JPS6341082A - Photovoltaic device - Google Patents
Photovoltaic deviceInfo
- Publication number
- JPS6341082A JPS6341082A JP61185457A JP18545786A JPS6341082A JP S6341082 A JPS6341082 A JP S6341082A JP 61185457 A JP61185457 A JP 61185457A JP 18545786 A JP18545786 A JP 18545786A JP S6341082 A JPS6341082 A JP S6341082A
- Authority
- JP
- Japan
- Prior art keywords
- film
- type
- amorphous silicon
- heterojunction
- silicon 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.)
- Pending
Links
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 24
- 239000004065 semiconductor Substances 0.000 claims abstract description 11
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 229910021476 group 6 element Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 2
- 239000010935 stainless steel Substances 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052951 chalcopyrite Inorganic materials 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- JXUKLFVKZQETHF-UHFFFAOYSA-N 1-$l^{1}-selanyl-n,n'-dimethylmethanimidamide Chemical compound CNC([Se])=NC JXUKLFVKZQETHF-UHFFFAOYSA-N 0.000 description 1
- -1 2: n-type Cu1nSe Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar 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
- 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
Abstract
Description
本発明は、Ｃｕ Ｅ ｎＸ□（Ｘは周期表■族元素）な
る分子式を有するカルコパライト系半導体を用いた光起
電力装置に関する。The present invention relates to a photovoltaic device using a chalcopalite semiconductor having a molecular formula of Cu E nX□ (X is an element from group Ⅰ of the periodic table).
カルコパライト （黄ｗｉ ｔＸｃｕＦｅｓ霊）と同様
の結晶構造をもつＣｕ１ｎＳｅｚやＣｕ１ｎＳｚは、禁
制帯幅約１ｅＶで直接遷移形の帯構造をもつ半導体で、
ｐ、ｎ両形の電卓を示し、高い吸収係数をもつので高効
率の太陽電池が得られる可能性がある材料としても注目
され、研究開発が進められている。
この材料を用いた光起電力装置は、一般にｎ形ＣｄＳと
のへテロ接合の構造をとる。 ＣｄＳは、Ｃｕ１ｎＸｔ
の格子との不整合の比較的小さい理由から光入射側の窓
層として選択されているが、しかしこの場合にも格子の
不整合による光起電力特性の低下はさけられないという
問題点がある。Cu1nSez and Cu1nSz, which have a crystal structure similar to that of chalcopalite (yellow with XcuFes spirit), are semiconductors with a direct transition type band structure with a forbidden band width of about 1 eV.
Since it exhibits both p- and n-type calculators and has a high absorption coefficient, it is attracting attention as a material with the potential to produce highly efficient solar cells, and research and development is progressing. A photovoltaic device using this material generally has a heterojunction structure with n-type CdS. CdS is Cu1nXt
It is selected as the window layer on the light incident side because of the relatively small mismatch with the lattice of .
本発明は、上述のＣｕＩｎＸ、の分子式をもつ半導体の
他の半導体とのへテロ接合を形成した際の格子の不整合
の問題を解決し、高い性能をもつ光起電力装置を提供す
ることを目的とする。The present invention aims to solve the problem of lattice mismatch when forming a heterojunction between a semiconductor having the molecular formula of CuInX and another semiconductor, and to provide a photovoltaic device with high performance. purpose.
本発明は、−導電形のＣｕＪｎＬ半導体膜と他導電形の
アモルファスシリコン側とからなるヘテロ接合のアモル
ファスシリコン腹側を光入射側として光起電力装置を構
成するもので、ヘテロ接合の一例がアモルファス半導体
であるため、接合における格子の不整合の問題がなくな
り、上述あ目的が達成される。The present invention configures a photovoltaic device with the amorphous silicon belly side of a heterojunction consisting of a - conductivity type CuJnL semiconductor film and a different conductivity type amorphous silicon side as the light incident side, and an example of the heterojunction is an amorphous silicon film. Since it is a semiconductor, there is no problem of lattice mismatch at the junction, and the above objective is achieved.
