TW201133889A - Substrate with transparent conducting layer for solar cell, solar cell, and producing method therefor - Google Patents

Substrate with transparent conducting layer for solar cell, solar cell, and producing method therefor Download PDF

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Publication number
TW201133889A
TW201133889A TW100103481A TW100103481A TW201133889A TW 201133889 A TW201133889 A TW 201133889A TW 100103481 A TW100103481 A TW 100103481A TW 100103481 A TW100103481 A TW 100103481A TW 201133889 A TW201133889 A TW 201133889A
Authority
TW
Taiwan
Prior art keywords
layer
conductive film
transparent conductive
solar cell
substrate
Prior art date
Application number
TW100103481A
Other languages
Chinese (zh)
Inventor
Hirohisa Takahashi
Hiroto Uchida
Tatsumi Usami
Junsuke Matsuzaki
Yoshinobu Ue
Tadamasa Kobayashi
Kenichi Imakita
Shoji Samitsu
Yoshiaki Yamamoto
Shinichi Asahina
Kazuya Saito
Masahide Matsubara
Satoshi Okabe
Toshiyuki Gotou
Taketo Maruyama
Original Assignee
Ulvac Inc
Mitsubishi Gas Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ulvac Inc, Mitsubishi Gas Chemical Co filed Critical Ulvac Inc
Publication of TW201133889A publication Critical patent/TW201133889A/en

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    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
    • H01L31/076—Multiple junction or tandem solar cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/702—Amorphous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • 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
    • Y02E10/548—Amorphous silicon PV cells

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Photovoltaic Devices (AREA)
  • Physical Vapour Deposition (AREA)
  • Weting (AREA)

Abstract

The present invention provides a method for producing a solar cell having a transparent substrate, a transparent conducting layer which is provided on the transparent substrate and includes ZnO as a major component, a P-I-N type photoelectric conversion unit which has laminated silicon-base amorphous thin layers of a first p-layer, an i-layer, and n-layer, and a middle layer which has a silicon-base crystalline thin layer of a second p-layer arranged between the transparent conducting layer and the first p-layer, the method including: forming the transparent conducting layer on the transparent substrate; forming a fine texture on a surface of the transparent conducting layer by performing a wet etching; forming the middle layer on the transparent conducting layer, and forming the first p-layer, the i-layer, and the n-layer on the middle layer.

Description

201133889 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種太陽電池用附透明導電膜之基板、太 陽電池及該等之製造方法。更詳細而言，本發明係關於一 種可於包含ZnO系材料之透明導電膜中形成自由度較高且 具有所需粗糙度之微細紋理的太陽電池用附透明導電膜之 基板、太陽電池及該等之製造方法。 本申請案係基於且主張2010年2月2曰在曰本申請之專利 特願2010-21407號之優先權’且將其内容引用於此。 【先前技術】 太陽光所含之被稱為光子之能量粒子若觸及丨層，則由 於光伏效應而產生電子與電洞（h〇ie)，電子朝向11層、電洞 朝向P層移動。利用上部電極與背面電極將藉由該光伏效應 而產生之電子取出，將光能轉換成電能之元件為太陽電池。 圖20係非晶矽太陽電池之概略剖面圖。太陽電池丨〇〇中 積層有以下構件：構成表面之玻璃基板1〇1、設於玻璃基 板101上之包含氧化鋅系之透明導電膜之上部電極1〇3、以 非BS矽構成之上層電池1〇5、設於上層電池1〇5與下述下層 電池109之間的包含透明導電膜之中間電極1〇7、以微晶石夕 構成之下層電池1G9、包含透明導電膜之緩衝層11〇、及包 含金屬膜之背面電極lu。 上層電池105係以P層〇〇5p) ' i層（l〇5i)、η層（105η)三層 構造構成，其中i層（105i)係以非晶石夕形成。又下層電池 109亦與上層電池1Q5相同，以p層（⑽p)、^層（⑽〇、打層 153816.doc 201133889 (109η)三層構造構成，其中i層（i〇9i)係以微晶矽構成。 此種太陽電池100中，自玻璃基板101側入射之太陽光通 過上部電極103、上層電池l〇5(p-i-n層）、緩衝層11〇而由 背面電極111所反射。為於太陽電池中使光能之轉換效率 提昇’而設法利用背面電極11 1反射太陽光，或對上部電 極101設置以延長所入射之太陽光之光路的稜鏡效果與光 之封閉效果為目的之被稱為紋理之構造等。緩衝層11 〇係 以防止背面電極111所用之金屬膜之擴散等為目的。 視太陽電池之元件構造不同’光伏效應所使用之波長帶 域不同’但對於構成上部電極之透明導電膜而言，均要求 透過光之性質與將藉由光伏產生之電子取出的電傳導性， 故一直使用在Sn02中添加氟作為雜質之FTO或ZnO系氧化 物半導體薄膜。對於緩衝層，亦要求透過光之性質與電傳 導性。 太陽電池中使用之透明導電膜所要求之特性大致分為導 電性、光學特性、紋理構造三要素。關於第1個要素導電 性，為將所產生之電取出而要求較低之電阻。通常太陽電 池用透明導電膜所使用之FTO係在利用CVD(Chemical Vapor Deposition，化學氣相沈積）而製作之透明導電膜中 於Sn〇2中添加F，藉此F取代Ο而獲得導電性。又，作為 post ITO而受到高度關注的ZnO系材料可藉由濺鍍進行成 膜，藉由將缺氧或含有A1或Ga之材料添加至ZnO中，而獲 得導電性。 第二’由於太陽電池用透明導電膜主要係於入射光側使 153816.doc 201133889 用’故要求使發電層所吸收之波長帶域透過之光學特性。 第三’為利用發電層有效率地吸收太陽光，必需使光散 射之紋理構造。通常’利用濺鍍製程製作之Zn〇系薄膜成 為平坦之表面狀態，故必須進行於透明基板上形成紋理、 或於透明電極上形成紋理之處理。 將此種形成有紋理之透明導電膜配置於透明基板上而成 的附透明導電膜之基板已由各種玻璃廠商等所開發（例如 參照專利文獻1、2)。 然而’此種一般銷售之附透明導電膜之基板係預先規定 透明導電膜表面之紋理形狀，選擇之自由度較低，難以獲 得具有所需粗糙度之微細紋理的附透明導電膜之基板。 因此’謀求開發出自由度較高、於表面具有所需粗糙度 之微細紋理之太陽電池用附透明導電膜之基板及其製造方 法。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2009-140930號公報 [專利文獻2]曰本專利特開2002-158366號公報 【發明内容】 [發明所需解決之問題] 本發明係鑒於此種先前之實際情況而設計，其第一目的 在於提供一種可於藉由濺鍵而形成之透明導電膜之表面形 成自由度較高且具有所需粗糙度之微細紋理、且可充分獲 得由紋理構造所得之稜鏡效果與光之封閉效果的太陽電池 用附透明導電膜之基板之製造方法。 153816.doc 201133889 又，本發明之第二目的在於提供一種於透明導電膜之表 面具有自由度較高且具有所需粗糙度之微細紋理、可充分 獲得由紋理構造所得之稜鏡效果與光之封閉效果的太陽電 池用附透明導電膜之基板。 又本發明之第二目的在於提供一種轉換效率較高之太 陽電池。 又，本發明之第四目的在於提供一種可於透明導電膜之 表面形成自由度較高且具有所需粗糙度之微細紋理、且可 充分獲得由紋理構造所得之稜鏡效果與光之封閉效果、轉 換效率較高之太陽電池之製造方法。 [解決問題之技術手段] 為解決上述課題’本發明採用以下手段。 (1)本發明之第一態樣係一種太陽電池之製造方法，其係 具有以下構件之太陽電池之製造方法：透明基板；設置於 上述透明基板上、以Zn〇為主成分之透明導電膜；將作為 非曰a質之石夕系薄膜之第ip層、i層及η層積層而形成之pin型 之光電轉換單元；及配置於上述透明導電膜與上述第邙層 之間、由作為結晶質之矽系薄膜之第2p層所形成之中間 層’並且該太陽電池之製造方法依序包括以下步驟：於所 需之製程氣體環境中，對構成上述透明導電膜之母材之靶 材施加濺鍍電壓而進行濺鍍，於上述透明基板上形成上述 透明導電膜；對上述透明導電膜進行濕式蝕刻，於上述透 明導電膜之表面形成微細紋理；於上述透明導電膜上形成 上述中間層；及於上述中間層上依序形成上述第1{)層、上 153816.doc 201133889 述i層及上述η層。 (2) 如上述（〗）之太陽電池之製造方法，其中亦可於上述濕 式蝕刻中，使用含有以下水溶液中之至少—種之蝕刻液： 選自甲酸、乙酸、檸檬酸、乳酸、蘋果酸、丙二酸、琥珀 酸、二醇酸中之羧酸水溶液，選自甲酸銨、乙酸銨、檸檬 酸銨、乳酸銨、蘋果酸銨、丙二酸銨 '琥珀酸銨、二醇酸 銨中之羧酸銨水溶液，選自二伸乙基三胺、三伸乙基四 胺、四伸乙基五胺中之多胺水溶液。 (3) 如上述（1)或（2)之太陽電池之製造方法，其進而包括 於上述濕式蝕刻後，使用選自氫氧化鉀、氫氧化四甲基銨 水溶液中之鹼性水溶液中之至少一種進行後處理的步驟。 (4) 本發明之第2態樣係一種太陽電池，其具備：透明基 板；設置於上述透明基板上，以Ζη〇為主成分，且具有藉 由濕式蝕刻而形成之紋理之透明導電膜；將作為非晶質之 石夕系薄膜之第lp層、i層及η層積層而形成之pin型之光電轉 換單X ;及配置於上述透明導電膜與上述第lp層之間、由 作為結晶質之矽系薄膜之第2p層而形成之中間層。 (5) 本發明之第3態樣係一種太陽電池用附透明導電膜之 基板之製造方法，其係藉由透明基板、及設置於上述透明 基板上之以Zn0為主成分之透明導電膜而形成的太陽電池 用附透明導電膜之基板之製造方法；並且該太陽電池用附 透明導電膜之基板之製造方法依序包括以下步驟：於製程 氣體環境中’對構成上述透明導電膜之母材之靶材施加滅 錄電壓而進行濺鍍’於上述透明基板上形成上述透明導電 153816.doc 201133889 膜’及對上述透明導電膜進行濕式蝕刻，於透明導電膜表 面形成微細紋理；並且 使用在ZnO或ZnO中添加有添加物之材料作為上述母 材。 (6) 如上述（5)之太陽電池用附透明導電膜之基板之製造方 法，其中亦可於上述濕式蝕刻中，使用含有以下水溶液中 之至少一種之蝕刻液：選自曱酸、乙酸、檸檬酸、乳酸、 蘋果酸、丙二酸、琥珀酸、二醇酸中之羧酸水溶液，選自 曱酸銨、乙酸銨、檸檬酸銨、乳酸銨、蘋果酸銨、丙二酸 銨、琥珀酸銨' 二醇酸銨中之羧酸銨水溶液，選自二伸乙 基二胺、二伸乙基四胺、四伸乙基五胺中之多胺水溶液。 (7) 如上述（5)或（6)之太陽電池用附透明導電膜之基板之 製造方法，其進而具備於上述濕式蝕刻後，使用選自氫氧 化卸氮氧化四甲基錄水溶液中之驗性水溶液中之至少一 種進行後處理之步驟。 (8) 本發明之第4態樣係一種太陽電池用附透明導電膜之 基板，其係藉由如上述（5)之方法而製造。 [發明之效果] 本發明中，形成透明導電膜時，使用以Zn〇為主成分之 材料作為母材進行濺鍍，藉此於透明基板上形成透明導電 膜，其後，對透明導電膜進行濕式蝕刻，於表面形成微細 紋理。此時，可藉由改變濺鍍及濕式蝕刻之各種條件而控 制紋理之形狀。藉此可形成自由度較高且具有所需粗糙度 之微細紋理。其結果為，利用本發明之製造方法，可製作 1538l6.doc 201133889 能充分獲得由紋理構造所得之稜鏡效果與光之封閉效果的 太陽電池用附透明導電膜之基板。又，可根據所形成之 pm層之性能、例如所使用之波長區域而形成紋理，故可 提南發電效率，。 又，本發明之太陽電池用附透明導電膜之基板係藉由上 述本發明之方法而製造，故於透明導電膜之表面形成有自 由度較高且具有所需粗糙度之微細紋理。其結果為，本發 明之太陽電池用附透明導電膜之基板可充分獲得由紋理構 造所得之稜鏡效果與光之封閉效果。 根據本發明之太陽電池，構成pin型之光電轉換單元之 第lp層、i層及η層包含非晶質之矽系薄膜，且於上述透明 導電膜與構成上述光電轉換單元之上述第lp層之間配置有 包含結晶質之矽系薄膜之第2ρ層作為中間層，故可緩和透 明導電膜與包含非晶質之矽系薄膜之第lp層之界面的失 配。藉此，可增大光電轉換單元之填充因子（FF，fuiBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate with a transparent conductive film for a solar cell, a solar cell, and a method of manufacturing the same. More specifically, the present invention relates to a substrate, a solar cell, and a solar cell with a transparent conductive film for a solar cell which can form a fine texture having a high degree of freedom and a desired roughness in a transparent conductive film containing a ZnO-based material. And other manufacturing methods. The present application is based on and claims the priority of Japanese Patent Application No. 2010-21407, the entire disclosure of which is hereby incorporated by reference. [Prior Art] If the energy particles called photons contained in sunlight touch the enamel layer, electrons and holes are generated due to the photovoltaic effect, and the electrons move toward the 11th layer and the holes move toward the P layer. The electrons generated by the photovoltaic effect are taken out by the upper electrode and the back electrode, and the element that converts light energy into electrical energy is a solar cell. Figure 20 is a schematic cross-sectional view of an amorphous germanium solar cell. In the solar cell, the following components are laminated: a glass substrate 构成1 constituting the surface, an upper electrode 1〇3 of a transparent conductive film containing zinc oxide provided on the glass substrate 101, and an upper battery formed of a non-BS 矽1〇5, an intermediate electrode 1〇7 including a transparent conductive film between the upper layer battery 1〇5 and the lower layer battery 109 described below, a lower layer battery 1G9 composed of a microcrystalline stone, and a buffer layer 11 including a transparent conductive film. 〇, and the back electrode lu containing the metal film. The upper battery 105 is constructed by a three-layer structure of a P layer 〇〇5p) 'i layer (10〇5i) and an η layer (105η), wherein the i layer (105i) is formed by amorphous austenite. The lower layer battery 109 is also the same as the upper layer battery 1Q5, and is composed of a p layer ((10)p), a layer ((10) 〇, a layer 153816.doc 201133889 (109η), and the i layer (i〇9i) is microcrystal. In the solar cell 100, sunlight incident from the side of the glass substrate 101 passes through the upper electrode 103, the upper battery 105 (pin layer), and the buffer layer 11〇, and is reflected by the back electrode 111. In order to improve the conversion efficiency of light energy, it is called to use the back electrode 11 1 to reflect sunlight, or to set the upper electrode 101 to extend the effect of the light path of the incident sunlight and the light blocking effect. The structure of the texture, etc. The buffer layer 11 is designed to prevent the diffusion of the metal film used for the back surface electrode 111. The component structure of the solar cell is different, 'the wavelength band used for the photovoltaic effect is different' but is transparent to the upper electrode. In the case of a conductive film, the nature of transmitted light and the electrical conductivity of electrons generated by photovoltaics are required. Therefore, FTO or ZnO-based oxide semiconductor thin film in which fluorine is added as an impurity in Sn02 has been used. For the buffer layer, the properties and electrical conductivity of the transmitted light are also required. The characteristics required for the transparent conductive film used in solar cells are roughly classified into three factors: conductivity, optical properties, and texture structure. Regarding the conductivity of the first element, In order to take out the generated electricity, a lower resistance is required. Generally, the FTO used for a transparent conductive film for a solar cell is in a transparent conductive film produced by CVD (Chemical Vapor Deposition) in Sn 〇 2 F is added to obtain conductivity by replacing yttrium with F. Further, a ZnO-based material which is highly regarded as post ITO can be formed by sputtering, by adding an oxygen-deficient or material containing A1 or Ga to Conductivity is obtained in ZnO. Secondly, since the transparent conductive film for solar cells is mainly applied to the incident light side, the optical characteristics of the wavelength band absorbed by the power generation layer are required. In order to utilize the power generation layer to efficiently absorb sunlight, it is necessary to scatter the texture of the light. Generally, the Zn-based film produced by the sputtering process has a flat surface state. It is necessary to form a texture on the transparent substrate or to form a texture on the transparent electrode. The substrate with the transparent conductive film formed by disposing the textured transparent conductive film on the transparent substrate has been used by various glass manufacturers and the like. Development (for example, refer to Patent Documents 1 and 2). However, the substrate of the transparent conductive film generally sold in advance defines the texture shape of the surface of the transparent conductive film, and the degree of freedom of selection is low, and it is difficult to obtain a desired roughness. A substrate having a transparent conductive film with a fine texture. Therefore, it has been desired to develop a substrate with a transparent conductive film for a solar cell having a high degree of freedom and a fine texture having a desired roughness on the surface, and a method for producing the same. [Prior