporated from two evaporation sources, or a mixture of CdS and ZnS or a solid solution is evaporated by a sputtering method and deposited on a substrate to form a solid solution thin film. There is a method of forming. For example, in the former case, CdS and ZnS are simultaneously vaporized from different vaporization sources and the respective vaporization rates are adjusted to form a CdS-ZnS solid solution thin film having a desired composition ratio on a glass substrate kept at 100 ° C or lower. be able to.
【０００４】[0004]
【発明が解決しようとする課題】通常、半導体薄膜を蒸
着形成する際には基板温度を１００℃以上に加熱してお
く。この加熱によって欠陥の少ない膜が形成される。し
かしながら、上述のように例えばＣdＳとＺnＳを２源蒸
着法で蒸着形成すると基板温度が１００℃以下でないと
基板上に固溶体薄膜が形成できない。これは付着膜の再
蒸発によるものである。基板温度を１００℃以上にして
もＣdＳーＺnＳ固溶体薄膜が形成できる方法を提供す
る。Generally, when forming a semiconductor thin film by vapor deposition, the substrate temperature is heated to 100 ° C. or higher. By this heating, a film with few defects is formed. However, as described above, when CdS and ZnS are vapor-deposited by the two-source vapor deposition method, the solid solution thin film cannot be formed on the substrate unless the substrate temperature is 100 ° C. or lower. This is due to re-evaporation of the deposited film. A method for forming a CdS-ZnS solid solution thin film even when the substrate temperature is 100 ° C or higher.
【０００５】[0005]
【課題を解決するための手段】基板上に、ＣdＳおよび
Ｚnを同時に蒸着する。CdS and Zn are simultaneously deposited on a substrate.
【０００６】また、透明導電層を設けた透光性基板上
に、ＣdＳおよびＺnを同時に蒸着する方法でＣdＳ-Ｚn
Ｓ固溶体薄膜を主体とするｎ型半導体の窓層を形成し、
その上にｐ型半導体の光吸収層を、さらにその上に電極
層を形成することにより、太陽電池を製造する。In addition, CdS-Zn is formed by a method in which CdS and Zn are simultaneously vapor-deposited on a transparent substrate provided with a transparent conductive layer.
Forming an n-type semiconductor window layer mainly composed of an S solid solution thin film,
A p-type semiconductor light absorption layer is further formed thereon, and an electrode layer is further formed thereon to manufacture a solar cell.
【０００７】[0007]
【作用】本発明の製造方法によれば、このＣdＳーＺnＳ
固溶体薄膜を、ＣdＳとＺnの２源による同時蒸着によっ
て容易に形成できる。According to the manufacturing method of the present invention, this CdS-ZnS
The solid solution thin film can be easily formed by simultaneous vapor deposition with two sources of CdS and Zn.
【０００８】また、本発明の太陽電池の製造方法によれ
ば、窓層として用いるＣdＳ−ＺnＳ固溶体のバンドギャ
ップがＣdＳに比較して広いので窓層を透過する光量が
増え、そのためｐ型半導体の光吸収層に吸収される光量
が増え、また固溶体薄膜形成時の温度も高いので欠陥が
少なく、従って電気特性に優れその結果太陽電池の効率
が向上する。Further, according to the method for manufacturing a solar cell of the present invention, the band gap of the CdS-ZnS solid solution used as the window layer is wider than that of CdS, so that the amount of light transmitted through the window layer is increased, and therefore the p-type semiconductor Since the amount of light absorbed by the light absorption layer is increased and the temperature at which the solid solution thin film is formed is high, there are few defects, and therefore the electrical characteristics are excellent, and as a result, the efficiency of the solar cell is improved.
【０００９】[0009]
【実施例】以下、本発明の実施例における固溶体薄膜の
製造方法を説明する。EXAMPLE A method for manufacturing a solid solution thin film in an example of the present invention will be described below.
【００１０】ガラス基板(コーニング社,＃７０５９）上
に基板温度１００〜２００℃で、２つの蒸発源を用いて
ＣdＳとＺnを同時に蒸発させ、ＣdＳとＺnＳのモル比を
広範囲に変えた厚さ約０.５μm のＣdＳーＺnＳ固溶体
薄膜（Ｃｄ1-xＺnxＳ）を形成した。これら薄膜のＸ線
回折法での解析によると、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た。また、Ｚ
nＳの組成ｘの増大に従って格子常数ａ,ｃが直線的に変
化しＺnＳのそれに至ること従来既知の通りである。分
光透過率は従来知られている様にその吸収端波長はＺn
Ｓの組成ｘが増大すると短波長側に移動し、バンドギャ
ップが広くなる。基板温度が１００℃未満だと蒸着膜が
黒くなり、２００℃を越えると付着レートが小さくなり
付着し難くなる。On a glass substrate (# 7059, Corning Co., Ltd.) at a substrate temperature of 100 to 200 ° C., CdS and Zn were simultaneously vaporized by using two vaporization sources, and the molar ratio of CdS and ZnS was varied over a wide range. A CdS-ZnS solid solution thin film (Cd 1-x Zn x S) of about 0.5 μm was formed. According to the X-ray diffraction analysis of these thin films, a wide solid solution range (0 <x <1)
Showed the same wurtzite crystal structure as CdS. Also, Z
It is well known that the lattice constants a and c change linearly as the composition x of nS increases and reach that of ZnS. Spectral transmittance is known to be the absorption edge wavelength of Zn.