７ｆｊ１図は本発明の一実施例を示すもので、例えばス
テンレス鋼からなる金属基板１の上にｎ形多結晶Ｃｕ１
ｎＳｅｚ膜２を１〜３μの厚さに形成し、次にほう素な
どをドープしたｎ形アモルフアスシリコン膜３を１００
〜５００人の厚さに形成し、つづいてＩＴ○、 ５ｎＯ
ｚ’１ｌｆ４などの透明導電膜４を基板１との対向電極
として形成して、光起電力装置を構成する。このばあい
、Ｃｕ１ｎＳｅ膜は、ＣｕＣ１，ＩｎＣ１，。
（：ＨｓＮＨＣ３ｅＮＨＣＨｓ （ジメチルセレノウレ
ア）の水溶液をスプレー法などにより霧状にして２５０
〜３００℃に加熱した基板１に吹きつけて化学分解させ
て形成した。なお、このＣｕ１ｎＳｅｚ膜は、Ｃｕ ＋
Ｉ ｎ ＋ Ｓ ｅのそれぞれの同時真空蒸着法によ
っても、あるいはＣｕ１ｎＳｅｚ化合物を粉体にしたも
のを有機物とのペースト状にしたものに印刷し、６００
℃で焼結して得る方法によっても形成できる。ｐ形アモ
ルファスシリコン膜は、５ｉＨａ、 Ｂ！）１６および
ｈの混合ガスのグロー放電分解により形成した。この膜
にはｐ形アモルファスシリコンカーバイト膜を用いても
よい。
このような禁制帯幅約ＩｅＶで高吸収係数のｎ形Ｃｕ１
ｎＳｅ、膜の光入射側に禁制帯幅１．８〜２ｅＶのｐ形
アモルファスシリコン膜を積層してヘテロ接合させた構
成において、ｐ形アモルファスノリコン膜がアモルファ
ス構造であるために、格子の不整合に対する制約が緩和
されて良好なヘテロ接合が形成できる結果、高い光起電
力特性が得られる利点がある。この構成の場合、ＡＭｌ
ｌｏｏｍ ／ ｃｄ下で、開放電圧ｖ、、０．５ｖ、短
絡電流Ｊ ｓｃ ２３ｍＡ ／ ｃｎｌ 、フィル・フ
ァクタＦＦ０．５５．変換効率６．３％が得られた。従
来のｎ ＣｄＳ ／ ｐ ＣｕＩｎ５ｅｔのへテロ接合
構造の場合の特性が、Ｖ ６Ｃ０，３Ｖ 、 Ｊ ３
Ｃ２３１１１Ａ／ ｏＡ 、 ＦＦＯ，２９，変換効率
２％であったから、本発明の効果は明らかである。逆に
ｐ形のＣｕｒｎＳｅｇを用い、ｎ形アモルファスシリコ
ン膜とのへテロ接合としても同様の効果がある。Ｃｕ１
ｎＳｅ、の導電形は、Ｃｕ／Ｉｎ比を０．９以下にする
とｎ形、１．０以上にするとｐ形が得られる。
第２図は、基板としてガラス板５を用いた実施例で、第
１図の場合と形成順序が逆であり、ガラス基板２の上に
透明導電膜４を被着し、次いでｎ形アモルフアスシリコ
ン膜３を１００〜５００人厚に形成する。つづいて２０
０〜３００℃という低温で膜形成が可能のスプレー法で
ｎ形ＣｕＩｎＳａｇ ｌ！！ ２を形成し、最後にＭな
どの金属電極膜６を蒸着法で形成した。この場合には光
はガラス側から入射させることになる。この場合も、第
１図の実施例と同ｔｓ ｎ形アモルファスシリコン膜と
ｐ形ＣｕＩｎ５ｅｔ Ｉｌｌとの組合わせでもよい。
第３図および第４図はｐ−１−ｎアモルファスシリコン
セルとＣｕＴｎＳｅｚセルとのタンデム構造の光起電力
装置の実施例を示す、第３図の場合は、金属基板１の上
に第１図の場合と同様ｎ形Ｃｕ１ｎＳｅ４、膜２とｎ形
アモルフアスシリコン膜３を積層したのち、ひきつづい
てｎ形、ｉ形、ｎ形アモルフアスシリコン膜７．８．３
を順次形成し、その上に透明感ｔｌｌ１４を被着する。
第４図は、ガラス基板を用いた場合のタンデム構造の実
施例で、第２図で示した実施例の構造の透明導電膜４と
ｎ形アモルフアスシリコン膜３の間にｐ形、ｉ形、ｎ形
アモルフアスシリコン膜３゜８．７が挿入されるような
順序で膜形成を行い、タンデム構造としたものである。
このようなタンデム構造により、先ずｐ−１−ｎアモル
ファスシリコンセルで太陽光輻射のうちの４００〜６０
０ｎｍの光波長領域の光電変換を行い、次いで６００〜
１１０００ｎの波長領域の光はＣｕＩｎ５ｅｔへテロ接
合セルで光電変換を行う結果、高い性能の光起電力袋：
が得られる。
以上のＣｕｌｎＸｇ半導体としてＣｕ１ｎＳｅｚを用い
た実施例について述べたが、Ｃｕ１ｎＳｚを用いる場合
も同様な成膜法によって実施でき、すぐれた性能の光起
電力装置を製作することができる。Figure 7fj1 shows an embodiment of the present invention, in which n-type polycrystalline Cu1 is placed on a metal substrate 1 made of stainless steel, for example.
