JP2001210845A - Method of manufacturing thin film photoelectric conversion device - Google Patents
Method of manufacturing thin film photoelectric conversion deviceInfo
- Publication number
- JP2001210845A JP2001210845A JP2000016940A JP2000016940A JP2001210845A JP 2001210845 A JP2001210845 A JP 2001210845A JP 2000016940 A JP2000016940 A JP 2000016940A JP 2000016940 A JP2000016940 A JP 2000016940A JP 2001210845 A JP2001210845 A JP 2001210845A
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- layer
- plasma region
- zinc oxide
- substrate
- 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
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 123
- 239000010409 thin film Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000010410 layer Substances 0.000 claims abstract description 152
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 239000011787 zinc oxide Substances 0.000 claims abstract description 60
- 229910052709 silver Inorganic materials 0.000 claims abstract description 56
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000004332 silver Substances 0.000 claims abstract description 55
- 239000012790 adhesive layer Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000004544 sputter deposition Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract 3
- 229910052751 metal Inorganic materials 0.000 claims description 57
- 239000002184 metal Substances 0.000 claims description 57
- 239000002019 doping agent Substances 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 6
- 239000010946 fine silver Substances 0.000 abstract 1
- 210000002381 plasma Anatomy 0.000 description 40
- 239000004065 semiconductor Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 16
- 229910021417 amorphous silicon Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 150000002736 metal compounds Chemical class 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000000956 alloy Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 3
- 241000409201 Luina Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
-
- 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
- Y02E10/52—PV systems with concentrators
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Photovoltaic Devices (AREA)
- Light Receiving Elements (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は薄膜光電変換装置の
製造方法に係り、特には、光電変換ユニットとの接着強
度に優れた裏面電極を有する薄膜光電変換装置の製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a thin-film photoelectric conversion device, and more particularly to a method for manufacturing a thin-film photoelectric conversion device having a back electrode having excellent adhesion strength to a photoelectric conversion unit.
【０００２】[0002]
【従来の技術】近年、半導体薄膜を光電変換層として利
用した太陽電池を始めとする薄膜光電変換装置の開発が
精力的に行なわれている。このような薄膜光電変換装置
は、一般に、裏面電極と、裏面電極の前面側に設けら
れ、ｐｉｎまたはｎｉｐ接合構造を有する薄膜光電変換
ユニットと、光電変換ユニットの前面側に設けられた前
面透明電極とを絶縁性基板上に備える。かかる薄膜光電
変換装置は、太陽電池ばかりでなく、光センサ等種々の
用途への応用が期待されている。2. Description of the Related Art In recent years, thin film photoelectric conversion devices such as solar cells using a semiconductor thin film as a photoelectric conversion layer have been vigorously developed. Such a thin film photoelectric conversion device is generally provided with a back electrode, a thin film photoelectric conversion unit having a pin or nip junction structure provided on the front side of the back electrode, and a front transparent electrode provided on the front side of the photoelectric conversion unit. Are provided on an insulating substrate. Such thin-film photoelectric conversion devices are expected to be applied not only to solar cells but also to various uses such as optical sensors.
【０００３】かかる薄膜光電変換装置においては、光電
変換量を向上させるべく種々の改善がなされてきてい
る。光電変換ユニットに対する裏面電極を光反射率のき
わめて高い銀で形成することもその一例である。光電変
換ユニットに入射した光はこの高光反射率の銀裏面電極
と前面透明電極との間で反射を繰り返し、それにより光
電変換層による光吸収が増大させ、もって光電変換量が
向上する。In such a thin-film photoelectric conversion device, various improvements have been made to improve the amount of photoelectric conversion. For example, the back electrode for the photoelectric conversion unit is formed of silver having a very high light reflectance. Light incident on the photoelectric conversion unit is repeatedly reflected between the silver back electrode and the front transparent electrode having high light reflectance, whereby light absorption by the photoelectric conversion layer is increased, and thus the amount of photoelectric conversion is improved.
【０００４】また、近年、光反射性金属層と光電変換ユ
ニットとの間に酸化亜鉛等の透明導電層（以下、裏面透
明導電層という）を設けた光電変換装置も数多く提案さ
れている（例えば、特開平３−９９４７７公報、特開平
７−２６３７３１号公報等）。このように裏面電極の光
反射性金属層と光電変換ユニットとの間に裏面透明導電
層を介在させることによって、それらの間の熱膨張係数
の相違による熱歪みを緩和し、かつ金属原子がシリコン
系光電変換ユニット内へ拡散して混入することを防止し
得る。その結果、得られる光電変換装置の歩留まりと信
頼性が向上するのみならず、光感度が改善されて光電変
換特性も向上する。In recent years, a large number of photoelectric conversion devices having a transparent conductive layer of zinc oxide or the like (hereinafter referred to as a back transparent conductive layer) between a light-reflective metal layer and a photoelectric conversion unit have been proposed (for example, there are many proposals). And JP-A-3-99477, JP-A-7-263731 and the like. By interposing the back transparent conductive layer between the light-reflective metal layer of the back electrode and the photoelectric conversion unit in this manner, thermal distortion due to the difference in the coefficient of thermal expansion between them is reduced, and the metal atoms are reduced to silicon. It can be prevented from being diffused and mixed into the system photoelectric conversion unit. As a result, not only the yield and reliability of the obtained photoelectric conversion device are improved, but also the photosensitivity is improved and the photoelectric conversion characteristics are improved.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、銀は薄
膜半導体やセラミックなどに対する接着強度が劣ってお
り、薄膜光電変換装置の裏面電極として実用レベルの接
着強度が得られていない。銀裏面電極と光電変換ユニッ
トとの間に上記のような裏面透明導電層を設けた場合に
は、接着強度は若干向上するものの、到底実用レベルで
利用できる水準ではなく、裏面透明導電層の本来奏する
上記効果が十分に得られないのである。However, silver has an inferior adhesive strength to thin-film semiconductors and ceramics, so that a practical level of adhesive strength has not been obtained as a back electrode of a thin-film photoelectric conversion device. When the back transparent conductive layer as described above is provided between the silver back electrode and the photoelectric conversion unit, although the adhesive strength is slightly improved, it is not at a level that can be used at a practical level at all, and the original of the back transparent conductive layer is not provided. That is, the above effect cannot be sufficiently obtained.
【０００６】したがって、本発明は、裏面透明導電層に
対する接着強度が優れた銀裏面電極を備えた光電変換装
置の製造方法を提供することを課題とする。Accordingly, it is an object of the present invention to provide a method for manufacturing a photoelectric conversion device having a silver back electrode having excellent adhesion strength to the back transparent conductive layer.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上述の課題
を解決すべく検討を重ねる中で、本出願人の出願に係る
特開平８−１０７２２５号公報に開示されている技術に
着目した。この技術は、絶縁性透明基板上に透明電極
層、薄膜半導体層および第１の透明導電性金属化合物層
を順次積層形成した後、反応室内において形成した透明
導電性金属化合物による第１のプラズマ領域と金属によ
る第２のプラズマ領域中を第１のプラズマ領域側から第
２のプラズマ領域に向かって基板を移動させることによ
って、第１の透明導電性金属化合物層上に第２の透明導
電性金属化合物層と金属層を形成するものである。第１
の透明導電性金属化合物層と金属層は、第２の透明導電
性金属化合物層を介して強固に接着し、一体の裏面電極
を構成する。In order to solve the above-mentioned problems, the present inventor has focused on the technique disclosed in Japanese Patent Application Laid-Open No. Hei 8-107225 filed by the present applicant. . In this technique, a transparent electrode layer, a thin film semiconductor layer, and a first transparent conductive metal compound layer are sequentially formed on an insulating transparent substrate, and then a first plasma region is formed by the transparent conductive metal compound formed in the reaction chamber. A second transparent conductive metal on the first transparent conductive metal compound layer by moving the substrate from the first plasma region side to the second plasma region in a second plasma region made of a metal and a metal. It forms a compound layer and a metal layer. First
The transparent conductive metal compound layer and the metal layer are firmly adhered to each other via the second transparent conductive metal compound layer to form an integral back electrode.
【０００８】この技術をさらに検討した結果、本発明者
は、金属層として銀を選択した場合、第１の透明導電性
金属化合物としては酸化亜鉛が銀との密着性等の点で最
適であり、しかも接着層として作用する第２の透明導電
性金属化合物層としては同様に酸化亜鉛が最適であるこ
と、さらには、接着層としての酸化亜鉛層と銀層とを形
成する際の反応室内の圧力が酸化亜鉛層と銀層との接着
性に密接に関係することを見いだした。本発明はこの知
見に基づく。As a result of further study of this technique, the present inventors have found that when silver is selected as the metal layer, zinc oxide is the most suitable as the first transparent conductive metal compound in terms of adhesion to silver and the like. In addition, zinc oxide is also optimal for the second transparent conductive metal compound layer acting as an adhesive layer, and furthermore, the inside of the reaction chamber when forming the zinc oxide layer and the silver layer as the adhesive layer. It has been found that pressure is closely related to the adhesion between the zinc oxide layer and the silver layer. The present invention is based on this finding.