When the composition x of S increases, it moves to the shorter wavelength side and the band gap becomes wider. If the substrate temperature is lower than 100 ° C., the deposited film becomes black, and if it exceeds 200 ° C., the deposition rate becomes small and the deposition becomes difficult.
【００１１】次に、本発明の他の実施例における太陽電
池の製造方法を説明する。透明導電層ＩＴＯを設けたガ
ラス基板上に、基板温度１５０℃でＣdＳとＺnの同時蒸
着によりＣdＳとＺnＳのモル比が５：５で、全体の厚さ
０.５μmのＣdＳーＺnＳ固溶体膜Ｃｄ0.5Ｚn0.5Ｓを形
成する。この膜にＩnを添加する。すなわち、Ｃｄ0.5Ｚ
n0.5Ｓ膜の上に全体の１％のＩnを蒸着し、Ｎ2ガス中４
００℃で３０分加熱し、拡散させＩnの有効添加を施
す。この表面を約１００Åエッチング法で除去して形成
したn型半導体窓層の上に、５μｍ厚のＣdＴeを主体と
するｐ型半導体光吸収層を蒸着形成し、その上にＡu電
極を形成する。比較のため、固溶体窓層を従来の製法す
なわちＣdＳとＺnＳの同時蒸着(基板温度、室温)で形成
した他は上記と同様にした太陽電池の特性についても調
べてある。これら太陽電池のＡＭ１.５（８４mW/cm2）
の照射光に対する特性を第１表（本発明１と従来型）に
て示す。またＰt電極層を設けたガラス基板上にｐ型Ｃd
Ｔe層、その上にｎ型Ｃd0.5Ｚn0.5Ｓ固溶体薄膜、その
上に透明導電層ＩＴＯを積層する構成とした他は上記同
様にした太陽電池も形成した。この結果も第１表（本発
明２）に示してある。なおＶOC（Ｖ）は解放電圧、ＪSC
（mA/cm2）は閉路電流、η（％）は変換効率、F.F.は曲
線因子を表す。Next, a method of manufacturing a solar cell according to another embodiment of the present invention will be described. A CdS-ZnS solid solution film Cd having a molar ratio of CdS and ZnS of 5: 5 and a total thickness of 0.5 μm by co-evaporating CdS and Zn at a substrate temperature of 150 ° C. on a glass substrate provided with a transparent conductive layer ITO. 0.5 Zn 0.5 S is formed. In is added to this film. That is, Cd 0.5 Z
On the n 0.5 S film, 1% of the total amount of In was deposited, and 4% in N 2 gas was deposited.
It is heated at 00 ° C. for 30 minutes to diffuse it and effectively add In. On the n-type semiconductor window layer formed by removing this surface by an etching method of about 100Å, a p-type semiconductor light absorption layer mainly containing CdTe having a thickness of 5 μm is formed by vapor deposition, and an Au electrode is formed thereon. For comparison, the characteristics of a solar cell similar to the above except that the solid solution window layer is formed by the conventional method, that is, the simultaneous vapor deposition of CdS and ZnS (substrate temperature, room temperature) are also examined. AM1.5 (84mW / cm 2 ) of these solar cells
The characteristics of the above with respect to irradiation light are shown in Table 1 (Invention 1 and conventional type). Also, p-type Cd is formed on the glass substrate provided with the Pt electrode layer
A solar cell was also formed in the same manner as described above except that a Te layer, an n-type Cd 0.5 Zn 0.5 S solid solution thin film thereon, and a transparent conductive layer ITO were laminated thereon. The results are also shown in Table 1 (Invention 2). Note that V OC (V) is the release voltage, J SC
(MA / cm 2 ) is the closed current, η (%) is the conversion efficiency, and FF is the fill factor.
【００１２】[0012]
【表１】 [Table 1]
【００１３】（表１）に見られる様に本発明の製法で得
られた太陽電池の特性は従来の製法で得られる太陽電池
の特性よりはるかに優れている。これは本発明の太陽電
池のＣdＳ-ＺnＳ固溶体膜は従来の太陽電池のＣｄＳ−
ＺnＳ膜に比べて欠陥が少なく分光透過率が大であるか
らと考えられる。As shown in Table 1, the characteristics of the solar cell obtained by the manufacturing method of the present invention are far superior to those of the solar cell obtained by the conventional manufacturing method. This is because the CdS-ZnS solid solution film of the solar cell of the present invention is the CdS- of the conventional solar cell.
It is considered that the number of defects is smaller and the spectral transmittance is higher than that of the ZnS film.
