TW201044626A - Photoelectric conversion device and manufacturing method thereof, solar cell, and target - Google Patents

Photoelectric conversion device and manufacturing method thereof, solar cell, and target Download PDF

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TW201044626A
TW201044626A TW099109630A TW99109630A TW201044626A TW 201044626 A TW201044626 A TW 201044626A TW 099109630 A TW099109630 A TW 099109630A TW 99109630 A TW99109630 A TW 99109630A TW 201044626 A TW201044626 A TW 201044626A
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metal
photoelectric conversion
layer
conversion device
substrate
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TW099109630A
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TWI482301B (en
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Hiroyuki Kobayashi
Shinya Suzuki
Toshiaki Fukunaga
Hiroshi Kubo
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Fujifilm Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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    • 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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
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    • 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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03923—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
    • 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
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    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • 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
    • 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
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    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

Forming an alkali (earth) metal layer of a photoelectric conversion device with high productivity. In manufacturing a photoelectric conversion device having a photoelectric conversion layer that includes, as a major component, a compound semiconductor having a chalcopyrite structure formed of a group Ib element, a group IIIb element, and a group VIb element, an alkali (earth) metal supply layer is formed by a sputtering method using a semi-conductive or conductive target that includes one or more types of alkali metals and/or alkali earth metals. Alternatively, an alkali (earth) metal supply layer is formed by a reactive sputtering method in the presence of oxygen and/or nitrogen using a semi-conductive or conductive target that includes one or more types of alkali metals and/or alkali earth metals.

Description

201044626 六、發明說明： 【發明所屬之技術領域】 本發明是關於一種光電轉換裝置（ph〇toeiectric conversion device)，其具有下電極（1〇wer electr〇de)、藉 由吸收光產生電之光電轉換半導體層（ph〇t〇eiectric conversion semiconductor layer )以及上電極（upper electrode)之疊層結構；以及其製造方法。本發明亦關於 一種具有所述光電轉換裝置之太陽電池（s〇lar cell)。本發 明進一步關於一種適合用於製造所述光電轉換裝置之靶 材。 【先前技術】 具有下電極（背接觸電極）、藉由吸收光產生電流之 光電轉換半導體層以及上電極之疊層結構的光電轉換裝置 用於各種應用中，諸如太陽電池以及其類似物。大部分習 知太陽電池是使用塊狀單晶石夕、多晶石夕或薄膜非晶石夕之石夕 基電池。然而，最近，已研究並開發不依賴於矽之基於化 合物半導體之太陽電池。已知兩種類型之基於化合物半導 體之太陽電池’其中一者是塊狀系統’諸如GaAs系統以 及其類似物，且另一者是薄膜系統，諸如由第比族元素、 第Illb族元素以及第Vlb族元素形成之CIS (Cu-In-Se) 系統、CIGS (Cu-In-Ga-Se)或其類似物。據報導所述CIS 系統或CIGS系統具有高光吸收速率以及高能量轉換效率。 對於太陽電池基板’目前使用玻璃基板。但是，玻璃 基板不具有可撓性且因此不能用於太陽電池之連續製程 201044626 軸式»程）t °此外’㈣基板由於不可撓性而容易斷 裂且亦難以減小太陽電池之厚度以及重量。 因此，已研究對於太陽電池使用可撓性基板。可橈性 基板可包含諸如Al、Cu、Ti、不鑛鋼基板之金屬基板，以 及諸如聚gt亞胺之触基板。若考慮防熱溫度 ，則金屬基 板為更k。當使用金屬基板時，有必要在所述基板表面上 提供絕緣薄膜以防止基板與形成於基板上之電極或光電轉 換層之間短路。 、較佳地，基板與形成於其上之每—層之_熱膨脹係 t差很小以防止基板由於熱應力而彎曲。關於金屬基板， 當考慮成本、作為太陽電池之所需特徵以及基板之熱膨脹 係數與光電轉制或下電極之_歸脹係數差時 ’認為 铭基基板較佳。 曰本未審查專利公開㈣2__34號提出使用由 表面上具有陽極化膜（Al2Q3膜）之紹基質形成的陽極化 基板。所述方法使得即使當使用大面積基板時，仍易於形 G I絕緣賴而整個基板表面上無任何針孔（pinh〇ie)。 在CIS或CIGS光電轉換裝置中，已知光電轉換層之 結晶得到改良且光電轉換效率藉由使驗（土）金屬（較佳 為鈉（Na))擴散於光電轉換層中來增加。通常，鈉擴散 於光電轉換層中已藉由使用含有納之納舞玻璃（她彻e glass ; SLG)基板來實現。 虽使用曰本未審查專利公開案第2〇〇〇_34932〇號中所 述之陽極化基板或其他上述基板中之一者時，較佳提供驗 5 201044626 g以向光電轉換層供應鹼金屬，因為所述基板不包含 驗（土）合屬。I,, 、'舉例而言，產業技術總合研究所（AIST) 3B^523屆歐洲光伏太陽能展覽會（23rd EU-PVSEC) 祚或細4 3中七田述藉由射頻（RF)賤鑛，使用納妈玻璃（S L G ) 材，在基板與M〇下電極之間提供鈉鈣玻璃層作為 一籀—供f ^。國際專利公開案第W02003/069684號描述 错^又/貝法在M〇下電極上形成驗金屬供應層之 驗金屬供:層種藉由噴霧法絲。下電極上形成 覽會=5業合研究所在第23屆歐洲光伏太陽能展 σ'所述之方法中，若藉由濺鍍形成膜，則別 田Ϊ使用处賤鑛’因為納約玻璃⑽絕緣 面^ 流（dc)_°然而’处濺鑛在膜形成方 璃二)nm，，不具有生產力。此外，觸玻 雜質可能會不利:二:=:居品質具有變化，且所述 換效率降級轉換層之軸，從錢光電轉 ，，公開案第wo勒/G69684號巾所&賴 極以及:電供靖後形成之下電 間引入濕式式製程形成。在乾式製程之 形成驗⑷金屬層且以高生產力製造具:二= 201044626 效率之光電轉換裝置。本發明之 由上述方法製造之光電轉換裝置。0、在於提供-種藉 【發明内容】 本發明之第一光電轉換裝置 雜錄置之找，魏裝置具料光 藉由吸收光產生電流之光電轉換半導俨 *亟、 以及提供於所述基板與下電極之 Ο 金屬及/級土金屬且當形賴述光電 戶:述層供應所述一或多種類型之驗金屬及/或驗土:屬 光電轉換半導體層之主要組份是至少—種類型之化 合物半導體’所述化合物半導體具有由第此族元素、第馳 族兀素以及第VIb族元素形成的黃銅礦結構；且 鹼（土）金屬供應層是藉由濺鍍法（sputtering method)，使用包含-或多種類型之驗金屬及/或驗土金屬 的半導電或導電靶材來形成。 本發明之第二種光電轉換裝置製造方法是一種製造 光電轉換裝置之方法，所述裝置具有位於基板上之下電 極、藉由吸收光產生電流之光電轉換半導體層以及上電極 之疊層結構以及提供於所述基板與下電極之間的驗（土） 金屬供應層，所述驗（土）金屬供應層包含一或多種類型 之驗金屬及/或鹼土金屬且當形成所述光電轉換半導體層 時’向所述層供應所述一或多種類型之鹼金屬及/或鹼土金 201044626 屬，其中： 光電轉換半導體層之主要組份是至少一種類型之化 合物半導體，所述化合物半導體具有由第Ib族元素、第Inb 族元素以及第vib族元素形成的黃銅礦結構；且 驗（土）金屬供應層是藉由反應性減鍍法（reactive sputtering method) ’在氧氣及/或氮氣存在下，使用包含一 或多種類型之鹼金屬及/或鹼土金屬的半導電或導電靶材 來形成。 如本文中所使用’術語“半導電（semi_c〇nductive ) ” 定義為電阻率是10_3至1〇8 (歐姆/公分（Q/cm))。此外， 如本文中所使用，術語“導電（c〇nductive) ”定義為電陴 率小於UT3 (歐姆/公分）。 本發明之光電轉換裝置是藉由任一上述本發明之光 電轉換裝置製造方法所製造之裝置。 本發明之太陽電池是具有上述光電轉換裝置之太陽 電池。 本發明之靶材是用於濺鍍形成光電轉換裝置之鹼 (土）金屬供應層的靶材’其是半導電或導電的且包含一或 多種類型之鹼金屬及/或鹼土金屬。 根據本發明’可提供一種能夠以高生產力形成鹼（土） 金屬層且以高生產力製造具有極佳光電轉換效率之光電轉 換裝置的光電轉換裝置製造方法。此外，根據本發明，玎 提供一種藉由上述方法所製造之光電轉換裝置。 【實施方式】 201044626 [光電轉換裝置製造方法]201044626 VI. Description of the Invention: [Technical Field] The present invention relates to a photoelectric conversion device (p〇toeiectric conversion device) having a lower electrode and generating light by absorbing light a stacked structure of a conversion semiconductor layer and an upper electrode; and a method of manufacturing the same. The invention also relates to a solar cell having the photoelectric conversion device. The present invention is further directed to a target suitable for use in the manufacture of the photoelectric conversion device. [Prior Art] A photoelectric conversion device having a lower electrode (back contact electrode), a photoelectric conversion semiconductor layer that generates a current by absorbing light, and a stacked structure of an upper electrode is used in various applications such as a solar cell and the like. Most of the conventional solar cells use a monocrystalline single crystal, a polycrystalline stone or a thin film amorphous stone. Recently, however, solar cells based on compound semiconductors that do not depend on germanium have been researched and developed. Two types of compound semiconductor-based solar cells are known, one of which is a bulk system such as a GaAs system and the like, and the other is a thin film system such as a group element, a group Illb element, and A CIS (Cu-In-Se) system formed of a Vlb group element, CIGS (Cu-In-Ga-Se) or the like. The CIS system or CIGS system is reported to have high light absorption rates and high energy conversion efficiencies. For solar cell substrates, glass substrates are currently used. However, the glass substrate does not have flexibility and thus cannot be used in a continuous process of a solar cell. 201044626 Axial type) The other (4) substrate is easily broken due to inflexibility and it is difficult to reduce the thickness and weight of the solar cell. Therefore, the use of a flexible substrate for a solar cell has been studied. The substrate may comprise a metal substrate such as Al, Cu, Ti, a non-mineral steel substrate, and a contact substrate such as polygt imine. If the heat prevention temperature is considered, the metal substrate is more k. When a metal substrate is used, it is necessary to provide an insulating film on the surface of the substrate to prevent short-circuiting between the substrate and the electrode or photoelectric conversion layer formed on the substrate. Preferably, the difference between the substrate and each of the layers formed thereon is small to prevent the substrate from being bent due to thermal stress. Regarding the metal substrate, it is considered that the base substrate is preferable in consideration of cost, characteristics required as a solar cell, and a thermal expansion coefficient of the substrate and a difference in the coefficient of expansion of the photoelectric conversion or the lower electrode. The unexamined patent publication (d) No. 2__34 proposes the use of an anodized substrate formed of a substrate having an anodized film (Al2Q3 film) on its surface. The method makes it easy to form a G I insulation without any pinholes on the entire substrate surface even when a large-area substrate is used. In the CIS or CIGS photoelectric conversion device, it is known that the crystallization of the photoelectric conversion layer is improved and the photoelectric conversion efficiency is increased by diffusing a test (earth) metal (preferably sodium (Na)) in the photoelectric conversion layer. In general, the diffusion of sodium into the photoelectric conversion layer has been achieved by using a substrate containing Nasdaq glass (she is e glass; SLG). In the case of using one of the anodized substrate or other of the above-described substrates described in the Unexamined Patent Publication No. 2-34932, it is preferable to provide a test for 2010 20102626 g to supply an alkali metal to the photoelectric conversion layer. Because the substrate does not contain a test (soil) genus. I,,, 'For example, the Institute of Industrial Technology (AIST) 3B^523 European Photovoltaic Solar Energy Exhibition (23rd EU-PVSEC) 祚 or fine 4 3 七田述 by radio frequency (RF) antimony ore, Using Naoma Glass (SLG) material, a soda lime glass layer was provided as a 籀-for f ^ between the substrate and the M 〇 lower electrode. International Patent Publication No. WO2003/069684 describes the formation of a metal supply layer on the M 〇 lower electrode for the inspection of the metal for the layer: by spraying the filament. In the method described in the 23rd European Photovoltaic Solar Energy Exhibition, in the method described in the 23rd European Photovoltaic Solar Energy Exhibition σ', if the film is formed by sputtering, the use of the other is the use of the antimony mine because of the Nai glass (10) Insulation surface ^ flow (dc) _ ° however 'splashing in the film forming rim 2) nm, does not have productivity. In addition, the contact glass impurities may be unfavorable: two: =: the quality of the change has, and the conversion efficiency of the conversion layer of the axis, from the money photoelectric, the public case No. Wo / G69684 towel & Lai : The formation of electricity is introduced into the wet process after the formation of the wet process. In the dry process, the (4) metal layer is formed and manufactured with high productivity: 2 = 201044626 Efficiency photoelectric conversion device. The photoelectric conversion device manufactured by the above method of the present invention. 0. In the present invention, the first photoelectric conversion device of the present invention is used for searching, and the photoelectric device is configured to generate a photoelectric conversion semiconductor light by absorbing light, and is provided in the The substrate and the lower electrode are metal and/or graded metal and are in the form of a photocell: the layer supplies the one or more types of metal and/or soil: the main component of the photoelectric conversion semiconductor layer is at least— a compound semiconductor of the type 'the compound semiconductor has a chalcopyrite structure formed of the first group element, the chimeric element, and the group VIb element; and the alkali (earth) metal supply layer is sputtered (sputtering) Method), formed using a semiconducting or electrically conductive target comprising - or multiple types of metal and/or soil. A second photoelectric conversion device manufacturing method of the present invention is a method of manufacturing a photoelectric conversion device, the device having a stacked structure of a lower electrode on a substrate, a photoelectric conversion semiconductor layer that generates a current by absorbing light, and an upper electrode, and Providing a test (earth) metal supply layer between the substrate and the lower electrode, the test (earth) metal supply layer comprising one or more types of metal and/or alkaline earth metals and when forming the photoelectric conversion semiconductor layer Supplying the one or more types of alkali metal and/or alkaline earth gold 201044626 to the layer, wherein: the main component of the photoelectric conversion semiconductor layer is at least one type of compound semiconductor having the first a chalcopyrite structure formed by a group element, an Inb group element, and a vib group element; and the (earth) metal supply layer is in the presence of oxygen and/or nitrogen by a reactive sputtering method It is formed using a semiconducting or electrically conductive target comprising one or more types of alkali metals and/or alkaline earth metals. As used herein, the term "semi-conductive" is defined as a resistivity of 10_3 to 1 〇 8 (ohms/cm (Q/cm)). Moreover, as used herein, the term "conductive" is defined as having an electrical enthalpy of less than UT3 (ohms/cm). The photoelectric conversion device of the present invention is a device manufactured by any of the above-described photoelectron conversion device manufacturing methods of the present invention. The solar cell of the present invention is a solar cell having the above photoelectric conversion device. The target of the present invention is a target for sputtering an alkali (earth) metal supply layer forming a photoelectric conversion device. It is semiconductive or electrically conductive and contains one or more types of alkali metals and/or alkaline earth metals. According to the present invention, it is possible to provide a photoelectric conversion device manufacturing method capable of forming an alkali (earth) metal layer with high productivity and manufacturing a photoelectric conversion device having excellent photoelectric conversion efficiency with high productivity. Further, according to the present invention, 玎 provides a photoelectric conversion device manufactured by the above method. Embodiments 201044626 [Method of Manufacturing Photoelectric Conversion Device]