【０００９】すなわち、本発明によれば、裏面電極が酸
化亜鉛を包含する裏面透明導電層とその裏面側に設けら
れた銀を包含する光反射性金属層とを有する薄膜光電変
換装置の製造方法であって、前面透明電極、該前面透明
電極の裏面側に設けられた薄膜光電変換ユニットおよび
該光電変換ユニットの裏面側に設けられた前記裏面透明
導電層を絶縁性基板上にそれぞれ形成する各工程を備
え、前記光反射性金属層を形成する際に、反応室内にお
いて約０．１〜約０．２７Ｐａのスパッタガス圧力下に
酸化亜鉛微粒子を含む第１のプラズマ領域と銀微粒子を
含む第２のプラズマ領域とを形成し、該基板を前記反応
室内に形成された前記第１のプラズマ領域と第２のプラ
ズマ領域上を通過させて酸化亜鉛を包含する接着層と銀
を包含する光反射性金属層を形成し、それにより前記裏
面透明導電層と前記接着層と前記光反射性金属層を有す
る裏面電極を提供することを特徴とする薄膜光電変換装
置の製造方法が提供される。That is, according to the present invention, a method of manufacturing a thin-film photoelectric conversion device in which a back electrode has a back transparent conductive layer containing zinc oxide and a light-reflective metal layer containing silver provided on the back surface thereof. Wherein a front transparent electrode, a thin-film photoelectric conversion unit provided on the back side of the front transparent electrode, and the back transparent conductive layer provided on the back side of the photoelectric conversion unit are each formed on an insulating substrate. And forming a first plasma region containing zinc oxide fine particles and a silver fine particle under a sputtering gas pressure of about 0.1 to about 0.27 Pa in the reaction chamber when forming the light-reflective metal layer. A second plasma region, and passing the substrate over the first and second plasma regions formed in the reaction chamber to form an adhesive layer including zinc oxide and a light reflection including silver. sex Forming a genus layer, thereby producing a thin film photoelectric conversion device characterized by providing a back electrode having a light reflective metal layer and the adhesive layer and the back transparent conductive layer is provided.
【００１０】本発明において、ｐｉｎ接合構造の薄膜光
電変換ユニットを有する薄膜光電変換装置を製造する場
合には、基板上に、前面透明電極、薄膜光電変換ユニッ
トおよび裏面透明導電層を順次形成した後、その基板を
まず第１のプラズマ領域上を、ついで第２のプラズマ領
域上を通過させて裏面透明導電層上に酸化亜鉛を包含す
る接着層および銀を包含する光反射性金属層を順次形成
することができる。In the present invention, when manufacturing a thin-film photoelectric conversion device having a thin-film photoelectric conversion unit having a pin junction structure, a front transparent electrode, a thin-film photoelectric conversion unit and a rear transparent conductive layer are sequentially formed on a substrate. The substrate is first passed over a first plasma region and then over a second plasma region to sequentially form an adhesive layer containing zinc oxide and a light-reflective metal layer containing silver on the back transparent conductive layer. can do.
【００１１】本発明において、ｎｉｐ接合構造の薄膜光
電変換ユニットを有する薄膜光電変換装置を製造する場
合には、基板をまず第２のプラズマ領域上を、ついで第
１のプラズマ領域上を通過させて基板上に銀を包含する
光反射性金属層および酸化亜鉛を包含する接着層を順次
形成し、しかる後、裏面透明導電層、薄膜光電変換ユニ
ットおよび前面透明電極を順次形成することができる。In the present invention, when manufacturing a thin-film photoelectric conversion device having a thin-film photoelectric conversion unit having a nip junction structure, the substrate is first passed over the second plasma region and then over the first plasma region. A light-reflective metal layer containing silver and an adhesive layer containing zinc oxide are sequentially formed on a substrate, and then a rear transparent conductive layer, a thin film photoelectric conversion unit, and a front transparent electrode can be sequentially formed.
【００１２】好ましくは、第１のプラズマ領域をドーパ
ントを含有していてもよい酸化亜鉛スパッタターゲット
に放電電力を印加することによって形成し、第２のプラ
ズマ領域を銀スパッタターゲットに放電電力を印加する
ことによって形成する。その際、酸化亜鉛スパッタター
ゲットに印加する放電電力の電力密度は約０．１〜約４
Ｗ／ｃｍ2 であり、銀ターゲットに印加する放電電力の
電力密度は約１〜約２０Ｗ／ｃｍ2 であることが好まし
い。[0012] Preferably, the first plasma region is formed by applying discharge power to a zinc oxide sputter target which may contain a dopant, and the second plasma region is applied with discharge power to a silver sputter target. It forms by doing. At this time, the power density of the discharge power applied to the zinc oxide sputter target is about 0.1 to about 4
W / cm 2 , and the power density of the discharge power applied to the silver target is preferably about 1 to about 20 W / cm 2 .
【００１３】また、本発明において、第１のプラズマ領
域と第２のプラズマ領域とは、第2のプラズマ領域で形
成される光反射性金属の反射率を低下させない程度にそ
れらの一部が重なり合うように形成してもよい。Further, in the present invention, the first plasma region and the second plasma region partially overlap each other to such an extent that the reflectance of the light-reflective metal formed in the second plasma region is not reduced. It may be formed as follows.
【００１４】なお、本明細書において、光入射側を前面
といい、その反対側を裏面という。In this specification, the light incident side is called a front surface, and the opposite side is called a back surface.
【００１５】[0015]
【発明の実施の形態】以下、本発明をより具体的に説明
する。本発明の第１の実施の形態は、ｐｉｎ接合構造を
有する薄膜光電変換ユニットを備える薄膜光電変換装置
の製造方法に係る。この第１の実施の形態に係る製造方
法により得られる薄膜光電変換装置の一例を図１に示
す。この薄膜光電変換装置１０は、絶縁性基板１１上
に、前面透明電極１２と、薄膜光電変換ユニット１３
と、裏面電極１４とが順次形成されたものである。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically. The first embodiment of the present invention relates to a method for manufacturing a thin-film photoelectric conversion device including a thin-film photoelectric conversion unit having a pin junction structure. FIG. 1 shows an example of a thin-film photoelectric conversion device obtained by the manufacturing method according to the first embodiment. The thin-film photoelectric conversion device 10 includes a front transparent electrode 12 and a thin-film photoelectric conversion unit 13 on an insulating substrate 11.
And the back electrode 14 are sequentially formed.
【００１６】基板１１は、ＰＥＴやポリイミド等の耐熱
性プラスチックフィルム、セラミック、または低融点の
安価なガラス等の透明な絶縁性材料により構成すること
ができる。また、イオンバリヤー膜として酸化シリコン
（ＳｉＯ2 ）を表面にコートしたガラス基板を用いるこ
ともできる。The substrate 11 can be made of a transparent insulating material such as a heat-resistant plastic film such as PET or polyimide, ceramic, or low-melting glass. Alternatively, a glass substrate having silicon oxide (SiO 2 ) coated on its surface can be used as the ion barrier film.
【００１７】基板１１上には、前面透明電極１２が形成
される。前面透明電極１２は、透明導電性材料、特に透
明導電性酸化物材料により形成され、１層構造であって
も、多層構造であってもよい。前面透明電極１２は、好
ましくは、インジウム・スズ酸化物（ＩＴＯ）、酸化ス
ズ（ＳｎＯ2 ）、酸化亜鉛（ＺｎＯ）、それらの混合物
等から選択される透明導電性酸化物で形成される。これ
ら透明導電性酸化物には、フッ素をドープすることがで
きる。On the substrate 11, a front transparent electrode 12 is formed. The front transparent electrode 12 is formed of a transparent conductive material, particularly a transparent conductive oxide material, and may have a single-layer structure or a multilayer structure. The front transparent electrode 12 is preferably formed of a transparent conductive oxide selected from indium tin oxide (ITO), tin oxide (SnO 2 ), zinc oxide (ZnO), a mixture thereof, and the like. These transparent conductive oxides can be doped with fluorine.
【００１８】かかる前面透明電極１２は、真空蒸着、Ｃ
ＶＤ、またはスパッタ等のそれ自体既知の気相堆積法に
より形成することができる。The front transparent electrode 12 is formed by vacuum evaporation, C
It can be formed by a known vapor deposition method such as VD or sputtering.
