TW201246277A - Method of manufacturing transparent conductive substrate with surface electrode and method of manufacturing thin film solar cell - Google Patents

Method of manufacturing transparent conductive substrate with surface electrode and method of manufacturing thin film solar cell Download PDF

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TW201246277A
TW201246277A TW100138103A TW100138103A TW201246277A TW 201246277 A TW201246277 A TW 201246277A TW 100138103 A TW100138103 A TW 100138103A TW 100138103 A TW100138103 A TW 100138103A TW 201246277 A TW201246277 A TW 201246277A
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sheet resistance
transparent conductive
light transmittance
surface electrode
film
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TW100138103A
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Chinese (zh)
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Yasunori Yamanobe
Fumihiko Matsumura
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Sumitomo Metal Mining Co
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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
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators
    • 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

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

A transparent conductive substrate with surface electrode (11b), formed by sputtering a zinc oxide crystalline transparent conductive film (uneven film (22)), which has an uneven structure (2a) formed on the surface, on a translucent glass substrate (1) as a surface electrode (2), is treated with heat at 400 to 550 DEG C in a hydrogen gas atmosphere of 0.1 to 100 Pa. As a result, a surface electrode (2) with a higher light-trapping effect can be provided, and a thin-film solar cell (10) with higher photoelectric conversion efficiency can be obtained.

Description