本發明之第一光電轉換裝置製造方法是一種製造光 電轉換裝置之方法，所述裝置具有位於基板上之下電極、 藉由吸收光產生電流之光電轉換半導體層以及上電極之最 層結構以及提供於所述基板與下電極之間的鹼（土）金^ 供應層，所述鹼（土）金屬供應層包含一或多種類型=鹼 金屬及/或鹼土金屬且當形成所述光電轉換半導體層時，向 所述層供應所述一或多種類型之鹼金屬及/或鹼土二屬，其 光電轉換半導體層之主要組份是至少一種類型之化 合物半導體，所述化合物半導體具有由第Ib族元素、仍 族兀素以及第vib族元素形成的黃銅礦結構；且 所述鹼（土）金屬供應層是藉由麵法，使八一 之鹼金屬及/紐土金狀半導電辑電減 本發明之第二光電轉換裝置製造方法是—種光 =換裝置之錢，所魏置具有位於基板上之下電極、 =由吸收光產生電流之光電轉換半導體層以及上電極之爲 二吉及提供於所述基板與下電極之間的驗（!）金屬 =層供應所述—或多種_之驗金屬及/或驗土金屬，其 —種類型之化 光電轉換半導體狀主要組份是至少 201044626 導體具有由第Ib族元素、_ 素形成的黃鋼礦結構;且 氣及/或妓應麵法，在氧 法且驗^性崎法簡稱為（反應性）_ 鹼金屬及/或驗土金屬簡稱為驗（土）金屬。 裝置制限制，且可使跡何祕光電轉換 :於光電轉換裳置之基板，可包含例如 ί=，诸如_玻璃基板;金屬基板，諸如A1、Cu、 絲;由至少—側上具有陽極化膜之錄金屬 二。、 &極絲板’以及她基板，諸如聚I!亞胺基 ★制ί於1^由連續傳輸线高速製造光電轉換裝置（捲軸 二衣二^及減小其厚度與減少重量，較佳使用可撓性基 月匕其把。ί極化基板、上面形成有絕緣狀金屬基板或樹 =土 。备使用諸如聚醯亞胺基板之樹脂基板時，有必要 在不高於樹脂之防熱溫度Ueatp_ftempefatufe)的溫度 下形成光電轉換層，從而限制製程最多約4GG°C。因為難 以，所述溫度下提供高效能光f轉換層，所以需要一些諸 &(、月匕里辅助層（energy assist layer)之努力。 佳地’基板與形成於其上之每—層之間的熱膨服係 差很小以防止基板由於熱應力而彎曲。自與光電轉換層 ^下電極（背接觸電極）之熱膨脹係數差' 成本以及太陽 201044626 電池之所需特徵的觀點看，由至少一側上具有陽極化膜之 銘基金屬基質構成的陽極化基板尤為較佳。 如本文中所使用，“金屬基質之主要組份（major component of the metal base ) ” 是指佔 98 質量％或更多之 組份。金屬基質可為可包含微量元素之純鋁基質或鋁與另 一種金屬元素之合金基質。 如上文所述’由至少一側表面上具有陽極化膜之鋁基 金屬基質構成的陽極化基板與光電轉換層以及下電極具有 較小熱膨脹係數差。然而，若在超過5〇〇〇c之高溫下形成 半導體膜，則可能在膜形成時由於熱應力而出現斷裂以及 脫離。此外，光電轉換效率可能會由於由與基質材料之熱 膨脹係數差在化合物半導體中所引起之強内應力而降低。 為防止所述缺陷，基質材料與化合物半導體層之間的線 性熱膨脹係數差較佳小於7xl0-Vc，且更佳小於3χ1〇_6/χ：。 此處，線性熱膨脹係數以及線性熱膨脹差為室溫（23。〇 下之值。 以及熱膨脹係數與光電轉換半導體層3G之_脹係數相 當且具有南硬度錢高耐難之第二金屬基質整體形成的 金屬基板（被覆材料）’且在絲質上提 膜來提 供。 〇 因此，較佳基板可藉由使用由鋁基質（第一金屬基質） 形成於基板上之電極或光電轉換層 主要組份”是指佔80質量％ 如本文中所使用，形 或任何其他所提供之層的 或更多之組份。 201044626 在本發明之第一製造方法中，所形成之鹼（土）金屬 供應層像乾材一樣是半導電或導電的。在本發明之第二製 造方法中，膜是藉由反應性滅鍵，在氧氣及/或氮氣存在下 來形成，此引起氧化及/或氮化且所形成之驗（土）金屬供 應層絕緣。 备使用上面形成有絕緣膜之金屬基板或由至少—側 上具有陽極化膜之鋁基金屬基質構成的陽極化基板時，絕 緣鹼（土）金屬供應層為較佳，因為其增加基板與下電極 之間的絕緣，藉此可防止基板之介質擊穿（didectric breakdown) ° 對光電轉換半導體層之主要組份無任何限制，只要其 是至少一種類型之由第lb族元素、第IIIb族元素=及第 VIb族元素形成的化合物半導體即可。 ，光電轉換層之主要組份較佳為至少一種類型之由以 下形成的化合物半導體：至少一種類型之由Cu以及A 構成的族群中選出之第IbW素，至少一種類型之由八卜 Ga、以及hi所構成的族群中選出之第lnb族元素以 之由Μ以及Μ構成的族群中選出之 本文中之第幾族元素表示是基於短週期週The first photoelectric conversion device manufacturing method of the present invention is a method of manufacturing a photoelectric conversion device, which has a bottom layer electrode on a substrate, a photoelectric conversion semiconductor layer that generates a current by absorbing light, and a layer structure of the upper electrode and provides An alkali (soil) metal supply layer between the substrate and the lower electrode, the alkali (earth) metal supply layer comprising one or more types of alkali metal and/or alkaline earth metal and when the photoelectric conversion semiconductor layer is formed Supplying the one or more types of alkali metal and/or alkaline earth genus to the layer, the main component of the photoelectric conversion semiconductor layer being at least one type of compound semiconductor having a group Ib element a chalcopyrite structure formed by the elemental group and the vib group element; and the alkali (earth) metal supply layer is electrically reduced by the surface method to make the alkali metal and/or neodymium gold semiconducting series The second photoelectric conversion device manufacturing method of the present invention is a kind of light=changing device, and the device has a lower electrode on the substrate, and a photoelectric conversion half generated by the absorbed light. The body layer and the upper electrode are two yokes and the test (!) metal layer provided between the substrate and the lower electrode supplies the metal or/or the soil of the test, or the type of the test metal. The main component of the photoelectric conversion semiconductor is at least 201044626. The conductor has a yellow iron ore structure formed of a Group Ib element and a γ element; and the gas and/or 妓 surface method is abbreviated as a reaction in the oxygen method and the method. Sex) _ alkali metal and / or soil test metal referred to as test (earth) metal. The device is limited in limitation, and can be used for photoelectric conversion: a substrate for photoelectric conversion, which may include, for example, ί=, such as a _glass substrate; a metal substrate such as A1, Cu, wire; having anodization from at least the side The film is recorded in metal II. , & filament board' and her substrate, such as poly-I! imine-based system, high-speed manufacturing of photoelectric conversion devices from continuous transmission lines (reel two clothes and reduce their thickness and weight, preferably The flexible substrate is used to polarize the substrate, and an insulating metal substrate or tree = soil is formed thereon. When a resin substrate such as a polyimide substrate is used, it is necessary to be not higher than the heat resistance temperature of the resin. The photoelectric conversion layer is formed at a temperature of Ueatp_ftempefatufe), thereby limiting the process to a maximum of about 4 GG ° C. Because it is difficult to provide a high-efficiency optical f-conversion layer at the temperature, some efforts are needed for the & energy-saving layer. The substrate is formed with each layer formed thereon. The difference between the thermal expansion is small to prevent the substrate from being bent due to thermal stress. From the point of view of the difference between the thermal expansion coefficient of the lower electrode (back contact electrode) and the required characteristics of the solar cell 201044626, An anodized substrate composed of a metal substrate having an anodized film on at least one side is particularly preferred. As used herein, "major component of the metal base" means 98% by mass. Or more components. The metal matrix may be a pure aluminum matrix which may contain trace elements or an alloy matrix of aluminum and another metal element. As described above, 'aluminum-based metal matrix having an anodized film on at least one side surface The formed anodized substrate has a small difference in thermal expansion coefficient from the photoelectric conversion layer and the lower electrode. However, if a semiconductor film is formed at a high temperature exceeding 5 〇〇〇c, it may be When the film is formed, cracking and detachment occur due to thermal stress. Further, photoelectric conversion efficiency may be lowered due to strong internal stress caused by a difference in thermal expansion coefficient from the matrix material in the compound semiconductor. To prevent the defect, the matrix material and The linear thermal expansion coefficient difference between the compound semiconductor layers is preferably less than 7x10-Vc, and more preferably less than 3χ1〇_6/χ: Here, the linear thermal expansion coefficient and the linear thermal expansion difference are room temperature (23. And a metal substrate (coating material) having a thermal expansion coefficient equivalent to the swell coefficient of the photoelectric conversion semiconductor layer 3G and having a south metal hardness and high resistance, and a film is formed on the silk. 〇 Therefore, Preferably, the substrate can be formed by using an electrode or a photoelectric conversion layer main component formed on the substrate from an aluminum matrix (first metal substrate)" means 80% by mass as used herein, or any other provided layer In the first manufacturing method of the present invention, the alkali (earth) metal supply layer formed is half like a dry material. Electrically or electrically conductive. In the second manufacturing method of the present invention, the film is formed by reactive debonding in the presence of oxygen and/or nitrogen, which causes oxidation and/or nitridation and formation of the test (earth). The metal supply layer is insulated. When an anodized substrate having an insulating film formed thereon or an anodized substrate composed of an aluminum-based metal substrate having an anodized film at least on the side is used, an insulating alkali (earth) metal supply layer is preferable because It increases the insulation between the substrate and the lower electrode, thereby preventing dielectric breakdown of the substrate. There is no limitation on the main component of the photoelectric conversion semiconductor layer as long as it is at least one type of element lb. A compound semiconductor formed of a Group IIIb element = and a Group VIb element may be used. The main component of the photoelectric conversion layer is preferably at least one type of compound semiconductor formed by at least one type of IbW element selected from the group consisting of Cu and A, at least one type of Babu Ga, and The group of elements selected from the group of lnb elements selected by hi consisting of Μ and Μ are represented by short-period weeks.

Γΐίί本二元/以及第VIb族元素 γ ¥體在本文巾有4表示為簡稱“第随_VI 體之、、且成π素的弟Ib族元素、帛IIIb族元素以VIb 12 201044626 族元素各可為一種類型或兩種或雨種以上類型之元素。 驗金屬可包含Li、Na、Κ、Rb以及Cs且鹼土金屬可 包含Be、Mg、Ca、Sr以及Ba。其中’自易於獲得化學穩 定且易於處置之化合物，可易於藉由加熱自鹼（土）金屬 供應層釋放’且改良光電轉換層之結晶之有利作用的觀點 看，至少一種類型之由Na、K、Rb以及Cs所構成的族群 中選出之驗金屬為較佳，Na及/或K為更佳，且Na尤為 較佳。 ΟΓΐίί 本 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / Each of the elements may be of one type or two or more types of rain. The metal may include Li, Na, yttrium, Rb, and Cs and the alkaline earth metal may include Be, Mg, Ca, Sr, and Ba. A stable and easy-to-handle compound, which can be easily formed by heating an alkali (earth) metal supply layer and improving the crystallization of the photoelectric conversion layer, at least one type consisting of Na, K, Rb and Cs The metal selected from the group is preferred, Na and/or K are more preferred, and Na is particularly preferred.

把材可包含單獨驗（土）金屬或呈化合物形式之驗 (土）金屬。 驗金屬化合物可包含無機鹽’諸如氟化鈉（s〇dium fluoride)、氟化鉀（p0tassiuni fluoride)、硫化鈉（s〇dium sulfide)、硫化鉀（p〇tassiUm sulfide)、碼化納（s〇dium selemde)、硒化鉀（potassium selenide)、氯化鈉（s〇dium chloride)、碳酸鈉（s〇dium carb〇nate)、銦酸鈉（s〇dium molybdate)(包含水合物）、氣化鉀（p〇tassium chi〇ride) 以及其類似物。其中，氟化鈉、碳酸鈉以及鉬酸鈉為較佳， 且氟化鈉為更佳。 鹼土金屬化合物可包含無機鹽，諸如氟化鈣 鎂、硫化鈣、硫化鎂、硒化鈣以及其類似物。 材巾之—或多種麵之鹼金屬及/或驗土金屬的 Lit任何特別限制，且#於自*(土）金屬供應層向光 敎地供應適合含量之驗土金屬，總量較佳為工 原子/° (—)至30原子％、更佳為5原子％至20原子％ 13 201044626 且進—步較佳為ίο原子％至15原子％。 物質可能會變成在DC频時阻礙穩定放過量之此等 對乾材之基質組成無任何特別限制 或導電的且允許添加驗（土）金屬或其化=其疋半V電 之^質組成可包含諸如碎之半導體以及諸二m 广材i純度，(土)金屬供應層與下 】==i係數差、膜形成速度、膜形 成^本以及其類姻素，較佳使用包含1或兩種或兩種 以上驗金屬及/或驗土金屬之石夕I巴材。 在本毛明中，驗（土）金屬供應層是藉由雜法或反 應性_法來形成，所述方法允許藉由乾式製程形成驗 (土）金屬供應層以及隨後下電極以及光電轉換層。與國際 專利公開案第W02003/069684號中所述之浸潰法以及 “先前技術”中所引用之喷霧法相比，此方法更具生產力。 一在產業技術總合研究所在第23屆歐洲光伏太陽能展 覽會3BV.5.43中所述之方法中，若藉由濺鍍形成膜，則別 無選擇’只有使用RF濺鑛，因為鈉鈣玻璃（SLG)絕緣。 但RF濺鍍在膜形成方面較慢，需要昂貴裝備，且不具有 生產力。 相比之下，本發明使用半導電或導電靶材以致鹼（土） 金屬供應層可藉由除RF濺鑛外之濺鐘法來形成。舉例而 言，鹼（土）金屬供應層可藉由DC (反應性）濺鍍（DC (reactive) sputtering)、脈衝 DC (反應性）濺鑛（pulse DC (reactive) guttering)、磁控（反應性）濺鍍（magnetron 14 201044626 (reactive) sputtering)或雙磁控（反應性）濺鍍（d^ magnetron (reactive) spmtering)來形成。此等方法比虾 濺鑛更具生產力且裝備成本亦可比RF濺鑛有所降低。儘 管自生產力以及成本之觀點看並非較佳，但RF濺鍍亦可 用於本發明中。 Ο ΟThe material may comprise a separate (earth) metal or a test (earth) metal in the form of a compound. The metal compound may comprise an inorganic salt such as sdium dium fluoride, p0tassiuni fluoride, s dium dium sulfide, potassium sulphide (p〇tassiUm sulfide), coded sodium (s 〇dium selemde), potassium selenide, s〇dium chloride, s〇dium carb〇nate, s〇dium molybdate (including hydrate), gas Potassium (p〇tassium chi〇ride) and its analogs. Among them, sodium fluoride, sodium carbonate, and sodium molybdate are preferred, and sodium fluoride is more preferred. The alkaline earth metal compound may contain inorganic salts such as calcium magnesium fluoride, calcium sulfide, magnesium sulfide, calcium selenide, and the like. Any particular limitation of the material towel or the various alkali metals and/or the soil-receiving Lit, and the supply of the appropriate amount of the soil to the bare metal from the * (soil) metal supply layer, the total amount is preferably The working atom / ° (-) to 30 atom%, more preferably 5 atom% to 20 atom% 13 201044626 and further preferably ίο atom% to 15 atom%. The substance may become a barrier to stable release in the DC frequency. There is no particular restriction or conductivity on the matrix composition of the dry material, and it is allowed to add the test (earth) metal or its chemical composition. Including, for example, a semiconductor such as shredded semiconductors, and a purity of (a) metal supply layer and a lower [==i coefficient difference, a film formation speed, a film formation method, and a genus thereof, preferably containing one or two Species or two or more metals and/or soil-measuring metals. In the present invention, the (earth) metal supply layer is formed by a heterogeneous or reactive method which allows the formation of the earth (metal) supply layer and the subsequent lower electrode and the photoelectric conversion layer by a dry process. This method is more productive than the impregnation method described in International Patent Publication No. WO2003/069684 and the spray method cited in the "Prior Art". In the method described in the 23rd European Photovoltaic Solar Energy Exhibition 3BV.5.43 by the Institute of Industrial Technology, if the film is formed by sputtering, there is no choice but to use only RF sputtering because of soda lime glass. (SLG) insulation. However, RF sputtering is slow in film formation, requires expensive equipment, and is not productive. In contrast, the present invention uses a semiconducting or electrically conductive target such that the alkali (earth) metal supply layer can be formed by a sputtering process other than RF sputtering. For example, the alkali (earth) metal supply layer can be subjected to DC (reactive) sputtering, pulsed DC (reactive) guttering, and magnetic control (reaction). Sputtering (magnetron 14 201044626 (reactive) sputtering) or dual magnetron (reactive) sputtering (d^ magnetron (reactive) spmtering). These methods are more productive than shrimp spills and the cost of equipment can be reduced compared to RF splashing. Although not preferred from the viewpoint of productivity and cost, RF sputtering can also be used in the present invention. Ο Ο

藉由普通DC (反應性）濺鍍法，使用矽靶材形成膜 有時會有困難，因為靶材具有低導電率。在所述情況下，' 膜可藉由脈衝DC (反應性）濺鍍、磁控（反應性）賤鑛 或雙磁控（反應性）濺鑛來形成。 X 當靶材之比電阻不超過1歐姆/公分時，膜可有利地藉 由DC (反應性）錢鍍來形成。因此，當使用石夕乾材時， 藉由DC (反應性）贿形成膜藉由因其中添加至少一種 類型之由A卜Ga以及B所構成的族群中選出之元素而改 良導電率（降低比電阻）來促進。亦即，較佳使用包含至 少一種由A卜Ga以及B所構成的族群中選出之元素的矽 乾材，且在所述情況下，膜可藉由Dc (反應性）濺鐘、 脈衝DC (反應性）雜、磁控（反應性）濺鍛或雙磁控 (反應性）濺鍍來形成。 獅靶材：之至少一種由义、Ga以及B所構成的族 群中選出之元素的總量無任何制限制，只要其在可使把 材之比電阻降低至1歐姆/公分或更小之範_即可述 不小於1G_4原子％，但較大量為更佳以使熱膨服係 數與基板以及光電轉換層之_脹係數相#。當熱膨服係 數與基板以及光電轉換層之熱膨脹係數相當時，在高溫環 15 201044626 出現斷裂以及脫離。因， 20原子^ 子％至3G原子％，且更佳為H)原子#Forming a film using a ruthenium target by conventional DC (reactive) sputtering is sometimes difficult because the target has a low electrical conductivity. In this case, the film can be formed by pulsed DC (reactive) sputtering, magnetron (reactive) ore or double magnetron (reactive) sputtering. X When the specific resistance of the target does not exceed 1 ohm/cm, the film can be advantageously formed by DC (reactive) money plating. Therefore, when using Shishi dry material, the film is formed by DC (reactive) bribe, and the conductivity is improved by adding at least one type of element selected from the group consisting of A, Ga, and B. Resistance) to promote. That is, it is preferred to use a dry material comprising at least one element selected from the group consisting of A, Ga, and B, and in this case, the film can be pulsed by Dc (reactive), pulsed DC ( Reactive, magnetically controlled (reactive) splash forging or dual magnetron (reactive) sputtering. Lion target: The total amount of at least one element selected from the group consisting of sense, Ga, and B is not subject to any restrictions, as long as it reduces the specific resistance of the material to 1 ohm/cm or less. _ can be described as not less than 1 G_4 atomic %, but a larger amount is more preferable so that the thermal expansion coefficient is the same as the substrate and the photoelectric conversion layer. When the thermal expansion coefficient is comparable to the thermal expansion coefficient of the substrate and the photoelectric conversion layer, breakage and detachment occur at the high temperature ring 15 201044626. Because, 20 atom ^ % to 3G atom%, and more preferably H) atom #