【００１９】なお、前面透明電極１２は、その表面がフ
ラットであってもよいが、図１に示すように表面凹凸構
造（テクスチャ構造）を有することが好ましい。そのよ
うな表面凹凸構造における凹凸の高低差は、１０〜１０
０ｎｍであることが好ましい。また、凹凸のピッチは凹
凸の高低差より大きくかつその２５倍以下であることが
好ましく、凹凸の高低差の４倍〜２０倍であることがよ
り好ましく、具体的には、凹凸のピッチが３００〜１０
００ｎｍであることが好ましい。The front transparent electrode 12 may have a flat surface, but preferably has a surface uneven structure (texture structure) as shown in FIG. The height difference of the unevenness in such a surface unevenness structure is 10 to 10
It is preferably 0 nm. Further, the pitch of the unevenness is preferably larger than the height difference of the unevenness and 25 times or less thereof, more preferably 4 to 20 times the height difference of the unevenness, and specifically, the pitch of the unevenness is 300. -10
It is preferably 00 nm.
【００２０】本明細書において、凹凸の高低差とは凸部
と凹部の高さの差の平均値であり、ピッチとはおよそ
０．１〜５μｍ周期で現れる、隣接する凸部と凸部また
は凹部と凹部の間の距離の平均値を表わす。このような
表面凹凸構造は、前面透明電極１２の断面ＴＥＭ（透過
型電子顕微鏡）写真の画像処理や、ＡＦＭ（原子間力顕
微鏡）による表面観察および表面形状測定によっても決
定することができる。In the present specification, the height difference between the concavities and convexities is the average value of the difference between the heights of the convex portions and the concave portions. The average value of the distance between the concave portions is shown. Such a surface uneven structure can also be determined by image processing of a cross-sectional TEM (transmission electron microscope) photograph of the front transparent electrode 12, surface observation by AFM (atomic force microscope), and surface shape measurement.
【００２１】このような表面凹凸構造を有する前面透明
電極１２は、それ自体既知の種々の方法により形成する
ことができる。例えば、基板１１の表面にエッチングな
どにより凹凸構造を形成し、その上に薄い前面透明電極
１２を形成して、前面透明電極１２の表面を基板１１の
凹凸構造に沿った凹凸構造にすることができる。The front transparent electrode 12 having such a surface uneven structure can be formed by various methods known per se. For example, an uneven structure is formed on the surface of the substrate 11 by etching or the like, and a thin front transparent electrode 12 is formed thereon, so that the surface of the front transparent electrode 12 has an uneven structure along the uneven structure of the substrate 11. it can.
【００２２】前面透明電極１２上には、薄膜光電変換ユ
ニット１３が形成される。薄膜光電変換ユニット１３
は、ｐ型半導体層１３１、ｉ型半導体層（光電変換層）
１３２、およびｎ型半導体層１３３を含む。On the front transparent electrode 12, a thin film photoelectric conversion unit 13 is formed. Thin-film photoelectric conversion unit 13
Denotes a p-type semiconductor layer 131, an i-type semiconductor layer (photoelectric conversion layer)
132, and an n-type semiconductor layer 133.
【００２３】前面透明電極１２上に形成されるｐ型半導
体層１３１は、ホウ素、アルミニウム等のｐ型不純物原
子がドープされたｐ型シリコン系半導体材料で形成する
ことができる。また、ｐ型半導体層１３１の材料として
は、非晶質シリコン、非晶質シリコンカーバイドや非晶
質シリコンゲルマニウム等の合金材料、多結晶もしくは
部分的に非晶質を含む微結晶のシリコンまたはその合金
材料を用いることもできる。なお、望まれる場合には、
堆積されたこのようなｐ型半導体層１３１にパルスレー
ザ光を照射することにより、その結晶化分率や導電型決
定不純物原子によるキャリア濃度を制御することもでき
る。The p-type semiconductor layer 131 formed on the front transparent electrode 12 can be formed of a p-type silicon-based semiconductor material doped with p-type impurity atoms such as boron and aluminum. Examples of the material of the p-type semiconductor layer 131 include amorphous silicon, alloy materials such as amorphous silicon carbide and amorphous silicon germanium, polycrystalline or microcrystalline silicon partially containing amorphous, Alloy materials can also be used. If you wish,
By irradiating such a deposited p-type semiconductor layer 131 with a pulsed laser beam, the crystallization fraction and the carrier concentration due to the impurity atoms determining the conductivity type can also be controlled.
【００２４】ｐ型半導体層１３１上に形成されるｉ型半
導体層（光電変換層）１３２は、実質的にノンドープの
真正半導体材料、好ましくはシリコン系半導体材料から
なる。このようなｉ型半導体層１３２は、非晶質シリコ
ン薄膜、多結晶シリコン薄膜、体積結晶化分率が８０％
以上の微結晶シリコン薄膜、または微量の不純物を含む
弱ｐ型もしくは弱ｎ型で光電変換機能を十分に備えてい
るシリコン系薄膜で構成することができる。しかし、こ
の光電変換層１３２はこれらに限定されず、シリコンカ
ーバイドやシリコンゲルマニウム等の合金材料を用いて
形成されてもよい。このような光電変換層１３２は、必
要かつ十分な光電変換を可能とするの厚差を有する。そ
のためには、非晶質シリコン系半導体からなる光電変換
層は一般に０．３〜０．４μｍの厚さを有し、結晶質シ
リコン系半導体からなる光電変換層は一般に０．５〜２
０μｍの厚さを有する。The i-type semiconductor layer (photoelectric conversion layer) 132 formed on the p-type semiconductor layer 131 is made of a substantially non-doped genuine semiconductor material, preferably a silicon-based semiconductor material. Such an i-type semiconductor layer 132 has an amorphous silicon thin film, a polycrystalline silicon thin film, and a volume crystallization fraction of 80%.
The microcrystalline silicon thin film described above or a silicon-based thin film containing a small amount of impurities and having a weak p-type or weak n-type and having a sufficient photoelectric conversion function can be used. However, the photoelectric conversion layer 132 is not limited thereto, and may be formed using an alloy material such as silicon carbide or silicon germanium. Such a photoelectric conversion layer 132 has a thickness difference that enables necessary and sufficient photoelectric conversion. For this purpose, the photoelectric conversion layer made of an amorphous silicon-based semiconductor generally has a thickness of 0.3 to 0.4 μm, and the photoelectric conversion layer made of a crystalline silicon-based semiconductor generally has a thickness of 0.5 to 2 μm.
It has a thickness of 0 μm.
【００２５】ｉ型半導体層１３２上に形成されるｎ型半
導体層１３３は、リン、窒素等のｎ型不純物原子がドー
プされたｎ型シリコン系半導体材料で形成することがで
きる。ｎ型半導体層１３３の材料としては、非晶質シリ
コン、非晶質シリコンカーバイドや非晶質シリコンゲル
マニウム等の合金材料を用いることができ、多結晶もし
くは部分的に非晶質を含む微結晶のシリコンまたはその
合金材料を用いることもできる。The n-type semiconductor layer 133 formed on the i-type semiconductor layer 132 can be formed of an n-type silicon-based semiconductor material doped with n-type impurity atoms such as phosphorus and nitrogen. As a material of the n-type semiconductor layer 133, an alloy material such as amorphous silicon, amorphous silicon carbide, or amorphous silicon germanium can be used, and polycrystalline or microcrystalline partially containing amorphous can be used. Silicon or its alloy material can also be used.
【００２６】光電変換ユニット１３に含まれるすべての
半導体層は、４００℃以下の下地温度の下にプラズマＣ
ＶＤ法によって堆積させることができる。プラズマＣＶ
Ｄ法としては、一般によく知られている平行平板型のＲ
ＦプラズマＣＶＤや、周波数が１５０ＭＨｚ以下のＲＦ
帯からＶＨＦ帯までの高周波電源を利用するプラズマＣ
ＶＤを用いることができる。All the semiconductor layers included in the photoelectric conversion unit 13 have a plasma C under a base temperature of 400 ° C. or less.
It can be deposited by the VD method. Plasma CV
As the D method, a generally well-known parallel plate type R
F plasma CVD or RF with a frequency of 150 MHz or less
C using high-frequency power supply from band to VHF band
VD can be used.
【００２７】光電変換ユニット１３の上には、裏面電極
１４が形成される。この裏面電極は、酸化亜鉛を包含す
る裏面透明導電層１４１、酸化亜鉛を包含する接着層１
４２、および銀を包含する光反射性金属層１４３を備え
る。光反射性金属層１４３は、５００〜１２００ｎｍの
範囲内の波長の光に対して９５％以上の高い反射率を示
し得る。A back electrode 14 is formed on the photoelectric conversion unit 13. The back electrode includes a back transparent conductive layer 141 containing zinc oxide and an adhesive layer 1 containing zinc oxide.