Art Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2009-140930 [Patent Document 2] Japanese Patent Laid-Open Publication No. JP-A No. 2002-158366 (Summary of the Invention) [Problems to be Solved by the Invention] The present invention has been devised in view of such a prior art, and a first object thereof is to provide a fine texture having a high degree of freedom and a desired roughness, which can be formed on a surface of a transparent conductive film formed by a sputtering bond, and A method for producing a substrate with a transparent conductive film for a solar cell, which is obtained by a texture structure and a light-blocking effect. Further, a second object of the present invention is to provide a fine texture having a high degree of freedom on a surface of a transparent conductive film and having a desired roughness, and a sufficient effect obtained by the texture structure and light can be obtained. A solar cell with a closed conductive film is used for the sealing effect. Still another object of the present invention is to provide a solar cell having a high conversion efficiency. Further, a fourth object of the present invention is to provide a fine texture which has a high degree of freedom and a desired roughness on the surface of a transparent conductive film, and which can sufficiently obtain the enamel effect and the light-blocking effect obtained by the texture structure. A method for manufacturing a solar cell with high conversion efficiency. [Technical means for solving the problem] In order to solve the above problems, the present invention employs the following means. (1) A first aspect of the present invention is a method for producing a solar cell, which is a method for manufacturing a solar cell having the following members: a transparent substrate; and a transparent conductive film provided on the transparent substrate and having Zn〇 as a main component a pin-type photoelectric conversion unit formed as an ip layer, an i layer, and an η layer of a non-曰 a quality stone film; and disposed between the transparent conductive film and the second layer The intermediate layer formed by the second p layer of the crystalline lanthanide film and the method for manufacturing the solar cell sequentially includes the steps of: forming a target material of the base material of the transparent conductive film in a desired process gas atmosphere Depositing a sputtering voltage to form a transparent conductive film on the transparent substrate; wet etching the transparent conductive film to form a fine texture on a surface of the transparent conductive film; and forming the middle portion on the transparent conductive film And forming the first {) layer, the upper 153816.doc 201133889, the i layer, and the n layer on the intermediate layer. (2) The method for producing a solar cell according to the above (1), wherein in the wet etching, at least one of the following aqueous solutions may be used: from formic acid, acetic acid, citric acid, lactic acid, apple An aqueous solution of carboxylic acid in acid, malonic acid, succinic acid or glycolic acid, selected from the group consisting of ammonium formate, ammonium acetate, ammonium citrate, ammonium lactate, ammonium malate, ammonium malonate ammonium succinate, ammonium glycolate The aqueous ammonium carboxylate solution is selected from the group consisting of polyamine aqueous solutions of di-ethyltriamine, tri-ethylidenetetraamine and tetra-ethylpentamine. (3) The method for producing a solar cell according to the above (1) or (2), further comprising, after the wet etching, using an alkaline aqueous solution selected from the group consisting of potassium hydroxide and tetramethylammonium hydroxide aqueous solution; At least one step of performing post-treatment. (4) A solar cell comprising: a transparent substrate; a transparent conductive film provided on the transparent substrate and having Ζη〇 as a main component and having a texture formed by wet etching a pin-type photoelectric conversion unit X formed as a lp layer, an i layer, and an η layer of an amorphous slab film; and disposed between the transparent conductive film and the lp layer The intermediate layer formed by the second p layer of the crystalline ruthenium film. (5) A third aspect of the present invention provides a method for producing a substrate with a transparent conductive film for a solar cell, which comprises a transparent substrate and a transparent conductive film containing Zn0 as a main component provided on the transparent substrate. A method for manufacturing a substrate with a transparent conductive film for a solar cell to be formed; and a method for manufacturing a substrate with a transparent conductive film for the solar cell, comprising the steps of: 'in the process gas atmosphere, 'to the base material constituting the transparent conductive film The target is subjected to sputtering by sputtering, and the transparent conductive 153816.doc 201133889 film is formed on the transparent substrate, and the transparent conductive film is wet-etched to form a fine texture on the surface of the transparent conductive film; A material to which an additive is added to ZnO or ZnO is used as the above-mentioned base material. (6) The method for producing a substrate with a transparent conductive film for a solar cell according to the above (5), wherein in the wet etching, an etching solution containing at least one of the following aqueous solutions may be used: selected from the group consisting of citric acid and acetic acid. An aqueous solution of carboxylic acid in citric acid, lactic acid, malic acid, malonic acid, succinic acid or glycolic acid, selected from the group consisting of ammonium citrate, ammonium acetate, ammonium citrate, ammonium lactate, ammonium malate, ammonium malonate, An aqueous ammonium carboxylate solution in ammonium succinate 'ammonium glycolate, selected from the group consisting of polyamine aqueous solutions of diethylidene diamine, diethylidene tetraamine, and tetraethylidene pentaamine. (7) The method for producing a substrate with a transparent conductive film for a solar cell according to the above (5) or (6), further comprising: after the wet etching, using an aqueous solution selected from the group consisting of hydrogen oxynitride and tetramethyl hydride The step of post-treating at least one of the aqueous solutions. (8) A fourth aspect of the invention is a substrate for a solar cell with a transparent conductive film, which is produced by the method of the above (5). [Effects of the Invention] In the present invention, when a transparent conductive film is formed, a material having Zn 〇 as a main component is used as a base material for sputtering, thereby forming a transparent conductive film on a transparent substrate, and thereafter, performing a transparent conductive film on the transparent conductive film. Wet etching to form fine texture on the surface. At this time, the shape of the texture can be controlled by changing various conditions of sputtering and wet etching. Thereby, a fine texture having a high degree of freedom and having a desired roughness can be formed. As a result, according to the production method of the present invention, it is possible to produce a substrate with a transparent conductive film for a solar cell which can sufficiently obtain the effect of the enthalpy obtained by the texture structure and the light-blocking effect of 1538l6.doc 201133889. Further, the texture can be formed according to the performance of the formed pm layer, for example, the wavelength region used, so that the power generation efficiency can be improved. Further, since the substrate with a transparent conductive film for a solar cell of the present invention is produced by the method of the present invention described above, a fine texture having a high degree of freedom and having a desired roughness is formed on the surface of the transparent conductive film. As a result, the substrate with the transparent conductive film for the solar cell of the present invention can sufficiently obtain the effect of the enamel effect and the light blocking effect obtained by the texture structure. According to the solar cell of the present invention, the lp layer, the i layer, and the η layer constituting the pin type photoelectric conversion unit include an amorphous lanthanoid film, and the transparent conductive film and the lp layer constituting the photoelectric conversion unit Since the second p layer including the crystalline ruthenium-based film is disposed as an intermediate layer, mismatching of the interface between the transparent conductive film and the lp layer including the amorphous lanthanoid film can be alleviated. Thereby, the fill factor of the photoelectric conversion unit can be increased (FF, fui

Factor)。其結果，本發明之太陽電池可發揮較高之轉換效 率。 上述太陽電池之製造方法中，於形成透明導電膜時，使 用上述以ZnO為主成分之材料作為母材進行濺鍍，藉此於 透明基板上形成透明導電膜，其後，對透明導電膜進行濕 式触刻’於表面形成微細紋理。此時，可藉由改變賤鑛及 濕式钱刻之各種條件而控制紋理之形狀。藉此可形成自由 度較高且具有所需粗糙度之微細紋理，故可獲得附有紋理 構造之太陽電池。該紋理構造發揮稜鏡效果與光之封閉效 153816.doc .10· 201133889 果，故本發明之太陽電池可發揮較高之轉換效率。 又，本發明中，於與構成上述光電轉換單元之上述第lp 層之：’形成包含結晶質之矽系薄膜之第2p層作為中間 層。藉此，可緩和透明導電膜、肖包含非晶質之矽系薄膜 之第ip層之界面的失配。藉此，可增大第一光電轉換單元 6之填充因子（ff)。 其結果為’制本發明之製造方法，可充分獲得由紋理 構造所得之稜鏡效果與光之封閉效果，可製作轉換效率較 高之太陽電池。 【實施方式】 以下，根據圖式對本發明之太陽電池及其製造方法之最 佳形態加以說明。再者，本實施形態料更良好地理解發 明之主旨而進行具體說明，只要無特別指定，則不限定本 發明。 (太陽電池） &lt;第一實施形態&gt; 本發明第-實施形態之太陽電池1A⑴係使用非晶矽型 之太陽電池作為第-光電轉換單元6(上㈣池），使用微晶 石夕型之太陽電池作為第二光電轉換單元7(下$電池），並將 該等積層而成之堆疊構造之太陽電池。 首先，根據圖1對本實施形態之太陽電池1Α(ι)加以說 明。圖1係表示太陽電池以⑴之構成之一例的剖面圖。 太陽電池1A(1)中積層有以下構件：構成表面之包含破 璃基板等之絕緣性透明基板2、設置於透明基板2上之包含 153816.doc -11- 201133889 氧化鋅系之透明導電膜4之上部電極3、以非晶矽構成之 一光電轉換單元6、以微晶矽構成之第二光電轉換單元7、 包含透明導電膜之緩衝層U、及包含金屬 興狀〈背面電極 12。透明基板2與設置於該透明基板2上之透明導電膜4構 成附透明導電膜之基板1〇。 該透明導電膜4係藉由下述製造方法而成膜’由此具有 所需粗糙度之微細紋理。藉此，太陽電池〖具有由紋理構 造所得之稜鏡效果與光之封閉效果，可發揮較高之轉換效 率。 又，太陽電池1係a-Si/微晶Si堆疊型太陽電池。此種堆 疊構造之太陽電池1中，以第一光電轉換單元6吸收短波長 光，以第二光電轉換單元7吸收長波長光，藉此可實現發 電效率之提昇。 再者’上部電極3之膜厚係以2000 A〜10000 A之膜厚而 形成。 第一光電轉換單元6係以p層（6p)、i層（6i)、η層（6n)之三 層構造構成’該等p層（6p)、i層（6i)及η層（6n)係以非晶矽 而形成。又’第二光電轉換單元7亦與第一光電轉換單元6 相同’以p層（7p)、i層（7i)、η層（7n)之三層構造構成，該 等p層（7p)、i層（7i)及η層（7n)係以微晶矽而構成。 而且’特別是本實施形態之太陽電池1A(1)之特徵在 於：於上述透明導電膜4與構成上述光電轉換單元之上述p 層（6p)之間’配置有包含結晶質之矽系薄膜之p層（第2p層） 作為中間層5。 153816.doc •12· 201133889 本實施形態中，於上述透明導電膜4與構成第一光電轉 換單元6之p層（6p)之間，配置有包含結晶質之矽系薄膜之p 層（第2p層）作為中間層5，故可緩和透明導電膜4與包含非 晶質之矽系薄膜之p層（6p)之界面的失配。藉此，可增大第 一光電轉換單元之填充因子（FF)。其結果，本實施形態之 太陽電池1 A( 1)可發揮較高之轉換效率。 此種構成之太陽電池1A(1)中，若太陽光所含之被稱為 光子之能量粒子觸及i層，則藉由光伏效應而產生電子與 電洞（hole)，電子朝向n層、電洞朝向口層而移動。可利用 上部電極3與背面電極12將藉由該光伏效應而產生之電子 取出’將光能轉換成電能。 又，自透明基板2側入射之太陽光通過各層而由背面電 極12反射《為提高光能之轉換效率，而於太陽電池丨中採 用以延長入射於上部電極3之太陽光之光路的稜鏡效果與 光之封閉效果為目的之紋理構造。 如下文所述，於形成構成上部電極3之透明導電膜4時， 使用以ΖηΟ為主成分之材料作為母材進行濺鍍，藉此於透 明基板2上形成透明導電膜，其後，對透明導電膜4進行濕 式#刻’於表面形成微細紋理。此時，可藉由改變濕式钱 刻之各種條件而控制紋理之形狀。藉此可形成自由度較高 且具有所需粗链度之微細紋理。 其結果，如此而獲得之太陽電池用附透明導電膜之基板 10中’於透明導電膜4之表面形成有自由度較高且具有所 需粗縫度之微細紋理。藉此，太陽電池用附透明導電膜之 153816.doc -13- 201133889 基板ίο可充分獲得藉由紋理構造所得之稜鏡效果與光之封 閉效果。特別是為適當地封閉第一光電轉換單元6與第二 光電轉換單元7所使用之波長之光，可選擇性形成微細纹 理。 再者’亦可於第一光電轉換單元6與第二光電轉換單元7 之間設置中間電極8。藉由在第一光電轉換單元6與第二光 電轉換單元7之間設置中間電極8，通過第一光電轉換單元 6而到達第二光電轉換單元7之光之一部分由中間電極8所 反射，再次入射至第一光電轉換單元6側，故電池之感度 特性提昇’有助於發電效率之提昇。特別是中間電極8較 佳為將第一光電轉換單元6中使用之波長之光反射，使第 二光電轉換單元7中使用之波長之光透過。 (太陽電池之製造方法） 繼而’對此種太陽電池1A(1)之製造方法加以說明。 本實施形態之太陽電池之製造方法係光入射側之上部電 極3包含以Zn〇為基本構成之透明導電膜4的太陽電池之製 造方法’至少依序進行以下步驟：於所需之製程氣體環境 中’ 一邊對構成上述透明導電膜4之母材之靶材施加濺鍍 電壓’一邊於該靶材之表面產生水平磁場而進行濺鍍，於 上述透明基板2上形成上述透明導電膜4;對上述透明導電 膜4進行濕式钮刻，於該透明導電膜4表面形成微細紋理； 於上述透明導電膜4上形成上述中間層5;及於上述中間層 5上依序形成上述第一光電轉換單元6之p層（6p)、丨層（6i)及 η層（6n)。此時’作為上述母材，使用&amp; Zn〇為主成分（7〇% I53816.doc 201133889 以上）之材料。 本實施形態之太陽電池1A(1)之製造方法中，於形成透 明導電膜4時，使用以Zn0為主成分之材料作為母材進行 濺鍍，藉此於透明基板2上形成透明導電膜4,然後對透明 導電膜4進行濕式蝕刻，於表面形成微細紋理。此時，可 藉由改變濕式蝕刻之各種條件而控制紋理之形狀。藉此可 I成自由度較南且具有所需粗糖度之微細紋理，故可獲得 附有紋理構造之太陽電池1A(1)。該紋理構造帶來適合於 發電層所使用之光之波長的棱鏡效果與光之封閉效果，故 本實施形態之太陽電池1A(1)可發揮較高之轉換效率。 又，本實施形態中，於透明導電膜4與構成第一光電轉 換單元6之p層（6p)之間，形成包含結晶質之矽系薄膜之p層 (第2p層）作為中間層5。 本實施形態中，於透明導電膜4與構成第一光電轉換單 元6且包含非晶質之矽系薄膜之p層π&quot;之間，形成包含結 晶質之矽系薄膜之p層（第2p層）作為中間層5，故可緩和透 明導電膜4與包含非晶質之石夕系薄膜之p層（6p)之界面的失 配。藉此，可增大第一光電轉換單元6之填充因子（FF)。 如此，本實施形態之太陽電池1A(1)f，藉由***中間層 5，可增大FF，可提高第一光電轉換單元6之發電效率，甚 至可提昇裝置整體之光電轉換效率。 其結果為’本實施形態之太陽電池之製造方法中，可充 刀獲得由紋理構造所得之稜鏡效果與光之封閉效果，可製 作轉換效率較高之太陽電池1A(1)。 153816.doc 15 201133889 中間層5之厚度例如較佳為5〜10 nm之範圍。例如可設定 為nm中間層5之厚度在5〜1〇 nm2範圍内，可看到填充 因子（FF)與電壓（voc)增大、光電轉換效率增大之效果。 