201246277 六、發明說明： 【發明所屬之技術領域】 本發明係有關於透光性基板上形成由透明導電膜所構 成之表面電極膜之附表面電極之透明導電基板的製造方法 及薄膜太陽能電池之製造方法。本申請案係於日本國中， 以2010年1〇月20日申請之日本專利申請案號2010-23 51 64爲基礎，主張優先權，參照此申請案，援用於本申 請案。 【先前技術】 使光由玻璃基板等透光性基板側入射，進行發電的薄 膜太陽能電池係利用在透光性基板上形成有光入射側電極 (以下稱爲「表面電極」）的透明導電玻璃基板。表面電 極係單獨或層合氧化錫、氧化鋅、氧化銦等之透明導電性 膜而形成的。此外，薄膜太陽能電池係利用多晶矽、微結 晶矽的結晶質矽薄膜或非晶質矽薄膜。此薄膜太陽能電池 的開發係蓬勃進行著，主要的目的係藉由在廉價的基板上 以低溫製程形成高品質的矽薄膜，而同時實現低成本化與 高性能化。 上述薄膜太陽能電池之一係具有在透光性基板上依序 形成由透明導電膜所構成的表面電極，依序被層合P型半 導體層、i型半導體層、η型半導體層的光電變換半導體 層，及含有光反射，性金屬電極之背面電極的構造者已爲人 知。此薄膜太陽能電池中，光電變換作用主要是在此i型 201246277 半導體層內產生，因此i型半導體層較薄時，光吸收係數 較小之長波長區域的光不會被充分吸收。換言之，光電變 換量，本質上受i型半導體層的膜厚所限制。因此，藉由 爲了更有效地利用入射至含有i型半導體層之光電變換半 導體層的光，而光射入側的表面電極設表面凹凸構造，使 光往光電變換半導體層內散射，進而在背面電極反射的光 進行亂反射。 這種薄膜太陽能電池，一般而言，該光射入側的表面 電極爲藉由在玻璃基板上依據熱CVD法之原料氣體的熱 分解形成摻雜氟的氧化錫薄膜的方法（例如參照專利文獻 1)形成表面凹凸構造。 但是具有表面凹凸構造的氧化錫膜，由於需要500°C 以上之高溫製程等理由導致成本較高。此外，因膜的比電 阻較高，因此增加膜厚時，透過率會下降，光電轉換效率 降低。 因此，提案在由氧化錫膜或摻雜了錫的氧化銦（ITO )膜所構成的底層電極上，藉由濺鍍形成摻雜鋁的氧化鋅 (AZO )膜，或摻雜鎵的氧化鋅（GZO )膜，藉由蝕刻容 易被蝕刻的氧化辞膜，形成具有表面凹凸構造的表面電極 的方法（例如參照專利文獻2 )。此外，在近紅外線區域 之透光性優異的摻雜鈦的氧化銦（ITiO )膜所構成的底層 電極上，藉由濺鍍形成在成膜時較少發生電弧放電（ arcing)或微粒（particle)之摻雜鋁與鎵的氧化鋅（ GAZO)膜，與專利文獻2之技術同樣，蝕刻氧化鋅膜形 201246277 成具有表面凹凸構造之表面電極的方法（例如參照專利文 獻3 )。 但是藉由蝕刻形成表面凹凸構造的手法中，凹凸膜上 容易產生銳利的突起，不易得到良好的光電轉換半導體層 ’無法提高光電轉換效率。此外，蝕刻後之洗淨不充分時 ’半導體層容易產生缺陷，爲了防止此缺陷，必須要複雑 的洗淨步驟，缺乏量產性。 〔先行技術文獻〕 〔專利文獻〕 [專利文獻1]特表平2-503615號公報 [專利文獻2]特開2〇〇〇-294812號公報 [專利文獻3]特開2010-34232號公報 【發明內容】 〔發明欲解決的課題：） 本發明係有鑑於上述以往技術問題點而提案者，提供 光電轉換效率高之附表面電極之透明導電基板之製造方法 及薄膜太陽能電池之製造方法。 〔解決課題的手段〕 本件發明人等精心檢討的結果，發現將於透光性玻璃 基板上’藉由濺鍍法形成之氧化鋅系之結晶質透明導電膜 所構成之凹凸膜，在導入氫氣體之還原氣氛中，進行熱處 理’增加透明導電膜之導電率，同時也增加光關閉效果之 201246277 指標的霧度率（散射透過率/全光線透過率）。 換言之’本發明之附表面電極之透明導電基板之製造 方法’其係將於透光性基板上，藉由濺鍍法形成有具有表 面形成有凹凸構造之氧化鋅系之結晶質透明導電膜之表面 電極之附表面電極的透明導電基板，在0.1〜lOOPa之氫氣 體氣氛下，以400~550°C實施熱處理。 又’本發明之薄膜太陽能電池之製造方法，其係於透 光性基板上，依序形成表面電極、光電轉換半導體層、背 面電極之薄膜太陽能電池的製造方法，其特徵係將於透光 性基板上’藉由濺鍍法形成有具有表面形成有凹凸構造之 氧化鋅系之結晶質透明導電膜之表面電極之附表面電極的 透明導電基板，在 0.1 ~l〇〇pa之氫氣體氣氛下，以 400〜5 5 0°C施予熱處理。 〔發明效果〕 依據本發明時，在透光性基板上形成表面形成有凹凸 構造之氧化鋅系之結晶質透明導電膜後，藉由在 0.1〜lOOPa之氫氣體氣氛中，以400~5 5 0°C施予熱處理，可 實現更高霧度率。