佳。應之驗（土）金屬，犯W 所用之石夕_^佳包含單獨他或他化舍物π 酸鈉以及鉬酸鈉二已3至少一種類型之由氟化釣，秘 ㈣鹽。尤其〆 如Na戶= 夕?材較佳為藉由鑄造以及燒結納鹽粉本(諸 包含不可合粉末所獲得之燒⑽ ⑹士包含儀w )斤之石夕乾材更佳為藉由鏵造以及 讀末且進—步包含含Α1粉本、含 人=1 3 B粉末之混合粉末所獲得之燒結體（其< 包含不可避免的雜質）。. 幻為向光電轉換層適當地供應驗金屬（alkali)直 2 錢供應層成為熱膨脹係數與基板以及光電 服係數相當的層’石綠材中較佳包含驗金屬 i (諸如Mg、Ca以及其類似金屬）。本發明之 毛月者已實際上成功地製備轉_ (織描述實例）。 產業技術總合研究所在第23屆歐洲光伏 會3BV.5.43中所述之鈉舞玻璃的乾材包含許多雜質，^ 具有變化’且所述雜質可能會不觀影響光電轉換層之來 成’從而使光電轉換效率降級。舉例而言，已知藉由卜 法（fl〇atingmethod)(其為_坡璃之主要製造方法= 16 201044626 造之納約玻璃易於包含Sn作為雜質。在本發明實施例中， 高純度靶材可藉由對於上述燒結體使用高純度材料來製 備。因此，可形成高純度鹼（土）金屬供應層，藉此可防 止可另外包含於鹼（土）金屬層中之雜質對光電轉換層之 不利影響且可穩定地製造具有極佳光電轉換效率之光電轉 換裝置。 如上文所述，根據本發明之第一及第二光電轉換層製good. Should be tested (earth) metal, the stone used in the eve of the eve _ ^ good contains him or his chemical π sodium and sodium molybdate two has 3 at least one type of fluoride fishing, secret (four) salt. In particular, for example, Na household = 夕 材 较佳 较佳 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造 铸造The sintered body obtained by the mixed powder containing the powder of Α1 and containing powder of human =1 3 B (which contains < unavoidable impurities) is produced and read. The illusion is to properly supply the metallurgical conversion layer to the photoelectric conversion layer, and the layer of thermal expansion coefficient is equivalent to the substrate and the photoelectric service coefficient. The stone green material preferably contains the metal i (such as Mg, Ca and its similar metal). ). The stalker of the present invention has actually succeeded in preparing a transfer woven article. The dry material of Sodium Dance Glass described in the 23rd European Photovoltaic Society 3BV.5.43 contains many impurities, and has a change 'and the impurities may not affect the photoelectric conversion layer.' Thereby the photoelectric conversion efficiency is degraded. For example, it is known that a nano-glass is easily contained as an impurity by a flo- ing method (which is a main manufacturing method of glaze = 16 201044626. In the embodiment of the invention, a high-purity target) It can be prepared by using a high-purity material for the above sintered body. Therefore, a high-purity alkali (earth) metal supply layer can be formed, whereby impurities which can be additionally contained in the alkali (earth) metal layer can be prevented from being applied to the photoelectric conversion layer. A photoelectric conversion device having excellent photoelectric conversion efficiency can be stably produced and adversely affected. As described above, the first and second photoelectric conversion layers are manufactured according to the present invention.

造方法，可以高生產力形成驗（土）金屬供應層且可以高 生產力製造具有極佳光電轉換效率之光電轉換裝置。 <DC濺鍍設備（脈衝DC濺鍍設備）> 現將參看圖1來描述DC濺鑛設備之實例結構。 圖1中所示之DC濺鍍設備1〇1基本上由具有能夠固 持基板B且將其加熱至預定溫度之基板固持器U1的直空 容器no以及能夠固持靶材τ之電漿電極（陰極）112、構 ，。電製電極m連接於位於真空容㈣11〇外之dc電源 113。 引入又備1G1中’藉由使電極112放電來使 其類似物之正離子。且產生諸如ΑΓ以及 Τ之细# _ 所產生之正離子濺鍍靶材T，且靶材 板B上^/釋放且以中性或離子化狀態沈積於基 膜形成賴示意性說明電聚空間。 體引入構件。所述，二有用於引入待電漿化之氣體G的氣 供應源（未體狀構件包含待電漿化之氣體㈣ 原（未圖不）以及氣體引入管118。另外，膜形成設 17 201044626 備101具有連接於排放構件（未圖示 似物）以排放真空容器中之氣體v =真空泵或其類 用之氣體G、Αι·或其類似物無任何特=119。對所使 麟使用相同設備以及例如待電漿;㈣。DC反應性 或氮氣的混合氣體作為氣體G。之Ar氣體與氧氣及/ 執彳询_，其㈣電漿電極 盆中t雷t 衝％軸中，執行脈衝驅動， /中中電極112間歇施加Dc電壓。在普通％滅鍵 時間連續形成膜，則電射累積於婦表面上且 弧二=成。脈衝DC濺鍍可藉由防止在靶材Τ附近電 =】而長時間形成高品質膜。脈衝Dc濺鑛可用具有低 導笔率之靶材形成膜。 濺鍍設備> 、，參看圖2來描述rf濺鍍設備之實例結構。與Dc 錢鍍設備U)1侧之組件給與相同參考魏且此處不再進 一步作詳細說明。 _ RF錢鍍設備102之基本結構與DC濺鍍設備相同，不 同之處僅為電漿電極丨12連接於高頻交流（AC )電源（汉尹 電源）114而非DC電源113。在RF濺鍍中，對電漿電柘 112施加高頻AC電壓。RF濺鍍可使用絕緣靶材。RF反應 性錢鍍使用與RF濺鍍相同之設備以及與DC反應性機餐 中相同之例如待電漿化之Ar氣體與氧氣及/或氮氣的渑合 氣體作為氣體G。 <磁控濺鍍設備> 18The manufacturing method can form a metal (metal) supply layer with high productivity and can manufacture a photoelectric conversion device having excellent photoelectric conversion efficiency with high productivity. <DC Sputtering Apparatus (Pulse DC Sputtering Apparatus)> An example structure of a DC sputtering apparatus will now be described with reference to Fig. 1. The DC sputtering apparatus 1〇1 shown in FIG. 1 is basically composed of a straight empty container no having a substrate holder U1 capable of holding the substrate B and heating it to a predetermined temperature, and a plasma electrode (cathode capable of holding the target τ) ) 112, structure,. The electroforming electrode m is connected to a dc power source 113 located outside the vacuum chamber (4). Introduced in 1G1, the positive ions of the analog are made by discharging the electrode 112. And generating a positive ion sputtering target T such as ΑΓ and Τ, and the target plate B is released and deposited in a neutral or ionized state on the base film to form a schematic explanation of the electropolymerization space. . Body introduction member. The second has a gas supply source for introducing the gas G to be pulverized (the non-body member contains the gas to be pulverized (four) original (not shown) and the gas introduction pipe 118. In addition, the film formation device 17 201044626 The preparation 101 has a gas connected to a discharge member (not shown) to discharge the gas in the vacuum vessel v = a vacuum pump or the like, G, Αι, or the like, without any special = 119. Equipment and, for example, to be plasma; (4) DC reactive or nitrogen mixed gas as gas G. Ar gas and oxygen and / / _ _, (4) in the plasma electrode basin t t rush in the % axis, perform the pulse The /, medium-to-middle electrode 112 intermittently applies the Dc voltage. When the film is continuously formed at the normal %-off key time, the electric radiation accumulates on the surface of the woman and the arc is equal to 2. The pulsed DC sputtering can prevent the electricity from being near the target. =] and a high quality film is formed for a long time. Pulse Dc sputtering can form a film with a target having a low pen rate. Sputtering Apparatus>, an example structure of an rf sputtering apparatus will be described with reference to Fig. 2. The components on the U1 side of the device give the same reference Wei and are no longer here. A detailed description will be made in one step. The basic structure of the RF money plating apparatus 102 is the same as that of the DC sputtering apparatus, except that the plasma electrode 12 is connected to a high frequency alternating current (AC) power source (Han Yin power source) 114 instead of the DC power source 113. In RF sputtering, a high frequency AC voltage is applied to the plasma electrode 112. Insulating targets can be used for RF sputtering. The RF reactive money plating uses the same equipment as the RF sputtering and the same as the DC reactive machine meal, for example, a gas of Ar gas to be pulverized with oxygen and/or nitrogen as the gas G. <Magnetron Sputtering Equipment> 18

Ο 201044626 將參看圖3來描述磁控賤鑛設備之實例結構。 濺鍍設備101以及RF、掩缺机也1nn 4 η /、 θ h $ f _同之組件給與相同 麥考付唬且此處不再進一步作詳細說明。 磁^鐘設備103之基本結構與RF濺鑛設備相同， 不同之處僅為具有多個磁體U5M之磁體單元ιΐ5連接於 電漿電極112且妹Τ安裝於其上。在磁控賴中，對電 f電極112施加高頻AC電壓，其中在姆了附近由磁體 早兀115產生磁場。可對電漿電極112施加dc電虔。磁 控麟可藉由保持電聽子遠縣板㈣有效地讀乾材 T 〇 <雙磁控濺鍍設備> 將參看圖4來描述雙磁控減錄設備之實例結構。與磁 控巍鍍設備103_之_給與相同參考符號且此處不再 進一步作詳細說明。 雙磁控雜設備HM之基本結構與磁控錢鑛設備1〇3 相同，不同之處僅為提供她電聚電極112以及磁體單元 115。兩個電漿電極112連接於共用高頻Ac電源ιΐ6，其 中所述電極中之任-者作為陰極驅動且另—者作祕極驅 動。在雙磁控麵中，在兩個·電極112之間施加高頻 AC電壓且藉由改變每-電極112之極性來形成膜。 雙磁㈣鍍可麟有低導電率之妹形成膜。此外，所述 方法可使舰緣㈣。雙題反紐_使用錢磁控反 應性麟相同之設備以及與DC反應性錢中相同之例如 待電聚化之Αι·氣體魏氣及/魏氣的混合氣體作為氣體 19 201044626 G。 對用於本發明之製造方法的膜形成條件無任何特別 限制。在任一種方法中，背景之真空為例如約1χ1〇'5至約 ΙΟχΗΤ5 帕斯卡（Pa)。 對於DC (反應性）濺鍍或脈衝DC (反應性）機錢而 言’較佳在藉由改變引入氣體之流速、施加電壓以及此外 對於脈衝DC濺鍍而言根據設備之結構以及尺寸、所用氣 體類型以及其類似因素改變脈衝週期以及脈波寬度來獲得 用於膜形成速度、膜品質、膜形成穩定性以及其類似物之 最佳條件後，執行膜形成。當形成膜時，基板溫度一般因 ^累積而增加至100。(：至30〇π以致不需要加熱基板，但有 時可能需要進行冷卻。對於DC磁控（反應性）濺錢同樣 對用於RF (反應性）濺鍍之膜形成條件無任何特別 限制，且較佳在除施加高頻功率外基本上以與上述DC(反 2性）濺鍍相同之方式來獲得最佳條件後，執行膜形成。 述情况亦適用於DC磁控（反應性）濺鍍。 別限ί用於雙磁控（反應性）麟之卿成條件無任何特 (反'"制，且較佳在除施加高頻功率外基本上以與上述Dc 極仙同之方式來獲得最佳條件以致兩個電聚電 作為陽極以及陰極操作後，執行膜形成。 [靶材] 方去中 身用於本發明之第一以及第二光電轉換裝置製造 的靶材（濺鍍靶材）亦為新穎的且包含於本發明中。 20 Ο ❹ 201044626 亦即，本發明之靶材是用於濺鍍形成待提供於光電轉 換裝置中之驗（土）金屬供應層的輕材， 電且包含—或多種類型之驗金屬及/或 ’本《明之树中之—種或兩種或兩種以上驗金屬 及/或鹼土金屬的總量無任何特別限制且 _子％ '更佳為5原子％至㈣子％=_\ ίΪ 子％至Μ原子％。已知過量之此等物質可能 曰受成在DC賤鑛時阻礙穩定放電之原因。 、 本發明之乾材的基質較佳為半導電物質。本發明之輕 ίΤ圭t含—❹麵叙驗觸及7綠土金屬的石夕 靶材。當树之比電阻不超過！歐姆/公分時，可有利地夢 應性）濺鍍形成膜。因此’當使用矽靶材時，曰 藉由DC (反應性）賴形賴藉由因向其中添加至少一 3二Ga以及B所構成的族群中選出之元素而改良導 電率（降減電阻）來促進。亦即，較佳使用包含至少一 = 所構成_群切出之元素的石夕革巴材， ^所述十月況下，可藉由DC (反應性）_、脈衝DC (反 磁控（反應性）賤 君^材1之至少一種由A1'Ga以及b所構成的族 群中k出之凡素的總量無任何特別限制，只要其在 材之比電阻降低至1歐姆/公分或更小的範圍内即可，所= 總量可不小於10-4原子％，但較大量為更佳。因此， 較佳為丨原子％至㈣子％且更佳為1G原子％至20= 21 201044626 %。 此外，諸如]^ 矽乾材中以使乾材Γ勒 類似物之驗土元素可包含於 層之熱膨脹係數”、、祕爐更接近於絲或光電轉換 t發明之t材較佳包含單麵錢化合物。 a 之妹較佳包含至少—麵型之域化納、碳 二二構成的族群中選出之鈉鹽。已知過量之 此等物質可能會變成在Dc減鍍時阻礙穩定放電之原因。 本發月之乾材較佳為藉由鑄造以及燒結鈉鹽粉末（諸 如NaF私末）與⑪粉末之混合/粉末所獲得之燒結體（其可 此包3不可避免的雜幻。本發日月之崎更佳為藉由禱造以 及燒結包含鈉鹽粉末以及矽粉末且進一步包含含ai粉 末、含Ga粉末以及含B粉末之混合粉末所獲得之燒結體 (其可能包含不可避免的雜質）。 使用本發明之靶材可使得以高生產力形成鹼（土）金 屬供應層且以咼生產力製造具有極佳光電轉換效率之光電 轉換裝置。 ' [光電轉換裝置] 參看隨附圖式來描述根據本發明之—實施例之光電 轉換裝置的結構。圖5是光電轉換裴置之縱向示意性剖視 圖。圖6是陽極化基板之示意性剖視圖，其說明所述基板 之結構，且圖7是陽極化基板之透視圖，其說明所述基板 之製造方法。在圖式中，各組件未按比例緣製以有助於目 視識別。 22 201044626 光電轉換裝置1是藉由上述本發明之 轉換裝置製造方法所製造之裝置。光電轉換裳 疊層結構作為其基本結構之裝置，复+ 八 極）20、找轉換半導體層3G衝^極（背接觸電 以此順序堆妓基板1G上。以下上電極％ 為“光電轉換層”。 先電轉換半導體層簡稱 光電轉換裝置i包含㈣基板ω與 Ο 鹼（土）金屬供應層70,其包含—或多 β、 /或驗土金屬且當形成光電轉換層 =之驗金屬及 述一或多種麵线金纽㈣述層供應所 在縱剖視圖中，光電轉換裝置丄具有 ΐ第: = ΓΓ，穿過光電轉換層3〇以及緩衝層4〇之 ==第層3°、緩衝_ 上述組態可提供之結構為裝置被第 至:3=多電池(·此外， 此可獲得某1池c之上電㈣串聯連 接於相鄰電池c之下電極20的結構。 (陽極化基板） 屬夷3發Π施例中，陽極化基板10是藉由使銘基金 )之金屬基板14的至少-側陽極化 j Γ %極化基板1G可為如圖6左側所說明之每 側上形成有陽極化膜12之鋁基質u， 說明之任—侧上形成有陽極化膜U之喊質 23 201044626 膜12疋主要由ai2〇3組成之膜。 較佳地，基板10是如圖6左側所說明之鋁基質丨1的 基板’在每一側上形成有陽極化膜12以防止基板由於鋁與Ο 201044626 An example structure of a magnetron boring facility will be described with reference to FIG. The sputtering apparatus 101 and the RF and masking machines are also provided with the same components as 1nn 4 η /, θ h $ f _ and will not be further described in detail herein. The basic structure of the magnet device 103 is the same as that of the RF sputtering device except that the magnet unit ι 5 having a plurality of magnets U5M is connected to the plasma electrode 112 and the sister is mounted thereon. In the magnetron, a high frequency AC voltage is applied to the electric f-electrode 112, wherein a magnetic field is generated by the magnet early 115 in the vicinity of the magnet. A dc power can be applied to the plasma electrode 112. The magnetron can effectively read the dry material by keeping the electro-acoustic remote board (4) T 〇 < dual magnetron sputtering apparatus> An example structure of the dual magnetron subtraction apparatus will be described with reference to FIG. The same reference numerals are given to the magnetron plating apparatus 103_ and will not be further described in detail herein. The basic structure of the dual magnetic control device HM is the same as that of the magnetic control money mining device 1-3, except that the electropolymer electrode 112 and the magnet unit 115 are provided. The two plasma electrodes 112 are connected to a common high frequency Ac power source ι6, wherein any of the electrodes is driven as a cathode and the other is driven by a secret. In the dual magnetron plane, a high frequency AC voltage is applied between the two electrodes 112 and a film is formed by changing the polarity of each electrode 112. Double magnetic (four) plated with a low conductivity sister film. Furthermore, the method can make the ship's edge (4). Double-reverse anti-news_Use the same equipment as the magnetic control reactor and the same as the DC reactive money, for example, the mixed gas of gas, gas, and Wei gas to be electropolymerized as a gas 19 201044626 G. The film formation conditions used in the production method of the present invention are not subject to any particular limitation. In either method, the vacuum of the background is, for example, from about 1 χ 1 〇 '5 to about ΙΟχΗΤ 5 Pascals (Pa). For DC (reactive) sputtering or pulsed DC (reactive) machine money, 'preferably by changing the flow rate of the introduced gas, applying voltage and, in addition, for pulsed DC sputtering, depending on the structure and size of the device, Film formation is performed after the gas type and its like factors change the pulse period and the pulse width to obtain optimum conditions for film formation speed, film quality, film formation stability, and the like. When the film is formed, the substrate temperature generally increases to 100 due to accumulation. (: to 30 〇 π so that the substrate does not need to be heated, but cooling may be required sometimes. For DC magnetron (reactive) splashing, there is no particular limitation on the film formation conditions for RF (reactive) sputtering. It is preferable to perform film formation after substantially obtaining the optimum conditions in the same manner as the above-described DC (anti-two-effect) sputtering except for application of high-frequency power. The case is also applicable to DC magnetron (reactive) sputtering. Plating. 别 ί 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双The film formation is performed after the optimum conditions are obtained such that the two electropolymers are operated as the anode and the cathode. [Target] The target used for the manufacture of the first and second photoelectric conversion devices of the present invention (sputter target) The material is also novel and is included in the present invention. 20 Ο ❹ 201044626 That is, the target of the present invention is a light material for sputtering to form a metal supply layer to be provided in a photoelectric conversion device, Electricity and contains - or multiple types of metal and / or There is no particular limitation on the total amount of the metal or/or alkaline earth metal in the tree of the Ming Dynasty, and the _ sub% is more preferably 5 atom% to (four) sub%=_\ Ϊ % % To the atomic %. It is known that an excessive amount of such a substance may be hindered by a stable discharge when it is formed into a DC antimony ore. The substrate of the dry material of the present invention is preferably a semiconducting substance. - ❹ 叙 触 触 触 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7促进 Promoted by DC (reactive) by improving the conductivity (reduction resistance) by adding an element selected from at least one of the groups consisting of at least 3,Ga, and B. That is, it is preferably used. Containing at least one = the elements of the group _ group cut out of the stone, ^ under the conditions of the October, can be by DC (reactive) _, pulse DC (anti-magnetism (reactive) 贱 ^ ^ There is no particular limitation on the total amount of k in the group of at least one of A1'Ga and b, as long as it The specific resistance of the material may be reduced to a range of 1 ohm/cm or less, and the total amount may be not less than 10-4 atom%, but a larger amount is more preferable. Therefore, it is preferably 丨 atom% to (4) % and more preferably 1 G atom% to 20 = 21 201044626 %. In addition, such as [^ 矽 dry materials in order to make the dry material Muller analog soil elements can be included in the layer thermal expansion coefficient", the secret furnace is closer Preferably, the t-material of the wire or photoelectric conversion t comprises a single-faced money compound. The sister of a preferably comprises at least a sodium salt selected from the group consisting of a domain-type nano- and a carbon-dioxide group. Such materials may become the cause of hindering stable discharge during Dc deplating. The dry material of this month is preferably sintered by casting and sintering a mixture of sodium salt powder (such as NaF sterling) and 11 powder/powder. Body (which can be inevitable for this package 3). It is more preferable that the present invention is a sintered body obtained by praying and sintering a sodium salt powder and a tantalum powder and further containing a powder containing ai powder, Ga powder, and powder containing B powder (which may contain inevitable Impurities). The use of the target of the present invention makes it possible to form an alkali (earth) metal supply layer with high productivity and to manufacture a photoelectric conversion device having excellent photoelectric conversion efficiency with ruthenium productivity. '[Photoelectric Conversion Device] The structure of the photoelectric conversion device according to the embodiment of the present invention will be described with reference to the accompanying drawings. Fig. 5 is a longitudinal schematic cross-sectional view of the photoelectric conversion device. Fig. 6 is a schematic cross-sectional view of an anodized substrate illustrating the structure of the substrate, and Fig. 7 is a perspective view of the anodized substrate illustrating a method of manufacturing the substrate. In the drawings, the components are not to scale to facilitate visual recognition. 22 201044626 The photoelectric conversion device 1 is a device manufactured by the above-described conversion device manufacturing method of the present invention. The photoelectric conversion stack structure as a device of its basic structure, complex + octapole 20, find the conversion semiconductor layer 3G rushing pole (back contact electricity is stacked on the substrate 1G in this order. The lower upper electrode % is "photoelectric conversion layer" The electro-conversion semiconductor layer is referred to as a photoelectric conversion device i, which comprises (4) a substrate ω and a strontium (earth) metal supply layer 70, which comprises - or a plurality of β, / or soil-checking metals and when forming a photoelectric conversion layer = metal and In the longitudinal cross-sectional view of the one or more noodle gold (4) layers, the photoelectric conversion device has the following: = ΓΓ, passing through the photoelectric conversion layer 3〇 and the buffer layer 4〇 == layer 3°, buffer _ The above configuration can provide a structure in which the device is up to: 3 = multi-cell (in addition, this can obtain a structure in which one cell c is powered (four) is connected in series to the electrode 20 below the adjacent cell c. (Anodized substrate In the embodiment of the invention, the anodized substrate 10 is anodized by at least one side of the metal substrate 14 of the foundation. The substrate 1G can be polarized on each side as illustrated on the left side of FIG. An aluminum substrate u having an anodized film 12 is formed, and an anode is formed on the side The film of the film U 23 201044626 The film 12 is mainly composed of a film of ai 2 〇 3. Preferably, the substrate 10 is an aluminum substrate 丨 1 substrate as illustrated on the left side of FIG. 6 is anodized on each side Membrane 12 to prevent the substrate from being aluminum