首先，對本實施形態之太陽電池之製造方法中適合於形 成構成上部電極3之氧化鋅系之透明導電膜4的濺鍍裝置 (成膜裝置）之一例加以說明。 (濺鍍裝置1) 圖2係表示本實施形態之太陽電池1之製造方法所使用之 濺鍍裝置（成膜裝置）之一例的概略構成圖，圖3係表示該濺 鑛裝置之成膜室之主要部分的剖面圖。賤鑛裝置係將基 板以豎立狀態搬送之立式往覆式之濺鍍裝置，例如具備搬 入/搬出無鹼玻璃基板（未圖示）等基板之裝入/取出室22、 及於基板上形成氧化鋅系之透明導電膜4之成膜室（真空容 器）23。 於裝入/取出室22中’設有對該室内進行粗真空抽吸之 旋轉泵等粗抽吸排氣機構24，於其室内，可移動地配置有 用以保持·搬送基板之基板托盤25。 另一方面’於成膜室23之一個側面23a上，以g立方式 設有加熱基板26之加熱器3 1，於另一側面23b上，以暨立 方式設有保持氧化鋅系材料之靶材27並施加所需之滅：錄$ 壓之濺鍍陰極機構（靶材保持手段）32，進而設有對該^ 進行高真空抽吸之渦輪分子泵等高真空排氣機構33、對&amp; 材27施加濺鍍電壓之電源34、及對該室内導入氣體之氣體 導入機構35。 153816.doc -16 - 201133889 濺鍍陰極機構3 2係包含板狀之金屬板、用以利用焊材等 藉由焊接（固定）而固定乾材27者。 電源34係用以對靶材27施加將高頻電壓疊加於直流電壓 而成之濺鍍電壓者，具備直流電源與高頻電源（省略圖 示）。 氣體導入機構35具備導入Ar等濺鍍氣體之濺鍍氣體導入 機構35a、導入氫氣之氫氣導入機構35b、導入氧氣之氧氣 導入機構35c、導入水蒸氣之水蒸氣導入機構35d。 再者，該氣體導入機構35中，關於氫氣導入機構35b〜水 蒸氣導入機構35d，只要視需要而選擇使用即可，例如亦 可如氫氣導入機構35b與氧氣導入機構35c、氫氣導入機構 35b與水蒸氣導入機構35d般由2個機構所構成。 (濺鍍裝置2) 圖4係表示本實施形態之太陽電池之製造方法所使用之 其他濺鍍裝置之一例、即往覆式之磁控濺鍍裝置之成膜室 之主要部分的剖面圖。圖4所示之磁控濺鑛裝置4〇與圖2、 3所示之濺鍍裝置20的不同點在於：於成膜室以之一個側 面23b，以豎立方式設有保持氧化鋅系材料之靶材27並產 生所需之磁場之濺鍍陰極機構（靶材保持機構）42。 濺鍍陰極機構42具備以焊材等焊接（固定）有靶材27之背 面板43、及沿著背面板43之背面配置之磁路44。該磁路44 於靶材27之表面產生水平磁場，將複數個磁路單元(圖艸 為2個）44a、44b藉由托架45加以連結而成為一體，磁路單 凡44a、44b分別具備背面板43側之表面之極性互不相同之 I53816.doc •17· 201133889 第1磁石46及第2磁石47、與安裝該等磁石之磁軛48。 該磁路44中，藉由背面板43側之極性不同之第！磁石扑 及第2磁石47，產生磁力線49所表示之磁場。藉此，於第i 磁石46與第2磁石47之間的把材7之表面，產生垂直磁場成 為〇(水平磁場最大）之位置50。於該位置5〇生成高密度電 漿，由此可提高成膜速度。 此種圖4所示之成膜裝置中，於成膜室23之一個側面23b 以豎立方式設有產生所需磁場之濺鑛陰極機構42，故藉由 將跑鍵電壓設為340 V以下，將靶材27表面之水平磁場強 度之最大值a又為600局斯以上’可形成晶格對準之氧化鋅 系之透明導電膜。該氧化鋅系之透明導電膜即便於成膜後 在尚baL下進行退火處理亦難以被氧化，可抑制電阻率之增 大’可使構成太陽電池1之上部電極的氧化鋅系之透明導 電膜成為耐熱性優異者。 繼而，作為本實施形態之太陽電池之製造方法之一例， 對使用圖2及圖4所示之濺鍍裝置1，於透明基板2上形成構 成太陽電池1之上部電極3的氧化鋅系之透明導電膜4之方 法加以例示。 首先’藉由焊材等將靶材27焊接固定於濺鍍陰極機構 42。此處’作為靶材’可列舉氧化鋅系材料、例如添加有 0.1〜10質量％之鋁（A1)之摻鋁氧化鋅（AZO)、添加有（My〇 質量％之鎵（Ga)之摻鎵氧化鋅（GZO)等，其中，就可形成 電阻率較低之薄膜之方面而言，較佳為摻鋁氧化鋅 (AZO)。 153816.doc •18- 201133889 繼而’於將包含例如玻璃之太陽電池1之基板26(透明基 板2)收容於裝入/取出室22之基板托盤25之狀態下，利用粗 抽吸排氣機構4對裝入/取出室22及成膜室23進行粗真空抽 吸。藉此’於裝入/取出室22及成膜室23達到特定之真空 度、例如0.27 Pa(2.0 mTorr)後，將基板26自裝入/取出室 22搬入至成膜室23中。將該基板26配置於設定為關閉之狀 態之加熱器3 1前’使該基板26對向於靶材27。繼而，藉由 加熱器31對該基板26進行加熱，調整為i〇〇&lt;&gt;c〜6〇〇ec之溫 度範圍内。 然後’利用高真空排氣機構33對成膜室23進行高真空抽 吸’於成膜室23達到特定之高真空度、例如2 7xl〇-4Factor). As a result, the solar cell of the present invention can exhibit a high conversion efficiency. In the method for producing a solar cell, when a transparent conductive film is formed, a material having ZnO as a main component is used as a base material, and a transparent conductive film is formed on the transparent substrate, and then the transparent conductive film is formed. Wet-touching 'forms fine texture on the surface. At this time, the shape of the texture can be controlled by changing various conditions of the strontium ore and wet money. Thereby, a fine texture having a high degree of freedom and having a desired roughness can be formed, so that a solar cell with a textured structure can be obtained. The texture structure exerts a 稜鏡 effect and a light blocking effect. Therefore, the solar cell of the present invention can exert a high conversion efficiency. Further, in the present invention, the second p layer including the crystalline ruthenium-based film is formed as an intermediate layer with the lp layer constituting the photoelectric conversion unit. Thereby, the mismatch of the interface between the transparent conductive film and the ip layer including the amorphous lanthanoid film can be alleviated. Thereby, the fill factor (ff) of the first photoelectric conversion unit 6 can be increased. As a result, the manufacturing method of the present invention can sufficiently obtain the enamel effect and the light-blocking effect obtained by the texture structure, and a solar cell having high conversion efficiency can be produced. [Embodiment] Hereinafter, a preferred embodiment of the solar cell of the present invention and a method for producing the same will be described based on the drawings. It is to be noted that the present invention will be specifically described with reference to the gist of the invention, and the present invention is not limited thereto unless otherwise specified. (Solar cell) &lt;First Embodiment&gt; The solar cell 1A(1) of the first embodiment of the present invention uses an amorphous germanium type solar cell as the first photoelectric conversion unit 6 (upper (four) cell), and uses a microcrystalline stone type. The solar cell is used as the second photoelectric conversion unit 7 (lower battery), and the stacked solar cells are stacked. First, the solar cell 1 (I) of the present embodiment will be described with reference to Fig. 1 . Fig. 1 is a cross-sectional view showing an example of the configuration of the solar cell (1). In the solar cell 1A (1), there are laminated members: an insulating transparent substrate 2 including a glass substrate or the like constituting the surface, and a transparent conductive film 4 comprising 153816.doc -11-201133889 zinc oxide based on the transparent substrate 2. The upper electrode 3, one of the photoelectric conversion units 6 made of amorphous germanium, the second photoelectric conversion unit 7 made of microcrystalline germanium, the buffer layer U including the transparent conductive film, and the metal-containing <back surface electrode 12. The transparent substrate 2 and the transparent conductive film 4 provided on the transparent substrate 2 constitute a substrate 1A with a transparent conductive film. The transparent conductive film 4 is formed into a film by the following production method, thereby having a fine texture of a desired roughness. Thereby, the solar cell has a high effect of converting the effect of the enamel effect and the light encapsulation effect obtained by the texture. Further, the solar cell 1 is an a-Si/microcrystalline Si stacked solar cell. In the solar cell 1 of such a stacked structure, the short-wavelength light is absorbed by the first photoelectric conversion unit 6, and the long-wavelength light is absorbed by the second photoelectric conversion unit 7, whereby the power generation efficiency can be improved. Further, the film thickness of the upper electrode 3 is formed by a film thickness of 2,000 Å to 10,000 Å. The first photoelectric conversion unit 6 is configured by a three-layer structure of a p layer (6p), an i layer (6i), and an n layer (6n). The p layers (6p), the i layers (6i), and the n layers (6n) are formed. It is formed by amorphous germanium. Further, the second photoelectric conversion unit 7 is also configured in the same manner as the first photoelectric conversion unit 6 in a three-layer structure of a p layer (7p), an i layer (7i), and an n layer (7n), and the p layers (7p), The i layer (7i) and the η layer (7n) are formed by microcrystalline germanium. In particular, the solar cell 1A (1) of the present embodiment is characterized in that a crystalline film containing a ruthenium film is disposed between the transparent conductive film 4 and the p layer (6p) constituting the photoelectric conversion unit. The p layer (the second p layer) serves as the intermediate layer 5. 153816.doc • 12· 201133889 In the present embodiment, a p-layer containing a crystalline lanthanoid film is disposed between the transparent conductive film 4 and the p-layer (6p) constituting the first photoelectric conversion unit 6 (2p) Since the layer is the intermediate layer 5, the mismatch of the interface between the transparent conductive film 4 and the p layer (6p) containing the amorphous lanthanoid film can be alleviated. Thereby, the fill factor (FF) of the first photoelectric conversion unit can be increased. As a result, the solar cell 1 A(1) of the present embodiment can exhibit a high conversion efficiency. In the solar cell 1A(1) having such a configuration, if the energy particles called photons contained in the sunlight touch the i-layer, electrons and holes are generated by the photovoltaic effect, and the electrons are directed toward the n-layer and the electricity. The hole moves towards the mouth layer. The upper electrode 3 and the back electrode 12 can be used to extract light energy generated by the photovoltaic effect into electrical energy. Further, the sunlight incident from the side of the transparent substrate 2 passes through the respective layers and is reflected by the back surface electrode 12. In order to increase the conversion efficiency of the light energy, the solar cell is used to extend the light path of the sunlight incident on the upper electrode 3. The texture structure for the purpose of the effect and the light blocking effect. As described below, when the transparent conductive film 4 constituting the upper electrode 3 is formed, a material having a composition of ΖηΟ as a base material is used as a base material to form a transparent conductive film on the transparent substrate 2, and then transparent. The conductive film 4 is wet-etched to form a fine texture on the surface. At this time, the shape of the texture can be controlled by changing various conditions of the wet money. Thereby, a fine texture having a high degree of freedom and having a desired thick chain degree can be formed. As a result, in the substrate 10 with a transparent conductive film for solar cells thus obtained, a fine texture having a high degree of freedom and having a desired rough degree is formed on the surface of the transparent conductive film 4. Thereby, the 153816.doc -13-201133889 substrate ίο with a transparent conductive film for a solar cell can sufficiently obtain the effect of the ruthenium obtained by the texture structure and the sealing effect of light. In particular, in order to appropriately block the light of the wavelength used by the first photoelectric conversion unit 6 and the second photoelectric conversion unit 7, fine texture can be selectively formed. Further, the intermediate electrode 8 may be provided between the first photoelectric conversion unit 6 and the second photoelectric conversion unit 7. By providing the intermediate electrode 8 between the first photoelectric conversion unit 6 and the second photoelectric conversion unit 7, a portion of the light that reaches the second photoelectric conversion unit 7 through the first photoelectric conversion unit 6 is reflected by the intermediate electrode 8, again Incident to the side of the first photoelectric conversion unit 6, the sensitivity characteristic of the battery is improved to contribute to an increase in power generation efficiency. In particular, the intermediate electrode 8 preferably reflects light of a wavelength used in the first photoelectric conversion unit 6 to transmit light of a wavelength used in the second photoelectric conversion unit 7. (Manufacturing Method of Solar Cell) Next, a method of manufacturing the solar cell 1A (1) will be described. The method for producing a solar cell according to the present embodiment is a method for manufacturing a solar cell in which the light-incident-side upper electrode 3 includes a transparent conductive film 4 having a Zn〇 basic structure, and at least sequentially performs the following steps: In the middle of the 'targeting material of the base material of the transparent conductive film 4, a sputtering magnetic field is applied, and a horizontal magnetic field is generated on the surface of the target to perform sputtering, and the transparent conductive film 4 is formed on the transparent substrate 2; The transparent conductive film 4 is wet-engraved to form a fine texture on the surface of the transparent conductive film 4; the intermediate layer 5 is formed on the transparent conductive film 4; and the first photoelectric conversion is sequentially formed on the intermediate layer 5 The p layer (6p), the germanium layer (6i) and the n layer (6n) of the unit 6. At this time, as the above-mentioned base material, a material containing & Zn 〇 as a main component (7 % I53816.doc 201133889 or more) was used. In the method of manufacturing the solar cell 1A (1) of the present embodiment, when the transparent conductive film 4 is formed, a material having Zn0 as a main component is used as a base material for sputtering, thereby forming a transparent conductive film 4 on the transparent substrate 2. Then, the