結果可提供光關閉效果更高的表面電極 ，可得到光電轉換效率更高的薄膜太陽能電池。 〔實施發明的形態〕 以下對於本發明之實施形態（以下稱爲「本實施形態 」）參照圖面，以下述順序詳細說明。 -8 - 201246277 1. 薄膜太陽能電池 1 -1 ·附表面電極之透明導電基板 1-2.光電轉換半導體層 1- 3.背面電極 2. 薄膜太陽能電池之製造方法 2- 1 ·附表面電極之透明導電基板 2-2.光電轉換半導體層 2-3.背面電極 3 .實施例 <1.薄膜太陽能電池> 圖1係表示本實施形態之薄膜太陽能電池之構成例的 斷面圖。薄膜太陽能電池1 0係具有於透光性玻璃基板1 上依序層合表面電極2'光電轉換半導體層3及背面電極 4的構造。相對於薄膜太陽能電池1〇，應被光電轉換的光 係如箭頭所示，由透光性玻璃基板1側入射。 <1-1.附表面電極之透明導電基板> 本實施形態之附表面電極之透明導電基板（透明導電 凹凸膜）係於透光性玻璃基板1上形成表面電極2。附表 面電極之透明導電基板例如有圖2A所示之附表面電極之 透明導電基板11a或圖2B所示之附表面電極之透明導電 基板1 1 b。附表面電極之透明導電基板1 1 a係於透光性玻 璃基板1上藉由濺鑛法形成以作爲底層膜21之氧化銦系 -9 - 201246277 的透明導電膜與作爲凹凸膜22之表面形成有凹凸構造之 氧化鋅系之結晶質透明導電膜的順序層合的層合膜。附表 面電極之透明導電基板lib係於透光性玻璃基板1上藉由 濺鍍法形成作爲表面電極2之凹凸膜22。以下，附表面電 極之透明導電基板1 1 a及附表面電極之透明導電基板1 1 b 總合簡稱爲「附表面電極之透明導電基板1 1」。 (透光性玻璃基板） 透光性玻璃基板1較佳爲太陽光之光譜可透過，在 3 5 0~1 2 00nm之波長域具有高透過率者。又，考慮屋外環 境下之使用，較佳爲電氣、化學、物理性安定者。這種透 光性玻璃基板1例如有碳酸鈉-石灰-矽土玻璃（Sod a-lime-silicate Glass)、硼酸鹽玻璃（Borate Glass)、低 含鹼玻璃、石英玻璃、其他各種玻璃等。 透光性玻璃基板1係防止離子由玻璃擴散至成膜於該 玻璃上面之透明導電膜所構成的表面電極，爲了將因玻璃 基板之種類或表面狀態影響膜之電特性壓抑到最小限度， 可在玻璃基板上施加氧化矽膜等鹼性障壁膜。 (表面電極） 表面電極2係如圖1所示，具有表面凹凸構造2a之 表面電極。表面電極2係與透光性玻璃基板1同樣，較佳 爲對於3 50〜1 200nm之波長的光具有80%以上之高透過率 者。又，表面電極2係在後述之氫氣氛中之熱處理後的片 -10- 201246277 電阻（表面抵抗）較佳爲10Ω/□以下，膜之霧度率較佳爲 15%以上，更佳爲20%以上。 表面電極2例如圖2 B所示，可以凹凸膜2 2單體所構 成。又，表面電極2，例如圖2A所示，可以底層膜21與 凹凸膜22之順序層合的層合體所構成。如圖2A所示之表 面電極2，將底層膜21置於透光性玻璃基板1與凹凸膜 22之間，如圖2A所示，相較於表面電極2可以凹凸膜22 單體所構成，可使凹凸膜22之厚度更薄，結果可使表面 電極2整體的厚度變薄，有利於透光性。又，底層膜21 係如後詳述，爲氧化銦系之透明導電膜，體積電阻率小於 氧化辞系之透明導電膜，結果在相同電阻率時，可使表面 電極2整體的厚度變薄。 表面凹凸構造2 a之凹凸程度係表示表面凹凸之指標 的霧度率，較佳爲20%以上，算術平均粗度（Ra)較佳爲 4〇〜12 0nm。依據具有這種霧度率及算術平均粗度（Ra) 之表面凹凸構造2a的表面電極2時，光關閉效果變高， 可提高薄膜太陽能電池10之光電轉換效率。 (底層膜） 底層膜21係摻雜了選自Ti、Sn、Ga之至少1種之氧 化銦系之非晶質透明導電膜。本說明書中，非晶質係指X 射線解析之繞射波峰強度爲結晶質之繞射波峰強度之20% 以下者。此種氧化銦系非晶質透明導電膜，例如可使用摻 雜了鈦的氧化銦（ITiO )膜。ITiO膜係近紅外線區域之光 -11 - 201246277 的透過率高’容易形成非晶質的膜，此外，可助長形成於 其上之氧化鋅系結晶的成長。ITiO膜中，摻雜Ti的量較 佳爲〇 · 5〜2.0質量％。 此外，氧化銦系之非晶質透明導電膜，也可使用摻雜 了 Sn、Ga的氧化銦（1丁00)膜。1丁00膜也可容易形成 非晶質膜’此外，可助長形成於其上之氧化鋅系結晶的成 長。