Al2〇3之間的熱膨脹係數差而彎曲，以及在裝置製造製矛呈 期間膜由於彎曲而脫離。用於兩側之陽極化方法可包^ 如藉由塗覆絕緣材料並行執行陽極化之方法以 侧陽極化之方法。 &肉 當在陽極化基板10之每—側上形成陽極倾12時， 較佳形成兩個具有實質上相同膜厚度之陽極化膜，或考慮 每側之間的熱應力平衡而使得所形成之上面不提供 轉，層以及-些其他層之陽極鋪12 _厚度比另一側 之陽極化膜12的膜厚度略厚。 11 (Japanese Industrial tan ar，JIS) i_純紹或叙與另一種金屬元 =合金、A1_Mg合金、从施询合金歸 二孟、A1-Sl合金、A1姆Si或其類似物㈤她聰 二二（日本λ 第 4 版，—Light Metal AssocIation， 1-5頁以及第抓功頁，溯）。金屬 體溶液狀態之微量各種金屬元素，諸如Fe、S1、Mn、1 口 Mg、fr、Zn、Bi、Ni、Ti以及其類似物。 ㈣光、由將作為陽極之視f要經清洗、藉由拋光 ΐΐ 之銘基質11與陰極一起浸沒於電 解質中’且在陽極與陰極之間施加 電解質無任限m 24 201044626 類型或兩種或兩種以上類型之酸的酸性電 = 鉻酸、乙二酸、丙二酸傭、 本石KS文、胺基-石頁酸以及其類似物。 6，雜化條件無任何特別限制，其視所用電解質而The coefficient of thermal expansion between Al2〇3 is poor and curved, and the film is detached due to bending during the manufacture of the spear. The anodizing method for both sides may include a method of performing side anodization by performing anodization in parallel by coating an insulating material. & Meat When forming an anode tilt 12 on each side of the anodized substrate 10, it is preferred to form two anodized films having substantially the same film thickness, or to form a thermal stress balance between each side. The anode layer 12 of the layer and the other layers is not slightly thicker than the film thickness of the anodized film 12 on the other side. 11 (Japanese Industrial tan ar, JIS) i_纯绍 or 叙 with another metal element = alloy, A1_Mg alloy, from the alloy to the second Meng, A1-Sl alloy, A1 Si Si or its analogues (5) she Cong Er Second (Japan λ 4th edition, - Light Metal AssocIation, 1-5 pages and the first page, traced). A trace amount of various metal elements in the state of the metal solution, such as Fe, S1, Mn, a port of Mg, fr, Zn, Bi, Ni, Ti, and the like. (4) The light, which is to be cleaned as an anode, is immersed in the electrolyte together with the cathode by polishing the substrate 11 and the electrolyte is applied between the anode and the cathode without any m 24 201044626 type or two or Acidic electricity of two or more types of acids = chromic acid, oxalic acid, malonic acid, native KS, amino-salt and analogs thereof. 6, the hybridization conditions are not subject to any particular limitation, depending on the electrolyte used

件，例如以下是適當的：電解質濃度為 貝里〇至8〇質篁％ ;溶液溫度為5〇c至85〇c ;電流密度 Ί.005安培/平方公分（A/cm2)至〇 6〇安培/平方公分； 電壓為1伏至200伏；且電解時間為3分鐘至5〇〇分鐘。 關於電解負，可較佳使用硫酸、磷酸、乙二酸或其混 合物。當使用所述電解質時，以下條件為較佳：電解質濃 度為4質量％至30質量％，電流密度為〇 〇5安培/平方公 分至0.30安培/平方公分，且電壓為3〇伏至15〇伏。 如圖7中所示，當使鋁基質u陽極化時，在實質上 垂直於表面11s之方向上自表面lls發生氧化反應，且形 成基於Α1ζ〇3之陽極化膜12。藉由陽極化所產生之陽極化 膜12具有的結構為多個在平面圖中各具有實質上規則六 k形形狀之細柱狀體緊密排列。每一細柱狀體12a具有實 質上位於中心、實質上在深度方向上自表面lls線性延伸 之細孔12b，且每一細柱狀體12a之底表面具有圓形形狀。 通常’在細柱狀體12a之底部區域形成無任何細孔i2b之 障壁層（一般厚度為0.01微米（从m)至0.4微米）。 對陽極化膜12之細孔12b的直徑無任何特別限制。 自表面光滑度以及絕緣性質之觀點看，細孔12b之直徑較 佳為200奈米（nm)或更小’且更佳為1〇〇奈米或更小。 25 201044626 有可能使細孔12b之直徑減小至約10奈米。 對陽極化膜12之細孔12b的孔隙密度無任何特別限 制。自絕緣性質之觀點看，細孔12b之孔隙密度較佳為1〇〇 個/平方微米至1〇,〇〇〇個/平方微米，且更佳為1〇〇個/平方 微米至5,〇〇〇個/平方微米，且尤其較佳為1〇〇個/平方微米 至1，000個/平方微米。 ^與無孔氧化鋁單層膜相比，多孔陽極化膜具有低揚氏 模數（Young’s modulus )，此產生高抗彎曲性以及高抗斷裂 性（所述斷裂由於在高溫下存在熱膨脹係數差而出現）。 =意，可對陽極化膜12之細孔⑽執行任何已知 封製程。舉例而言，使財性電㈣（諸如餐） =1=進:電解處理可產生緻密陽極化膜(無孔 有較厚障^ ί曰代安置多孔細柱狀體之陽極化膜。具 多孔藉由首先使用酸性電解質形成The following are suitable, for example, as follows: electrolyte concentration is Beri 〇 to 8 篁 篁 %; solution temperature is 5 〇 c to 85 〇 c; current density Ί .005 amps / cm ^ 2 (A / cm 2 ) to 〇 6 〇 Amperes per square centimeter; voltage is from 1 volt to 200 volts; and electrolysis time is from 3 minutes to 5 minutes. As the electrolysis negative, sulfuric acid, phosphoric acid, oxalic acid or a mixture thereof can be preferably used. When the electrolyte is used, the following conditions are preferred: the electrolyte concentration is 4% by mass to 30% by mass, the current density is 〇〇5 amps/cm 2 to 0.30 amps/cm 2 , and the voltage is 3 volts to 15 Torr. Volt. As shown in Fig. 7, when the aluminum substrate u is anodized, an oxidation reaction occurs from the surface 11s in a direction substantially perpendicular to the surface 11s, and an anodized film 12 based on Α1ζ〇3 is formed. The anodized film 12 produced by the anodization has a structure in which a plurality of fine columns each having a substantially regular hexagonal shape in plan view are closely arranged. Each of the thin columns 12a has pores 12b which are substantially centrally located and extend linearly from the surface lls substantially in the depth direction, and the bottom surface of each of the thin columns 12a has a circular shape. Usually, a barrier layer having no fine pores i2b (generally having a thickness of 0.01 μm (from m) to 0.4 μm) is formed in the bottom portion of the fine columnar body 12a. There is no particular limitation on the diameter of the pores 12b of the anodized film 12. The diameter of the pores 12b is preferably 200 nm or less and more preferably 1 nm or less from the viewpoint of surface smoothness and insulating properties. 25 201044626 It is possible to reduce the diameter of the fine hole 12b to about 10 nm. There is no particular limitation on the pore density of the pores 12b of the anodized film 12. From the viewpoint of the insulating property, the pore density of the fine pores 12b is preferably from 1 Å/m 2 to 1 Å, 〇〇〇/m 2 , and more preferably from 1 Å to 5 μm. One unit / square micrometer, and particularly preferably from 1 inch / square micron to 1,000 / square micron. ^ Compared with the non-porous alumina monolayer film, the porous anodized film has a low Young's modulus, which produces high bending resistance and high fracture resistance (the fracture has a difference in thermal expansion coefficient at high temperatures) And appear). = It is intended that any known sealing process can be performed on the pores (10) of the anodized film 12. For example, to make a financial electricity (four) (such as meals) = 1 = advance: electrolytic treatment can produce a dense anodized film (no pores have thicker barriers ^ 曰 generation of porous thin column anodized film. Porous By first using an acidic electrolyte

CJ 之膜。⑭、絲成。㈣障壁層可產生具有極佳絕緣性質 電轉=面。:2無， 棱度Ra較佳t 要高表面光滑度。表面粗 極化膜12之厚度無任何特·制H或更小。 肩具有令人滿意的絕 制。％極化膜只 衝擊弓丨起之浐作从 b 及足以在處置時防止由機;Η 起之才貝傷的表面硬度 ^万止由機械 問題。因此，她厚度 予起可撓性 子度在0.5微未至5〇微米之 26 201044626 或電壓的 度可基於恆定電流電解或恒定電壓電解時之電流 量值以及電解時間來控制。 、、、較，地，考慮到基板10之機械強度以及減小厚产 ，少重1，在陽極化之前，金屬基質u之厚度為例如^仍 耄米至〇.6毫米，且更佳為0.1毫米至0.3亳米。當考· 緣性質/機械強度以及減小厚度與減少重量時，陽極&膜 12之厚度的較佳範圍為〇.丨微米至ι〇〇微米。 、 ΟThe film of CJ. 14, silk into. (4) The barrier layer can produce excellent insulation properties. : 2 None, the edge Ra is better t to have a high surface smoothness. The thickness of the surface rough polarizing film 12 does not have any special H or less. The shoulder has a satisfactory seal. The % polarized film is only scratched by the impact bow from b and is sufficient to prevent the machine from being damaged at the time of disposal; Therefore, her thickness is given at a flexibility of 0.5 μm to 5 μm. 26 201044626 or the degree of voltage can be controlled based on the current magnitude of the constant current electrolysis or constant voltage electrolysis and the electrolysis time. And, in comparison with the mechanical strength of the substrate 10 and the reduction of the thickness, the weight is less than 1. Before the anodization, the thickness of the metal substrate u is, for example, still from 耄 to 6 mm, and more preferably 0.1 mm to 0.3 mm. The thickness of the anode & film 12 is preferably in the range of 〇. 丨 micron to ι 〇〇 micrometer when the thickness/mechanical strength and thickness reduction and weight reduction are measured. Ο

如已描述’當於超過5〇(rc之高溫下形成膜時，基板與 化，物半導體層3〇之間的線性熱膨脹係數差較佳/於；^ l〇_6/°C，且更佳小於3xl〇-6/t：。因此，較佳基板可藉由使 用由鋁基質（第一金屬基質）以及熱膨脹係數與光電轉換 半導體層30相當且具有高硬度以及高耐熱性之第二金屬 基質Π整體形成的金屬基板（被覆材料）14，且在鋁基質 上提供陽極化膜12來提供（圖8)。 圖8中所示之陽極化基板1〇，包含由金屬基質13以及 整合於金屬基質13之一個表面上的|g基質11形成之金屬 基板14 (被覆材料14)，以及具有藉由使鋁基質u之表面 %極化而形成作為電絕緣層之多孔結構的铭陽極化膜 12。因此，陽極化基板10,具有金屬基質13/鋁基質u/陽極 化膜12之三層結構。 金屬基質13之材料可為任何金屬，只要與鋁相比， 其具有較小線性熱膨脹係數、較高硬度以及較高耐熱性即 可。所述材料可適當地根據基於基板〗〇，之應力計算結果以 及提供於基板上之光電轉換電路的組態以及材料性質來選 27 201044626 擇。 在諸如CI(G)S之化合物半導體層的情況下，可 鋼材料、合金鋼或其類似物作為金屬基質13之材料。^例 較佳使用例如日本未審查專利公開案第細印纖 广了所述:之碳鋼以及奥氏體-鐵磁體不鏽鋼 =t:=:t:_esssteel> 此處’金物 13 較佳 赫姑ί官稍後將詳細描述待形成於陽極化基板1G上之光電 _ ^ 1'用作光轉換層之主要化合物半導體的線性熱膨 ，對^代表第m_v族化合物之仏〜為$議％， =代表第π_νι族化合物之CdTe為4⑽.％，且對於 代表第I-IIIf族化合物之Cu(InGa)Se2為咖〇 6/。〔。 nif基質13之厚度可基於半導縣置在製造製程以 A之可處置性（強度以及可撓性）任意地設定，但 幸父佳為1 〇微米至1毫米。 鋁基賀11可藉由任何方法與金屬基質接合，只要 二成夠整觀接合所述基質且獲得黏著性即可 。舉例而 二’所述基質可藉由使錢積於金屬基質13上、氣相製程 =如濺鑛）、將金屬基質13浸潰於溶融紹中之埶浸鑛、使 =水性電解質之ls麵或在表面清洗後之壓力接合來接 合在一起。 一，材料14可藉由將作為陽極之被覆材料Η與陰趣 low又於電解貝中且在陽極與陰極之間施加電壓來陽极 匕此處’當金屬基質13接觸電解質時，由金屬基質13 28 201044626 以及鋁基質Π形成自給電池（local battery )，以致需要用 遮罩使接觸電解質之金屬基質13絕緣。更特定言之，在具 有金屬基質13以及鋁基質11之雙層結構的被覆材料14 之情況下，有必要使鋼基質13之表面以及其端面絕緣。 陽極化處理與上述相同。 ΟAs described above, when the film is formed at a high temperature of more than 5 Å (the film is formed at a high temperature of rc, the linear thermal expansion coefficient difference between the substrate and the semiconductor layer 3 较佳 is preferably / ^ 〇 _ 6 / ° C, and more Preferably, it is less than 3xl〇-6/t: Therefore, a preferred substrate can be obtained by using a second metal having an aluminum matrix (first metal substrate) and a thermal expansion coefficient comparable to that of the photoelectric conversion semiconductor layer 30 and having high hardness and high heat resistance. The substrate is integrally formed of a metal substrate (coating material) 14 and an anodized film 12 is provided on the aluminum substrate to provide (Fig. 8). The anodized substrate 1 shown in Fig. 8 is comprised of a metal substrate 13 and integrated therein. a metal substrate 14 (coated material 14) formed of a |g substrate 11 on one surface of the metal substrate 13, and an anodized film having a porous structure formed as an electrically insulating layer by polarizing the surface of the aluminum substrate u 12. Thus, the anodized substrate 10 has a three-layer structure of a metal matrix 13 / an aluminum matrix u / anodized film 12. The material of the metal matrix 13 can be any metal as long as it has a smaller linear thermal expansion coefficient than aluminum. , higher hardness and higher heat resistance The material may be appropriately selected according to the calculation result based on the substrate, the configuration of the photoelectric conversion circuit provided on the substrate, and the material properties. In the compound semiconductor layer such as CI(G)S In the case of the steel material, the alloy steel or the like, the material of the metal substrate 13 is preferably used, for example, in the Japanese Unexamined Patent Publication, the entire disclosure of which is: carbon steel and austenite- Ferromagnetic stainless steel = t:=:t:_esssteel> Here, 'golden material 13' will be described in detail later. The photoelectric compound to be formed on the anodized substrate 1G is used as the main compound of the light conversion layer. The linear thermal expansion of the semiconductor, the ratio of ^ represents the m_v compound to 议%, = represents the CdTe of the π_νι compound is 4 (10).%, and for the Cu(InGa)Se2 representing the group I-IIIf compound Curry 6/. [. The thickness of the nif matrix 13 can be arbitrarily set based on the handleability (strength and flexibility) of A in the manufacturing process of the semi-conducting county, but the good father is preferably 1 〇 micrometer to 1 mm. Aluminum base He can be used by any method and metal Bonding, as long as 20% is sufficient to join the substrate and obtain adhesion. For example, the substrate can be accumulated on the metal substrate 13, vapor phase process (such as sputtering), metal The substrate 13 is immersed in the leaching of the smelting in the smelting, and the ls faces of the aqueous electrolyte or the pressure bonding after the surface cleaning are joined together. First, the material 14 can be an anode 匕 by applying a voltage between the coating material as the anode and the cathode and the anode and the cathode. When the metal matrix 13 contacts the electrolyte, the metal matrix 13 28 201044626 and the aluminum matrix Π form a local battery, so that a metal substrate 13 contacting the electrolyte needs to be insulated with a mask. More specifically, in the case of the covering material 14 having the two-layer structure of the metal substrate 13 and the aluminum substrate 11, it is necessary to insulate the surface of the steel substrate 13 and its end faces. The anodizing treatment is the same as described above. Ο