transparent conductive film 4 is wet-etched to form a fine texture on the surface. At this time, the shape of the texture can be controlled by changing various conditions of the wet etching. Thereby, the fine texture having a relatively small degree of freedom and having a desired coarse sugar degree can be obtained, so that the solar cell 1A (1) having the texture structure can be obtained. This texture structure brings about a prism effect and a light blocking effect suitable for the wavelength of light used in the power generation layer. Therefore, the solar cell 1A(1) of the present embodiment can exhibit high conversion efficiency. Further, in the present embodiment, a p-layer (second p-layer) containing a crystalline lanthanoid film is formed as the intermediate layer 5 between the transparent conductive film 4 and the p-layer (6p) constituting the first photoelectric conversion unit 6. In the present embodiment, a p-layer (second p-layer) containing a crystalline lanthanoid film is formed between the transparent conductive film 4 and the p-layer π&quot; which constitutes the first photoelectric conversion unit 6 and includes an amorphous lanthanoid thin film. As the intermediate layer 5, the mismatch of the interface between the transparent conductive film 4 and the p layer (6p) containing the amorphous slab film can be alleviated. Thereby, the fill factor (FF) of the first photoelectric conversion unit 6 can be increased. As described above, in the solar cell 1A(1)f of the present embodiment, by inserting the intermediate layer 5, the FF can be increased, the power generation efficiency of the first photoelectric conversion unit 6 can be improved, and the photoelectric conversion efficiency of the entire device can be improved. As a result, in the method for producing a solar cell according to the present embodiment, the effect of encapsulation obtained by the texture structure and the effect of blocking light can be obtained by a knife, and the solar cell 1A (1) having high conversion efficiency can be produced. 153816.doc 15 201133889 The thickness of the intermediate layer 5 is, for example, preferably in the range of 5 to 10 nm. For example, it can be set that the thickness of the nm intermediate layer 5 is in the range of 5 to 1 〇 nm2, and the effect of increasing the fill factor (FF) and voltage (voc) and increasing the photoelectric conversion efficiency can be seen. First, an example of a sputtering apparatus (film forming apparatus) suitable for forming the zinc oxide-based transparent conductive film 4 constituting the upper electrode 3 in the method for producing a solar cell of the present embodiment will be described. (Sputtering apparatus 1) Fig. 2 is a schematic configuration diagram showing an example of a sputtering apparatus (film forming apparatus) used in the method of manufacturing the solar battery 1 of the present embodiment, and Fig. 3 is a view showing a film forming chamber of the sputtering apparatus. A cross-sectional view of the main part. The tantalum ore apparatus is a vertical-type sputtering apparatus that transports a substrate in an upright state, and includes, for example, a loading/unloading chamber 22 for loading and unloading a substrate such as an alkali-free glass substrate (not shown), and forming on the substrate. A film forming chamber (vacuum container) 23 of a transparent conductive film 4 of zinc oxide. In the loading/unloading chamber 22, a rough suction/exhaust mechanism 24 such as a rotary pump that performs rough vacuum suction into the room is provided, and a substrate tray 25 for holding and transporting the substrate is movably disposed in the chamber. On the other hand, on one side surface 23a of the film forming chamber 23, a heater 31 for heating the substrate 26 is provided on the other side surface 23b, and a target for holding a zinc oxide-based material is provided in a standing manner. The material 27 is applied with the required extinction: a sputtering sputtering cathode mechanism (target holding means) 32 is recorded, and a high vacuum evacuation mechanism 33 such as a turbo molecular pump that performs high vacuum suction is provided, and the &amp; The material 27 is supplied with a sputtering voltage source 34 and a gas introduction mechanism 35 for introducing a gas into the chamber. 153816.doc -16 - 201133889 The sputtering cathode mechanism 3 2 includes a plate-shaped metal plate and is used for fixing the dry material 27 by welding (fixing) with a welding material or the like. The power source 34 is for applying a sputtering voltage in which a high-frequency voltage is superimposed on a DC voltage to the target 27, and includes a DC power supply and a high-frequency power supply (not shown). The gas introduction mechanism 35 includes a sputtering gas introduction mechanism 35a that introduces a sputtering gas such as Ar, a hydrogen gas introduction mechanism 35b that introduces hydrogen gas, an oxygen introduction mechanism 35c that introduces oxygen, and a water vapor introduction mechanism 35d that introduces water vapor. In the gas introduction mechanism 35, the hydrogen introduction mechanism 35b to the water vapor introduction mechanism 35d may be selected and used as needed. For example, the hydrogen introduction mechanism 35b, the oxygen introduction mechanism 35c, and the hydrogen introduction mechanism 35b may be used. The steam introduction mechanism 35d is composed of two mechanisms. (Sputtering device 2) Fig. 4 is a cross-sectional view showing a main part of a film forming chamber of a magnetic-type sputtering device of a superposed type, which is an example of another sputtering device used in the method for producing a solar cell of the present embodiment. The magnetron sputtering apparatus 4 shown in FIG. 4 is different from the sputtering apparatus 20 shown in FIGS. 2 and 3 in that a zinc oxide-based material is provided in an upright manner on one side surface 23b of the film forming chamber. The target 27 generates a sputtering cathode mechanism (target holding mechanism) 42 of a desired magnetic field. The sputtering cathode mechanism 42 includes a backing plate 43 to which the target 27 is welded (fixed) with a welding material or the like, and a magnetic path 44 disposed along the back surface of the back surface plate 43. The magnetic circuit 44 generates a horizontal magnetic field on the surface of the target 27, and a plurality of magnetic circuit units (two in the figure) 44a and 44b are connected by a bracket 45, and the magnetic circuit units 44a and 44b are respectively provided. I53616.doc •17· 201133889 The first magnet 46 and the second magnet 47, and the yoke 48 on which the magnets are mounted, are different from each other in the polarity of the surface on the side of the back plate 43. In the magnetic circuit 44, the polarity of the side of the back plate 43 is different! The magnet and the second magnet 47 generate a magnetic field represented by a magnetic line 49. Thereby, a position where the vertical magnetic field becomes 〇 (the horizontal magnetic field is the largest) is generated on the surface of the material 7 between the i-th magnet 46 and the second magnet 47. At this position, a high-density plasma is formed at 5 Å, whereby the film formation speed can be increased. In the film forming apparatus shown in FIG. 4, the sputtering cathode mechanism 42 for generating the required magnetic field is provided in an upright manner on one side surface 23b of the film forming chamber 23, so that the running key voltage is set to 340 V or less. The maximum value a of the horizontal magnetic field strength of the surface of the target 27 is again 600 Å or more 'a zinc oxide-based transparent conductive film which can form a lattice alignment. The zinc oxide-based transparent conductive film is hardly oxidized even after annealing in the form of a film, and can suppress the increase in the resistivity, and the zinc oxide-based transparent conductive film constituting the upper electrode of the solar cell 1 can be formed. It is excellent in heat resistance. Then, as an example of the method for producing a solar cell of the present embodiment, the zinc oxide-based transparent film constituting the upper electrode 3 of the solar cell 1 is formed on the transparent substrate 2 by using the sputtering apparatus 1 shown in Figs. 2 and 4 . The method of the conductive film 4 is exemplified. First, the target 27 is welded and fixed to the sputtering cathode mechanism 42 by a welding material or the like. Here, the "target" may be a zinc oxide-based material, for example, aluminum-doped zinc oxide (AZO) to which 0.1 to 10% by mass of aluminum (A1) is added, and aluminum (Ga) mixed with (My% by mass). Gallium zinc oxide (GZO), etc., wherein aluminum oxide zinc oxide (AZO) is preferred in terms of forming a film having a lower resistivity. 153816.doc • 18- 201133889 Then, it will contain, for example, glass. When the substrate 26 (transparent substrate 2) of the solar cell 1 is housed in the substrate tray 25 of the loading/unloading chamber 22, the roughing and exhausting mechanism 4 performs a rough vacuum on the loading/unloading chamber 22 and the film forming chamber 23. By suction, the substrate 26 is carried into the film forming chamber 23 from the loading/unloading chamber 22 after the loading/unloading chamber 22 and the film forming chamber 23 reach a specific degree of vacuum, for example, 0.27 Pa (2.0 mTorr). The substrate 26 is placed in front of the heater 3 1 in a state of being turned off, and the substrate 26 is placed facing the target 27. Then, the substrate 26 is heated by the heater 31 to be adjusted to i〇〇&lt;;&gt; c ~ 6 〇〇 ec temperature range. Then 'high vacuum evacuation mechanism 33 to the film forming chamber 23 high vacuum pumping 'In the film forming chamber 23 reaches a certain high degree of vacuum of, for example, 2-4 7xl〇

Pa(2,〇Xl(r2 mTorr)後，藉由濺鍍氣體導入機構35導入Ar等 滅锻氣體至成膜室23’將成膜室23内調整為特定之壓力 (濺鍍壓力）。 繼而，藉由電源34對靶材27施加濺鍍電壓、例如對直流 電壓疊加高頻電壓而成之難電壓。藉由施加韻電壓， 於基板26上產生電衆，由該電漿所激發之Ar等濺鍍氣體之 離子撞擊靶材27，使構成摻鋁氧化鋅（AZO)、摻鎵氧化鋅 (GZO)等氧化鋅系材料之原子自該靶材27飛出，於基板％ 上形成包含氡化鋅系材料之透明導電膜4。 此處，對濺鍍時之成膜壓力與成膜速度之關係加以說 明。 雖然亦依存⑽材材料或製減體之錢，但利用磁控 激鑛法進行成膜之情形時，通常選擇2mT(^至2GmT〇ra 153816.doc -19- 201133889 間之成膜壓力。於成膜壓力低於2 mTorr時，電漿之阻^_ 較高而無法放電，或即便可放電亦係電漿變得不穩定。反 之’於成膜壓力高於20 mTorr時’製程氣體與被濺鍍之把 材材料散射’由此對基板之附著效率（成膜速度）下降戋 者經濺鍍之靶材材料附著於陰極周邊零件而成膜，由此陰 極與接地線短路，生產性下降。 如上所述般於基板26上形成包含氧化鋅系材料之透明導 電膜4後，將該基板26(透明基板2)自成膜室23搬送至裝入/ 取出至2，解除該裝入/取出室2之真空，取出該形成有氧 化鋅系之透明導電膜4之基板26(透明基板2)。 繼而，對上述透明導電膜4進行濕式蝕刻處理。此時， 可藉由改變濕式蝕刻之各種條件而控制紋理之形狀。藉 此，於透明導電膜4之表面形成自由度較高且具有所需形 狀之微細紋理。 如此，可獲得於透明基板2上形成氧化鋅系之透明導電 膜4而成之附透明導電膜之基板1〇β該透明導電膜4於表面 具有自由度較高且具有所需形狀之微細之紋理構造。 藉由將此種附透明導電膜之基板1〇用於太陽電池 1Α(1)，可最大限度地獲得延長所人射之太陽光之光路的 稜鏡效果與光之封閉效果，從而可製作光電轉換效率較高 之太陽電池1Α(1)。 繼而，對使用此種附透明導電膜之基板1〇的堆叠構造之 太陽電池1Α(1)之製造方法按步驟依序說明。 首先，於附透日月導電膜之基板1〇之透明導電膜4上，分 153816.doc •20· 201133889 別於各電漿CVD反應室内形成p型半導體層（中間層5)、第 一光電轉換單元6之p型半導體層6p、i型半導體層6i、η型 半導體層6η及第二光電轉換單元7之ρ型半導體層7ρβ即， 开&gt;成於第一光電轉換單元6之η型半導體層6η上設有構成第 二光電轉換單元7之ρ型半導體層7ρ之太陽電池第一中間 品° 繼而，使第二光電轉換單元7之？型半導體層邙暴露於大 氣中後’在暴露於大氣中之Ρ型半導體層邙上，於相同之 電毁CVD反應室内形成構成第二先電轉換單元7之丨型矽層 (結晶質矽層）7i、η型半導體層7η。即，形成於第一光電轉 換單元ό上設有第二光電轉換單元7之太陽電池第二中間 品° 然後’於第二光電轉換單元7之η型半導體層化上形成緩 衝層11、背面電極12，藉此形成圖1所示般之太陽電池 1Α(1)。 特別是本實施形態中，藉由在透明導電膜4與第一光電 轉換單元6之口層6ρ之間利用個別之成膜室形成中間層$， 可獲得具有良好之特性之太陽電池1A(i)。 繼而，根據圖式對該太陽電池1a〇r t造系統加以說 明〇 本實施形態之太陽電池〖之製造系統係將所謂連續式之 第一成膜裝置6G、使第二光電轉換單元7之ρ層暴露於大氣 中之暴露裝置、及所謂批次式之第二成膜裝置職序配置 而成者，上述所謂連續式之第一成膜裝置6〇係將分別形成 153816.doc 201133889 第-光電轉換單元6之p型半導體層6p、㈤石夕層（非晶質石夕 層）6i、η型半導體層6n與第二光電轉換單元7之？型半導體 層7P各層的被稱為腔室之成膜反應室以複數條直線狀連結 配置而成，上述所謂批次式之第二成膜裝置7〇係於同一成 膜反應室内對複數個基板同時進行處理而形成第二光電轉 換單元7之i型矽層（結晶質矽層）7i、n型半導體層π。 將該太陽電池之製造系統示於圖5中。 製造系統如圖5所示，係由第—成膜裝置6〇、第二成膜 裝置70、及將於第一成膜裝置6〇中經處理之基板暴露於大 氣中後向第二成膜裝置70移動之暴露裝置8〇所構成。 製把系統之第一成膜裝置6〇配置有最初搬入基板並調整 為減壓環境下之裝入（L : L〇rdg61。再者，於L室之後 •k視程不，亦可設置將基板溫度力口熱至一定溫度為 止之加熱腔室。繼而，以直線狀而連續配置有於透明導電 膜4上形成包含結晶質之石夕系薄膜之p層（第2?層）作為中間 層5的p層成膜反應室62、形成第一光電轉換單元6之^型半 導體層6pip層成膜反應室63、形成該第一光電轉換單元6 之1型矽層（非晶質矽層）6丨之丨層成膜反應室64、形成該第一 光電轉換單tg6之η型半導體層以之n層成膜反應室65、形 成第二光電轉換單元7之ρ型半導體層7pip層成膜反應室 66。而且，最後配置使減壓狀態回到大氣環境並搬出基板 之取出（UL : Unlord)室67而構成。 此時，於圖5中A處，準備於透明基板2上形成有透明導 電膜4之附透明導電膜之基板1〇。又，於圖5中8處，形成 153816.doc -22- 201133889 有在成膜於透明基板2上之透明導電膜4上設有p型半導體 層（中間層5)、第一光電轉換單元6之？