42, and a light-reflective metal layer 143 containing silver. The light-reflective metal layer 143 may have a high reflectance of 95% or more for light having a wavelength in the range of 500 to 1200 nm.
【００２８】光電変換ユニット１３の上に形成される酸
化亜鉛系裏面透明導電層１４１は、アルミニウム等のド
ーパントを含有していてもよい酸化亜鉛ターゲットを用
いたそれ自体既知のスパッタにより形成することができ
る。The zinc oxide-based transparent conductive layer 141 formed on the photoelectric conversion unit 13 can be formed by a known sputtering method using a zinc oxide target which may contain a dopant such as aluminum. it can.
【００２９】図１に示す薄膜光電変換装置を製造するた
めには、基板１１上に前面透明電極１２、薄膜光電変換
ユニット１３および酸化亜鉛系裏面透明導電層１４を順
次形成した後、以後詳述する方法により酸化亜鉛系接着
層１４２および銀系光反射性金属層１４３を順次形成す
る。In order to manufacture the thin-film photoelectric conversion device shown in FIG. 1, a front transparent electrode 12, a thin-film photoelectric conversion unit 13 and a zinc oxide-based rear transparent conductive layer 14 are sequentially formed on a substrate 11, and then described in detail. Then, a zinc oxide-based adhesive layer 142 and a silver-based light-reflective metal layer 143 are sequentially formed.
【００３０】なお、図１に示すｐｉｎ接合構造の光電変
換ユニット１３を有する光電変換装置１０では、光電変
換されるべき光は、基板１１側から入射される。In the photoelectric conversion device 10 having the photoelectric conversion unit 13 having the pin junction structure shown in FIG. 1, light to be photoelectrically converted enters from the substrate 11 side.
【００３１】本発明の第２の実施の形態は、ｎｉｐ接合
構造を有する薄膜光電変換ユニットを備える薄膜光電変
換装置の製造方法に係る。この第２の実施の形態に係る
製造方法により得られる薄膜光電変換装置の一例を図２
に示す。この薄膜光電変換装置２０は、絶縁性基板２１
上に、裏面電極２２と、薄膜光電変換ユニット２３と、
前面透明電極２４とが順次形成されたものである。The second embodiment of the present invention relates to a method for manufacturing a thin film photoelectric conversion device having a thin film photoelectric conversion unit having a nip junction structure. FIG. 2 shows an example of a thin-film photoelectric conversion device obtained by the manufacturing method according to the second embodiment.
Shown in This thin-film photoelectric conversion device 20 includes an insulating substrate 21
Above, a back electrode 22, a thin film photoelectric conversion unit 23,
The front transparent electrodes 24 are sequentially formed.
【００３２】基板２１は、図１の光電変換装置１０にお
ける基板１１と同様の基板材料で形成することができ
る。しかし、基板２１は、透明である必要がないので、
ステンレス鋼等の金属材料で形成することもできる。The substrate 21 can be formed of the same substrate material as the substrate 11 in the photoelectric conversion device 10 of FIG. However, since the substrate 21 does not need to be transparent,
It can also be formed of a metal material such as stainless steel.
【００３３】基板２１上に形成される裏面電極３２は、
図１における裏面電極１４に対応するものである。すな
わち、この裏面電極３２は、基板２１上に形成された銀
を包含する光反射性金属層２２１、その上に形成された
酸化亜鉛を包含する接着層２２２およびその上に形成さ
れた酸化亜鉛を包含する透明導電層２２３を含む。酸化
亜鉛系透明酸化物層２２３は、図１の酸化亜鉛系透明酸
化物層１４１と同様の方法により形成することができ
る。The back electrode 32 formed on the substrate 21
This corresponds to the back electrode 14 in FIG. That is, the back electrode 32 is formed of a light-reflective metal layer 221 containing silver formed on the substrate 21, an adhesive layer 222 containing zinc oxide formed thereon, and zinc oxide formed thereon. Including a transparent conductive layer 223. The zinc oxide-based transparent oxide layer 223 can be formed by a method similar to that of the zinc oxide-based transparent oxide layer 141 in FIG.
【００３４】なお、この裏面電極２２、特にその光反射
性金属層２２１は、表面凹凸構造（表面テクスチャ構
造）を有することが好ましい。そのような光反射性金属
層２２１の上表面における凹凸構造は、基板２１の表面
を予めエッチング等によって凹凸構造に加工し、その凹
凸構造をそれ自体の上表面に伝達し得るような薄い光反
射性金属層２２１を後述する方法により形成することに
よって得ることができる。あるいは、基板２１上に凹凸
表面を有する透明導電層（図示せず）を堆積した後に、
その凹凸構造をそれ自体の上表面に伝達し得るような薄
い光反射性金属層２２１を後述する方法により形成する
ことによっても得られる。It is preferable that the back electrode 22, especially the light-reflective metal layer 221 has a surface uneven structure (surface texture structure). Such an uneven structure on the upper surface of the light-reflective metal layer 221 is formed by processing the surface of the substrate 21 into an uneven structure in advance by etching or the like, and transmitting the uneven structure to the upper surface of itself. It can be obtained by forming the conductive metal layer 221 by a method described later. Alternatively, after depositing a transparent conductive layer (not shown) having an uneven surface on the substrate 21,
It can also be obtained by forming a thin light-reflective metal layer 221 capable of transmitting the uneven structure to the upper surface thereof by a method described later.
【００３５】光反射性金属層２２１の表面凹凸構造にお
ける凹凸の高低差は０．０１〜２μｍの範囲内にあると
ともに、凹凸のピッチはその高低差より大きくかつその
２５倍以下であることが好ましく、４〜２０倍の範囲内
にあることがより好ましい。このような表面凹凸構造を
有する光反射性金属層２２１を用いることにより、開放
端電圧の低下や製造歩留まりの低下を伴うことなく、光
閉じ込め効果を改善して高性能の光電変換装置を得るこ
とができる。なお、このような表面凹凸構造は、上述し
たように、裏面電極２２の断面のＴＥＭ（透過型電子顕
微鏡）写真やＡＦＭ（原子間力顕微鏡）による表面観察
によって測定することができる。The height difference of the unevenness in the surface uneven structure of the light-reflective metal layer 221 is preferably in the range of 0.01 to 2 μm, and the pitch of the unevenness is preferably larger than the height difference and 25 times or less. More preferably, it is within the range of 4 to 20 times. By using the light-reflective metal layer 221 having such a surface unevenness structure, it is possible to improve the light confinement effect and obtain a high-performance photoelectric conversion device without lowering the open-circuit voltage or lowering the production yield. Can be. In addition, such a surface uneven structure can be measured by a TEM (transmission electron microscope) photograph or a surface observation by an AFM (atomic force microscope) of the cross section of the back electrode 22 as described above.
【００３６】裏面電極２２上に形成される薄膜光電変換
ユニット２３は、図１におけるｐ型半導体層１３１とｎ
型半導体層１３３の配置を逆転させた以外は図１の光電
変換装置１０における光電変換ユニット１３と同様の構
成を有する。すなわち、光電変換ユニット２３は、基板
２１側から、図１のｎ型半導体層１３３に相当するｎ型
半導体層２３１、図１の光電変換層１３２に相当する薄
膜光電変換層２３２、および図１のｐ型半導体層１３１
に相当するｐ型半導体層２３３を備える。The thin-film photoelectric conversion unit 23 formed on the back electrode 22 has the same structure as the p-type semiconductor layer 131 and the n-type semiconductor layer 131 shown in FIG.
It has the same configuration as the photoelectric conversion unit 13 in the photoelectric conversion device 10 of FIG. 1 except that the arrangement of the mold semiconductor layer 133 is reversed. That is, the photoelectric conversion unit 23 includes, from the substrate 21 side, an n-type semiconductor layer 231 corresponding to the n-type semiconductor layer 133 in FIG. 1, a thin-film photoelectric conversion layer 232 corresponding to the photoelectric conversion layer 132 in FIG. p-type semiconductor layer 131
And a p-type semiconductor layer 233 corresponding to.
【００３７】光電変換ユニット２３上に形成される前面
透明電極２４は、図１における前面透明電極１２に相当
するものであり、同様の材料および手法により形成する
ことができる。The front transparent electrode 24 formed on the photoelectric conversion unit 23 corresponds to the front transparent electrode 12 in FIG. 1, and can be formed by the same material and method.