如上文所述’陽極化基板10'包含由金屬基質13以及 整合於金屬基質13之一個表面上的鋁基質Η形成之被覆 材料14,以及形成於被覆材料14之鋁基質u的表面上之 陽極化膜。因此，陽極化基板1〇,可甚至防止伴隨高溫（不 小於500°C )化合物半導體之光電轉換層30在基板上形成 膜的製程中陽極化膜12產生斷裂，藉此可維持高絕緣能 力。此可能歸因於鋁基質n之熱膨脹受限於金屬基質= 且整個被覆材料14之熱膨脹受金屬基f 13之熱膨^性 控制’且由金屬基質13與陽極化膜12之間的熱膨脹差所 引起之陽極化膜12的應力因在金屬基f 13與陽極化膜12 之間插入具有小彈性模數之鋁基質11來減輕。 、 (光電轉換層） 層之=二===對所述As described above, the anodized substrate 10 includes a covering material 14 formed of a metal substrate 13 and an aluminum matrix enthalpy integrated on one surface of the metal substrate 13, and an anode formed on the surface of the aluminum substrate u of the covering material 14. Film. Therefore, by anodizing the substrate, the anodized film 12 can be prevented from being broken even in the process of forming a film on the substrate by the photoelectric conversion layer 30 of the compound semiconductor with high temperature (not less than 500 ° C), whereby high insulating ability can be maintained. This may be attributed to the fact that the thermal expansion of the aluminum matrix n is limited to the metal matrix = and the thermal expansion of the entire covering material 14 is controlled by the thermal expansion of the metal matrix f 13 and the difference in thermal expansion between the metal matrix 13 and the anodized film 12 The induced stress of the anodized film 12 is alleviated by inserting the aluminum matrix 11 having a small elastic modulus between the metal base f 13 and the anodized film 12. , (photoelectric conversion layer) layer = two === for the

Go種:具有黃銅礦結構的化合物半導體: ί Ibi Γ 為的化合物半導體： 換層之主絲她物 29 201044626 物半導體：至少一種類型之由Cu以及Ag所構成的族群中 選出之第lb族元素’至少一種類型之由a卜Ga以及In所 構成的族群中選出之第Illb族元素，以及至少一種類型之 由S、Se以及Te所構成的族群中選出之第vib族元素。 上述化合物半導體包含CuA1S2、CuGaS2、CuInS2、 CuAlSe2、CuGaSe2、CuInSe2 ( CIS )、AgAlS2、AgGaS2、 AgInS2、AgAlSe2、AgGaSe2' AgInSe2、AgAlTe2、AgGaTe2、 AgInTe2 ' Cu(Ini.xGax)Se2 ( CIGS ) ^ Cu(Ini.xAlx)Se2 ' Cu(In!.xGax) (S,Se)2 ' Ag(In,.xGax)Se2 > Ag(In,.xGax) (S,Se)2 以及其類似物。 光電轉換層30尤其較佳包含CuInSe2 (CIS)或與Ga 一起固化之化合物’亦即Cu(In，Ga)S2 (CIGS)。CIS以及 CIGS是具有黃銅礦結構之半導體且據報導其具有高光吸 收速率以及高能量轉化效率。此外，其耐久性極佳且由曝 光以及其類似因素引起之轉換效率退化較小。 光電轉換層30包含用於獲得所欲半導體導電類型之 雜質。所述雜質可藉由自相鄰層擴散及/或藉由主動摻雜而 包含於光電轉換層30中。 光電轉換層30可具有第MII-VI族半導體之組成元素 及/或雜質的濃度分佈，且可具有多個不同半導體導電率 (semiconductivity)之層區域，諸如n型、p型、丨=及 其〇= 員型二舉例而言，在CIGS系統中’若光電轉換層 之Ga含量在厚度方向上分佈5則可控制能帶 載流子遷移率以及其類似物，藉此可設計較高光電轉換= 30 201044626 率值。 、光電轉換層30可包含一或多種類型除第族半 導體外之半導體。除第ι·πι·νι族半導體外之半導體可包 含第ivb族元素之半導體，諸如矽（第IV族半導體”第 Illb族το素與第vb族元素之半導體，諸如GaAs (第 族半導體）；以及第lib族與第VIb族元素之半導體，Go species: compound semiconductor with chalcopyrite structure: ί Ibi 化合物 compound semiconductor: the main layer of the layered material 29 201044626 semiconductor: at least one type of lb selected from the group consisting of Cu and Ag The element 'at least one type of the group Illb element selected from the group consisting of a Ga and In, and at least one type of the selected vib element selected from the group consisting of S, Se, and Te. The compound semiconductor includes CuA1S2, CuGaS2, CuInS2, CuAlSe2, CuGaSe2, CuInSe2 (CIS), AgAlS2, AgGaS2, AgInS2, AgAlSe2, AgGaSe2'AgInSe2, AgAlTe2, AgGaTe2, AgInTe2'Cu(Ini.xGax)Se2(CIGS)^Cu( Ini.xAlx)Se2 'Cu(In!.xGax) (S,Se)2 'Ag(In,.xGax)Se2 > Ag(In,.xGax)(S,Se)2 and analogs thereof. The photoelectric conversion layer 30 particularly preferably contains CuInSe2 (CIS) or a compound which solidifies together with Ga', that is, Cu(In,Ga)S2 (CIGS). CIS and CIGS are semiconductors with a chalcopyrite structure and are reported to have high light absorption rates and high energy conversion efficiencies. In addition, its durability is excellent and the conversion efficiency degradation caused by exposure and the like is small. The photoelectric conversion layer 30 contains impurities for obtaining a conductivity type of a desired semiconductor. The impurities may be included in the photoelectric conversion layer 30 by diffusion from an adjacent layer and/or by active doping. The photoelectric conversion layer 30 may have a concentration distribution of constituent elements and/or impurities of the MII-VI semiconductor, and may have a plurality of layer regions of different semiconductor conductivity, such as n-type, p-type, 丨= and 〇 = member type 2 For example, in the CIGS system, if the Ga content of the photoelectric conversion layer is distributed in the thickness direction 5, the carrier mobility can be controlled and its analog can be designed, thereby designing a higher photoelectric conversion. = 30 201044626 Rate value. The photoelectric conversion layer 30 may comprise one or more types of semiconductors other than the group semiconductor. A semiconductor other than the ι·πι·νι semiconductor may include a semiconductor of the ivb element, such as a semiconductor of Group IV semiconductor Group Illb and a Group Vb element such as GaAs (Group Semiconductor); And semiconductors of the lib and group VIb elements,

CdTe (第㈣族半導體）。 光電轉換層30可包含任何除半導體以及雜質外用於 使半導體變成所欲導電型之任意組份，其限制條件為不影 響性質。 關於形成CIGS層之方法，已知1 )多源共蒸發 (multi-source co-evaporation)、2 )硒化（selenization)、3 ) >賤鐘、4)混合藏鑛（hybrid sputtering)、5)機械化學製程 (mechano-ehemical process )以及其類似方法。CdTe (Group (4) semiconductors). The photoelectric conversion layer 30 may contain any component other than a semiconductor and impurities for making the semiconductor into a desired conductivity type, with the restriction being non-impact property. Regarding the method of forming the CIGS layer, it is known that 1) multi-source co-evaporation, 2) selenization, 3) > cuckoo clock, 4) hybrid sputtering, 5 ) Mechano-ehemical process and similar methods.

1 )關於多源共蒸發，已知三階段生長製程（J.R. Tuttle 等人，"The Performance of Cu(In，Ga)Se2-Based Solar Cells ❹ in Conventional and Concentrator Applications", Material Research Society (MRS) Symposium Proceedings,第 426 卷， 第143-151頁，1996，以及其類似文獻）以及EC群組之共 蒸發（L. Stolt 等人，"THIN FILM SOLAR CELL MODULES BASED ON CU (IN, GA) SE2 PREPARED BY THE COEVAPORATIONMETHOD", Proceedings of the 13th European Photovoltaic Solar Energy Conference,第 1451-1455頁，1995，以及其類似文獻）。 31 201044626 所述三階段生長製程是如下方法：於高度真空下於 300°C之基板溫度下使In、Ga以及Se同時沈積，接著藉由 使基板溫度增加至500°C至56(TC使Cu以及se同時沈積， 且進一步使In、Ga以及Se同時沈積。所述EC群組之共 蒸發是在初始階段使C u過量之CIG S沈積且在稍後階段使 In過量之CIGS沈積的方法。 改良CIGS膜之結晶的上述方法之修改包含以下： a)使用離子化Ga之方法（H. Miyazaki等人，’’Growth of high-quality CuGaSe2 thin films using ionized Ga precursor”，Physica status solidi (a),第 203 卷，第 11 期，第 2603-2608頁，2006，以及其類似文獻）； b )使用裂解Se之方法（M. Kawamura等人，"Growth of Cu (In^xGax) Se2 thin films using cracked selenium", Proceedings of the 68th Autumn Meeting of the Japan Society of Applied Physics (2007 年在北海道工業大學 (Hokkaido Institute of Technology )舉行），演講編號 7p-L-6，以及其類似文獻）； c )使用自由基Se之方法（S. Ishizuka等人， "Preparation of Cu(In1.xGax)Se2 thin films using a Se-radical beam source and solar cell performance", Proceedings of the 54th Spring Meeting of the Japan Society of Applied Physics (2007 年在青山學院大學（Aoyama Gakuin University)舉 行)，演講編號29p-zw-10，以及其類似文獻）；以及 d)使用光激發製程之方法（Y. Ishii等人，"High Quality 32 201044626 GIGS Thin Films and Devices by Photo-Excited Deposition Process", in the Proceedings of the 54th Spring Meeting of the Japan Society of Applied Physics (2007 年在青山學院大 學（Aoyama Gakuin University )舉行），演講編號 29p-ZW-14 ’以及其類似文獻）。 2)亦稱作兩階段生長製程之硒化是如下方法：首先 藉由濺鍍、沈積或電沈積形成疊層膜之金屬前驅物（諸如 ⑶層/111層、（Cu_Ga)層/In層或其類似物），且接著在硒蒸 氣中或在硒化氳中經由熱擴散將金屬前驅物加熱至450°C 至550C ’形成砸化合物’諸如CuGni-xGaJSez。此方法稱 作氣相硒化。此外，固相硒化是使固相硒沈積於金屬前驅 物膜上且藉由固相擴散，使用固相硒作為硒源使金屬前驅 物石西化。 在硒化時，已知以下兩種用於防止硒化時出現之快速 體積膨脹的方法：預先將硒以某一比率混合於金屬前驅物 膜中（T. Nakada 等人，”CuInSe2-based solar cells by 〇 Se-vapor selenization from Se-containing precursors", Solar1) For multi-source co-evaporation, a three-stage growth process is known (JR Tuttle et al., "The Performance of Cu(In,Ga)Se2-Based Solar Cells ❹ in Conventional and Concentrator Applications", Material Research Society (MRS) Symposium Proceedings, Vol. 426, pp. 143-151, 1996, and similar documents) and co-evaporation of EC groups (L. Stolt et al., "THIN FILM SOLAR CELL MODULES BASED ON CU (IN, GA) SE2 PREPARED BY THE COEVAPORATION METHOD HOD ", Proceedings of the 13th European Photovoltaic Solar Energy Conference, pp. 1451-1455, 1995, and similar documents). 31 201044626 The three-stage growth process is a method of simultaneously depositing In, Ga, and Se at a substrate temperature of 300 ° C under high vacuum, and then increasing the substrate temperature to 500 ° C to 56 (TC makes Cu And se simultaneously deposits, and further deposits In, Ga, and Se simultaneously. The co-evaporation of the EC group is a method of depositing C u excess CIG S at an initial stage and depositing In excess CIGS at a later stage. Modifications of the above method for improving the crystal of the CIGS film include the following: a) Method of using ionized Ga (H. Miyazaki et al., ''Growth of high-quality CuGaSe2 thin films using ionized Ga precursor', Physica status solidi (a) , vol. 203, No. 11, pp. 2603-2608, 2006, and similar documents); b) using a method of cleavage Se (M. Kawamura et al., "Growth of Cu (In^xGax) Se2 thin films Using cracked selenium", Proceedings of the 68th Autumn Meeting of the Japan Society of Applied Physics (held at the Hokkaido Institute of Technology in 2007), speech number 7p-L-6, and Similar to the literature); c) the method of using free radical Se (S. Ishizuka et al., "Preparation of Cu(In1.xGax)Se2 thin films using a Se-radical beam source and solar cell performance", Proceedings of the 54th Spring Meeting of the Japan Society of Applied Physics (held at Aoyama Gakuin University in 2007), lecture number 29p-zw-10, and similar documents); and d) methods using photoexcitation processes (Y. Ishii et al., "High Quality 32 201044626 GIGS Thin Films and Devices by Photo-Excited Deposition Process", in the Proceedings of the 54th Spring Meeting of the Japan Society of Applied Physics (2007 at Aoyama Gakuin University) Held), speech number 29p-ZW-14 'and its similar literature). 2) Selenization, also known as two-stage growth process, is a method of first forming a metal precursor of a laminated film by sputtering, deposition or electrodeposition (such as (3) layer / 111 layer, (Cu_Ga) layer / In layer or Its analog), and then the metal precursor is heated to a temperature of 450 ° C to 550 ° C in a selenium vapor or in a cesium selenide to form a bismuth compound such as CuGni-xGaJSez. This method is called gas phase selenization. In addition, solid phase selenization is the deposition of solid phase selenium on the metal precursor film and diffusion by solid phase, using solid phase selenium as the selenium source to make the metal precursor stone. In the case of selenization, the following two methods for preventing rapid volume expansion occurring during selenization are known: Selenium is previously mixed in a metal precursor film at a certain ratio (T. Nakada et al., "CuInSe2-based solar Cells by 〇Se-vapor selenization from Se-containing precursors", Solar

Energy Materials and Solar Cells,第 35 卷，第 209-214 頁， 1994,以及其類似文獻）；以及藉由在金屬薄膜之間插入硒 來形成多層前驅物之方法，例如Cu層/In層/Se層…-Cu層 /In 層/Se 層（T. Nakada 等人，'THIN FILMS OF CuInSe2 PRODUCED BY THERMAL ANNEALING OF MULTILAYERS WITH ULTRA-THIN STACKED ELEMENTAL LAYERS", Proceedings of the 10th European 33 201044626Energy Materials and Solar Cells, Vol. 35, pp. 209-214, 1994, and similar documents); and methods for forming multilayer precursors by intercalating selenium between metal thin films, such as Cu layer/In layer/Se Layer...-Cu layer/In layer/Se layer (T. Nakada et al., 'THIN FILMS OF CuInSe2 PRODUCED BY THERMAL ANNEALING OF MULTILAYERS WITH ULTRA-THIN STACKED ELEMENTAL LAYERS", Proceedings of the 10th European 33 201044626