ITGO膜中，摻雜Sn、Ga之量較佳爲3.0〜15質量。/〇。 氧化銦系之非晶質透明導電膜，也可使用摻雜了 T i、 Sn的氧化銦（ITiTO)膜。ITiTO膜相較於ITiO膜，可更 進一步助長氧化鋅系結晶的成長。ITiTO膜中，摻雜Ti、 Sn之量較佳爲0.01〜2.0質量％。 底層膜 21的厚度較佳爲 1〇〇〜500nm，更佳爲 200~400nm。膜厚低於100nm時，底層膜21所導致之霧 度（haze )率增加的效果明顯變小，而超過500nm時，透 過率減少，抵消霧度率增加之光關閉效果。 (凹凸膜） 凹凸膜22係摻雜了選自A卜Ga、B、In、F、Si、Ge 、Ti、Zr、Hf之至少1種之氧化鋅系的結晶質透明導電膜 。此種氧化鋅系的結晶質透明導電膜，例如有同時摻雜了 A1與Ga之氧化鋅（GAZO )膜、摻雜了 A1之氧化鋅（ AZO )膜、摻雜了 Ga之氧化鋅（GZO )膜。此等氧化鋅 膜中，GAZO膜在藉由職鍍法成膜時，不易發生電弧放電 (arcing ) ’故更佳。GAZO膜中’摻雜A丨與Ga之量較 -12- 201246277 佳爲〇1〜〇.5質量％。又，GZO膜中’摻雜Ga的量較佳爲 0.2 ~ 6 · 0 質量 ％。 凹凸膜22之膜厚較佳爲300〜2000nm ’更佳爲 400〜1 600nm。膜厚小於300nm時’凹凸不會變大’有時 膜之霧度率低於10%。又’膜厚超過2000nm時’透過率 明顯降低。 <1-2.光電轉換半導體層> 光電轉換半導體層3係於表面電極2上依序層合P型 半導體層31、i型半導體層32、η型半導體層33。p型半 導體層31與η型半導體層33，其順序可相反，通常太陽 能電池係在光之入射側配置Ρ型半導體層。 ρ型半導體層31係例如由摻雜了作爲雜質原子Β (硼 )之微結晶矽的薄膜所構成。此外，替代微結晶矽，可使 用多晶矽、非晶質矽、碳化矽、矽鍺（SiGe )等材料。此 外，雜質原子不限於硼，也可使用鋁等。 i型半導體層32係例如由未被摻雜之微結晶矽的薄膜 所構成。此外’替代微結晶矽，也可使用多晶矽、非晶質 矽、碳化矽、矽鍺（SiGe )等材料。此外，也可使用含有 微量雜質之弱P型半導體材，或弱η型半導體，充分具備 光電轉換功能的矽系薄膜材料。 η型半導體層33係例如由摻雜了雜質原子ρ (磷）之 η型微結晶矽所構成。此外，替代微結晶矽，也可使用多 晶矽、非晶質矽、碳化矽、矽鍺（Si(Je )等材料。此外， 201246277 雜質原子不限於磷（p)，也可使用N (氮）等。 <1-3.背面電極> 背面電極4係於n型半導體層33上依序形成透明導 電性氧化膜4 1與光反射性金屬電極42。 透明導電性氧化膜4 1並非必要，但藉著提高η型半 導體層33與光反射性金屬電極42之附著性，提高光反射 性金屬電極42的反射效率，且具有保護η型半導體層33 不受化學變化影響的功能。 透明導電性氧化膜41係選自由氧化鋅膜、氧化銦膜 、氧化錫膜等之至少1種所形成的。特別是於氧化鋅膜係 摻雜鋁（Α1 )、鎵（Ga )中至少1種類，於氧化銦膜中摻 雜Sn、Ti、W、Ce、Ga、Mo中至少1種類，以提高導電 性較佳。此外，η型半導體層3 3所鄰接之透明導電性氧化 膜41的比電阻，較佳爲1 .5 X 1 0·3 Ω cm以下。 <2.薄膜太陽能電池之製造方法> 其次說明本實施形態之薄膜太陽能電池1 0之製造方 法。薄膜太陽能電池1 〇係如圖1所示，透光性玻璃基板1 上依序形成表面電極2、光電轉換半導體層3、背面電極4 。首先，說明構成薄膜太陽能電池1〇之附表面電極之透 明導電基板1 1的製造方法。 <2-1.附表面電極之透明導電基板> • 14- 201246277 如圖2(A)所示之附表面電極之透明導電基板lla 係首先使透光性玻璃基板1之溫度保持於2 0〜7 0 °C之範圍 ，導入氣體例如使用氬與氧之混合氣體，藉由濺鍍法形成 由氧化銦系之非晶質透明導電膜所構成之底層膜2 1。透光 性玻璃基板1之溫度即使低於2 0 °C，也可得到氧化銦系之 非晶質透明導電膜，但是濺鍍裝置內，必須設置冷卻透光 性玻璃基板之機構，成本增加，故不佳。又，透光性玻璃 基板1之溫度超過7〇 °C時，很難得到氧化銦系之非晶質透 明導電膜。 附表面電極之透明導電基板lla中之凹凸膜22係於 氬等惰性氣體氣氛中，在調整IPa以上之氣體壓力的高氣 體壓力環境下，藉由濺鍍成膜於底層膜21上。 形成凹凸膜22時之氣體壓較佳爲1〜i〇Pa。氣體壓力 高於10Pa時，霧度率上昇，成膜速度極端降低。