【００３８】さらに、この前面透明電極２４上には、好
ましくはＡｌ、Ａｇ、Ａｕ、ＣｕおよびＰｔから選択さ
れた少なくとも１種以上の金属またはこれらの合金で形
成された櫛型金属電極（グリッド電極）２５が形成され
る。Further, on the front transparent electrode 24, a comb-shaped metal electrode (grid electrode) made of at least one or more metals selected from Al, Ag, Au, Cu and Pt or an alloy thereof is preferable. ) 25 is formed.
【００３９】図２に示す薄膜光電変換装置を製造するた
めには、基板２１上に以後詳述する方法により光反射性
金属層２２１と接着層２２２を順次形成した後、酸化亜
鉛系裏面透明導電層２２３、薄膜光電変換ユニット２
３、前面透明電極２４を上述の方法によりを順次形成す
る。しかる後、それ自体既知の方法によりグリッド電極
２５を形成する。In order to manufacture the thin-film photoelectric conversion device shown in FIG. 2, a light-reflective metal layer 221 and an adhesive layer 222 are sequentially formed on a substrate 21 by a method described in detail below, and then a zinc oxide-based transparent conductive film is formed. Layer 223, thin-film photoelectric conversion unit 2
3. The front transparent electrode 24 is sequentially formed by the above-described method. Thereafter, the grid electrode 25 is formed by a method known per se.
【００４０】このようなシリコン系薄膜光電変換装置２
０において、光電変換されるべき光ｈνは、前面透明電
極２４側から照射される。Such a silicon-based thin-film photoelectric conversion device 2
At 0, the light hν to be photoelectrically converted is emitted from the front transparent electrode 24 side.
【００４１】さて、本発明において、裏面電極を構成す
る銀系光反射性金属層１４３または２２１、並びに裏面
透明導電性層１４１または２２３と該光反射性金属層１
４３または２２１との間に介在して両者を強固に接着す
る接着層１４２または２２２を形成するために、反応室
内に、酸化亜鉛形成用第１のプラズマ領域と銀形成用第
２のプラズマ領域とを形成する。各プラズマ領域を形成
した後、所定の基板を第１のプラズマ領域および第２の
プラズマ領域上を通過させる。こうして、酸化亜鉛を含
む接着層と銀を包含する光反射性金属層とが形成され、
それにより裏面透明導電層と光反射性金属層とが接着層
を介して強固に結合した裏面電極が完成する。In the present invention, the silver-based light-reflective metal layer 143 or 221 constituting the back electrode, the back transparent conductive layer 141 or 223, and the light-reflective metal layer 1
In order to form an adhesive layer 142 or 222 interposed between 43 and 221 and firmly bonding the two, a first plasma region for forming zinc oxide and a second plasma region for forming silver are formed in the reaction chamber. To form After forming each plasma region, a predetermined substrate is passed over the first plasma region and the second plasma region. Thus, an adhesive layer containing zinc oxide and a light-reflective metal layer containing silver are formed,
This completes the back electrode in which the back transparent conductive layer and the light-reflective metal layer are firmly connected via the adhesive layer.
【００４２】本発明においては、この第１および第２の
プラズマ領域は、反応室内を不活性ガスにより約０．１
〜約０．２７Ｐａの圧力に設定して形成する。反応室内
を約０．２７Ｐａ以下の圧力に設定することにより、銀
系光反射性金属層と酸化亜鉛系裏面透明導電層との接着
層を介する接着力が向上し、たとえ１６０℃程度の高温
に加熱しても銀系光反射性層は、酸化亜鉛系裏面透明導
電層から剥離しないという優れた接着力を示す。また、
反応室内を０．１Ｐａ以上の圧力に設定することによ
り、成膜時の放電が安定するので、均一な層を形成する
ことができる。In the present invention, the first and second plasma regions are formed in the reaction chamber by an inert gas of about 0.1.
The pressure is set to about 0.27 Pa. By setting the pressure in the reaction chamber to about 0.27 Pa or less, the adhesive force between the silver-based light-reflective metal layer and the zinc oxide-based rear transparent conductive layer via the adhesive layer is improved. Even when heated, the silver-based light-reflective layer shows an excellent adhesive force that does not peel off from the zinc oxide-based backside transparent conductive layer. Also,
By setting the pressure in the reaction chamber to 0.1 Pa or more, the discharge during film formation is stabilized, so that a uniform layer can be formed.
【００４３】本発明において、第１のプラズマ領域およ
び第２のプラズマ領域は、アルミニウム等のドーパント
を含有していてもよい酸化亜鉛ターゲットおよび銀ター
ゲットにそれぞれ放電電力を印加することによって形成
することが好ましい。なお、第１のプラズマ領域と第２
のプラズマ領域とを第２のプラズマ領域で形成される光
反射性金属の反射率を低下させない程度にそれらの一部
が重なり合うように形成してもよく、それにより接着性
がさらに増し得る。In the present invention, the first plasma region and the second plasma region can be formed by applying discharge power to a zinc oxide target and a silver target which may contain a dopant such as aluminum, respectively. preferable. Note that the first plasma region and the second plasma region
The plasma region may be formed so that a part of the light-reflective metal formed in the second plasma region is overlapped to the extent that the reflectance of the light-reflective metal is not reduced, thereby further increasing the adhesiveness.
【００４４】次に、図３を参照して、酸化亜鉛系透明導
電層と酸化亜鉛系接着層の形成方法をより具体的に説明
する。図３には、マグネトロン式インラインスパッタ装
置１００が概略的に示されている。このスパッタ装置１
００の反応室１０１内には、２つのスパッタターゲッ
ト、すなわちスパッタターゲット１０２（ドーパントを
含有していてもよい酸化亜鉛ターゲットまたは銀ターゲ
ット）およびスパッタターゲット１０３（ターゲット１
０２が酸化亜鉛ターゲットである場合には、銀ターゲッ
トであり、ターゲット１０２が銀ターゲットである場合
には、ドーパントを含有していてもよい酸化亜鉛ターゲ
ットである）が配置されている。一方のターゲット１０
２は、接地された高周波電源１０５に接続され、他方の
ターゲット１０３は、接地された別の高周波電源１０６
に接続されている。２つのターゲット１０２および１０
３に離間・対向して共通対向電極１０４が配置され、こ
の対向電極１０４は、接地されている。反応室１０１の
底壁には、反応室１０１を排気するための真空ポンプ１
０７が接続され、他方反応室１０１の上壁には、弁Ｖを
有するガス導入管１０８が接続されている。ガス導入管
１０８は、図示しない不活性ガス源に接続されている。
いうまでもなく、装置１００には、図示しないマグネッ
トが付設されている。Next, a method of forming the zinc oxide-based transparent conductive layer and the zinc oxide-based adhesive layer will be described more specifically with reference to FIG. FIG. 3 schematically shows a magnetron-type in-line sputtering apparatus 100. This sputtering apparatus 1
00, two sputter targets, a sputter target 102 (a zinc oxide target or a silver target which may contain a dopant) and a sputter target 103 (a target 1).
In the case where 02 is a zinc oxide target, the target is a silver target, and when the target 102 is a silver target, the target is a zinc oxide target which may contain a dopant). One target 10
2 is connected to a grounded high-frequency power supply 105, and the other target 103 is connected to another grounded high-frequency power supply 106.
It is connected to the. Two targets 102 and 10
A common opposing electrode 104 is arranged at a distance from and opposing to 3, and this opposing electrode 104 is grounded. A vacuum pump 1 for evacuating the reaction chamber 101 is provided on the bottom wall of the reaction chamber 101.
07 is connected, and a gas introduction pipe 108 having a valve V is connected to the upper wall of the reaction chamber 101. The gas introduction pipe 108 is connected to an inert gas source (not shown).
Needless to say, the device 100 is provided with a magnet (not shown).
【００４５】酸化亜鉛系裏面透明導電層と酸化亜鉛系接
着層を形成するために、まず真空ポンプ１０７により反
応室１０１内を例えば６×１０-6Ｔｏｒｒ程度の高真空
に排気する。ついで、弁Ｖを開き、ガス導入管１０８か
らスパッタガス、好ましくはアルゴン（Ａｒ）ガスを導
入して、反応室１０１内を約０．１〜約０．２７Ｐａの
圧力に設定し、この圧力を維持する。In order to form a zinc oxide based transparent conductive layer and a zinc oxide based adhesive layer, the inside of the reaction chamber 101 is first evacuated to a high vacuum of about 6 × 10 −6 Torr by a vacuum pump 107. Next, the valve V is opened, and a sputtering gas, preferably an argon (Ar) gas, is introduced from the gas introduction pipe 108 to set the inside of the reaction chamber 101 to a pressure of about 0.1 to about 0.27 Pa. maintain.