Photovoltaic Solar Energy Conference (EUPVSEC)，第 887-890頁，1991，以及其類似文獻）。 此外，作為漸變能帶隙（graded band gap ) CIGS膜形 成方法’知道如下方法：首先使Cu-Ga合金膜沈積，接著 使In膜沈積於其上’且當使膜硒化時，藉由自然熱擴散使 膜厚度方向上之Ga濃度漸變（κ· Kushiya等人，Tech. Digest 9th Photovoltaic Science and Engineering Conf. Miyazaki，1996 (Intn. PVSEC-9, Tokyo 1996)第 149 頁，以 及其類似文獻). 3)關於濺鍍，已知以下方法： a )使用CuInSe2多晶作為乾材之方法； b) 使用Cu2Se以及In2Se3作為靶材且使用H2Se/Ar 混合氣體作為濺鍍氣體之兩源濺鍍法（J.H. Ermer等人, "CdS/CuInSe2 JUNCTIONS FABRICATED BY DC MAGNETRON SPUTTERING OF Cu2Se AND In2Se3”, Proceedings of the 18th IEEE Photovoltaic Specialists Conference,第1655-1658頁，1985，以及其類似文獻）；以 及 c) 在Ar氣體中濺鍍Cu靶材、In靶材以及Se或CuSe 革巴材之三源藏鍛法（T. Nakada等人，"Polycrystalline CuInSe2 Thin Films for Solar Cells by Three-Source Magnetron Sputtering", Japanese Journal of Applied Physics, 第32卷，第2部分，第8B期，第L1169-L1172頁，1993， 以及其類似文獻）。 34 201044626 4) 關於混合濺鍍，已知DC濺鍍Cu以及In金屬且在 上述濺鍍法中僅使Se沈積之混合濺鍍法（T. Nakada等人， "Microstructural Characterization for Sputter-Deposited CuInSe2 Films and Photovoltaic Devices", Japanese Journal of Applied Physics,第 34 卷，第 1 部分，第 9A 期，第 4715-4721頁，1995，以及其類似文獻）。 5) 機械化學製程是如下方法：將根據CIGS之組成的 材料置於行星式球磨機（planet ball mill)中且藉由機械能 ® 混合所述材料以獲得CIGS粉末，接著藉由網版印刷 (screen printing)將所述粉末施力σ於基板上且退火以獲得 CIGS 膜（Τ· Wada 等人，"Fabrication of Cu(In，Ga)Se2 thin films by a combination of mechanochemical and screen-printing/sintering processes", Physica status solidi (a), 第203卷，第11期，第2593-2597頁，2006,以及其類似文 獻）。 其他CIGS膜形成方法包含網版印刷、近接昇華 O ( Pr〇ximity sublimation )、金屬有機物化學氣相沈積 (MOCVD)、喷霧以及其類似方法。舉例而言，具有所需 組成之晶體可藉由在基板上形成包含第lb族元素、第mb 族元素以及第VIb族元素之粒子膜且對所述粒子膜進行熱 解處理（其可於第VIb族元素氛圍下進行）來獲得（曰本 未審查專利公開案第9 (1997)-074065號以及第9 (1997)-074213號，以及其類似文獻）。 圖1 〇說明主要I-III-VI化合物半導體之晶格常數與能 35 201044626 帶隙之間的關係。圖8展示各種能帶隙可藉由改變組成比 率來獲得。當能量大於能帶隙之光子入射於半導體上時， 超過月b帶隙之能1的量變成熱損失。藉由理論計算已知， 在太1%光§晋與能帶隙之間的組合下轉換效率在約1.4電子 伏（eV)至1.5電子伏時變得最大。 舉例而言’可增加Cu(In, Ga)Se2 ( CIGS )中之Ga濃 度、Cu(In, Al) Se2 中之 A1 濃度或 Cu(In, Ga) (S, Se) 2 中之 S濃度以增加能帶隙以便提高光電轉換效率，藉此可獲得 高轉換效率能帶隙。在CIGS之情況下，可將能帶隙調節 在1.04電子伏至1.68電子伏之範圍内。 能帶結構可藉由改變膜厚度方向上之組成比率來漸 變。已知兩種類型之漸變結構，其中一者為能帶隙自光入 射窗一側向相反的電極一側增加之單漸變能帶隙，且其中 另一者為能帶隙自光入射窗一側向PN接面減少且穿過pn 接面後增加之雙漸變能帶隙（T. Dullweber等人，”A new approach to high-efficiency solar cells by band gap grading in Cu(In,Ga)Se2 chalcopyrite semiconductors',, Solar EnergyPhotovoltaic Solar Energy Conference (EUPVSEC), pp. 887-890, 1991, and similar documents). Further, as a graded band gap CIGS film formation method, 'the following method is known: first, a Cu-Ga alloy film is deposited, and then an In film is deposited thereon' and when the film is selenized, by nature Thermal diffusion causes a gradual change in the Ga concentration in the thickness direction of the film (K. Kushiya et al., Tech. Digest 9th Photovoltaic Science and Engineering Conf. Miyazaki, 1996 (Intn. PVSEC-9, Tokyo 1996) p. 149, and the like) 3) Regarding sputtering, the following methods are known: a) a method of using CuInSe2 polycrystal as a dry material; b) a two-source sputtering method using Cu2Se and In2Se3 as targets and using H2Se/Ar mixed gas as a sputtering gas (JH Ermer et al., "CdS/CuInSe2 JUNCTIONS FABRICATED BY DC MAGNETRON SPUTTERING OF Cu2Se AND In2Se3", Proceedings of the 18th IEEE Photovoltaic Specialists Conference, pp. 1655-1658, 1985, and similar documents); and c) Three-source forging method for sputtering Cu target, In target, and Se or CuSe leather in Ar gas (T. Nakada et al., "Polycrystalline CuInSe2 Thin Films for Solar Cells by Three-Source Magnetron Sputtering", Japanese Journal of Applied Physics, Vol. 32, Part 2, Issue 8B, pp. L1169-L1172, 1993, and similar documents. 34 201044626 4) About mixed sputtering, known A mixed sputtering method in which DC is sputtered with Cu and In metal and Se is deposited only in the above sputtering method (T. Nakada et al., "Microstructural Characterization for Sputter-Deposited CuInSe2 Films and Photovoltaic Devices", Japanese Journal of Applied Physics , Vol. 34, Part 1, Issue 9A, pp. 4715-4721, 1995, and similar documents). 5) Mechanochemical process is a method in which a material according to the composition of CIGS is placed in a planetary ball mill and the material is mixed by mechanical energy to obtain CIGS powder, followed by screen printing (screen Printing) applying the powder to the substrate and annealing to obtain a CIGS film (Τ·Wada et al., "Fabrication of Cu(In,Ga)Se2 thin films by a combination of mechanochemical and screen-printing/sintering processes&quot ;, Physica status solidi (a), Vol. 203, No. 11, pp. 2593-2597, 2006, and similar documents). Other CIGS film formation methods include screen printing, near-sublimation O (Pulsing), metal organic chemical vapor deposition (MOCVD), spraying, and the like. For example, a crystal having a desired composition can be formed by forming a particle film containing a Group lb element, a Group mb element, and a Group VIb element on a substrate and subjecting the particle film to pyrolysis (which may be It is carried out in the atmosphere of the group VIb element (Japanese Unexamined Patent Publication No. Hei 9 (1997)-074065 and No. 9 (1997)-074213, and the like). Figure 1 shows the relationship between the lattice constant of the main I-III-VI compound semiconductor and the band gap of energy 2010. Figure 8 shows that various energy band gaps can be obtained by varying the composition ratio. When a photon having an energy greater than the band gap is incident on the semiconductor, the amount of energy 1 exceeding the band b of the month b becomes a heat loss. It is known by theoretical calculation that the conversion efficiency becomes maximum at a combination of too much 1% electron volts (eV) to 1.5 electron volts. For example, 'can increase the Ga concentration in Cu(In, Ga)Se2 ( CIGS ), the A1 concentration in Cu(In, Al) Se2 or the S concentration in Cu(In, Ga) (S, Se) 2 The band gap is increased in order to increase the photoelectric conversion efficiency, whereby a high conversion efficiency band gap can be obtained. In the case of CIGS, the bandgap can be adjusted from 1.04 electron volts to 1.68 electron volts. The band structure can be changed by changing the composition ratio in the film thickness direction. Two types of gradual structures are known, one of which is a single gradual band gap that increases the band gap from one side of the light incident window to the opposite side of the electrode, and the other is a band gap from the light incident window. The lateral PN junction is reduced and the double gradient energy band gap is increased after passing through the pn junction (T. Dullweber et al., "A new approach to high-efficiency solar cells by band gap grading in Cu(In,Ga)Se2 chalcopyrite Semiconductors',, Solar Energy

Materials and Solar Cells,第 67 卷，第 145-150 頁，2001， 以及其類似文獻）。在任一情況下，由光誘發之載流子很可 能由於因能帶結構之梯度在内部所產生之電場所引起的加 速而到達電極’藉此降低重組中心之重組可能性且增加光 電轉換效率（國際專利公開案第W02004/090995號，以及 其類似文獻）。 對於每一光譜範圍使用多個具有不同能帶隙之半導 36 201044626 體可降低由光子能與能帶隙之間的不符引起之敎 加電力產生效率。使用-個疊-個的多個所述光電轉換; 被稱為串聯式（tandem type )。在雙層串聯（_ tandem)之情況下，電力產生效率可例如藉由使用^電 子伏與1.7電子伏之組合而增加。 (電極、緩衝層） Ο ❹ 下電極2G以及上電極5〇各由導電材料製成 輸入一側上之上電極50是透明的。 •較佳使用 之厚=何特別限制且較佳使用。 佳使用 厚度=特別限制且較佳使用心 (諸如或上電極5阿騎單層結構或疊層結構 制，之方法無任何特別限 便用軋相沈積方法，諸如雷孚击να 對緩衝層40之主|电子束蒸發以及频。 ⑽、ZnS、Ζη〇、ζ ί ^ 任何特別限制且較佳使用Materials and Solar Cells, Vol. 67, pp. 145-150, 2001, and similar documents). In either case, the light-induced carriers are likely to reach the electrode due to the acceleration caused by the internal potential generated by the gradient of the band structure, thereby reducing the recombination possibility of the recombination center and increasing the photoelectric conversion efficiency ( International Patent Publication No. WO2004/090995, and similar documents). The use of multiple semiconductors with different band gaps for each spectral range 36 201044626 reduces the power generation efficiency caused by discrepancies between photon energy and band gap. A plurality of said photoelectric conversions using one stack is referred to as a tandem type. In the case of a double layer series (_ tandem), power generation efficiency can be increased, for example, by using a combination of electron volts and 1.7 electron volts. (Electrode, Buffer Layer) Ο The lower electrode 2G and the upper electrode 5 are each made of a conductive material. The upper electrode 50 is transparent on the input side. • Thickness of preferred use = what is particularly limited and preferred for use. Preferably, the use thickness = special limitation and better use of the core (such as or the upper electrode 5 a riding single layer structure or a laminated structure, the method is not limited to a rolling phase deposition method, such as a rifle να to the buffer layer 40 The main | electron beam evaporation and frequency. (10), ZnS, Ζη〇, ζ ί ^ Any special restrictions and better use

層40之厚;^ §、ZnS(〇, 〇H)或其、叙合。對緩衝 微米之Γ ㈣職似難㈣_微米至（HThickness of layer 40; ^ §, ZnS (〇, 〇H) or its sum. For buffering micron (4) job seems difficult (four) _ micron to (H

光電轉換層例如M〇下電極/CdS緩衝層/CIGS 37 201044626 對光電轉換層30、緩衝 型無任何特別限制。一般，光電轉二公=之導電類 層或其類似物一 以及❿〇或其類似物）。#所層結構（獅層 層與上電極5G之間形成p_n接=電類型在光電轉換 認為在光電轉換岸3〇上撻二，面或P+n接面。此外， 散在光電轉換；。之表緩衝層40導致_ 層3〇内:ft，形成n層’藉此在光電轉換 (驗(土二光嶋層3〇内形成一。 鹼（土）金屬供應層7〇是包含—$ 屬及/輪土金屬之層且'轉㈣^貞型之驗金 時，向所述層供應所述驗金/及1 驗光電轉換層3〇 屬，〇可具有單層結構或不同組成 在本發明實施例中，驗（土）金屬供;^構: 开，成之層··藉由濺鍍法 2層70疋如下 =土)金屬之半導電或導電 =含在氧氣及二 電或導電靶材來:4 之鹼金屬及/或鹼土金屬之半導 =乾材來形成（本發明之第二製造方法）。 在圖5中，以與下電極2〇 f，。圖案化。當驗⑴金屬=:以金 _圖案化以防止相鄰電池之間的短二若二， 38 201044626. 金屬供應層70絕緣’則不需要所述圖案化。 (其他層） 光電轉換裝置1可視需要進一步包含任何除上述層外 之層。舉例而言，可在陽極化基板1〇與鹼（土）金屬^應 層7〇之間提供防止擴散層（diffusion preventi(mlaye^ 防止鹼（土）金屬供應層70中所包含之鹼（土）金屬擴散 於基板10中。此外，可視需要在基板1〇與下電極2〇之間 ❹ 及/或在下電極2〇與光電轉換層30之間提供黏著層（緩衝 層）以增強所述層之黏著力。 根據本發明實施例之光電轉換裝置丨是以如上文所述 之方式經結構化。 根據本發明實施例之光電轉換裝置丨是使用陽極化基 板10之裝置以致其重量輕且具有可撓性並可以低成本製 造。 在本發明實施例中，在基板1〇與光電轉換層30之間 提七、驗（土）金屬供應層70，以致當形成光電轉換層30 〇 ，，鹼（土）金屬可有效地擴散供應至所述層。在本發明 實施=中，向光電轉換層30穩定地供應所需濃度之鹼金 屬，藉此改良光電轉換層之結晶且可提供具有極佳轉換效 率之光電轉換裝置1。 ,在本發明實施例中，鹼（土）金屬供應層7〇是如下 形成之層：藉由濺鍍法，使用包含一或多種類型之鹼金屬 及/或驗土金屬之半導電或導電靶材來形成；或藉由反應性 濺鍍法，在氧氣及/或氮氣存在下，使用包含一或多種類型 39 201044626 之鹼金屬及/或鹼土金屬之半導電或導命 本發明實施例，鹼（土）金屬供應層7〇电。材來形成。根據 且具有極佳轉換效率之光電轉換梦 θ可以高生產力形成 造。 直1可以高生產力製 光電轉換裝置1可較佳用作太 要連接防護玻璃罩（⑺赠細）、保護膜也以 變成太陽電池。 及其類似物而 [設計變化] 本發明並不限於上述實施例，且可 精神的情況下視情況進行設計變化。 本毛明之 [實例] 現將描述本發明之實例。 (實例1) 使用铭合金1050(!呂純度為99.5%，厚度為〇 3〇毫米 作為基貝材料且使所述基質材料陽極化以在基質材料之每 -側上形成陽極健’接制水清洗且鱗，藉此獲得陽 極化基板。所述陽極化膜之厚度為9 〇微米（包含〇 38微 米之Ρ早壁層厚度）且孔隙直徑為約奈米。 陽極化條件如下： 電解液：16°c水溶液，其包含〇·5 Μ乙二酸；DC電 壓電源；電壓為40。 h後’在1¼極化基板上形成驗金屬供應層。缚造以及 燒結NaF粉末（純度為99.99% )與Si粉末（純度為99.999% ) 之混合粉末以獲得燒結體（Na含量為10原子％)。接著， 40 201044626 藉由雙磁控濺鏟，使用所述燒結體 供應層。膜形成條件如下。在本實芍靶材來形成鹼金屬 驗金屬供應層歷時約3分鐘。 ，中，以高生產力形成 〈膜形成條件&gt; 驗金屬供應層厚度·· 2〇〇奈米 基板溫度：室溫至3〇(rG ’ AC功率：800瓦 乾材與基板之間的距離：8公八 濺鍍氣體：Ar 乃 老厅、真空.5x1 〇·5帕斯卡 濺鍍氣體壓力：0.5帕斯卡 此後’藉由DC濺觀作為 度為〇·6微米。接I藉由多源共基發^^積，其厚 薄膜之沈積是在10-4帕斯卡之真j2/米/邮印㈣ 内提供CU沈積源、In、、少 、:又下，藉由在真空容器 〇來執行。膜形成域由^每源从&amp;沈積源 施，其:中最大基板溫度為54〇。^積源控制沈積速率來實 厚度ΪΪ 50藉Λ化學:f使作為緩衝層之㈣ ”'、 不未接者，藉由RF濺鍍在緩衝屛上带忐古 電阻ZnO膜（圖5巾去艰隹、、友衡層上形成问 形成作為上^且接連 個積於基板成多 “形破置’藉此製造總共20個光電轉換裝置。 201044626 &lt;評估光導電效率&gt; 使用氣團（Air Mass ; AM) = 1_5、1〇〇毫瓦/平方公 分之擬太陽光（pseudo sunlight)來評估每一所製造出之光 電轉換裝置的光電轉換效率。亦即，評估2〇個樣品中之每 一者的光電轉換效率’且光電轉換效率為最大值之8〇%或 更多的樣品評估為合格產品（acceptabie pr〇duct)且將除 合格產品外之樣品評估為不合格產品。合格產品之光電轉 換效率為13%至15%。 本發明之發明者已證實，驗金屬供應層亦可藉由 DC濺鍍以及磁控濺鍍，使用與實例丨相同之靶材 (實例2) &gt;成。 以與實例1相同之方式獲得光電轉換裝置， 屬供應層是藉由脈衝DC反應性濺鑛在氧氣流下來, 膜形成條件如下。膜形成時間為約5分鐘。 夕。 &lt;膜形成條件&gt; 驗金屬供應層厚度：2〇〇奈米 基板溫度：室溫至300。(： DC功率·· 700瓦 乾材與基板之間的距離：8公分 濺鍍氣體：Ar以及〇2 背景真空：5xl(T5帕斯卡 濺鍍氣體壓力：0.8帕斯卡 轉換效率且結果為 以與Λ例1相同之方式量測光電 13%至 15〇/0 〇 42 201044626 Λ,土明之發明者已證實，鹼金屬供應層亦可藉由磁控 二/賤鍍以及雙磁控反應性減鍵，使用與實 靶材來形成。 (實例3 )The photoelectric conversion layer such as the M〇 lower electrode/CdS buffer layer/CIGS 37 201044626 does not have any particular limitation on the photoelectric conversion layer 30 and the buffer type. Generally, a photoelectrically conductive layer or a similar one thereof and cerium or the like are used. #层层结构(p_n connection between the lion layer and the upper electrode 5G = electrical type in the photoelectric conversion is considered to be on the photoelectric conversion shore 3 挞 ,, face or P + n junction. In addition, scattered in photoelectric conversion; The surface buffer layer 40 causes _ layer 3 〇: ft, forming n layer 'by virtue of photoelectric conversion (testing (the formation of one in the earthy bismuth layer 3 . The alkali (earth) metal supply layer 7 〇 is containing -$ genus and When the layer of the wheeled metal is used and the gold of the 'turning (four) type is used, the gold and/or the photoelectric conversion layer 3 is supplied to the layer, and the crucible may have a single layer structure or a different composition in the present invention. In the embodiment, the test (earth) metal supply; ^ structure: open, layered · by sputtering method 2 layers 70 疋 as follows = soil) semi-conducting or conductive metal = contained in oxygen and two electric or conductive targets Material: 4 semi-conducting metal and/or alkaline earth metal = dry material to form (the second manufacturing method of the present invention). In Fig. 5, the pattern is formed with the lower electrode 2〇f. Metal =: Patterned with gold to prevent shortness between adjacent cells, 38 201044626. Metal supply layer 70 is insulated 'the pattern is not required. (Other layers) Light The electric conversion device 1 may further include any layer other than the above layer as needed. For example, a diffusion preventing layer (diffusion preventi (mlaye^) may be provided between the anodized substrate 1〇 and the alkali (earth) metal layer 7〇. The alkali (earth) metal contained in the alkali (earth) metal supply layer 70 is prevented from diffusing into the substrate 10. Further, between the substrate 1 and the lower electrode 2, and/or at the lower electrode 2, and photoelectric conversion, as needed An adhesive layer (buffer layer) is provided between the layers 30 to enhance the adhesion of the layers. The photoelectric conversion device according to an embodiment of the present invention is structured in the manner as described above. Photoelectric conversion according to an embodiment of the present invention The device 丨 is a device that uses the anodized substrate 10 so that it is light in weight and flexible and can be manufactured at low cost. In the embodiment of the present invention, seven (test) are provided between the substrate 1 〇 and the photoelectric conversion layer 30. The metal supply layer 70 is such that when the photoelectric conversion layer 30 is formed, an alkali (earth) metal can be efficiently diffused and supplied to the layer. In the practice of the present invention, the desired concentration is stably supplied to the photoelectric conversion layer 30. The metal, thereby improving the crystallization of the photoelectric conversion layer and providing the photoelectric conversion device 1 having excellent conversion efficiency. In the embodiment of the present invention, the alkali (earth) metal supply layer 7 is a layer formed by sputtering Plating, using a semiconducting or electrically conductive target comprising one or more types of alkali metals and/or soil-measuring metals; or by reactive sputtering, in the presence of oxygen and/or nitrogen, including one or A semi-conducting or a semi-conducting or a derivative of an alkali metal and/or an alkaline earth metal of various types 39 201044626, an alkali (earth) metal supply layer 7 is formed by a material. The photoelectric conversion dream according to and having excellent conversion efficiency Can be formed with high productivity. Straight 1 can be highly productive. The photoelectric conversion device 1 can be preferably used to connect a protective glass cover ((7) gift) and the protective film to become a solar cell. And its analogs [Design change] The present invention is not limited to the above embodiment, and design changes may be made as the case may be. [First Example] [Examples] An example of the present invention will now be described. (Example 1) Using Ming alloy 1050 (! Lu purity of 99.5%, thickness of 〇3 〇 mm as a base material and anodizing the matrix material to form anode jian's water on each side of the matrix material The anodized substrate was obtained by washing and scalding, and the thickness of the anodized film was 9 〇 micrometers (including the thickness of the Ρ 38 μm Ρ early wall layer) and the pore diameter was about nm. The anodizing conditions were as follows: 16 °c aqueous solution containing 〇·5 Μ oxalic acid; DC voltage source; voltage is 40. After h 'formation of metal supply layer on 11⁄4 polarized substrate. Binding and sintering of NaF powder (purity of 99.99%) A mixed powder of Si powder (purity of 99.999%) was obtained to obtain a sintered body (Na content of 10 atom%). Next, 40 201044626 The sintered body supply layer was used by a double magnetron splashing blade. The film formation conditions were as follows. In the present invention, the alkali metal metal supply layer is formed for about 3 minutes. In the middle, high productivity is formed. <Film formation conditions> Metal supply layer thickness is measured. · 2 〇〇 Nano substrate temperature: room temperature to 3〇 (rG 'AC power: 800 watt dry material Distance from the substrate: 8 male eight sputtering gas: Ar is the old hall, vacuum. 5x1 〇 · 5 Pascal sputtering gas pressure: 0.5 Pascal after this 'by DC sputtering as a degree of 〇 · 6 microns. By multi-source common-based emission, the deposition of thick film is provided in the true j2 / m / stamp (4) of 10-4 Pascals, CU deposition source, In, less, and below, by vacuum The container is formed by a membrane. The film formation domain is applied from the source to the deposition source. The maximum substrate temperature is 54 〇. The accumulation source controls the deposition rate to the actual thickness ΪΪ 50 by chemical: f is used as a buffer layer. (4) "", not unsuccessful, by RF sputtering on the buffer 屛 with a ohmic resistance ZnO film (Figure 5 towel tough, and the formation of the formation on the balance layer as a top ^ and successively accumulated in the substrate A plurality of "shapes" are used to manufacture a total of 20 photoelectric conversion devices. 201044626 &lt;Evaluation of Photoconductive Efficiency&gt; Using Air Mass (AM) = 1_5, 1 〇〇mW/cm 2 of pseudo-sunlight (pseudo Sunlight) to evaluate the photoelectric conversion efficiency of each manufactured photoelectric conversion device. That is, to evaluate 2 samples Samples having a photoelectric conversion efficiency of 'each and having a photoelectric conversion efficiency of 8〇% or more of the maximum value were evaluated as acceptable products (acceptabie pr〇duct) and samples other than the qualified products were evaluated as non-conforming products. The photoelectric conversion efficiency is 13% to 15%. The inventors of the present invention have confirmed that the metal supply layer can also be used by DC sputtering and magnetron sputtering, using the same target as the example (Example 2) &gt; A photoelectric conversion device was obtained in the same manner as in Example 1, in which the supply layer was flowed down by oxygen by pulsed DC reactive sputtering, and the film formation conditions were as follows. The film formation time was about 5 minutes. Xi. &lt;Film formation conditions&gt; Metal supply layer thickness: 2 Å Nano substrate temperature: room temperature to 300. (: DC power · · 700 watt dry material and substrate distance: 8 cm sputtering gas: Ar and 〇 2 background vacuum: 5xl (T5 Pascal sputtering gas pressure: 0.8 Pascal conversion efficiency and the results are with 1 Measurement of photoelectricity in the same way 13% to 15〇/0 〇42 201044626 Λ, the inventor of Tuming has confirmed that the alkali metal supply layer can also be used by magnetron two/贱 plating and dual magnetron reactive reduction. Formed with a solid target. (Example 3)