An nSez film 2 is formed to a thickness of 1 to 3 μm, and then an n-type amorphous silicon film 3 doped with boron or the like is formed to a thickness of 100 μm.
Formed to a thickness of ~500 mm, followed by IT○, 5nO
A photovoltaic device is constructed by forming a transparent conductive film 4 such as z'1lf4 as a counter electrode to the substrate 1. In this case, the Cu1nSe film is CuC1, InC1, etc. (:HsNHC3eNHCHs (dimethylselenourea) aqueous solution is made into a mist using a spray method etc.
It was formed by chemically decomposing it by spraying it onto the substrate 1 heated to ~300°C. Note that this Cu1nSez film is Cu +
By simultaneous vacuum evaporation of I n + S e, or by printing on a powdered Cu1nSez compound and a paste with an organic material, 600
It can also be formed by sintering at ℃. The p-type amorphous silicon film is 5iHa, B! ) It was formed by glow discharge decomposition of a mixed gas of 16 and h. A p-type amorphous silicon carbide film may be used for this film. Such an n-type Cu1 with a forbidden band width of about IeV and a high absorption coefficient
nSe, in a structure in which a p-type amorphous silicon film with a forbidden band width of 1.8 to 2 eV is stacked on the light incident side of the film to form a heterojunction, since the p-type amorphous silicon film has an amorphous structure, the lattice defect As a result of relaxing constraints on matching and forming a good heterojunction, there is an advantage that high photovoltaic properties can be obtained. For this configuration, AMl
Under room/cd, open circuit voltage v,,0.5v, short circuit current Jsc 23mA/cnl, fill factor FF0.55. A conversion efficiency of 6.3% was obtained. The characteristics of the conventional n CdS/p CuIn5et heterojunction structure are V 6C0,3V, J 3
Since the C23111A/oA, FFO, and conversion efficiency were 2%, the effect of the present invention is clear. Conversely, a similar effect can be obtained by using a p-type CurnSeg and forming a heterojunction with an n-type amorphous silicon film. Cu1
The conductivity type of nSe is n-type when the Cu/In ratio is 0.9 or less, and p-type when it is 1.0 or more. FIG. 2 shows an example in which a glass plate 5 is used as a substrate, and the formation order is reversed from that in FIG. A silicon film 3 is formed to a thickness of 100 to 500 layers. Continued 20
n-type CuInSag l! using a spray method that allows film formation at low temperatures of 0 to 300°C. ! 2 was formed, and finally a metal electrode film 6 of M or the like was formed by vapor deposition. In this case, the light will be incident from the glass side. In this case as well, a combination of the same ts n-type amorphous silicon film and p-type CuIn5et Ill as in the embodiment of FIG. 1 may be used. 3 and 4 show an embodiment of a photovoltaic device having a tandem structure of a p-1-n amorphous silicon cell and a CuTnSez cell. In the case of FIG. 3, the photovoltaic device shown in FIG. After laminating the n-type Cu1nSe4 film 2 and the n-type amorphous silicon film 3 in the same way as in the case of , the n-type, i-type, and n-type amorphous silicon films 7.8.3
are sequentially formed, and a transparent TLL14 is applied thereon. FIG. 4 shows an example of a tandem structure using a glass substrate, in which p-type, i-type, and , n-type amorphous silicon film 3° 8.7° are inserted, forming a tandem structure. With such a tandem structure, the p-1-n amorphous silicon cell first captures 400 to 60% of the solar radiation.
Photoelectric conversion is performed in the optical wavelength region of 0 nm, and then 600 ~
As a result of photoelectric conversion of light in the wavelength range of 11000n using a CuIn5et heterojunction cell, a high-performance photovoltaic bag is produced:
is obtained. Although the embodiment using Cu1nSez as the Cu1nXg semiconductor has been described above, the same film formation method can be used when Cu1nSz is used, and a photovoltaic device with excellent performance can be manufactured.