型半導體層6p、is 石夕層（非晶質矽層）6i、η型半導體層6n、及第二光電轉換單 元7之p型半導體層7p各層的太陽電池第一中間品。 又，製造系統中之第二成膜裝置70配置有用以最初搬入 在第一成膜裝置60中經處理之太陽電池i第一中間品1〇£1並 調整為減壓環境下、或將處於減壓下之基板調整為大氣環 境並搬出基板之裝入·取出（L/UL)室71。繼而，經由該裝 入’取出（L/UL)室71，配置在第二光電轉換單元7之p型半導 體層7p上於同一反應室内依序形成第二光電轉換單元？之1 型石夕層（結晶質矽層）7i、η型半導體層7n的可對複數個基板 同時進行處理之成膜反應室72而構成。 此時’於圖5中C處’形成有於第一光電轉換單元6上設 有第二光電轉換單元7之太陽電池第二中間品。 又，圖5中，連續式之第一成膜裝置60係以同時處理2個 基板之方式表示’將i層成膜反應室64示作由4個反應室 64a、64b、04c、64d所構成者。又，圖5中，批次式之第 二成膜裝置70係以同時處理6個基板之方式表示。 &lt;第二實施形態&gt; 繼而，對本發明之第二實施形態之太陽電池加以說明。 再者，以下說明中’主要對與上述第一實施形態不同之 部分進行說明，對與第一實施形態相同之部分省略其說 明。 圖6係表示本實施形態之太陽電池ib(i)之層構成之構造 153816.doc •23- 201133889 剖面圖》 上述第一實施形態中對堆疊構造之太陽電池進行了說 明，但本實施形態之太陽電池不限定於堆疊構 ° 亦可應 用於單獨構造之太陽電池。 該太陽電池1Β(1)係使用附透明導電膜之基板1〇，並於 上述透明導電膜4上依序重疊設置將ρ型半導體層化層^口、' 實質上本徵之i型半導體層（i層）9i、η型半導體層以層^^^積 層而成之pin型之第三光電轉換單元9而成。 而且，本實施形態之太陽電池1B(1)之特徵在於：構成 上述第三光電轉換單元9之p層9p、i層9i、η層9n包含非晶 矽系薄膜’且於透明導電膜4與上述p層9P之間，配置有包 含結晶質之矽系薄膜之p層作為中間層5。 該太陽電池1B(1)_ ’亦於透明導電膜4與上述p層9?)之 間配置有包含結晶質之矽系薄膜之p層作為中間層5，故可 緩和透明導電膜4與包含非晶質之矽系薄膜之p層（9p)的界 面之失配。藉此’可增大第三光電轉換單元9之填充因子 (FF)。其結果為，本實施形態之太陽電池1 B(丨）可發揮較高 之轉換效率。 又’該太陽電池1B(1)亦於透明導電膜4之表面形成有自 由度較高且具有所需粗糙度之微細紋理。該紋理構造帶來 稜鏡效果與光之封閉效果，故本實施形態之太陽電池 1B(10)可發揮較高之轉換效率。 構成太陽電池1B(1)之附透明導電膜之基板1〇、中間層 5、p層9p、i層9i及η層9n均係與上述第一實施形態之附透 I53816.doc •24· 201133889 明導電膜之基板10、中間層5 ' P層6p、i層以及11層6n同樣 地形成。 以上，對本發明之太陽電池用附透明導電膜之基板、太 陽電池及該等之製造方法進行了說明，但本發明不限定於 此’於不偏離發明主旨之範圍内可適當變更。 作為蝕刻液，可列舉：鹽酸、硫酸、硝酸等無機酸水溶 液，甲酸、乙酸、檸檬酸、乳酸、蘋果酸、丙二酸、琥珀 酸、二醇酸等羧酸水溶液，甲酸銨、乙酸銨、檸檬酸銨、 乳蘋果酸銨、丙二酸敍、號珀酸録、二醇酸錄等叛 酉文銨水，谷液，二伸乙基三胺、三伸乙基四胺、四伸乙基五 胺等多胺水溶液。 蝕刻液之濃度只要為可調整水溶液之範圍則並無限制， 只要考慮姓刻速率而決定即可。 蚀亥！度較理想為室溫至5〇°c。若為室溫以下，則触刻 速率變慢而生產效率下降，故欠佳1為超過5(rc之钱刻 溫度，則水分之蒸發劇烈，由濃縮引起之蝕刻速率之變化 變大，故欠佳》 進而，為於蝕刻後清洗透明導電膜表面及改善紋理形 狀’亦可利用氫氧化鉀、氫氧化四甲基錢水溶液等驗性水 溶液進行處理。 [實施例] 以下，根據實施例對本發明加以更詳細說明。 使用圖2及圖4所示般之成膜裝置（賤鍵裝置），於基板上 形成透明導電膜。 1538l6.doc -25· 201133889 (樣品1) 首先’於濺鍍陰極機構42中安裝300 mmx610 mm之靶材 27。靶材27係使用在ZnO中添加有2質量％之八丨2〇3作為雜 質之材料。其後，於裝入/取出室22中放入無鹼玻璃基板 (基板26) ’利用粗抽吸排氣機構24排氣後，搬送至成膜室 23中。此時’成膜室23係藉由高真空排氣機構33保持於特 定之真空度。 自賤錢氣體導入機構35以270 seem導入Ar氣體作為製程 氣體後，藉由傳導閥將壓力調整成所需之濺鍍壓力（〇 67After Pa(2, 〇X1 (r2 mTorr), the sputtering gas introduction mechanism 35 introduces a forging gas such as Ar into the film forming chamber 23' to adjust the inside of the film forming chamber 23 to a specific pressure (sputtering pressure). A hard voltage is applied to the target 27 by a power source 34, for example, by superposing a high-frequency voltage on the DC voltage. By applying a rhyme voltage, a battery is generated on the substrate 26, and the Ar is excited by the plasma. When the ions of the sputtering gas collide with the target 27, atoms constituting the zinc oxide-based material such as aluminum-doped zinc oxide (AZO) or gallium-doped zinc oxide (GZO) fly out from the target 27, and yttrium is formed on the substrate %. A transparent conductive film 4 of a zinc-based material. Here, the relationship between the film forming pressure at the time of sputtering and the film forming speed will be described. Although it is also dependent on the material of the material or the body, the magnetron-exciting method is used. In the case of film formation, the film formation pressure between 2mT (^ to 2GmT〇ra 153816.doc -19- 201133889 is usually selected. When the film formation pressure is lower than 2 mTorr, the resistance of the plasma is higher and cannot be discharged. Or even if it can be discharged, the plasma becomes unstable. Otherwise, when the film formation pressure is higher than 20 mTorr The gas is scattered with the sputtered material, so that the adhesion efficiency (film formation speed) of the substrate is lowered, and the target material of the sputter is attached to the peripheral part of the cathode to form a film, whereby the cathode is short-circuited with the ground line. When the transparent conductive film 4 containing a zinc oxide-based material is formed on the substrate 26 as described above, the substrate 26 (transparent substrate 2) is transferred from the film forming chamber 23 to the loading/unloading to 2, and the removal is performed. The vacuum of the chamber 2 is taken in and taken out, and the substrate 26 (transparent substrate 2) on which the zinc oxide-based transparent conductive film 4 is formed is taken out. Then, the transparent conductive film 4 is subjected to a wet etching treatment. The shape of the texture is controlled by changing various conditions of the wet etching, whereby a fine texture having a high degree of freedom and a desired shape is formed on the surface of the transparent conductive film 4. Thus, a zinc oxide system can be formed on the transparent substrate 2. The transparent conductive film 4 is formed by a substrate 1 〇 β with a transparent conductive film. The transparent conductive film 4 has a fine texture structure having a high degree of freedom and a desired shape on the surface. Substrate 1〇 It is used for solar cell 1Α(1), which can maximize the effect of the light path of the sunlight that is emitted by the person and the light blocking effect, so that the solar cell with high photoelectric conversion efficiency can be produced (1). The manufacturing method of the solar cell 1 (1) using the stacked structure of the substrate 1 with the transparent conductive film is described in order. First, the transparent conductive film 4 of the substrate 1 to which the solar cell is adhered 153816.doc •20· 201133889 Forming a p-type semiconductor layer (intermediate layer 5), a p-type semiconductor layer 6p of the first photoelectric conversion unit 6, an i-type semiconductor layer 6i, and an n-type in each plasma CVD reaction chamber The p-type semiconductor layer 7ρβ of the semiconductor layer 6n and the second photoelectric conversion unit 7 is opened, and the p-type semiconductor layer constituting the second photoelectric conversion unit 7 is provided on the n-type semiconductor layer 6n of the first photoelectric conversion unit 6. The first intermediate product of the solar cell of 7ρ, and then the second photoelectric conversion unit 7? After exposure to the atmosphere, the semiconductor layer is formed on the germanium-type semiconductor layer exposed to the atmosphere, and a germanium-type germanium layer (crystal layer) constituting the second electro-conversion unit 7 is formed in the same electro-destructive CVD reaction chamber. 7i, n-type semiconductor layer 7n. That is, the solar cell second intermediate product provided on the first photoelectric conversion unit 设有 is provided with the second photoelectric conversion unit 7 and then the buffer layer 11 and the back surface electrode are formed on the n-type semiconductor layer of the second photoelectric conversion unit 7 12, thereby forming a solar cell 1 (1) as shown in FIG. In particular, in the present embodiment, by forming the intermediate layer $ between the transparent conductive film 4 and the mouth layer 6p of the first photoelectric conversion unit 6 by using a separate film forming chamber, a solar cell 1A having excellent characteristics can be obtained (i). ). Next, the solar cell 1a 〇 造 system will be described with reference to the drawings. The manufacturing system of the solar cell of the present embodiment is a so-called continuous first film forming device 6G and a second photoelectric conversion unit 7 ρ layer. The exposed device exposed to the atmosphere and the so-called batch type second film forming device are arranged, and the so-called continuous first film forming device 6 will form 153816.doc 201133889 first-photoelectric conversion The p-type semiconductor layer 6p of the unit 6, the (5) the layer (amorphous layer) 6i, the n-type semiconductor layer 6n and the second photoelectric conversion unit 7? The film formation reaction chamber called a chamber of each layer of the semiconductor layer 7P is formed by a plurality of linear connection arrangements, and the so-called batch type second film formation apparatus 7 is connected to a plurality of substrates in the same film formation reaction chamber. At the same time, the i-type germanium layer (crystalline germanium layer) 7i and the n-type semiconductor layer π of the second photoelectric conversion unit 7 are formed. The solar cell manufacturing system is shown in FIG. The manufacturing system is as shown in FIG. 5, and the second film forming device 6〇, the second film forming device 70, and the substrate to be processed in the first film forming device 6〇 are exposed to the atmosphere and then formed into a second film. The device 70 is configured to move the exposure device 8 . The first film forming apparatus 6 of the system is placed in the first substrate and placed in a reduced pressure environment (L: L〇rdg61. Further, after the L chamber, the path is not set, and the substrate may be provided. The heating chamber is heated to a certain temperature. Then, a p-layer (second layer) containing a crystalline stone-like film formed on the transparent conductive film 4 is continuously disposed in a straight line as the intermediate layer 5 a p-layer film formation reaction chamber 62, a semiconductor layer 6pip layer forming reaction chamber 63 forming the first photoelectric conversion unit 6, and a 1 type germanium layer (amorphous germanium layer) forming the first photoelectric conversion unit 6 a ruthenium film formation reaction chamber 64, an n-type semiconductor layer forming the first photoelectric conversion unit tg6, an n-layer film formation reaction chamber 65, and a p-type semiconductor layer 7pip layer forming a second photoelectric conversion unit 7 In the chamber 66. Finally, the pressure-reduced state is returned to the atmosphere and the substrate (UL: Unlord) chamber 67 is removed. At this point, at A in FIG. 5, transparent conductive is prepared on the transparent substrate 2. The substrate 4 of the film 4 with the transparent conductive film is formed, and is formed at 8 in FIG. 153816.doc -22-201133889 There is a p-type semiconductor layer (intermediate layer 5), a semiconductor layer 6p of the first photoelectric conversion unit 6, and an ischemic layer on the transparent conductive film 4 formed on the transparent substrate 2. The first intermediate product of the solar cell of each layer of the layer (amorphous germanium layer) 6i, the n-type semiconductor layer 6n, and the p-type semiconductor layer 7p of the second photoelectric conversion unit 7. Further, the second film forming apparatus 70 in the manufacturing system The arrangement is such that the first intermediate product of the solar cell i processed in the first film forming apparatus 60 is initially loaded and adjusted to a reduced pressure environment, or the substrate under reduced pressure is adjusted to an atmospheric environment and the substrate is carried out. The loading/unloading (L/UL) chamber 71. Then, via the loading 'extraction (L/UL) chamber 71, the p-type semiconductor layer 7p disposed on the second photoelectric conversion unit 7 is sequentially placed in the same reaction chamber. The formation of the second photoelectric conversion unit, the type 1 layer (crystal layer) 7i, and the n-type semiconductor layer 7n, can be formed by simultaneously processing a plurality of substrates into the film formation reaction chamber 72. At this time, FIG. Wherein the middle C is formed on the first photoelectric conversion unit 6 and is provided with a second photoelectric conversion sheet In the fifth embodiment of the solar cell of Fig. 5, in Fig. 5, the first film forming apparatus 60 of the continuous type shows that the i-layer film forming reaction chamber 64 is represented by four reaction chambers by simultaneously processing two substrates. Further, in Fig. 5, the batch type second film forming apparatus 70 is formed by simultaneously processing six substrates. <Second embodiment> Next, the present invention In the following description, a portion different from the above-described first embodiment will be mainly described, and the description of the same portions as those of the first embodiment will be omitted. Fig. 6 is a cross-sectional view showing a structure of a layer configuration of a solar cell ib(i) of the present embodiment. 