氣體壓 力低於IPa時，膜表面不易生成凹凸形狀，霧度率極端降 低。 凹凸膜22之進行濺鍍時的基板溫度爲3 00 °C以上，較 佳爲300-55 0 °C。基板溫度之上限爲透光性玻璃基板1之 軟化點以下時，最大可爲8 00 °C。一般太陽能電池用途的 透光性玻璃基板時，軟化點大多爲600〜650°C者，使用此 等時，超過550°C時，接近軟化點溫度，因此基板之強度 降低，結果製造良率降低。 圖2B所示之附表面電極之透明導電基板1 1 b係與上 述附表面電極之透明導電基板lla同樣，藉由濺鍍法於透 -15- 201246277 光性玻璃基板1上形成作爲表面電極2之凹凸膜22。 其次，將所得之附表面電極之透明導電基板1 1在 0.1〜lOOPa之氫氣體氣氛中，施予400〜550 °C的熱處理。具 體而言，依以下順序’對附表面電極之透明導電基板11 施予熱處理較佳。如此’在導入有氫氣體的還原氣氛中， 藉由施予熱處理，去除氧化鋅結畢中之不安定氧鍵結，形 成載體，增加構成表面電極2之透明導電膜的導電率，可 實現更高的霧度率。 首先，將收納有附表面電極之透明導電基板11之氣 氛爐內，以氬氣體等惰性氣體取代後，將該氣氛爐內藉由 真空幫浦形成未達O.lPa之真空度。其次，將氫氣體導入 該氣氛爐內，同時調整氣氛爐與真空幫浦間之閥之開閉， 使氣氛爐內之壓力保持〜l〇〇Pa，實現0.1〜lOOPa之氫 氣體氣氛，加熱至400〜5 5 0 °C，進行熱處理。 爐內之氣體壓超過l〇〇Pa時，氫導入量較多時，氣氛 爐內之氫濃度升高，故不佳。又，氣體壓低於0.1 Pa時， 還原效果減弱，還原所需時間明顯增長，生產性變差，不 實用，故不佳。 熱處理之加熱溫度低於400°C時，儘管是氫氣體氣氛 ，也幾乎無還原_效果，片電阻（sheet resistance)超過 8Ω/□時，無法得到提高膜之霧度率的效果，故不佳。又 ，加熱溫度超過550°C時，因過多的還原，膜失去透明度 ，對於3 50〜1 200nm之波長光之透過率（全光透過率）會 低於80%，故不佳。 -16- 201246277 如此，依據本實施形態之附表面電極之透明導電基板 的製造方法時，透光性玻璃基板1上形成凹凸膜22、或底 層膜21與凹凸膜22後，在0.1〜10 OP a之氫氣體氣氛中， 以400〜5 50°C施予熱處理。藉此可實現更高霧度率，結果 可提供光關閉效果更高的表面電極2。 圖3係表示氫氣體導入之熱處理前後之霧度率的關係 曲線圖。具體而言，圖3係準備初期霧度値不同之圖2A 所示之附表面電極之透明導電基板11a，以氫氣體壓 0.1 Pa、熱處理溫度45 0 °C，顯示熱處理效果的結果圖。此 附表面電極之透明導電基板11a係依作爲凹凸膜22之 GAZO膜、作爲底層膜21之ITiTO膜、透光性玻璃基板1 的順序層合。曲線圖之橫軸係表示對附表面電極之透明導 電基板11施予熱處理前的霧度率，曲線圖之縱軸係表示 對附表面電極之透明導電基板11施予熱處理後的霧度率 。圖3之曲線圖之虛線係說明熱慮理前後之霧度率之改善 比的基準線。無熱處理效果時，此虛線上存在著測定點。 依據圖3所示的結果時，可知對附表面電極之透明導 電基板11之熱處理具有提高霧度率的效果，但是熱處理 前（初期），對於無霧度之附表面電極之透明導電基板11 ，無提高霧度率的效果。 使用上述附表面電極之透明導電基板11a，以氫氣體 壓0.1 Pa、熱處理溫度45〇°C。進行熱處理時，較佳爲使用 霧度率爲12%以上之附表面電極之透明導電基板。藉此， 可使熱處理後之附表面電極之透明導電基板1 1之霧度率 -17- 201246277 成爲1 5%以上。 <2-2.光電轉換半導體層> 其次’使用例如電漿 CVD ( Chemical VaP〇r Deposition)法在附表面電極之透明導電基板11的表面電 極2上，形成光電轉換半導體層3。此電漿CVD法也可使 用一般習知之平行平板型之RF電漿CVD’也可用利用由 頻率150MHz以下之RF帶域至VHF帶域之高頻電源的電 漿CVD法。 光電轉換半導體層3係依序層合p型半導體層31、i 型半導體層32、及η型半導體層33而形成的。又，必要 時，可對各半導體層照射脈衝雷射光（雷射退火），控制 結晶化分率或載體濃度。 <2-3.背面電極> 其次，在光電轉換半導體層3上形成背面電極4。背 面電極4係依序透明導電性氧化膜4 1、光反射性金屬電極 42的順序層合而形成的。 透明導電性氧化膜41係藉由真空蒸鍍、濺鍍等方法 所形成，較佳爲以ΖηΟ ' ΙΤΟ等之金屬氧化物所形成者。 