、=與實例1相同之方式獲得光電轉換裝置，除了鑄造 _粉末（純度為99·99%)、Sl粉末（純度為 〜植α °以及A1粉末（純度為&quot;‘99%)之混合粉末以獲 付1。體（Na含量為原子％且Α1含量為10原子％)， 且驗金屬供應層是藉由脈衝DC反應性減鑛，在氧氣流 下’使用燒結體作躲材來形成。卿絲件如下。膜形 成時間為約4分鐘。 、 &lt;膜形成條件&gt; 鹼金屬供應層厚度：200奈米 基板溫度：室溫至3〇〇。(： DC功率：500瓦 革巴材與基板之間的距離：8公分 賤錢氣體：Ar以及〇2 月景真空.5xl〇5帕斯卡 濺鍍氣體壓力：0.8帕斯卡 13%Γ二I例1相同之方式量測光電轉換效率且結果為, = Photoelectric conversion device was obtained in the same manner as in Example 1, except for casting powder (purity of 99.99%), Sl powder (purity of ~α°, and A1 powder (purity of '99%)) To obtain a body (Na content is atomic % and Α1 content is 10 atom%), and the metal supply layer is formed by pulsed DC reactive ore reduction, using a sintered body as a hiding material under oxygen flow. The filament was as follows. The film formation time was about 4 minutes. &lt;Film formation conditions&gt; Alkali metal supply layer thickness: 200 nm substrate temperature: room temperature to 3 Torr. (: DC power: 500 watt leather material and Distance between substrates: 8 cm Money: Ar and 〇 2 Moon vacuum. 5xl 〇 5 Pascal sputtering gas pressure: 0.8 Pascal 13% I 2 I Example 1 The same method was used to measure the photoelectric conversion efficiency and the result was

本發明之發明者已證實，驗金屬供應層亦可藉由DC 反應性麵、磁控反應性賴以及雙雜反應性濺鍵，使 用與實例3相同之乾材來形成。 43 201044626 [比較實例1]The inventors of the present invention have confirmed that the metal supply layer can also be formed by using the same dry material as in Example 3 by a DC reactive surface, a magnetron reactive reactance, and a double hetero reactive sputtering bond. 43 201044626 [Comparative Example 1]

與實例3相同之方式獲得㈣轉換裝置，除了 W 子是藉由RF$賤錢，使用納舞玻璃（犯含量為。 0作為乾材來形成。臈形成條件如下，除RF '、 ;膜开:：之條件相同。因此，膜形成時間為40分鐘，亦 即膜形成速度降低至實例3中之1/1〇。 亦 以與實例3相^对量㈣換 13% 至 15%。 丁 果為 〈膜形成條件&gt; 驗金屬供應層厚度：2〇〇奈米 基板溫度：室溫至3〇〇它 RF功率：800瓦 乾材與基板之間的距離：8公分 濺鍍氣體：Ar以及〇2 背景真空：5χ1(Τ5帕斯卡 濺鍍氣體壓力：0.8帕斯卡 (實例4 ) 鑄造以及燒結Si粉末（純度為99.999%)、&amp; 中所列之摻雜物粉末（純度為99.99%)以及表 下表1 =粉末（純度為99.999%)的混合粉知獲概之 2以及換雜物含量展示於表1中）。驗金屬供^fWNa 磁控濺鍍，使用以與實例丨相同之方式所庐二9疋错由 成。在相同條件下每一靶材形成五次犋，:材來形 1中。 /、、纟5果展示於表 44 201044626 在電孤之評二:i1:上：内存在或不存 1中，X指示在五次膜形成=獅成時間為3分鐘。在表 在五次膜形成之每-次中均出現電弧，〇指示 次膜形成之一次至四次中出放電，且△指示在五 表1In the same manner as in Example 3, the (four) conversion device was obtained, except that the W sub was made by RF$, using Nawu glass (with a content of 0 as a dry material). The formation conditions of the crucible were as follows, except RF ',; The conditions were the same. Therefore, the film formation time was 40 minutes, that is, the film formation speed was lowered to 1/1 〇 in Example 3. It was also changed to 13% to 15% with the amount of Example 3 (4). For <film formation conditions> Metal supply layer thickness: 2 〇〇 Nano substrate temperature: room temperature to 3 〇〇 RF power: 800 watts Distance between dry material and substrate: 8 cm of sputtering gas: Ar and 〇2 Background vacuum: 5χ1 (Τ5 Pascal sputtering gas pressure: 0.8 Pascal (Example 4) Casting and sintering Si powder (purity 99.999%), dopant powders listed in &amp; purity (99.99%) and table Table 1 below = powder (purity of 99.999%) mixed powder knowledge 2 and the content of the inclusions are shown in Table 1. The metal is provided for ^fWNa magnetron sputtering, using the same method as the example庐二9疋错由成. Under the same conditions, each target is formed five times, and the material is shaped into 1. /,, 纟5 fruit shown in Table 44 201044626 In the electric solitary evaluation 2: i1: on: in memory or not in 1, X indicates in five times film formation = lion time is 3 minutes. In the table in five times An arc occurs every time the film is formed, and 〇 indicates one to four times of discharge of the secondary film formation, and △ is indicated in Table 1.

NaF (1〇原子％) Na2Mo〇4 (5 原子％) Na2MoO4(10原子％) Na2C〇3 (5 原子％) Na2C03 (10 原子％)NaF (1〇 atom%) Na2Mo〇4 (5 atom%) Na2MoO4 (10 atom%) Na2C〇3 (5 atom%) Na2C03 (10 atom%)

Ο Ο 推雜物 、在乾材中之 ♦度，原 « \〇) (在乾材中之 濃度，原子％)Ο 推 Pushing things, ♦ degrees in dry materials, original « \〇) (concentration in dry materials, atomic %)

NaF (Γ^%) (實例5) 鑄造以及燒結NaF粉末（純 度為99.999%)、A1粉末(純度為99 - 末： 度為99.99°/。）以及Ca粉末（純许 。）g籾末（，，屯 以獲得燒結體（Na含量為1〇原二’、、&quot;.99%)之混合粉末 Mg含量為2原子％且Ca含量A 9°、A1含量為10原子0/〇、 3相同之方式，使職結體作^ =子％)。接著以與實例 般成功地形成滿意的膜。’、、、_細彡成紅如實例3 藉由X射線光電子光譜 ^ ^ X-ray photoelectron 45 201044626 spectroscopy ; XPS)對所獲得之膜進行定性分析且獲得圖 9中所示之光譜’藉此證實不包含任何雜質。此外，將xps 光§普強度與具有已知組成之樣品相比以獲得膜組成，兑会士 果展示於以下表2中。 表2 組份 膜組成（原子％ ) Si - 24.3 Na _ 7.2 A1 47 Ca 1.8 Mg 2.1 0 59.9 本發明之光電轉換裝置以及其製造方法可較佳應用 於太陽電池、紅外線感應器（infrared sensor )以及其類似 物。 【圖式簡單說明】 圖1是DC濺鍍設備之示意圖，其說明所述設備之結 構。 圖2是RF濺鍍設備之示意圖，其說明所述設備之結 構。 圖3磁控濺鍍設備之示意圖，其說明所述設備之結構。 圖4雙磁控濺鍍設備之示意圖，其說明所述設備之結 構。 圖5是根據本發明之一實施例之光電轉換裝置沿縱向 的示意性剖視圖。 圖6說明陽極化基板之剖視圖，其説明所述基板之結 構。 46 201044626 圖7陽極化基板之透視圖，其說明所述基板之製造方 法。 圖8疋使用兩層被覆材料（ciad material)之陽極化基 板的示意性橫截面圖，其說明所述基板之結構。 圖9是實例5中獲得之薄膜的XPS光譜。 圖10說明I-III-VI化合物半導體之晶格常數與能帶隙 之間的關係。 【主要元件符號說明】 〇 1 :光電轉換裝置 10 :基板/陽極化基板 10':基板/陽極化基板 11 · ：!呂基金屬基質/紹基質 11s :表面 12 .陽極化膜/銘陽極化膜 12a :細柱狀體 12b :細孔 Q 13 :第二金屬基質/金屬基質 14 :金屬基板/被覆材料 20 .下電極（背接觸電極）/下電極 30 ·光電轉換半導體層/光電轉換層/化合物半導體屌 40 :緩衝層 9 50 :上電極 61 :第一分隔凹槽 62 :第二分隔凹槽 47 201044626 63 :第三分隔凹槽 70 :鹼（土）金屬供應層 101 : DC濺鍍設備/成膜設備 102 : RF濺鍍設備 103 :磁控濺鍍設備 104 :雙磁控濺鍍設備 110 :真空容器 111 :基板固持器 112 :電漿電極（陰極） 113 : DC電源 114 :高頻AC電源（RF電源） 115 :磁體單元 115M :磁體 116 .面頻AC電源 118 :氣體引入管 119 :排氣管 B ·基板 C :電池 G :氣體 P :電漿空間 T :靶材 V :氣體 48NaF (Γ^%) (Example 5) Cast and sintered NaF powder (purity of 99.999%), A1 powder (purity of 99 - end: degree of 99.99 ° /.) and Ca powder (pure.) g籾 ( , 屯 to obtain a sintered body (Na content of 1 〇 original two ',, &quot;.99%) mixed powder Mg content of 2 atom% and Ca content A 9 °, A1 content of 10 atom 0 / 〇, 3 In the same way, the job is made ^^ child%). A satisfactory film was then successfully formed as in the example. ',,, _ fine 彡 red as Example 3 by X-ray photoelectron spectroscopy ^ ^ X-ray photoelectron 45 201044626 spectroscopy ; XPS) qualitative analysis of the obtained film and obtain the spectrum shown in Figure 9 It was confirmed that it did not contain any impurities. In addition, the xps light intensity was compared to a sample having a known composition to obtain a film composition, and the redemption was shown in Table 2 below. Table 2 Component film composition (atomic %) Si - 24.3 Na _ 7.2 A1 47 Ca 1.8 Mg 2.1 0 59.9 The photoelectric conversion device of the present invention and the method of manufacturing the same can be preferably applied to a solar cell, an infrared sensor, and the like. Its analogues. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a DC sputtering apparatus illustrating the structure of the apparatus. Figure 2 is a schematic illustration of an RF sputtering apparatus illustrating the structure of the apparatus. Figure 3 is a schematic illustration of a magnetron sputtering apparatus illustrating the structure of the apparatus. Figure 4 is a schematic illustration of a dual magnetron sputtering apparatus illustrating the structure of the apparatus. Figure 5 is a schematic cross-sectional view of a photoelectric conversion device in a longitudinal direction according to an embodiment of the present invention. Figure 6 illustrates a cross-sectional view of an anodized substrate illustrating the structure of the substrate. 46 201044626 Figure 7 is a perspective view of an anodized substrate illustrating the method of fabricating the substrate. Figure 8 is a schematic cross-sectional view of an anodized substrate using two layers of ciad material illustrating the structure of the substrate. Figure 9 is an XPS spectrum of the film obtained in Example 5. Figure 10 illustrates the relationship between the lattice constant of the I-III-VI compound semiconductor and the band gap. [Explanation of main component symbols] 〇1: Photoelectric conversion device 10: Substrate/anodized substrate 10': Substrate/anodized substrate 11 · :! Luki metal substrate / substrate 11s: Surface 12. Anodized film / anodized Film 12a: fine columnar body 12b: pores Q 13 : second metal substrate / metal substrate 14 : metal substrate / covering material 20 . lower electrode (back contact electrode) / lower electrode 30 · photoelectric conversion semiconductor layer / photoelectric conversion layer / compound semiconductor 屌 40 : buffer layer 9 50 : upper electrode 61 : first separation groove 62 : second separation groove 47 201044626 63 : third separation groove 70 : alkali (earth) metal supply layer 101 : DC sputtering Apparatus/film forming apparatus 102: RF sputtering apparatus 103: magnetron sputtering apparatus 104: dual magnetron sputtering apparatus 110: vacuum vessel 111: substrate holder 112: plasma electrode (cathode) 113: DC power source 114: high Frequency AC power source (RF power source) 115: Magnet unit 115M: Magnet 116. Area frequency AC power source 118: Gas introduction tube 119: Exhaust pipe B • Substrate C: Battery G: Gas P: Plasma space T: Target V: Gas 48