153816.doc • 23-201133889 A solar cell having a stacked structure is described in the first embodiment, but the present embodiment is The solar cell is not limited to the stack structure and can also be applied to a solar cell of a separate configuration. In the solar cell, the substrate 1 is provided with a transparent conductive film, and a p-type semiconductor layered layer and a substantially intrinsic i-type semiconductor layer are sequentially stacked on the transparent conductive film 4. The (i layer) 9i and the n-type semiconductor layer are formed by layer-forming the third photoelectric conversion unit 9 of a pin type. Further, the solar cell 1B (1) of the present embodiment is characterized in that the p-layer 9p, the i-layer 9i, and the n-layer 9n constituting the third photoelectric conversion unit 9 include an amorphous lanthanum-based film and are in the transparent conductive film 4 and Between the p layers 9P, a p layer containing a crystalline lanthanoid film is disposed as the intermediate layer 5. In the solar cell 1B(1)_', a p-layer containing a crystalline lanthanoid film is disposed as the intermediate layer 5 between the transparent conductive film 4 and the p-layer 9?, so that the transparent conductive film 4 and the like can be alleviated. Mismatch in the interface of the p-layer (9p) of the amorphous lanthanide film. Thereby, the fill factor (FF) of the third photoelectric conversion unit 9 can be increased. As a result, the solar cell 1 B (丨) of the present embodiment can exhibit a high conversion efficiency. Further, the solar cell 1B (1) is also formed with a fine texture having a high degree of freedom and having a desired roughness on the surface of the transparent conductive film 4. Since the texture structure brings about a 稜鏡 effect and a light blocking effect, the solar cell 1B (10) of the present embodiment can exhibit a high conversion efficiency. The substrate 1 〇, the intermediate layer 5, the p layer 9p, the i layer 9i, and the η layer 9n constituting the transparent conductive film of the solar cell 1B(1) are both attached to the above-described first embodiment. I53816.doc •24·201133889 The substrate 10 of the bright conductive film, the intermediate layer 5' P layer 6p, the i layer, and the 11 layer 6n are formed in the same manner. In the above, the substrate with a transparent conductive film for a solar cell of the present invention, the solar cell, and the method for producing the same have been described. However, the present invention is not limited thereto, and can be appropriately changed without departing from the scope of the invention. Examples of the etching solution include aqueous solutions of inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; aqueous solutions of carboxylic acids such as formic acid, acetic acid, citric acid, lactic acid, malic acid, malonic acid, succinic acid, and glycolic acid; ammonium formate and ammonium acetate; Ammonium citrate, ammonium maloacetate, malonate, crocetin, diol acid, etc. Rebel ammonium water, gluten solution, di-ethyltriamine, tri-ethyltetramine, tetra-bend An aqueous solution of a polyamine such as pentamine. The concentration of the etching solution is not limited as long as it is within the range of the adjustable aqueous solution, and may be determined in consideration of the rate of the surname. Eclipse! The degree is preferably from room temperature to 5 ° ° C. If it is at room temperature or lower, the etch rate is slowed down and the production efficiency is lowered. Therefore, the poor 1 is more than 5 (the evaporation temperature of the rc is severe, and the change of the etching rate caused by the concentration becomes large, so Further, in order to clean the surface of the transparent conductive film after etching and to improve the texture shape, it may be treated with an aqueous solution of potassium hydroxide or tetramethylammonium hydroxide aqueous solution. [Examples] Hereinafter, the present invention is applied according to examples. The transparent conductive film is formed on the substrate by using the film forming apparatus (贱 key device) as shown in Fig. 2 and Fig. 4. 1538l6.doc -25· 201133889 (Sample 1) First, the sputtering cathode mechanism A target of 300 mm x 610 mm is mounted in 42. The target 27 is made of a material in which 2% by mass of erbium 2 〇 3 is added as an impurity in ZnO. Thereafter, an alkali-free is placed in the loading/unloading chamber 22. The glass substrate (substrate 26) 'is exhausted by the rough suction and exhaust mechanism 24, and then transferred to the film forming chamber 23. At this time, the film forming chamber 23 is held at a specific degree of vacuum by the high vacuum exhaust mechanism 33. The self-depositing gas introduction mechanism 35 introduces A at 270 seem After the gas is used as the process gas, the pressure is adjusted to the required sputtering pressure by the conduction valve (〇 67

Pa)後’對濺鑛陰極機構32藉由DC電源施加8.4 kW之電 力’藉此對安裝於濺鍍陰極機構32之ZnO系靶材進行賤 鐘。 將δ亥專作業視為一系列流程’於無驗玻璃基板上以3〇〇 nm之厚度形成Ζη0系透明導電膜。其後，自裝入/取出室 22中取出基板。 形成透明導電膜後’使用20重量％之乙酸銨水溶液於 35°C下進行180秒蝕刻’於透明導電膜之表面形成紋理。 (樣品2) 濺鍍時，以基板溫度達到250。(：之方式調整加熱器31之 設定’對成膜室23進行加熱》 又’濕式触刻時使用0.5重量％之鹽酸水溶液，於25。〇下 進行30秒之蝕刻。除此以外，與樣品1同樣地形成透明導 電膜’並於該透明導電膜之表面形成紋理。 (樣品3) 153816.doc •26· 201133889 濕式蝕刻時使用1.0重量％之硝酸水溶液，於25°C下進行 25秒之蝕刻，除此以外，與樣品2同樣地形成透明導電 膜，並於該透明導電膜之表面形成紋理。 (樣品4) 濕式蝕刻時使用5.0重量％之乙酸水溶液，於35 °C下進行 80秒之蝕刻，除此以外，與樣品2同樣地形成透明導電 膜，並於該透明導電膜之表面形成紋理。 (樣品5) 濕式蝕刻時使用4.3重量％之丙二酸水溶液，於35。(：下進 行95秒之蝕刻，除此以外，與樣品2同樣地形成透明導電 膜’並於該透明導電膜之表面形成紋理。 (樣品6) 濕式蝕刻時使用5.3重量％之檸檬酸水溶液，並於35。(：下 進行250秒之蝕刻，除此以外，與樣品2同樣地形成透明導 電膜’並於該透明導電膜之表面形成紋理。 (樣品7) 濕式儀刻時使用6 · 3重量％之二醇酸水溶液，於3 5 °C下進 行220秒之触刻，除此以外，與樣品2同樣地形成透明導電 膜’並於該透明導電膜之表面形成紋理。 (樣品8) 濕式钮刻時使用重量％之乙酸銨水溶液，於35°C下進 行240秒之蝕刻’除此以外，與樣品2同樣地形成透明導電 膜，並於該透明導電膜之表面形成紋理。 (樣品9) 153816.doc -27- 201133889 濕式蝕刻時使用1〇重量％之曱酸銨水溶液，於35°C下進 行5 0秒之#刻，除此以外，與樣品2同樣地形成透明導電 膜，並於該透明導電膜之表面形成紋理。 (樣品10) 濕式蝕刻時使用10重量％之琥珀酸銨水溶液，於4(Tc下 進行240秒之蝕刻，除此以外，與樣品2同樣地形成透明導 電膜，並於該透明導電膜之表面形成紋理。 (樣品11) 濕式蝕刻時使用1 0重量％之丙二酸銨水溶液，於40。(：下 進行150秒之蝕刻，除此以外，與樣品2同樣地形成透明導 電膜，並於該透明導電膜之表面形成紋理。 (樣品12) 濕式蝕刻時使用5.0重量％之二伸乙基三胺水溶液，於 3 5 °C下進行4〇秒之蝕刻，除此以外，與樣品2同樣地形成 透明導電膜，並於該透明導電膜之表面形成紋理。 (樣品1 3 ) 濕式蝕刻時使用5.0重量％之三伸乙基四胺水溶液，於 35°C下進行300秒之蝕刻，除此以外’與樣品2同樣地形成 透明導電膜，並於該透明導電膜之表面形成紋理。 (樣品14 ) 賤鑛時將濺鍍壓力設定為2 Pa，除此以外，與樣品8同 樣地形成透明導電膜，並於該透明導電膜之表面形成紋 理。 (樣品15) 153816.doc -28- 201133889 使透明導《為2層構成。下層之第_層成膜時製程氣 體中不導人氧氣’上層之第二層成膜時於製程氣體中進一 步導入10 seem之氧氣進行濺鍍。 又。’濕式蝕刻時使用5.0重量％之二伸乙基三胺水溶液， 於35 C下進行4G秒之#刻。除此以外，與樣品2同樣地形 成透明導電膜，於該透明導電膜之表面形成紋理。 (樣品16) 濕式蝕刻時使用1〇重量％之四伸乙基五胺水溶液，於 35°C下進行40秒之蝕刻，除此以外’與樣品15同樣地形成 透明導電冑’並於該透明導電膜之表面形成紋理。 (樣品17) 濕式姓刻時使用5. 〇重量％之乙酸水溶液，於3 5。匸下進行 12 0秒之姓刻後，使用〇 $重量％之氫氧化卸水溶液於 25 C下進行60秒之處理，除此以外，與樣品丨5同樣地形成 透明導電膜，並於該透明導電膜之表面形成紋理。 (樣品18) 使透明導電膜為2層構成。將下層之第一層成膜時之濺 鍍壓力没定為0.67 Pa，將上層之第二層成膜時之濺鍍壓力 設定為4 Pa。 又’濕式姓刻時使用5_〇重量％之乙酸水溶液，於35。匚下 進行120秒之蝕刻。除此以外，與樣品2同樣地形成透明導 電膜’並於該透明導電膜之表面形成紋理。 (樣品19) 濕式敍刻時使用5.0重量。/〇之乙酸水溶液，於35°c下進行 153816.doc •29- 201133889 90秒之蚀刻後，使用0.5重量％之氫氧化钟水溶液，於25°C 下進行180秒之處理，除此以外，與樣品18同樣地形成透 明導電膜，並於該透明導電膜之表面形成紋理。 (樣品20) 濕式银刻時使用5.0重量％之乙酸水溶液進行120秒之触 刻，並使用0·5重量°/〇之氫氧化舒水溶液進行12〇秒之處 理’除此以外’與樣品19同樣地形成透明導電膜，並於該 透明導電膜之表面形成紋理。 (樣品21) 濕式蝕刻時使用5 · 0重量。/。之酒石酸水溶液，於3 5。(：下進 行60秒之蝕刻後，使用〇 5重量％之氫氧化鉀水溶液，於 25°C下進行60秒之處理，除此以外，與樣品19同樣地形成 透明導電膜，並於該透明導電膜之表面形成紋理。 (樣品22) 濕式蝕刻時使用5.0重量。/。之蘋果酸水溶液，於35°C下進 行90秒之蝕刻後，使用〇 5重量。之氫氧化鉀水溶液，於 25°C下進行60秒之處理，除此以外，與樣品19同樣地形成 透明導電膜，並於該透明導電膜之表面形成紋理。 (樣品2 3 ) 濕式蝕刻時使用5.0重量％之乳酸水溶液，於351下進行 90秒之银刻後’使用0.5重量❶/。之氫氧化鉀水溶液，於25 °C 下進行60秒之處理，除此以外，與樣品19同樣地形成透明 導電膜，並於該透明導電膜之表面形成紋理。 (樣品24) 1538l6.doc 201133889 濕式蝕刻時使用5.0重量％之檸檬酸水溶液，於35°C下進 行60秒之蝕刻後，使用0.5重量％之氫氧化鉀水溶液，於 25°C下進行60秒之處理，除此以外，與樣品19同樣地形成 透明導電膜，並於該透明導電膜之表面形成紋理。 (樣品25) 濕式蝕刻時使用5.0重量％之乙酸水溶液，於35。(：下進行 30秒之钮刻後，使用〇.5重量％之氫氧化卸水溶液，於25°C 下進行240秒之處理《蝕刻後進行濺鍍，將透明導電膜之 厚度形成為800 A，除此以外，與樣品19同樣地形成透明 導電膜，並於該透明導電膜之表面形成紋理。 (樣品26) 姓刻後進行濺鍍’將透明導電膜之厚度形成為4〇〇 A， 除此以外，與樣品1 9同樣地形成透明導電膜，並於該透明 導電膜之表面形成紋理。 為對如上所述般製作之樣品1〜樣品2 6之透明導電膜驗證 紋理形狀之效果，使用HAZE METER HM i5〇(村上色彩技 術研究所股份有限公司冑造），對上述樣品卜26之單膜測 定光學特性（霧值率）。 將該等結果與成膜條件、姓刻條件一併示於表艸。 153B16.doc •31- 201133889 [表i] 樣品 編號 成膜時 之加熱 成膜壓 力(Pa) 氧 添加 蝕刻液 濺鍍之 有無 霧值率 (%) 1 非加熱 0.67 無 乙酸銨水溶液 無 23.30 2 加熱 0.67 無 鹽酸 無 3.20 3 加熱 0.67 無 硝酸 無 2.50 4 加熱 0.67 無 乙酸 無 7.70 5 加熱 0.67 無 丙二酸 無 19.90 6 加熱 0.67 無 檸檬酸 無 12.70 7 加熱 0.67 無 二醇酸 無 8.80 8 加熱 0.67 無 乙酸銨水溶液 無 8.90 9 加熱 0.67 無 曱酸銨水溶液 無 8.70 10 加熱 0.67 無 琥珀酸敍水溶液 無 15.30 11 加熱 0.67 無 丙二酸敍水溶液 無 18.60 12 加熱 0.67 無 二伸乙基三胺酸敍水溶液 無 5.20 13 加熱 0.67 無 三伸乙基四胺水溶液 無 7.00 14 加熱 2 無 乙酸銨水溶液 無 42.30 15 加熱 0.67 無/有 二伸乙基三胺水溶液 無 8.70 16 加熱 0.67 無/有 四伸乙基五胺水溶液 無 6.50 17 加熱 0.67 無/有 乙酸水溶液/氫氧化钟水溶液 無 37.00 18 加熱 0.67/4 無 乙酸水溶液 無 2.50 19 加熱 0.67/4 無 乙酸水溶液/氫氧化钟水溶液 無 13.30 20 加熱 0.67/4 無 乙酸水溶液/氫氧化钟水溶液 無 12.10 21 加熱 0.67/4 無 酒石酸水溶液/氫氧化鉀水溶液 無 18.60 22 加熱 0.67/4 無 蘋果酸水溶液/氫氧化钟水溶液 無 4.20 23 加熱 0.67/4 無 乳酸水溶液/氫氧化斜水溶液 無 5.60 24 加熱 0.67/4 無 檸檬酸水溶液/氫氧化鉀水溶液 無 7.20 25 加熱 0.67/4 無 乙酸水溶液/氫氧化針水溶液 有 11.70 26 加熱 0.67/4 無 乙酸水溶液/氫氧化針水溶液 有 16.60 由表1可知，藉由變更成膜條件或蝕刻液，可獲得具有 各種值的霧值率（具體而言為2.5〜42.30%)的透明導電膜。 由圖7〜圖17明確得知，藉由變更成膜條件、蝕刻條件， 而於透明導電膜的表面形成具有各種形狀（粗糙度）的微細 紋理。藉此，可形成自由度較高且具有所需之粗糙度之微 細紋理。 (樣品27〜樣品32) 153816.doc -32- 201133889 使用於表面形成有微細紋理之透明導電膜作為上部電 極’製作構成pin型之光電轉換單元之p層、i層及η層包含 非晶質之矽系薄膜之太陽電池。 此時，於樣品28〜樣品32中，於透明導電膜與構成光電 轉換單元之上述ρ層之間，形成包含結晶質之矽系薄膜之ρ 層（第2ρ層）作為中間層。 進而’將中間層之厚度於.樣品28〜樣品30中變更為5 nm、於樣品31中變更為10 nm、於樣品32中變更為15 nm 而製作太陽電池。 對於樣品27〜樣品32中所製作之太陽電池，使用太陽光 模擬器[SPI SyN SIMULATOR 4800i(Spire Corporation公 司製造）]’分別評價作為太陽電池性能的開路電壓（v〇c)、 短路電流（JSC)、最大輸出功率（pmax)、串聯電阻（Rs)、並 聯電阻（Rsh)、填充因子（FF)、光電轉換效率（Effp將其結 果不於表2。 又，將最大輪出功率（pmax)與辛間層厚度之關係示於圖 1 8 ’將填充因子（FF)與中間層厚度之關係示於圖丨9。 [表2] 樣品編號 中間 (nm) Voc (V) Isc (A) Pmax (W) Rs (Ω) Rsh (Q) FF Eff (〇/〇) 27 0 103.3 1.67 111.1 9.12 772 0.64 \/0) 7.65 28 5 104.3 1.71 120.1 7.74 802 0.67 8.27 29 in r 104.7 1 1.67 119.1 7.74 1750 0 68 8.20 31 5 1 A 104.3 1.70 120.3 7.42 700 0.68 8.29 1U 102.5 1.70 115.7 7.54 730 0.66 7.97 .32 t c 10 ---- 99.5 1.67 100.5 9.48 631 0.61 6.92 由表2明確得知’配置有十間層之樣品中，將膜厚設定 I53816.doc •33· 201133889 為5〜H) nm之樣品28〜樣品3 i與不配置中間層之樣品η相比 較，串聯電阻（RS)變低。又，對於該等樣㈣〜樣品加 言’開路電時。〇、Μ路電流（Ise)、最大輸出功率 (Pmax)、填充因子（FF)、光電轉換效率（Eff)均可獲得優異 之值’故可驗證本發明於太陽電池之高效率化方面有效。 又，由圖18及圖19表明，於中間層之厚度為5〜i〇 之 犯圍内，可見填充因子（FF)與開路電壓（v〇c)增大、光電轉 換效率增大的效果。 [產業上之可利用性] 本發明可敍地應詩作為光人㈣之電力取出電極發 揮力flb之上σ卩電極具備以ZnO為基本構成之透明導電膜的 太陽電池用附透明導電膜之基板、太陽電池及該等之製造 方法。 【圖式簡單說明】 圖1係表示本發明第一實施形態之太陽電池的剖面圖。 圖2係表示適合於太陽電池之製造方法的成膜裝置之概 略構成圖。 圖3係於圖2之成膜裝置中表示成膜室之主要部之剖面 圖。 圖4係表示成膜裝置之另一例之剖面圖。 圖5係表示連續成膜裝置之一例之示意圖。 圖6係表示本發明第二實施形態之太陽電池之剖面圖。 圖7係表示實施例中獲得之透明導電膜之SEM像的圖。 圖8係表示實施例中獲得之透明導電膜之SEM像的圖。 153816.doc • 34· 201133889 圖9係表示實施例中獲得之透明導電膜之SEM像的圖。 圖係表示實施例中獲得之透明導電膜之SEM像的圖。 圖Π係表示實施例中獲得之透明導電膜之SEM像的圖。 圖12係表示實施例中獲得之透明導電膜之SEM像的圖。 圖13係表示實施例中獲得之透明導電膜之sem像的圖。 圖Η係表示實施例中獲得之透明導電膜之sem像的圖。 圖15係表示實施例中獲得之透明導電膜之SEM像的圖。 圖16係表示實施例中獲得之透明導電膜之SEM像的圖。 圖1 7係表示實施例中獲得之透明導電膜之SEM像的圖。 圖is係對實施例中獲得之太陽電池表示最大輸 與中間層厚度之關係的圖。 圖19係對實施例中獲得之太陽電池表示填充因子（FF)與 中間層厚度之關係的圖。 圖20係表示先前之太陽電池之一例的剖面圖。 【主要元件符號說明】 1、ΙΑ、1B、100 太陽電池 101 玻璃基板（透明基板） 3 ' 103 上部電極 4 透明導電膜 5 中間層 6 第一光電轉換單元 6i ' 7i、9i、105i、109i i型半導體層 6n、7n、9n、105η、109n n型半導體層 6ρ、7ρ、9ρ、105ρ、109η ρ型半導體層 153816.doc -35- 201133889 7 第二光電轉換單元 8、107 中間電極 9 第三光電轉換單元 10 附透明導電膜之基板 11 、 110 緩衝層 12 、 111 背面電極 20 濺鍍裝置 22 裝入/取出室 23 成膜室 23a、23b 側面 24 粗抽吸排氣機構 25 基板托盤 27 靶材 32 ' 42 濺鍍陰極機構 33 高真空排氣機構 34 電源 35 氣體導入機構 35a 濺鍍氣體導入機構 35b 氫氣導入機構 35c 氧氣導入機構 35d 水蒸氣導入機構 43 背面板 44 磁路 44a、44b 磁路單元 153816.doc -36· 201133889 45 托架 46 第1磁石 47 第2磁石 48 磁李厄 49 磁力線 50 位置 60 第一成膜裝置 61 裝入室 62 ' 63 ' 66 P層成膜反應室 64 i層成膜反應室 64a、64b、64c、64d 反應室 65 η層成膜反應室 67 取出室 70 第二成膜裝置 71 裝入·取出室 72 成膜反應室 80 暴露裝置 105 上層電池 109 下層電池 A、B、C 處 153816.doc -37-Pa) After the sputtering cathode mechanism 32 applies a power of 8.4 kW by a DC power source, the ZnO-based target attached to the sputtering cathode mechanism 32 is quenched. The δ hai special operation was regarded as a series of processes. A Ζη-type transparent conductive film was formed on the non-inspective glass substrate at a thickness of 3 〇〇 nm. Thereafter, the substrate is taken out from the loading/unloading chamber 22. After the transparent conductive film was formed, the surface of the transparent conductive film was textured by using a 20% by weight aqueous solution of ammonium acetate at 180 ° C for 180 seconds. (Sample 2) When sputtering, the substrate temperature reached 250. (: The setting of the heater 31 is adjusted to "heat the film forming chamber 23". In the case of wet etching, a 0.5% by weight aqueous hydrochloric acid solution is used, and etching is performed for 25 seconds at 25° C. In addition, Sample 1 similarly formed a transparent conductive film 'and formed a texture on the surface of the transparent conductive film. (Sample 3) 153816.doc •26·201133889 Wet etching was performed using a 1.0% by weight aqueous solution of nitric acid at 25 ° C. A transparent conductive film was formed in the same manner as in Sample 2, and a texture was formed on the surface of the transparent conductive film. (Sample 4) A wet etching solution was carried out using a 5.0% by weight aqueous acetic acid solution at 35 ° C. A transparent conductive film was formed in the same manner as in Sample 2 except that the etching was performed for 80 seconds, and a texture was formed on the surface of the transparent conductive film. (Sample 5) A 4.3% by weight aqueous solution of malonic acid was used for wet etching. 