光反射性金屬電極42係藉由真空蒸鍍 '濺鍍等方法 所形成，較佳爲以選自八§、八\1、八1、（：11及？1中之1種 或含有此等之合金所形成者。例如以100〜3 3 0它，更佳爲 200〜300°C之溫度藉由真空蒸鍍形成光反射性較高的Ag爲 -18- 201246277 佳。 如上述，本實施形態之薄膜太陽能電池10之製造方 法係於透光性玻璃基板1上，形成凹凸膜22、或底層膜 21與凹凸膜22作爲表面電極2後，在0.1〜l〇〇Pa之氫氣 體氣氛中，以400〜550t施予熱處理，製造附表面電極之 透明導電基板1 1。藉此，不必使用蝕刻手法，可形成由良 好凹凸所構成之表面電極2，可實現更高霧度率。結果可 提供光關閉效果更高的表面電極2，可得到光電轉換效率 更高的薄膜太陽能電池1 〇。 【實施方式】 〔實施例〕 以下使用實施例說明本發明，本發明不限於此等實施 例者。 (實施例1 ) 藉由以下製造條件製作如圖2A所示之構造之由氧化 銦系之透明導電膜所構成之底層膜與由氧化鋅系之結晶質 透明導電膜所構成之凹凸膜之層合構造所成的附表面電極 之透明導電基板。 首先，透光性玻璃基板1使用碳酸鈉-石灰-矽土玻璃 基板，此玻璃基板上依序形成底層膜21與凹凸膜22作爲 表面電極2。底層膜21係使用氧化銦中摻雜了氧化鈦1質 量％、氧化錫〇.〇1質量％的ITiTO膜，凹凸膜22係使用 -19 - 201246277 氧化鋅中摻雜了氧化鎵0 · 5 8質量％、氧化鋁〇 . 3 2質量％之 GAZO 膜。 ‘成膜係使用DC磁控濺鍍法。使用的靶係φ 6吋大小 ，基板與靶的間隔爲6 0 m m。 將碳酸鈉-石灰-矽土玻璃基板的溫度設定爲25。(：，導 入氣體使用氬與氧之混合氣體（氬：氧=99:1),藉由濺 鍍法形成膜厚成爲200nm的ITiO膜。其次，將碳酸鈉-石 灰-矽土玻璃基板的溫度設定爲 30(TC，以濺鍍功率 DC400W、導入氣體爲氬氣體100%，氣體壓調整爲7Pa， 形成總膜厚成爲1 200nm的GAZO膜。 使用表面電阻計LORESTAAP (三菱化學（股）製造 ，MCP-T400)，測定了表面電極之片電阻。此外，使用 霧度計（村上色彩技術硏究所製，HR-2 00 )測定霧度率。 成膜隨後之表面電極係片電阻爲9.7Ω/□、全光透過率爲 8 3.4 %、霧度率爲1 4.7 %。 關於氫氣體還原環境中之熱處理係在氫氣體以每分鐘 2L的流量流入，氣氛爐內之壓力保持O.lPa，將形成有表 面電極之透光性玻璃基板之溫度加熱至400°C，進行熱處 理。 結果氫氣氛中之熱處理後，片電阻値成爲6.9Ω/〇、 全光透過率成爲82.8%、霧度率成爲19.1%，改善了片電 阻與霧度率。全光透過率幾乎未變化。 (實施例2 ) -20- 201246277 實施例2係除了將形成有表面電極2之透光性玻璃基 板1之溫度加熱至450 °C，進行熱處理外，與實施例1同 樣製作附表面電極之透明導電基板。 結果成膜隨後之片電阻値爲9.4Ω/□、全光透過率爲 8 3.1%、霧度率爲14.5 %者在氫氣氛中之熱處理後，片電 阻値成爲6.4Ω/□、全光透過率成爲82.4%、霧度率成爲 19.8%，改善了片電阻與霧度率。全光透過率幾乎未變化 (實施例3 ) 實施例3係除了形成有表面電極2之透光性玻璃基板 1的溫度加熱至50(T_C，進行熱處理外，與實施例1同樣 製作附表面電極之透明導電基板》 結果，成膜隨後的片電阻値爲9.9Ω/□、全光透過率 爲84.0%、霧度率爲14.8%者在氫氣氛中之熱處理後，片 電阻値成爲6.2Ω/□、全光透過率成爲83.0%、霧度率成 爲2 1.2%，改善了片電阻與霧度率。全光透過率幾乎未變 化。 (實施例4 ) 實施例4係除了形成有表面電極2之透光性玻璃基板 1的溫度加熱至5 5 0°C，進行熱處理外，與實施例1同樣 製作附表面電極之透明導電基板。 結果成膜隨後的片電阻値爲9.9Ω/□、全光透過率爲 201246277 84.0%、霧度率爲14.5%者在氫氣氛中之熱處理後，片電 阻値成爲5.9Ω/□、全光透過率成爲82.9%、霧度率成爲 21.7%，改善了片電阻與霧度率。全光透過率幾乎未變化 (實施例5〜8 ) 實施例5 ~ 8係對於與實施例1同樣步驟在玻璃基板上 所製作的透明導電膜，將氫氣體以每分鐘2L的流量流入 ，氣氛爐內之壓力保持IPa’且形成有表面電極2之透光 性玻璃基板1的溫度，實施例5係加熱至4 0 0 °C，實施例 6係加熱至4 5 0 °C、實施例7係加熱至5 0 0 °C、實施例8係 加熱至55 0°C，進行熱處理。 