Claims (1)

201044626 七、申請專利範圍： 1· 一種製造光電轉㈣置之方法，所述裂置具有位於 基板上之下電極'藉由吸收光產生電流之光電轉換半 層以及上電極之疊層結構以及提供於所述基板與下電= 間白=^〇金屬供應層，所述驗（土）金屬供應層 金屬及/或驗土金屬且當形成所述光電 Ο Ο 夕種類型之鹼金屬及/或鹼土金屬，其中： 次 ^斤述光電轉換半導體層之主要組份是至少 =半:體’所述化合物半導體具有由第Ib族元二 所、=及第VIb族元素形成的黃銅確結構；且 、、所述驗（土）金屬供應層是藉由賴法，使 類型之鹼金屬及/或驗土金屬的半導電或i電 某板綠轉難置之妓，所魏置具有位於 f 下電極、藉由吸收光產生電流之光電轉換丰尊辦 層以及上_之4層結構以及提供於騎基㈣下且 間的驗（土）金屬供應層’所述鹼（ 二電極之 -或多種類型之驗金屬及/或驗土 者層包含 轉換半導體層時，向所述光電轉換/ 所述光電 多種類型之驗金屬及/或驗土金屬體層供應所述-或 所述光電轉換半導體層之主要袓 之化合物半導體，所述化合物半導體具有動:型 弟族元素以及第VIb族元素形成的黃銅礦結構=、 49 201044626 &quot;所述驗（土）金屬供應層是藉由反應性濺鑛法，在氧 耽及/或II氣存在下’使用包含所述—或多種類型之驗金屬 及/或鹼土金屬的半導電或導電靶材來形成。 3. 如申料鄕圍第丨項所叙製減電轉換裝置 之方法’其中所述驗（土）金屬供應層是藉由直流（DC) 錢鍍法、脈衝DC濺鑛法、磁控續法、雙磁控滅鐘法或 射頻（RF)贿法，使用包含半導電基料及所述一或多 種類型之鹼金屬及/或驗土金屬的靶材來形成。 4. 如申請專利範圍第2項所述之製造光電轉換裝置 之方法’其中所述驗（土）金屬供應層是藉由Dc賤鑛法、 脈衝DC歲鍍法、磁控滅鑛法、雙磁控漱鑛法或錢鑛 法’使用包含轉電基質以及所述—或多_型之驗金屬 及/或驗土金屬的乾材來形成。 5. 如申印專利範圍第3項所述之製造光電轉換裝置 之方法，其中所述驗（土）金屬供應層是藉由所述脈衝DC 濺鍍法、磁控濺鑛法或雙磁控濺鍍法來形成。 6. 如申请專利範圍第4項所述之製造光電轉換裝置 之方法，其中所述鹼（土）金屬供應層是藉由所述脈衝DC 濺鍍法、磁控濺鍍法或雙磁控濺鍍法來形成。 7. 如申凊專利範圍第1項所述之製造光電轉換裝置 之方法，其中所述靶材中之所述一或多種類塑之鹼金屬及/ 或驗土金屬的總量為1原子％至30原子％。 8. 如申請專利範圍第2項所述之製造光電轉換裝置 之方法，其中所述靶材中之所述一或多種類犁之鹼金屬及/ 50 201044626 或鹼土金屬的總量為1原子％至30原子％。 9. 如申請專利範圍第1項所述之製造光電轉換裝置 之方法，其中所述靶材中之所述一或多種類型之鹼金屬及/ 或鹼土金屬的總量為5原子％至20原子％。 10. 如申請專利範圍第2項所述之製造光電轉換裝置 之方法，其中所述靶材中之所述一或多種類型之鹼金屬及/ 或鹼土金屬的總量為5原子％至20原子％。 11. 如申請專利範圍第1項所述之製造光電轉換裝置 〇 之方法，其中所述革巴材是包含所述一或多種類型之驗金屬 及/或驗土金屬的石夕革巴材。 12. 如申請專利範圍第2項所述之製造光電轉換裝置 之方法，_其中所述革巴材是包含所述一或多種類型之驗金屬 及/或驗土金屬的石夕革巴材。 13. 如申請專利範圍第11項所述之製造光電轉換裝 置之方法，其中所述矽靶材包含至少一種類型之由A卜Ga 以及B所構成的族群中選出之元素。 Q 14.如申請專利範圍第12項所述之製造光電轉換裝 置之方法，其中所述矽靶材包含至少一種類型之由A卜Ga 以及B所構成的族群中選出之元素。 15. 如申請專利範圍第13項所述之製造光電轉換裝 置之方法，其中所述矽靶材中之所述至少一種類型之由 A卜Ga以及B所構成的族群中選出之元素的總量為1原 子％至20原子％。 16. 如申請專利範圍第14項所述之製造光電轉換裝 51 201044626 置之方法，其中所述矽靶 A卜Ga以及B所構成的族之所述至少一種類型之由 子％至20原子％。 選出之元素的總量為1原 17.如申凊專利範圍 置之方法，其中述之製造光電轉換裳 认如申請專利範圍第7早獨納或納化合物。 置之方法，其中所述矽乾姑入f所述之製造光電轉換裝 19. 如中請專利範_^3早_或齡合物。 置之方法，其中所述矽靶 ^員所述之製造光電轉換裝 納、石炭酸細及細_所構=^ —種類型之由氟化 20. 如申請專利範圍第、^令選出之納鹽。 置之方法，其中所述石綠材包人項f述之製造光電轉換裝 鈉、碳酸鈉以及顧酸納所構成的3 由氟化 置之第19項所述 置之方法，其中所述石夕革巴材是藉由鱗造以及燒=裝 -種_之鈉鹽粉末與石夕粉末的混合粉賴獲二J 體，其可包含不可避免的雜質。 乂、、、。 22.如申請專利範圍第2G項所述之製造光 置之方法，其崎是―造歧燒結所述至= -種類变之鈉鹽私末”⑪粉末的混合粉末所 體，其玎包含不可避免的雜質。 心、、、。 ’23.如申請專利範圍第i項所述之製造光電轉換裝置 之方法，其中. 所述第Ib族元素是至少―種類型之由Cu以及Ag所 52 201044626 » . 構成的族群中選出之元素； 所IIIb麵7°素是至少-種類型之由A1、Ga以及 In所構成的族群中選出之元素；且 a以及 所述第VIb族元素暑$ ,丨、 所構成_群中選出之元素^ 划之由S、Se以及Te 之方料利難第2項所述之製造光電轉換裝置 Ο 〇 播第1素是至少—種類型之由Cu以及Ag所 構成的奴群中選出之元素； Ag所 I所It第mb知疋素是至少—種類型之由M、Ga以及 In所構成的族群中選出之元素；且 a以及 所爐^第穩族元素是至少—種類型之由W以及Te 所構成的族群中選出之元素。 乂及Te 項二種造 恭搞27二種光電轉換裝置，其包括陽極化基板，其中下 二物半導體之光電轉換半導體層以及上電極層以 板，i宜層於㈣練上，所㈣極化基板包含金屬基 二所述金屬基板之至少—個表面上具有ls基質，以及 二：所述鋁基質之至少一側表面上的所述鋁基質之陽極 化祺作為電絕緣層，其中： 至少一個鹼金屬供應層是提供於所述陽極化基板與 53 201044626 所述下電極之_當軸舰光電轉 1 斤述光電轉換半導體層之主要組份是至少一種類型 之化5物半導體，所述化合物半導體具有由第㈣元素、 第素^ VIb崎料峨 ';且 金屬==供應層包含至少，型之臉 述：電=池’其具有如申請專利範圍⑽所 述^電轉^⑽其具㈣__26項所 述之Γ電轉電池，其具有如申請專利範圍第27項所 種用於錢錢形成光電轉換 供應層的乾材，所述姆是=置之驗（土）金屬 種類型之驗金屬及/或驗土金^電的且包含一或多 32·如申請專利範圍第31 電轉縣置之驗（土）金屬供應層 於舰形成^ 多種類型之驗金収/紐土金屬的其情述一或 原子％。 主/蜀扪總里為1原子％至30 電二以:範=31項所述之用於濺鑛形成光 之比電衫超過1歐姆/公分。_’其帽述树 34·如申請專利範圍第33項所述之用於濺鍵形成光 54 201044626 電轉換装置之驗（土）金屬供應層的乾材， 是包含所述-或多種類型之驗金屬及 其中所述把材 材。 夂/或鹼土金屬的矽靶 35. 如申請專利範圍第34項所述 電轉換裝置之驗（土）金屬供應層的 於賤鑛形成光 包含至少〆種類型之由A卜Ga 其中所述把材 出之元素。 叹ΰ所構成的族群中選 36. 如申請專利範圍第35項所 0 t轉換裝置之驗(土）金屬供應層的t用，鑛形成光 -種類型之由Al、Ga以及B所構成; 的總量為1原子％至3〇原子。/〇。 中k出之兀素 37. 如申請專利範圍第36項所 電，裝置之驗(土)金屬供應層的乾材， 二:ί以及B所構成的族群中選出之元素 J〜里馬10原子％至20原子％。 ◎電二Ϊ =範圍Γ4項所述之用於_成光 V/ 置之驗（土）金屬供應 衫單獨納或納化合物。 料其中所述树 電轉專利範圍第38項所述之臟練形成光 包人$丨、&amp;幻金屬供應層的乾材，其中所述乾材 由氟化納、碳酸納叹賴納所構成 命隸1〇#如中凊專利賴第39項所述之用於賤鑛形成光 电、凌置之驗（土）金屬供應層的革巴材，其中所述革巴材 55 201044626 是藉由鑄造以及燒結所述至少一種類型之鈉鹽粉末與矽粉 末的混合粉末所獲得之燒結體，其可包含不可避免的雜質。 56201044626 VII. Patent application scope: 1. A method for manufacturing a photoelectric conversion (four), wherein the crack has a laminated structure of a photoelectric conversion half layer and an upper electrode for generating a current by absorbing light on a lower electrode of the substrate and providing And the metal supply layer of the metal (or earth) metal supply layer and/or the soil test metal, and when forming the alkali metal of the photoelectric type and/or An alkaline earth metal, wherein: the main component of the photoelectric conversion semiconductor layer is at least = half: body 'the compound semiconductor has a brass structure formed of a group Ib element II, = and a group VIb element; And the metal supply layer of the test (soil) is made by the Lai method, the semi-conducting metal of the type of alkali metal and/or the earth-measuring metal or the green plate of the soil is difficult to set, and the set is located at f a lower electrode, a photoelectric conversion layer which generates a current by absorbing light, and a 4-layer structure of the upper layer and a metal supply layer provided under the riding base (four) (the two electrodes - or Various types of metal and/or inspection When the layer includes a conversion semiconductor layer, the compound semiconductor of the said or the photoelectric conversion semiconductor layer is supplied to the photoelectric conversion/photoelectric various types of metal and/or soil-measuring metal layers, the compound The semiconductor has a moving: type of chalcogen element and a chalcopyrite structure formed by a group VIb element =, 49 201044626 &quot; The test (earth) metal supply layer is by reactive sputtering method, in oxo and/or II In the presence of gas, 'is formed using a semiconducting or electrically conductive target containing the above-mentioned or more types of metal and/or alkaline earth metals. 3. Method of reducing power conversion device as described in the item 申Wherein the test (earth) metal supply layer is controlled by direct current (DC) money plating, pulsed DC sputtering, magnetron continuous method, double magnetic control clock ring method or radio frequency (RF) bribe method, including semiconducting A base material and a target of the one or more types of alkali metals and/or earth-grown metals. 4. The method of manufacturing a photoelectric conversion device according to claim 2, wherein the test (earth) metal The supply layer is made by Dc , pulsed DC plating method, magnetron ore killing method, double magnetron ore mining method or money mining method 'using dry materials containing a rotating substrate and the above-mentioned or multi-type metal and/or soil for soil inspection 5. The method of manufacturing a photoelectric conversion device according to claim 3, wherein the metal (metal) supply layer is by the pulsed DC sputtering method, the magnetron sputtering method or the double 6. The method of manufacturing a photoelectric conversion device according to claim 4, wherein the alkali (earth) metal supply layer is by the pulsed DC sputtering method, magnetically controlled 7. The method of manufacturing a photoelectric conversion device according to claim 1, wherein the one or more plastic alkali metals in the target material are formed by the sputtering method or the double magnetron sputtering method. And / or the total amount of soil inspected is from 1 atom% to 30 atom%. 8. The method of manufacturing a photoelectric conversion device according to claim 2, wherein the total amount of the one or more kinds of plow alkali metals and/or 50 201044626 or alkaline earth metals in the target is 1 atom% Up to 30 atom%. 9. The method of manufacturing a photoelectric conversion device according to claim 1, wherein the total amount of the one or more types of alkali metals and/or alkaline earth metals in the target is 5 atom% to 20 atoms. %. 10. The method of producing a photoelectric conversion device according to claim 2, wherein the total amount of the one or more types of alkali metals and/or alkaline earth metals in the target is 5 atom% to 20 atoms. %. 11. The method of manufacturing a photoelectric conversion device according to claim 1, wherein the leather material is a stone material comprising the one or more types of metal and/or soil testing metals. 12. The method of manufacturing a photoelectric conversion device according to claim 2, wherein the leather material is a stone material comprising the one or more types of metal and/or soil testing metals. 13. The method of producing a photoelectric conversion device according to claim 11, wherein the bismuth target comprises at least one type of element selected from the group consisting of Ab and Ga. The method of manufacturing a photoelectric conversion device according to claim 12, wherein the bismuth target comprises at least one type of element selected from the group consisting of A and Ga and B. 15. The method of manufacturing a photoelectric conversion device according to claim 13, wherein the total amount of the elements selected from the group consisting of the A and Ga and B in the at least one type of the target of the target It is 1 atom% to 20 atom%. 16. The method of producing a photoelectric conversion device 51 201044626 according to claim 14, wherein the at least one type of the at least one type of the group of the target objects A and Ga and B is from 20% to 20 atom%. The total amount of selected elements is 1 original. 17. The method of claiming the patent range, wherein the manufacturing of the photoelectric conversion is as long as the application of the patent range 7th early or nano compound. The method of manufacturing the photoelectric conversion device described in the above, wherein the patent is _^3 early or aged. The method of the present invention, wherein the yttrium target device manufactures a photoelectric conversion device, a fine carbonic acid, and a fine _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . The method of the present invention, wherein the method for producing a photoelectric conversion device comprising sodium, sodium carbonate, and sodium citrate is described in claim 19, wherein the method is The material is obtained by the scale powder and the mixed powder of the sodium salt powder and the Shishi powder, which may contain unavoidable impurities.乂,,,. 22. The method for producing an optical device according to the scope of claim 2G, which is a mixed powder of the powder of the "salt-sintered to the sodium salt of the type", which contains no powder. A method of manufacturing a photoelectric conversion device according to the invention of claim 1, wherein the Group Ib element is at least one type of Cu and Ag 52 201044626 » The elements selected from the group consisting of; the IIIb surface is at least one type of element selected from the group consisting of A1, Ga, and In; and a and the group VIb element summer $, 丨The elements selected from the group _ group are manufactured by S, Se, and Te. The photoelectric conversion device is manufactured as described in item 2. The first element is at least one type of Cu and Ag. The element selected from the group of slaves; the mb of the Ag Institute I is the element selected from the group consisting of M, Ga, and In; and a and the furnace element Is at least one type of element selected from the group consisting of W and Te乂 and Te items are made of 27 kinds of photoelectric conversion devices, including anodized substrates, in which the photoelectric conversion semiconductor layer of the lower two semiconductors and the upper electrode layer are plated, i should be layered on (4), and the (four) pole The substrate comprises a metal substrate, at least one surface of the metal substrate has an ls matrix, and two: an anodized germanium of the aluminum substrate on at least one surface of the aluminum substrate serves as an electrical insulating layer, wherein: An alkali metal supply layer is provided on the anodized substrate and the lower electrode of 53 201044626. The main component of the photoelectric conversion semiconductor layer is at least one type of semiconductor semiconductor. The compound semiconductor has a fourth element, a second element, and a metal layer = a supply layer containing at least a type of face: electricity = pool 'which has the electromotive force (10) as described in the patent application scope (10). (4) The electric relay battery according to item __26, which has the dry material for forming a photoelectric conversion supply layer according to the 27th item of the patent application scope, and the m is = the type of the test (earth) metal type Metal and / or soil test gold ^ electricity and contains one or more 32 · If the application for the scope of the 31st electric transfer county inspection (soil) metal supply layer in the formation of the ship ^ various types of gold collection / New Zealand metal The situation is one or atomic %. The main / 蜀扪 total is 1 atom% to 30 electricity two: Fan = 31 items for splashing to form light than the electric shirt more than 1 ohm / cm. _ 'Cap The tree 34 is a dry material for the metal (s) metal supply layer of the electrotransformation device as described in claim 33, and includes the metal of the type or types of The material of the handle.矽/or alkaline earth metal yttrium target 35. The yttrium ore metal supply layer of the electrical conversion device according to claim 34 of claim 34 includes at least one of the types of light formed by the yttrium. The elements of the material. Among the ethnic groups formed by the sighs, 36. If the metal supply layer of the (t) conversion device of the 35th conversion device of the patent application scope is used, the mineral-forming light type is composed of Al, Ga and B; The total amount is from 1 atom% to 3 atom. /〇. In the case of the application of the scope of the 36th item of the patent, the dry material of the metal supply layer of the device (soil), the element selected from the group consisting of ί and B J ~ Rima 10 atom % to 20 atom%. ◎Electricity Ϊ=Scope Γ4 items for _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The dried material described in Item 38 of the patent scope is formed into a dry material of the optical package, and the dried material is composed of sodium fluoride and carbonate. Li 〇################################################################################################# A sintered body obtained by sintering a mixed powder of the at least one type of sodium salt powder and cerium powder, which may contain unavoidable impurities. 56
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