【００４６】しかる後、２つのターゲット１０２および
１０３にそれぞれ高周波電源１０５および１０６から所
定の高周波電力を印加して両ターゲットを放電させる。
銀ターゲットに印加する放電電力の電力密度は、約１〜
約２０Ｗ／ｃｍ2 であることが好ましい。他方、酸化亜
鉛ターゲットに印加する放電電力の電力密度は、０．１
〜４Ｗ／ｃｍ2 であることが好ましい。いずれにしろ、
銀系光反射性金属層と酸化亜鉛系裏面透明導電層との密
着力は、少なくとも上記範囲内にある放電電力密度には
依存することがない。また、当該密着力は、銀系光反射
性金属層と酸化亜鉛系裏面透明導電層との形成時の基板
温度が少なくとも室温（２０℃）〜５０℃の範囲内であ
れば、基板温度に依存することがない。Thereafter, predetermined high-frequency power is applied from the high-frequency power supplies 105 and 106 to the two targets 102 and 103, respectively, to discharge both targets.
The power density of the discharge power applied to the silver target is about 1 to
Preferably, it is about 20 W / cm 2 . On the other hand, the power density of the discharge power applied to the zinc oxide target is 0.1
It is preferably about 4 W / cm 2 . in any case,
The adhesion between the silver-based light-reflective metal layer and the zinc oxide-based rear transparent conductive layer does not depend at least on the discharge power density within the above range. The adhesion depends on the substrate temperature when the substrate temperature at the time of forming the silver-based light-reflective metal layer and the zinc oxide-based transparent conductive layer is at least in the range of room temperature (20 ° C.) to 50 ° C. Never do.
【００４７】このようにして２つのターゲット１０２お
よび１０３を放電させると、図３に示すように、ターゲ
ット１０２上にはターゲット１０２の構成材料の微粒子
を含むプラズマ領域Ｐｘが、ターゲット１０３上にはタ
ーゲット１０３の構成材料の微粒子を含むプラズマ領域
Ｐｙが形成される。なお、既述のように、これら２つの
プラズマ領域ＰｘとＰｙの間にこれら両プラズマ領域の
一部が重ね合わさった部分、すなわち２つのプラズマに
おける両構成材料の微粒子が混在する極微弱なプラズマ
領域が形成されていてもよい。When the two targets 102 and 103 are discharged in this manner, as shown in FIG. 3, a plasma region Px containing fine particles of the constituent material of the target 102 is formed on the target 102, and the target 103 is formed on the target 103. A plasma region Py including fine particles of the constituent material 103 is formed. As described above, a portion where these two plasma regions are partially overlapped between these two plasma regions Px and Py, that is, an extremely weak plasma region in which fine particles of both constituent materials in the two plasmas are mixed. May be formed.
【００４８】このような放電状態において、所定の基板
ＳＵＢを、ターゲット１０２の前段側の基板位置Ａから
ターゲット１０３の後段側の基板位置Ｄまで移動させる
と、ターゲット１０２の構成材料の層と、ターゲット１
０３の構成材料の層が連続的に積層形成される。その
際、ターゲット１０２の近傍（基板位置Ｂ）ではターゲ
ット１０２の構成材料が積層される。そして、基板ＳＵ
Ｂを引き続きプラズマ領域Ｐｘからプラズマ領域Ｐｙへ
と移動させて行き、基板ＳＵＢがターゲット１０３の近
傍（基板位置Ｃ）に差しかかると、ターゲット１０３の
構成材料がほとんど１００％からなる層が積層されてゆ
く。In such a discharge state, when the predetermined substrate SUB is moved from the substrate position A on the upstream side of the target 102 to the substrate position D on the downstream side of the target 103, the layer of the constituent material of the target 102 and the target 1
Layers of the constituent material No. 03 are continuously laminated. At this time, the constituent material of the target 102 is stacked near the target 102 (substrate position B). Then, the substrate SU
B is continuously moved from the plasma region Px to the plasma region Py, and when the substrate SUB approaches the vicinity of the target 103 (substrate position C), a layer having almost 100% of the constituent material of the target 103 is laminated. go.
【００４９】図１に示すｐｉｎ接合構造の光電変換ユニ
ットを有する薄膜光電変換装置を製造する場合には、基
板ＳＵＢとして、図１に示す前面透明電極１２、光電変
換ユニット１３、および裏面透明導電層１４１を形成し
た基板１１を使用し、スパッタターゲット１０２として
ドーパントを含有していてもよい酸化亜鉛ターゲットを
用い、スパッタターゲット１０３として銀ターゲットを
使用することができる。かくして、裏面透明導電層１４
１の上に接着層１４２および銀系光反射性金属層１４３
がこの順に形成され、所望の薄膜光電変換装置が製造さ
れる。なお、銀系光反射性層１４３上に、チタンやアル
ミニウム等の保護金属層を設けてもよい。When manufacturing a thin-film photoelectric conversion device having a photoelectric conversion unit having a pin junction structure shown in FIG. 1, a front transparent electrode 12, a photoelectric conversion unit 13, and a rear transparent conductive layer shown in FIG. Using the substrate 11 on which 141 is formed, a zinc oxide target which may contain a dopant can be used as the sputter target 102, and a silver target can be used as the sputter target 103. Thus, the back transparent conductive layer 14
1 and a silver-based light-reflective metal layer 143
Are formed in this order, and a desired thin-film photoelectric conversion device is manufactured. Note that a protective metal layer such as titanium or aluminum may be provided on the silver-based light reflective layer 143.
【００５０】また、図２に示すｎｉｐ接合構造の光電変
換ユニットを有する薄膜光電変換装置を製造する場合に
は、基板ＳＵＢとして基板２１をそのまま使用し、スパ
ッタターゲット１０２として銀ターゲットを使用し、ス
パッタターゲット１０３としてドーパントを含有してい
てもよい酸化亜鉛ターゲットを用いることができる。あ
るいは、スパッタターゲット１０２として酸化亜鉛ター
ゲットを用い、スパッタターゲット１０３として銀ター
ゲットを用い、基板ＳＵＢを図３に関して説明した方向
とは逆方向に移動させてもよい。かくして、基板２１上
に銀系光反射性層２２１および接着層２２２がこの順に
形成される。しかる後、裏面透明導電層２２３、光電変
換ユニット２３、前面透明電極２４を上述の方法により
形成し、さらにグリッド電極２５を形成して所望の薄膜
光電変換装置を提供する。In the case of manufacturing a thin film photoelectric conversion device having a photoelectric conversion unit having a nip junction structure shown in FIG. 2, the substrate 21 is used as it is, the silver target is used as the sputtering target 102, and the sputtering target 102 is used. As the target 103, a zinc oxide target which may contain a dopant can be used. Alternatively, a zinc oxide target may be used as the sputter target 102, a silver target may be used as the sputter target 103, and the substrate SUB may be moved in a direction opposite to the direction described with reference to FIG. Thus, the silver-based light reflective layer 221 and the adhesive layer 222 are formed on the substrate 21 in this order. Thereafter, the back transparent conductive layer 223, the photoelectric conversion unit 23, and the front transparent electrode 24 are formed by the above-described method, and the grid electrode 25 is further formed to provide a desired thin film photoelectric conversion device.
【００５１】いずれの場合にも、酸化亜鉛系接着層は、
１ｎｍ〜１００ｎｍの厚さで、銀系光反射性層は、０．
１μｍ〜０．５μｍの厚さで形成することが好ましい。
より好ましくは、酸化亜鉛系接着層は、３ｎｍ〜３０ｎ
ｍの厚さで、銀系光反射性層は、０．２μｍ〜０．３μ
ｍの厚さで形成する。In any case, the zinc oxide-based adhesive layer
With a thickness of 1 nm to 100 nm, the silver-based light reflective layer has a thickness of 0.1 nm.
It is preferable to form it with a thickness of 1 μm to 0.5 μm.
More preferably, the zinc oxide-based adhesive layer has a thickness of 3 nm to 30 n.
m, the silver-based light-reflective layer has a thickness of 0.2 μm to 0.3 μm.
m.