【００１４】この様にＣdＳ、Ｚnの同時蒸着により得ら
れたＣdＳ-ＺnＳ固溶体膜を備えた太陽電池は優れた特
性を有する。Ｉnの添加は光透過率と電気伝導度を高め
る。ＣdＳとＺnＳの他の組成比の固溶体ＣdＳ-ＺnＳ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Ｚnの同時
蒸着で得られるが、蒸着時の基板温度は１００℃以上、
２００℃以下が好ましい。１００℃以下では形成膜が黒
っぽくなり透過率に劣り、２００℃以上では再蒸発によ
り膜形成のレートが著しく劣る。Thus, the solar cell provided with the CdS-ZnS solid solution film obtained by simultaneous vapor deposition of CdS and Zn has excellent characteristics. The addition of In enhances the light transmittance and the electric conductivity. Similar effects can be obtained by using a solid solution CdS-ZnS having another composition ratio of CdS and ZnS, or by using Al or Ga instead of In. This solid solution thin film can be obtained by simultaneous vapor deposition of CdS and Zn, but the substrate temperature during vapor deposition is 100 ° C or higher,
It is preferably 200 ° C or lower. When the temperature is 100 ° C or lower, the formed film becomes dark and the transmittance is poor, and when the temperature is 200 ° C or higher, the rate of film formation is remarkably poor due to re-evaporation.
【００１５】[0015]
【発明の効果】本発明によれば、膜質の優れたＣdＳ-Ｚ
nＳ固溶体薄膜を容易に形成することが可能となる。こ
のＣdＳ-ＺnＳ固溶体薄膜は太陽電池の変換効率向上に
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, CdS-Z having excellent film quality is obtained.
It becomes possible to easily form the nS solid solution thin film. This CdS-ZnS solid solution thin film is effective in improving the conversion efficiency of the solar cell, and can be applied to other photoelectric conversion devices, optical devices and the like.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 31/04 (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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Internal reference number FI Technical indication location H01L 31/04 (72) Inventor Takashi Hirao 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (5)
ることを特徴とするＣdＳ-ＺnＳ固溶体薄膜の製造方
法。1. A method for producing a CdS-ZnS solid solution thin film, which comprises simultaneously depositing CdS and Zn on a substrate.
あることを特徴とする請求項１記載のＣdＳ-ＺnＳ固溶
体薄膜の製造方法。2. The method for producing a CdS—ZnS solid solution thin film according to claim 1, wherein the substrate temperature is 100 ° C. or higher and 200 ° C. or lower.
ＳおよびＺnを同時に蒸着する方法でＣdＳ-ＺnＳ固溶体
薄膜を主体とするｎ型半導体の窓層を形成し、その上に
ｐ型半導体の光吸収層を、さらにその上に電極層を形成
することを特徴とする太陽電池の製造方法。3. Cd is formed on a transparent substrate provided with a transparent conductive layer.
Forming an n-type semiconductor window layer mainly composed of a CdS-ZnS solid solution thin film by a method of simultaneously depositing S and Zn, and forming a p-type semiconductor light absorption layer thereon, and further forming an electrode layer thereon. A method for manufacturing a solar cell, comprising:
た基板上に、ｐ型半導体の光吸収層を形成し、その上に
ＣdＳおよびＺnを同時に蒸着する方法でＣdＳ-ＺnＳ固
溶体薄膜を主体とするｎ型半導体の窓層を形成し、さら
にその上に透明導電層を形成することを特徴とする太陽
電池の製造方法。4. A CdS-ZnS solid solution thin film is formed by forming a p-type semiconductor light absorption layer on a substrate provided with an electrode layer or a substrate having an electrode property, and depositing CdS and Zn simultaneously on the light absorption layer. A method of manufacturing a solar cell, which comprises forming an n-type semiconductor window layer as a main component and further forming a transparent conductive layer thereon.
１００℃以上、２００℃以下であることを特徴とする請
求項３あるいは４記載の太陽電池の製造方法。5. The method for producing a solar cell according to claim 3, wherein the substrate temperature during the simultaneous vapor deposition of CdS and Zn is 100 ° C. or higher and 200 ° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09400492A JP3146612B2 (en) | 1992-04-14 | 1992-04-14 | Method for producing solid solution thin film and method for producing solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09400492A JP3146612B2 (en) | 1992-04-14 | 1992-04-14 | Method for producing solid solution thin film and method for producing solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05291139A true JPH05291139A (en) | 1993-11-05 |
| JP3146612B2 JP3146612B2 (en) | 2001-03-19 |
Family
ID=14098283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09400492A Expired - Fee Related JP3146612B2 (en) | 1992-04-14 | 1992-04-14 | Method for producing solid solution thin film and method for producing solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3146612B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101279370B1 (en) * | 2011-12-22 | 2013-07-04 | 한국에너지기술연구원 | PREPARATION METHOD OF CZTSe-BASED THIN FILM USING CO-EVAPORATION AND CZTSe-BASED THIN FILM PREPARED BY THE SAME |
-
1992
- 1992-04-14 JP JP09400492A patent/JP3146612B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3146612B2 (en) | 2001-03-19 |
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