本発明によれば、光の吸収係数の高いＣｕＩｎＳｅｚあ
るいはＣｕ１ｎＳ１のようなカルコパライト系のＣｕ１
ｎχ。
半４体とアモルファス構造で成膜技術の発達しているア
モルファスシリコン膜によりヘテロ接合構造を形成した
ため、接合における格子不整合の問題がなくなり、良好
な光起電力特性をもつ光起電力Ｕ Ｔｌを容易に得るこ
とができ、その効果は極めて大きい。According to the present invention, chalcopalite-based Cu1 such as CuInSez or Cu1nS1, which has a high light absorption coefficient,
nχ. Since the heterojunction structure is formed using an amorphous silicon film with well-developed film formation technology, it eliminates the problem of lattice mismatch at the junction and allows photovoltaic power U Tl with good photovoltaic properties to be generated. It can be easily obtained and its effects are extremely large.
第１図は本発明の一実施例の断面図、第２図は別の実施
例の断面図、第３図、第４図はタンデム構造の本発明の
異なる二つの実施例を示す断面図である。
ｌ：金属基板、２：ｎ形Ｃｕ１ｎＳｅ、膜、３：ｐ形ア
モルファスシリコン膜、４：ｉ３明導Ｗ膜、５：１，４
幻鵬電膿
第１図
第２図Fig. 1 is a sectional view of one embodiment of the present invention, Fig. 2 is a sectional view of another embodiment, and Figs. 3 and 4 are sectional views showing two different embodiments of the present invention having a tandem structure. be. l: metal substrate, 2: n-type Cu1nSe, film, 3: p-type amorphous silicon film, 4: i3 bright conductive W film, 5: 1,4
Figure 1 Figure 2
Claims (1)
式を有する半導体の一導電形の膜と他導電形のアモルフ
ァスシリコン膜からなるヘテロ接合を有し、該接合のア
モルファスシリコン側を光入射側としたことを特徴とす
る光起電力装置。1) It has a heterojunction consisting of a semiconductor film of one conductivity type and an amorphous silicon film of another conductivity type, which has a molecular formula of CuInX_2, where X is a group VI element of the periodic table, and the amorphous silicon side of the junction is the light incident side. A photovoltaic device characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61185457A JPS6341082A (en) | 1986-08-07 | 1986-08-07 | Photovoltaic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61185457A JPS6341082A (en) | 1986-08-07 | 1986-08-07 | Photovoltaic device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6341082A true JPS6341082A (en) | 1988-02-22 |
Family
ID=16171125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61185457A Pending JPS6341082A (en) | 1986-08-07 | 1986-08-07 | Photovoltaic device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6341082A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6121541A (en) * | 1997-07-28 | 2000-09-19 | Bp Solarex | Monolithic multi-junction solar cells with amorphous silicon and CIS and their alloys |
| WO2009011333A1 (en) * | 2007-07-13 | 2009-01-22 | Omron Corporation | Cis solar cell and method for manufacturing the cis solar cell |
| WO2009101925A1 (en) * | 2008-02-12 | 2009-08-20 | Tokyo Electron Limited | Solar cell wherein solar photovoltaic thin film is directly formed on base |
-
1986
- 1986-08-07 JP JP61185457A patent/JPS6341082A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6121541A (en) * | 1997-07-28 | 2000-09-19 | Bp Solarex | Monolithic multi-junction solar cells with amorphous silicon and CIS and their alloys |
| US6368892B1 (en) * | 1997-07-28 | 2002-04-09 | Bp Corporation North America Inc. | Monolithic multi-junction solar cells with amorphous silicon and CIS and their alloys |
| WO2009011333A1 (en) * | 2007-07-13 | 2009-01-22 | Omron Corporation | Cis solar cell and method for manufacturing the cis solar cell |
| US8575476B2 (en) | 2007-07-13 | 2013-11-05 | Omron Corporation | CIS solar cell and method for manufacturing the same |
| WO2009101925A1 (en) * | 2008-02-12 | 2009-08-20 | Tokyo Electron Limited | Solar cell wherein solar photovoltaic thin film is directly formed on base |
| US8841545B2 (en) | 2008-02-12 | 2014-09-23 | Tohoku University | Solar cell wherein solar photovolatic thin film is directly formed on base |
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