【００５２】なお、裏面透明導電層１４１または２２３
は、接着層１４２または２２２と光反射性金属層１４３
または２２１とを形成するためのスパッタ装置と同じス
パッタ装置１００を用いて形成することができる。より
具体的には、例えば酸化亜鉛ターゲット１０２と銀ター
ゲット１０３を設置した反応室１０１内において、酸化
亜鉛ターゲット１０２にのみ放電電力を印加して裏面透
明導電層を形成した後、基板ＳＵＢを基板位置Ａまで戻
して上述の方法により裏面導電性層および光反射性金属
層を形成するか、当該酸化亜鉛ターゲットに印加する放
電電力密度を接着層の形成のための電力密度に切り替え
るとともに銀ターゲットに放電電力を印加し上述のよう
に接着層を形成し、ついで光反射性金属層を形成するこ
とができる。あるいは、追加の酸化亜鉛ターゲットをさ
らに設け、２つの酸化亜鉛ターゲットのうち一方の酸化
亜鉛ターゲットを接着層の形成のために、他方の酸化亜
鉛ターゲットを裏面透明導電層を形成するために用いる
ことができる。なお、接着層形成のためのプラズマ領域
を反射性金属層のためのプラズマ領域を形成するために
銀ターゲットに印加した放電電力による誘導エネルギー
または寄生放電によって形成することもできる。The back transparent conductive layer 141 or 223
Is formed of the adhesive layer 142 or 222 and the light-reflective metal layer 143.
Alternatively, it can be formed using the same sputtering apparatus 100 as the sputtering apparatus for forming 221. More specifically, for example, in a reaction chamber 101 in which a zinc oxide target 102 and a silver target 103 are installed, a discharge power is applied only to the zinc oxide target 102 to form a back transparent conductive layer. A to form a back conductive layer and a light-reflective metal layer by the above method, or switch the discharge power density applied to the zinc oxide target to the power density for forming the adhesive layer and discharge the silver target. Power can be applied to form the adhesive layer as described above and then the light reflective metal layer. Alternatively, an additional zinc oxide target may be further provided, and one of the two zinc oxide targets may be used for forming an adhesive layer, and the other zinc oxide target may be used for forming a back transparent conductive layer. it can. In addition, the plasma region for forming the adhesive layer may be formed by inductive energy or discharge by the discharge power applied to the silver target to form the plasma region for the reflective metal layer.
【００５３】[0053]
【実施例】以下、本発明の実施例により説明するが、本
発明はこれら実施例により制限されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００５４】実施例１〜９、比較例１〜６ これらの例では、図１に示す構造の薄膜光電変換装置
（太陽電池）を以下のようにして作製した。Examples 1 to 9 and Comparative Examples 1 to 6 In these examples, a thin-film photoelectric conversion device (solar cell) having the structure shown in FIG. 1 was manufactured as follows.
【００５５】絶縁性透明基板１１として、５００Åの厚
さの酸化シリコン（ＳｉＯ2 ）をコートしたガラス基板
を用い、この基板１１の酸化シリコン膜上に、フッ素を
ドープしたＳｎＯ2 を約８０００Åの膜厚で形成して前
面透明電極１２を形成した。なお、ＳｎＯ2 前面透明電
極１２の表面には、微小凹凸構造を形成するようにし
た。ついで、この前面透明電極１２上にプラズマＣＶＤ
装置にてｐ型の水素化非晶質炭化シリコン（ａ−Ｓｉ
Ｃ：Ｈ）１３１を１５０Åの膜厚で、ｉ型の水素化非晶
質シリコン（ａ−Ｓｉ：Ｈ）１３２を４０００Åの膜厚
で、ｎ型の水素化微結晶シリコン（μｃ−Ｓｉ：Ｈ）１
３３を５００Åの膜厚で順次積層し薄膜光電変換ユニッ
ト１３を形成した。[0055] As the insulating transparent substrate 11, a glass substrate coated with silicon oxide (SiO 2) of 500Å thickness, over the silicon oxide film of the substrate 11, film of about 8000Å to SnO 2 doped with fluorine The front transparent electrode 12 was formed to have a thickness. It should be noted that a fine uneven structure was formed on the surface of the SnO 2 front transparent electrode 12. Next, the plasma CVD is performed on the front transparent electrode 12.
P-type hydrogenated amorphous silicon carbide (a-Si)
C: H) 131 with a thickness of 150 °, i-type hydrogenated amorphous silicon (a-Si: H) 132 with a thickness of 4000 °, and n-type hydrogenated microcrystalline silicon (μc-Si: H). ) 1
The thin film photoelectric conversion units 13 were formed by sequentially laminating 33 with a film thickness of 500 °.
【００５６】続いて、図３に示すようなマグネトロン式
インラインスパッタ装置１００の反応室１０１内に、上
記薄膜光電変換ユニット１３までを形成した基板ＳＵＢ
を基板位置Ａにセットし、反応室１０１内を真空ポンプ
１０７によって６×１０-6Ｔｏｒｒまで排気後、アルゴ
ンガスをガス導入管１０８から導入して反応室１０１内
を下記表１に示す圧力に設定し、０．８Ｗ／ｃｍ2 の高
周波電力密度で基板ＳＵＢを移動しながら酸化亜鉛ター
ゲット１０２（ドーパントとして酸化アルミニウム（Ａ
ｌ2 Ｏ3 ）の形で５重量％のアルミニウムを含有）をス
パッタし、厚さ８００Åの裏面透明導電層１４１を光電
変換ユニット１３上に積層した（基板位置Ｂ）。ＺｎＯ
ターゲット１０２と基板ＳＵＢとの間隔は約５ｃｍであ
った。ここで図３に示すように、本スパッタ装置１００
には、酸化亜鉛ターゲット１０２に隣設して銀ターゲッ
ト１０３が設けられているが、この裏面透明導電層１４
１を形成する際には、銀ターゲット１０３は放電させて
いない。Subsequently, the substrate SUB on which the thin-film photoelectric conversion unit 13 is formed is placed in a reaction chamber 101 of a magnetron-type in-line sputtering apparatus 100 as shown in FIG.
Is set at the substrate position A, the inside of the reaction chamber 101 is evacuated to 6 × 10 −6 Torr by the vacuum pump 107, and argon gas is introduced from the gas introduction pipe 108 to bring the inside of the reaction chamber 101 to the pressure shown in Table 1 below. The zinc oxide target 102 (aluminum oxide (A as a dopant) was set while moving the substrate SUB at a high frequency power density of 0.8 W / cm 2.
l 2 O 3 ) in the form of 5% by weight of aluminum) was sputtered, and a back transparent conductive layer 141 having a thickness of 800 ° was laminated on the photoelectric conversion unit 13 (substrate position B). ZnO
The distance between the target 102 and the substrate SUB was about 5 cm. Here, as shown in FIG.
Is provided with a silver target 103 adjacent to the zinc oxide target 102.
When forming No. 1, the silver target 103 was not discharged.
【００５７】次に、裏面透明導電層１４１が形成された
基板ＳＵＢを基板位置Ａまで戻し、酸化亜鉛ターゲット
１０２と銀ターゲット１０３に表１に示す電力密度で高
周波電力を印加して両ターゲットを放電させた後、表１
に示す温度に設定した基板ＳＵＢを、基板位置Ａから基
板位置Ｄまで移動させて接着層１４２と光反射性金属層
１４３を連続的に積層した。接着層１４２の厚さは、３
０ｎｍであり、光反射性金属層１４３の厚さは、０．２
５μｍであった。Next, the substrate SUB on which the back transparent conductive layer 141 is formed is returned to the substrate position A, and high-frequency power is applied to the zinc oxide target 102 and the silver target 103 at a power density shown in Table 1 to discharge both targets. Table 1
Was moved from the substrate position A to the substrate position D, and the adhesive layer 142 and the light-reflective metal layer 143 were continuously laminated. The thickness of the adhesive layer 142 is 3
0 nm, and the thickness of the light reflective metal layer 143 is 0.2
It was 5 μm.
【００５８】こうして作製した光電変換装置（太陽電
池）について裏面電極の接着強度を接着テープ剥離試験
で調べた。すなわち、ガラス基板の露出表面から銀系光
反射性金属層にかけて接着テープ（セロテープまたはガ
ムテープ）を貼着しこれをガラス基板側から引き剥が
し、以下の基準で接着強度を評価した。The adhesive strength of the back electrode of the photoelectric conversion device (solar cell) thus manufactured was examined by an adhesive tape peeling test. That is, an adhesive tape (cellophane tape or gum tape) was adhered from the exposed surface of the glass substrate to the silver-based light-reflective metal layer, peeled off from the glass substrate side, and the adhesive strength was evaluated according to the following criteria.
【００５９】Ａ…１６０℃で放置した後でも、銀系光反
射性金属層は剥離しない。A: Even after standing at 160 ° C., the silver-based light-reflective metal layer does not peel off.
【００６０】Ｂ…銀系光反射性金属層は、その形成直後
にはセロテープ剥離試験では剥離しないが、１６０℃で
３時間の加熱を行った後の剥離試験では剥離した。B: The silver-based light-reflective metal layer was not peeled off in the cellophane tape peeling test immediately after its formation, but peeled off in the peeling test after heating at 160 ° C. for 3 hours.