35. (: A transparent conductive film was formed in the same manner as the sample 2 except that etching was performed for 95 seconds, and a texture was formed on the surface of the transparent conductive film. (Sample 6) 5.3 wt% of lemon was used for wet etching. Acid water soluble Further, a transparent conductive film was formed in the same manner as the sample 2 except that the etching was performed for 250 seconds, and a texture was formed on the surface of the transparent conductive film. (Sample 7) 6 for wet etching A transparent conductive film ' was formed in the same manner as the sample 2 except that the diol acid aqueous solution having a weight of 3 wt% was subjected to a contact for 220 seconds at 35 ° C, and a texture was formed on the surface of the transparent conductive film. 8) A transparent conductive film was formed in the same manner as in Sample 2, except that the etching was carried out at 35 ° C for 240 seconds using a wet aqueous solution of ammonium acetate in a wet button, and a texture was formed on the surface of the transparent conductive film. (Sample 9) 153816.doc -27- 201133889 In the same manner as Sample 2, the wet etching was carried out in the same manner as in Sample 2 except that a 1% by weight aqueous solution of ammonium citrate was used at 35 ° C for 50 seconds. A transparent conductive film is formed on the surface of the transparent conductive film. (Sample 10) A wet etching is performed using a 10% by weight aqueous solution of ammonium succinate, and etching is performed at 4 (Tc for 240 seconds). 2 similarly forming a transparent conductive film, and the transparent conductive The surface of the film was textured. (Sample 11) Transparent etching was performed in the same manner as in Sample 2 except that 10% by weight of an aqueous solution of ammonium malonate was used for wet etching at 40° (for 150 seconds). a film formed on the surface of the transparent conductive film. (Sample 12) In the wet etching, a 5.0% by weight aqueous solution of diethyltriamine was used, and etching was performed at 35 ° C for 4 sec. A transparent conductive film was formed in the same manner as in Sample 2, and a texture was formed on the surface of the transparent conductive film. (Sample 13) Wet etching was carried out using a 5.0% by weight aqueous solution of triethylamine tetraamine at 35 ° C. A transparent conductive film was formed in the same manner as the sample 2 except for etching for 300 seconds, and a texture was formed on the surface of the transparent conductive film. (Sample 14) A transparent conductive film was formed in the same manner as Sample 8, except that the sputtering pressure was set to 2 Pa, and a texture was formed on the surface of the transparent conductive film. (Sample 15) 153816.doc -28- 201133889 The transparent guide is composed of two layers. When the second layer of the upper layer is formed in the process gas, the second layer of the upper layer is formed into a film, and 10 seeming oxygen is further introduced into the process gas for sputtering. also. In the wet etching, a 5.0% by weight aqueous solution of diethyltriamine was used, and 4 G seconds was performed at 35 C. Except for this, a transparent conductive film was formed in the same manner as in Sample 2, and a texture was formed on the surface of the transparent conductive film. (Sample 16) In the wet etching, a 1% by weight aqueous solution of tetraethylamethyleneamine was used, and etching was performed at 35 ° C for 40 seconds, and a transparent conductive crucible was formed in the same manner as in Sample 15 and The surface of the transparent conductive film is textured. (Sample 17) A wet acetic acid solution was used at a wetness of 5 〇. A transparent conductive film was formed in the same manner as the sample 丨5, and the transparent conductive film was formed in the same manner as the sample 丨5, except that the 姓$% by weight aqueous solution of hydrazine was used for 60 seconds. The surface of the conductive film is textured. (Sample 18) The transparent conductive film was composed of two layers. The sputtering pressure at the time of film formation of the first layer of the lower layer was not determined to be 0.67 Pa, and the sputtering pressure at the time of film formation of the second layer of the upper layer was set to 4 Pa. Further, when the wet type is engraved, a 5 wt% aqueous solution of acetic acid is used at 35. The underarm is etched for 120 seconds. Otherwise, a transparent conductive film ' was formed in the same manner as in Sample 2, and a texture was formed on the surface of the transparent conductive film. (Sample 19) 5.0 weight was used for wet sculpt. / 〇 〇 acetic acid aqueous solution, 153816.doc • 29- 201133889 90 seconds etching at 35 ° C, using a 0.5% by weight aqueous iodine solution, at 25 ° C for 180 seconds, in addition, A transparent conductive film was formed in the same manner as the sample 18, and a texture was formed on the surface of the transparent conductive film. (Sample 20) In the case of wet silver etching, a contact with a 5.0% by weight aqueous acetic acid solution for 120 seconds was carried out, and a treatment of 0.1 sec. 19 A transparent conductive film is formed in the same manner, and a texture is formed on the surface of the transparent conductive film. (Sample 21) A weight of 5.0 mm was used for wet etching. /. An aqueous solution of tartaric acid at 3 5 . (: After transparent etching for 60 seconds, a transparent conductive film was formed in the same manner as the sample 19, except that the 5% by weight aqueous potassium hydroxide solution was used at 25 ° C for 60 seconds, and the transparent conductive film was formed. The surface of the conductive film was textured. (Sample 22) Using a 5.0 wt.% malic acid aqueous solution for 90 seconds at 35 ° C for wet etching, a 氢氧化5 wt. potassium hydroxide aqueous solution was used. A transparent conductive film was formed in the same manner as the sample 19, and a texture was formed on the surface of the transparent conductive film, except that the film was treated at 25 ° C for 60 seconds. (Sample 2 3 ) 5.0% by weight of lactic acid was used for wet etching. A transparent conductive film was formed in the same manner as in the sample 19 except that the aqueous solution was subjected to a silver etching for 90 seconds at 351, and the aqueous potassium hydroxide solution of 0.5 wt% was used for 60 seconds at 25 °C. And forming a texture on the surface of the transparent conductive film. (Sample 24) 1538l6.doc 201133889 Wet etching uses a 5.0% by weight aqueous solution of citric acid, and after etching at 35 ° C for 60 seconds, 0.5% by weight of hydrogen is used. Potassium oxide aqueous solution, at 2 A transparent conductive film was formed in the same manner as the sample 19, and a texture was formed on the surface of the transparent conductive film, except that the treatment was performed at 5 ° C for 60 seconds. (Sample 25) 5.0% by weight of an aqueous acetic acid solution was used for wet etching. , at 35. (: After 30 seconds of button etching, use 〇5 wt% of the aqueous hydroxide solution to remove the solution at 25 ° C for 240 seconds. After etching, the thickness of the transparent conductive film is performed. A transparent conductive film was formed in the same manner as the sample 19, and a texture was formed on the surface of the transparent conductive film. (Sample 26) Sputtering was performed after the last name, and the thickness of the transparent conductive film was formed to 4 In the same manner as in the sample 19, a transparent conductive film was formed and a texture was formed on the surface of the transparent conductive film. The transparent conductive film of the samples 1 to 2 was prepared as described above to verify the texture. The effect of the shape was measured by HAZE METER HM i5 (manufactured by Murakami Color Technology Co., Ltd.), and the optical properties (haze value) of the single film of the above sample were measured. Condition 1 Shown in Table 153. 153B16.doc •31- 201133889 [Table i] Sample No. Heating filming pressure (A) when filming is formed Oxygen-added etching solution with or without fog rate (%) 1 Non-heating 0.67 No ammonium acetate Aqueous solution no 23.30 2 heating 0.67 no hydrochloric acid no 3.20 3 heating 0.67 no nitric acid no 2.50 4 heating 0.67 no acetic acid no 7.70 5 heating 0.67 no malonic acid no 19.90 6 heating 0.67 no citric acid no 12.70 7 heating 0.67 no diol acid no 8.80 8 Heating 0.67 Ammonium acetate-free aqueous solution No 8.90 9 Heating 0.67 Ammonium citrate-free aqueous solution No 8.70 10 Heating 0.67 No succinic acid aqueous solution No 15.30 11 Heating 0.67 No malonic acid aqueous solution No 18.60 12 Heating 0.67 No diethylene ethylamine Acid acid aqueous solution No 5.20 13 Heating 0.67 No three-stretching ethyltetramine aqueous solution No 7.00 14 Heating 2 No ammonium acetate aqueous solution No 42.30 15 Heating 0.67 No/with di-extension ethyltriamine aqueous solution No 8.70 16 Heating 0.67 No/with four extension Ethyl pentamine aqueous solution no 6.50 17 heating 0.67 no / with acetic acid aqueous solution / hydrazine hydroxide aqueous solution without 37.00 18 heating 0.6 7/4 No acetic acid aqueous solution No 2.50 19 Heating 0.67/4 No acetic acid aqueous solution / Hydroxide clock aqueous solution No 13.30 20 Heating 0.67/4 No acetic acid aqueous solution / Hydroxide clock aqueous solution No 12.10 21 Heating 0.67/4 No tartaric acid aqueous solution / potassium hydroxide No aqueous solution 18.60 22 Heating 0.67/4 No aqueous solution of malic acid / aqueous solution of oxidized bell No 4.20 23 Heating 0.67/4 No aqueous solution of lactic acid / aqueous solution of osmium hydroxide No 5.60 24 Heating 0.67/4 No citric acid aqueous solution / potassium hydroxide aqueous solution No 7.20 25 heating 0.67/4 aqueous solution without acetic acid/aqueous solution of hydrogen peroxide needle 11.70 26 heating 0.67/4 aqueous solution without acetic acid / aqueous solution of hydrogen peroxide needle 16.60 As can be seen from Table 1, by changing the film forming conditions or etching solution, various values can be obtained. A transparent conductive film having a haze value (specifically, 2.5 to 42.30%). As is clear from Fig. 7 to Fig. 17, a fine texture having various shapes (roughness) is formed on the surface of the transparent conductive film by changing the film formation conditions and etching conditions. Thereby, a fine texture having a high degree of freedom and having a desired roughness can be formed. (Sample 27 to Sample 32) 153816.doc -32- 201133889 The p-layer, the i-layer, and the η layer which are used to form a pin-type photoelectric conversion unit using a transparent conductive film having a fine texture formed on the surface as an upper electrode include amorphous The solar cell is a thin film. At this time, in Samples 28 to 32, a ρ layer (second p-layer) containing a crystalline ruthenium-based film was formed as an intermediate layer between the transparent conductive film and the p-layer constituting the photoelectric conversion unit. Further, the thickness of the intermediate layer was changed to 5 nm in Samples 28 to 30, 10 nm in Sample 31, and 15 nm in Sample 32 to prepare a solar cell. For the solar cells fabricated in Samples 27 to 32, an open circuit voltage (v〇c) and a short-circuit current (JSC) were evaluated as solar cell performance using a solar simulator [SPI SyN SIMULATOR 4800i (manufactured by Spire Corporation)]. ), maximum output power (pmax), series resistance (Rs), shunt resistance (Rsh), fill factor (FF), photoelectric conversion efficiency (Effp will not result in Table 2. Also, maximum wheel power (pmax) The relationship with the thickness of the symplectic layer is shown in Fig. 18. The relationship between the filling factor (FF) and the thickness of the intermediate layer is shown in Fig. 9. [Table 2] Sample number intermediate (nm) Voc (V) Isc (A) Pmax (W) Rs (Ω) Rsh (Q) FF Eff (〇/〇) 27 0 103.3 1.67 111.1 9.12 772 0.64 \/0) 7.65 28 5 104.3 1.71 120.1 7.74 802 0.67 8.27 29 in r 104.7 1 1.67 119.1 7.74 1750 0 68 8.20 31 5 1 A 104.3 1.70 120.3 7.42 700 0.68 8.29 1U 102.5 1.70 115.7 7.54 730 0.66 7.97 .32 tc 10 ---- 99.5 1.67 100.5 9.48 631 0.61 6.92 It is clear from Table 2 that 'the sample with ten layers is configured Medium, set the film thickness I53816.doc •33· 201133889 to 5~H) The sample 28 to sample 3 i of nm is lower in series resistance (RS) than the sample η in which the intermediate layer is not disposed. Also, for the same (four) ~ sample plus 'open circuit. The enthalpy, the circuit current (Ise), the maximum output power (Pmax), the fill factor (FF), and the photoelectric conversion efficiency (Eff) can all be excellent. Thus, the present invention can be verified to be effective in increasing the efficiency of the solar cell. Further, as shown in Figs. 18 and 19, in the case where the thickness of the intermediate layer is 5 to i, the filling factor (FF) and the open circuit voltage (v〇c) are increased, and the photoelectric conversion efficiency is increased. [Industrial Applicability] The present invention can be used as a power extraction electrode of a light person (4), and a transparent conductive film for a solar cell having a transparent conductive film made of ZnO as a basic structure. A substrate, a solar cell, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a solar cell according to a first embodiment of the present invention. Fig. 2 is a schematic configuration view showing a film forming apparatus suitable for a method of manufacturing a solar cell. Fig. 3 is a cross-sectional view showing the main portion of the film forming chamber in the film forming apparatus of Fig. 2. Fig. 4 is a cross-sectional view showing another example of the film forming apparatus. Fig. 5 is a schematic view showing an example of a continuous film forming apparatus. Fig. 6 is a cross-sectional view showing a solar cell according to a second embodiment of the present invention. Fig. 7 is a view showing an SEM image of a transparent conductive film obtained in the examples. Fig. 8 is a view showing an SEM image of a transparent conductive film obtained in the examples. 153816.doc • 34· 201133889 Fig. 9 is a view showing an SEM image of a transparent conductive film obtained in the examples. The figure shows the SEM image of the transparent conductive film obtained in the Example. The figure shows the SEM image of the transparent conductive film obtained in the Example. Fig. 12 is a view showing an SEM image of a transparent conductive film obtained in the examples. Fig. 13 is a view showing a sem image of a transparent conductive film obtained in the examples. The figure is a view showing a sem image of a transparent conductive film obtained in the examples. Fig. 15 is a view showing an SEM image of a transparent conductive film obtained in Examples. Fig. 16 is a view showing an SEM image of a transparent conductive film obtained in the examples. Fig. 1 is a view showing an SEM image of a transparent conductive film obtained in the examples. Figure is a graph showing the relationship between the maximum transmission and the thickness of the intermediate layer for the solar cells obtained in the examples. Fig. 19 is a graph showing the relationship between the fill factor (FF) and the thickness of the intermediate layer for the solar cell obtained in the examples. Fig. 20 is a cross-sectional view showing an example of a prior solar cell. [Description of main component symbols] 1. ΙΑ, 1B, 100 Solar cell 101 Glass substrate (transparent substrate) 3 ' 103 Upper electrode 4 Transparent conductive film 5 Intermediate layer 6 First photoelectric conversion unit 6i '7i, 9i, 105i, 109i i Type semiconductor layer 6n, 7n, 9n, 105n, 109n n type semiconductor layer 6ρ, 7ρ, 9ρ, 105ρ, 109η p type semiconductor layer 153816.doc -35- 201133889 7 second photoelectric conversion unit 8, 107 intermediate electrode 9 third Photoelectric conversion unit 10 substrate 11 with transparent conductive film, 110 buffer layer 12, 111 back electrode 20 sputtering device 22 loading/unloading chamber 23 film forming chamber 23a, 23b side 24 coarse suction and exhaust mechanism 25 substrate tray 27 target Material 32 '42 Sputtering cathode mechanism 33 High vacuum exhaust mechanism 34 Power supply 35 Gas introduction mechanism 35a Sputter gas introduction mechanism 35b Hydrogen introduction mechanism 35c Oxygen introduction mechanism 35d Water vapor introduction mechanism 43 Back plate 44 Magnetic circuit 44a, 44b Magnetic circuit Unit 153816.doc -36· 201133889 45 Bracket 46 1st magnet 47 2nd magnet 48 Magnetic Lie 49 Magnetic field line 50 Position 60 First film forming device 61 Entrance chamber 62 ' 63 ' 66 P layer film formation reaction chamber 64 i layer film formation reaction chamber 64a, 64b, 64c, 64d reaction chamber 65 η layer film formation reaction chamber 67 extraction chamber 70 second film formation device 71 loading and unloading chamber 72 film formation reaction chamber 80 exposure device 105 upper battery 109 lower battery A, B, C at 153816.doc -37-

Claims (1)

201133889 七、申請專利範圍： 1· 一種太陽電池之製造方法，其特徵在於： 前述太陽電池係具備： 透明基板； 設置於上述透明基板上、以ZnO為主成分的透明導電 膜； 將作為非晶質之矽系薄膜之第Ip層、i層及η層積層而 形成的pin型之光電轉換單元；及 配置於上述透明導電膜與上述第lp層之間、由作為結 晶質之矽系薄膜之第2p層所形成之中間層； 並且該太陽電池之製造方法至少依序具備以下步驟： 於所需之製程氣體環境中，對構成上述透明導電膜之 母材之靶材施加濺鍍電壓而進行濺鍍，於上述透明基板 上形成上述透明導電膜； 對上述透明導電膜進行濕式蝕刻，於上述透明導電膜 之表面形成微細紋理； 於上述透明導電膜上形成上述中間層；及 於上述中間層上依序形成上述第1]3層、上述丨層及上述 η層。 2. 方法’其中於上述濕式蝕 之至少一種之蝕刻液：選 、蘋果酸、内二酸、琥珀 選自甲酸錢、乙酸鍵、檸 丙二酸銨、琥珀酸銨、二 如晴求項1之太陽電池之製造 刻中’使用含有以下水溶液中 自甲酸、乙酸、檸檬酸、乳酸 酸、二醇酸中之羧酸水溶液， 樣酸錄、乳酸銨 '蘋果酸銨、 153816.doc 201133889 醇酸銨中之羧酸銨水溶液，及選自二伸乙基三胺、三伸 乙基四胺、四伸乙基五胺中之多胺水溶液。 3. 如請求項1或2之太陽電池之製造方法，其進而包括於上 述濕式蝕刻後’使用選自氫氧化鉀、氫氧化四甲基銨水 溶液中之鹼性水溶液中之至少一種進行後處理的步驟。 4. 一種太陽電池’其特徵在於具備： 透明基板； 設置於上述透明基板上，以Zn〇為主成分，且具有藉 由濕式钱刻而形成之紋理之透明導電膜； 將作為非晶質之矽系薄膜之第lp層、丨層及n層積層而 形成的pin型之光電轉換單元；及 配置於上述透明導電膜與上述第lp層之間、由作為結 晶質之矽系薄膜之第2p層所形成之中間層。 5. —種太陽電池用附透明導電膜之基板之製造方法，其特 徵在於： 前述太陽電池用Μ透明導電膜之基板係藉由透明基 板、及設置於上述透明基板上之以Ζη〇為主成分之透明 導電膜而形成； 並且該太陽電池用附读 了边明導電膜之基板之製造方法至 少依序具備以下步驟： 於製程氣體環境中，斟 對構成上述透明導電膜之母材之 乾材施加濺鍍電壓而進扞 L ^ A 仃濺鍍，於上述透明基板上形成 上述透明導電膜；及 對上述透明導電膜進 叮，燕式钱刻，於上述透明導電膜 153816.doc 201133889 表面形成微細紋理；且 使用Zn〇或於Zn〇中加入有添加物之材料作為上述母 材。 6. 如請求項5之太陽電池用附透明導電膜之基板之製造方 法，其中於上述濕式蝕刻中，使用含有以下水溶液中之 至少一種之蝕刻液：選自甲酸、乙酸、檸檬酸、乳酸、 蘋果酸、丙二酸、琥珀酸、二醇酸中之羧酸水溶液，選 自甲酸銨、乙酸銨、擰檬酸銨、乳酸銨、蘋果酸銨、丙 二酸銨、琥珀酸銨、二醇酸銨中之羧酸銨水溶液；選自 一伸乙基三胺、三伸乙基四胺、四伸乙基五胺中之多胺 水溶液。 7. 如請求項5或6之太陽電池用附透明導電膜之基板之製造 方去，其進而包括於上述濕式蝕刻後，使用選自氫氧化 鉀 '氫氧化四曱基銨水溶液中之鹼性水溶液中之至少— 種進行後處理之步驟。 8. —種太陽電池用附透明導電膜之基板，其特徵在於藉由 請求項5之方法而製造。 153816.doc201133889 VII. Patent application scope: 1. A method for manufacturing a solar cell, characterized in that: the solar cell system includes: a transparent substrate; a transparent conductive film provided on the transparent substrate and containing ZnO as a main component; a pin-type photoelectric conversion unit formed by forming an Ip layer, an i layer, and an η layer of a ruthenium-based film; and a ruthenium-based film disposed between the transparent conductive film and the lp layer and being crystalline The intermediate layer formed by the second p layer; and the method for manufacturing the solar cell comprises the steps of: applying a sputtering voltage to a target material of the base material constituting the transparent conductive film in a required process gas atmosphere; Sputtering, forming the transparent conductive film on the transparent substrate; wet etching the transparent conductive film to form a fine texture on the surface of the transparent conductive film; forming the intermediate layer on the transparent conductive film; The first layer 3, the tantalum layer, and the n layer are sequentially formed on the layer. 2. Method 'The etching liquid in which at least one of the above wet etchings is selected: malic acid, endoic acid, amber selected from formic acid money, acetic acid bond, ammonium malonate, ammonium succinate, and the like In the manufacture of a solar cell, the use of an aqueous solution of carboxylic acid in formic acid, acetic acid, citric acid, lactic acid, or glycolic acid in the following aqueous solution is used, and the acid is recorded, ammonium lactate, ammonium malate, 153816.doc 201133889 alcohol An aqueous solution of ammonium carboxylate in ammonium acid, and an aqueous solution of a polyamine selected from the group consisting of di-ethyltriamine, tri-ethyltetramine, and tetra-ethylpentamine. 3. The method of manufacturing a solar cell according to claim 1 or 2, which further comprising, after said wet etching, using at least one of an alkaline aqueous solution selected from the group consisting of potassium hydroxide and tetramethylammonium hydroxide aqueous solution The steps of processing. 4. A solar cell comprising: a transparent substrate; a transparent conductive film provided on the transparent substrate and having Zn〇 as a main component and having a texture formed by wet etching; a pin-type photoelectric conversion unit formed by forming a lp layer, a ruthenium layer, and an n-layer layer of the ruthenium-based film; and a ruthenium-based film disposed between the transparent conductive film and the lp layer and being a crystalline ruthenium film The intermediate layer formed by the 2p layer. 5. A method of manufacturing a substrate with a transparent conductive film for a solar cell, characterized in that: the substrate for the transparent conductive film for a solar cell is mainly composed of a transparent substrate and a substrate provided on the transparent substrate. And forming the substrate with the transparent conductive film; and the solar cell is provided with the following steps at least in sequence: in the process gas environment, the ruthenium is formed on the base material constituting the transparent conductive film a transparent plating film is formed on the transparent substrate by applying a sputtering voltage to the surface of the transparent plating film; and the transparent conductive film is formed on the surface of the transparent conductive film 153816.doc 201133889 A fine texture is formed; and a material in which an additive is added to Zn〇 or Zn〇 is used as the above-mentioned base material. 6. The method for producing a substrate with a transparent conductive film for a solar cell according to claim 5, wherein in the wet etching, an etching solution containing at least one of the following aqueous solutions is used: selected from the group consisting of formic acid, acetic acid, citric acid, and lactic acid. An aqueous solution of carboxylic acid in malic acid, malonic acid, succinic acid or glycolic acid, selected from the group consisting of ammonium formate, ammonium acetate, ammonium citrate, ammonium lactate, ammonium malate, ammonium malonate, ammonium succinate, An aqueous solution of ammonium carboxylate in ammonium alkoxide; an aqueous solution of a polyamine selected from the group consisting of ethyltriamine, triethylamine, and tetraethylamine. 7. The solar cell of claim 5 or 6 for use in the manufacture of a substrate with a transparent conductive film, which is further included after the wet etching described above, using a base selected from the aqueous solution of potassium hydroxide 'tetradecylammonium hydroxide At least one of the aqueous solutions is a post-treatment step. A substrate for a solar cell with a transparent conductive film, which is produced by the method of claim 5. 153816.doc
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