【００６１】Ｃ…銀系光反射性金属層は、その形成直後
でさえ、セロテープ剥離試験で剥離した。C: The silver-based light-reflective metal layer was peeled off immediately after its formation by a cellophane tape peeling test.
【００６２】結果を表１に併記する。The results are shown in Table 1.
【００６３】[0063]
【表１】 [Table 1]
【００６４】表１に示す結果からもわかるように、本発
明によれば高温に加熱した場合でも剥離しない銀系光反
射性金属層を有する裏面電極を備えた薄膜光電変換装置
を製造することができる。As can be seen from the results shown in Table 1, according to the present invention, it is possible to manufacture a thin-film photoelectric conversion device having a back electrode having a silver-based light-reflective metal layer which does not peel off even when heated to a high temperature. it can.
【００６５】なお、本発明は、以上述べた１つのｐｉｎ
接合またはｎｉｐ接合構造を有する薄膜光電変換装置の
製造ばかりでなく、いわゆるタンデムタイプの光電変換
装置や集積型光電変換装置にも適用できる。It should be noted that the present invention relates to one pin described above.
The present invention can be applied not only to the manufacture of a thin film photoelectric conversion device having a junction or nip junction structure, but also to a so-called tandem type photoelectric conversion device and an integrated photoelectric conversion device.
【００６６】[0066]
【発明の効果】以上述べたように、本発明によれば、高
温に加熱した場合でも剥離しないという優れた接着性を
示す銀系光反射性金属層を有する裏面電極を備えた薄膜
光電変換装置の製造方法が提供される。As described above, according to the present invention, a thin-film photoelectric conversion device having a back electrode having a silver-based light-reflective metal layer exhibiting excellent adhesiveness which does not peel off even when heated to a high temperature. Is provided.
【図１】本発明の第１の実施の形態に係る製造方法によ
って得られる薄膜光電変換装置の一例を示す概略断面
図。FIG. 1 is a schematic sectional view showing an example of a thin-film photoelectric conversion device obtained by a manufacturing method according to a first embodiment of the present invention.
【図２】本発明の第２の実施の形態に係る製造方法によ
って得られる薄膜光電変換装置の一例を示す概略断面
図。FIG. 2 is a schematic cross-sectional view illustrating an example of a thin-film photoelectric conversion device obtained by a manufacturing method according to a second embodiment of the present invention.
【図３】本発明により裏面電極を形成する際に用いられ
るスパッタ装置の一例を示す概略図。FIG. 3 is a schematic diagram showing an example of a sputtering apparatus used when forming a back electrode according to the present invention.
１１，２１…絶縁性基板 １２，２４…前面透明電極 １３，２３…光電変換ユニット １３１，２３３…ｐ型半導体層 １３２，２３２…ｉ型半導体層 １３３，２３１…ｎ型半導体層 １４，２２…裏面電極 １４１，２２３…裏面導電層 １４２，２２２…接着層 １４３，２２１…光反射性金属層 ２５…グリッド電極 11, 21 ... insulating substrate 12, 24 ... front transparent electrode 13, 23 ... photoelectric conversion unit 131, 233 ... p-type semiconductor layer 132, 232 ... i-type semiconductor layer 133, 231 ... n-type semiconductor layer 14, 22 ... back surface Electrodes 141, 223 Back conductive layer 142, 222 Adhesive layer 143, 221 Light reflective metal layer 25 Grid electrode
Claims (6)
導電層とその裏面側に設けられた銀を包含する光反射性
金属層とを有する薄膜光電変換装置の製造方法であっ
て、前面透明電極、該前面透明電極の裏面側に設けられ
た薄膜光電変換ユニットおよび該光電変換ユニットの裏
面側に設けられた前記裏面透明導電層を絶縁性基板上に
それぞれ形成する各工程を備え、前記光反射性金属層を
形成する際に、反応室内において約０．１〜約０．２７
Ｐａのスパッタガス圧力下に酸化亜鉛微粒子を含む第１
のプラズマ領域と銀微粒子を含む第２のプラズマ領域と
を形成し、該基板を前記反応室内に形成された前記第１
のプラズマ領域と第２のプラズマ領域上を通過させて酸
化亜鉛を包含する接着層と銀を包含する光反射性金属層
を形成し、それにより前記裏面透明導電層と前記接着層
と前記光反射性金属層を有する裏面電極を提供すること
を特徴とする薄膜光電変換装置の製造方法。1. A method of manufacturing a thin-film photoelectric conversion device in which a back electrode has a back transparent conductive layer containing zinc oxide and a light-reflective metal layer containing silver provided on the back side of the back electrode. Forming an electrode, a thin-film photoelectric conversion unit provided on the back side of the front transparent electrode, and forming the back transparent conductive layer provided on the back side of the photoelectric conversion unit on an insulating substrate. In forming the reflective metal layer, about 0.1 to about 0.27
First containing zinc oxide fine particles under a sputtering gas pressure of Pa
And a second plasma region containing silver particles are formed, and the substrate is placed in the first chamber formed in the reaction chamber.
Forming an adhesive layer containing zinc oxide and a light-reflective metal layer containing silver by passing over the plasma region and the second plasma region, whereby the back transparent conductive layer, the adhesive layer, and the light reflection metal layer are formed. A method for manufacturing a thin-film photoelectric conversion device, comprising: providing a back electrode having a conductive metal layer.
光電変換ユニットおよび裏面透明導電層を順次形成した
後、該基板をまず前記第１のプラズマ領域上を、ついで
前記第２のプラズマ領域上を通過させることを特徴とす
る請求項１に記載の製造方法。2. After the front transparent electrode, the thin film photoelectric conversion unit, and the back transparent conductive layer are sequentially formed on the substrate, the substrate is first placed on the first plasma region, and then the second plasma region. 2. The method according to claim 1, wherein the light is passed through the upper part.
上を、ついで前記第１のプラズマ領域上を通過させ、し
かる後、前記裏面透明導電層、薄膜光電変換ユニットお
よび前面透明電極を順次形成することを特徴とする請求
項１に記載の製造方法。3. The substrate is first passed over the second plasma region and then over the first plasma region, and then the back transparent conductive layer, the thin film photoelectric conversion unit and the front transparent electrode are sequentially formed. The method according to claim 1, wherein:
していてもよい酸化亜鉛スパッタターゲットに放電電力
を印加することによって形成し、第２のプラズマ領域を
銀スパッタターゲットに放電電力を印加することによっ
て形成することを特徴とする請求項１ないし３のいずれ
か１項に記載の製造方法。4. The method of claim 1, wherein the first plasma region is formed by applying a discharge power to a zinc oxide sputter target which may contain a dopant, and the second plasma region is formed by applying a discharge power to a silver sputter target. The method according to claim 1, wherein:
する放電電力の電力密度が約０．１〜約４Ｗ／ｃｍ2 で
あり、前記銀ターゲットに印加する放電電力の電力密度
が約１〜約２０Ｗ／ｃｍ2 であることを特徴とする請求
項４に記載の製造方法。5. A power density of a discharge power applied to the zinc oxide sputter target is about 0.1 to about 4 W / cm 2 , and a power density of a discharge power applied to the silver target is about 1 to about 20 W / cm 2. The method according to claim 4, wherein the size is cm 2 .
マ領域とをそれらの一部が重なり合うように形成するこ
とを特徴とする請求項１ないし５のいずれか１項に記載
の製造方法。6. The method according to claim 1, wherein the first plasma region and the second plasma region are formed such that a part thereof overlaps with the first plasma region.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000016940A JP2001210845A (en) | 2000-01-26 | 2000-01-26 | Method of manufacturing thin film photoelectric conversion device |
| US09/536,092 US6500690B1 (en) | 1999-10-27 | 2000-03-24 | Method of producing a thin-film photovoltaic device |
| AU22572/00A AU777360B2 (en) | 1999-10-27 | 2000-03-24 | Method of producing a thin-film photovoltaic device |
| EP00105962.5A EP1096577B9 (en) | 1999-10-27 | 2000-03-24 | Method of producing a thin-film photovoltaic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000016940A JP2001210845A (en) | 2000-01-26 | 2000-01-26 | Method of manufacturing thin film photoelectric conversion device |
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| Publication Number | Publication Date |
|---|---|
| JP2001210845A true JP2001210845A (en) | 2001-08-03 |
Family
ID=18543999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000016940A Pending JP2001210845A (en) | 1999-10-27 | 2000-01-26 | Method of manufacturing thin film photoelectric conversion device |
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| Country | Link |
|---|---|
| JP (1) | JP2001210845A (en) |
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