實施例5在成膜隨後，片電阻値爲9.7Ω/□、全光透 過率爲82.5%、霧度率爲I4.8%者在氫氣氛中之熱處理後 ，片電阻値成爲6.1 Ω/|□、全光透過率成爲81.6%、霧度 率成爲2 1 . 1 %，改善了片電阻與霧度率。 實施例6在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲83.4%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲5.6 Ω/□、全光透過率成爲82.3%、霧度 率成爲22.5%，改善了片電阻與霧度率。 實施例7在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲S2.9%'霧度率爲8%者在氫氣氛中之熱處理後 ’片電阻値成爲5.4Ω/□、全光透過率成爲81.5%、霧度 率成爲2 3.2 %，改善了片電阻與霧度率。 -22- 201246277 實施例8在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲83.8%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲5.1Ω/□、全光透過率成爲82.4%、霧度 率成爲24.1%，改善了片電阻與霧度率。 (實施例9〜12 ) 對於與實施例1同樣步驟在玻璃基板上所製作的透明 導電膜，使氫氣體以每分鐘2L的流量流入，氣氛爐內之 壓力保持1 〇Pa，且形成有表面電極2之透光性玻璃基板1 的溫度，實施例9係加熱至400°C，實施例1 〇係加熱至 45 0°C、實施例1 1係加熱至500°C、實施例12係加熱至 550°C，進行熱處理。 實施例9在成膜隨後，片電阻値爲9.5 Ω/□、全光透 過率爲82.9%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲5.4Ω/□、全光透過率成爲81.7%、霧度 率成爲2 3 . 3 %，改善了片電阻與霧度率。 實施例10在成膜隨後，片電阻値爲10.0Ω/□、全光 透過率爲82.4%、霧度率爲14.6 %者在氫氣氛中之熱處理 後，片電阻値成爲5.0Ω/□、全光透過率成爲80.8%、霧 度率成爲23.8%，改善了片電阻與霧度率。 實施例11在成膜隨後，片電阻値爲6Ω/□、全光透 過率爲83.3%、霧度率爲14.6 %者在氫氣氛中之熱處理後 ，片電阻値成爲4.8Ω/□、全光透過率成爲81.7%、霧度 率成爲25.0%，改善了片電阻與霧度率。 -23- 201246277 實施例12在成膜隨後，片電阻値爲9.5 Ω/□、全光透 過率爲83.3%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲4.5 Ω/□、全光透過率成爲81·5 %、霧度 率成爲26.2%，改善了片電阻與霧度率。 (實施例1 3〜1 6 ) 實施例13〜16係對於與實施例1同樣步驟在玻璃基板 上所製作的透明導電膜，使氫氣體以每分鐘2L的流量流 入，氣氛爐內之壓力保持l〇〇Pa，且形成有表面電極2之 透光性玻璃基板1的溫度，實施例1 3係加熱至400 °C，實 施例1 4係4 5 0 °C、實施例1 5係加熱至5 0 0 °C '實施例1 6 係加熱至5 5 0 °C，進行熱處理。 實施例13在成膜隨後，片電阻値爲9.8Ω/□、全光透 過率爲83.3%、霧度率爲14.5 %者在氫氣氛中之熱處理後 ，片電阻値成爲4.7Ω/□、全光透過率成爲81.5%、霧度 率成爲24.6%，改善了片電阻與霧度率。 實施例14在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲82.8%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲4.3Ω/□、全光透過率成爲80.8%、霧度 率成爲26.0%，改善了片電阻與霧度率。 實施例15在成膜隨後，片電阻値爲9.8Ω/□、全光透 過率爲83.7%、霧度率爲M.6%者在氫氣氛中之熱處理後 ’片電阻値成爲4.4 Ω/□、全光透過率成爲817 %、霧度 率成爲27.2%，改善了片電阻與霧度率。 -24- 201246277 實施例16在成膜隨後，片電阻値爲9.4 Ω/□、全光透 過率爲83.7%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲4.1Ω/□、全光透過率成爲81.6%、霧度 率成爲29.0%，改善了片電阻與霧度率。 (比較例1~2) 比較例1〜2係對於與實施例1同樣步驟在玻璃基板上 所製作的透明導電膜，使氫氣體以每分鐘2L的流量流入 ，氣氛爐內之壓力保持O.lPa，且形成有表面電極2之透 光性玻璃基板1的溫度，比較例1係加熱至3 50°C、比較 例2係加熱至600 °C，進行熱處理。 比較例1在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲83.9%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲11.7Ω/□、全光透過率成爲84.2%、霧度 率成爲15.4%，片電阻與霧度率未見改善。 比較例2在成膜隨後，片電阻値爲9.3 Ω/□、全光透 過率爲82.7%、霧度率爲14.7%者在氫氣氛中之熱處理後 ’片電阻値成爲5.6Ω/|□、全光透過率成爲57.2%、霧度 率成爲20.6%，雖改善了片電阻與霧度率，但是透過率極 度降低，膜變得非透明。 (比較例3〜4 ) 比較例3〜4係對於與實施例1同樣步驟在玻璃基板上 所製作的透明導電膜，使氫氣體以每分鐘2L的流量流入 -25- 201246277 ’氣氛爐內之壓力保持IPa，且形成有表面電極之透光性 玻璃基板的溫度，比較例3係加熱至3 5 0 °C，比較例4加 熱至600°C，進行熱處理。 比較例3在成膜隨後，片電阻値爲9.7Ω/□、全光透 過率爲83.1%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲10.3Ω/□、全光透過率成爲83.2%、霧度 率成爲15.7%，片電阻與霧度率未見改善。 比較例4在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲83.3%、霧度率爲14.5%者在氫氣氛中之熱處理後 ，片電阻値成爲4.7Ω/□、全光透過率成爲57.0%、霧度 率成爲22.4%，雖改善了片電阻與霧度率，但是透過率極 度降低，膜變得非透明。 (比較例5~6) 比較例5〜6係對於與實施例1同樣步驟在玻璃基板上 所製作的透明導電膜，使氫氣體以每分鐘2L的流量流入 ，氣氛爐內之壓力保持l〇Pa，且形成有表面電極之透光性 玻璃基板的溫度，比較例5係加熱至3 5 0 °C，比較例6係 加熱至600°C進行熱處理。 比較例5在成膜隨後，片電阻値爲9.7Ω/□、全光透 過率爲83.0%、霧度率爲I4.9%者在氫氣氛中之熱處理後 ，片電阻値成爲10.9Ω/□、全光透過率成爲83.2%、霧度 率成爲15.7%，片電阻與霧度率未見改善。 比較例6在成膜隨後’片電阻値爲9.4Ω/□、全光透 -26- 201246277 過率爲82.9%、霧度率爲14_7 %者在氫氣氛中之熱處理後 ’片電阻値成爲4.0 Ω/□、全光透過率成爲56.5%、霧度 率成爲24.8%，雖改善了片電阻與霧度率，但是透過率極 度降低，膜變得非透明。 (比較例7〜8 ) 比較例7~8係對於與實施例1同樣步驟在玻璃基板上 所製作的透明導電膜，使氫氣體以每分鐘2L的流量流入 ，氣氛爐內之壓力保持lOOPa，且形成有表面電極之透光 性玻璃基板的溫度，比較例7係加熱至3 5 0°C，比較例8 係加熱至6 0 0 °C，進行熱處理。 比較例7在成膜隨後，片電阻値爲9.7Ω/□、全光透 過率爲82.6%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲10.6Ω/□、全光透過率成爲82.8%、霧度 率成爲15.8%，片電阻與霧度率未見改善。 比較例8在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲83.0%、霧度率爲14.8%者在氫氣氛中之熱處理後 ，片電阻値成爲3.8Ω/□、全光透過率成爲56.3%、霧度 率成爲27.0%，雖改善了片電阻與霧度率，但是透過率極 度降低，膜變得非透明。 (比較例9~10) 比較例9~ 1 0係對於與實施例1同樣步驟在玻璃基板 上所製作的透明導電膜，使氫氣體以每分鐘2L的流量流 -27- 201246277 入，氣氛爐內之壓力保持O.OlPa，且形成有表面電極之透 光性玻璃基板的溫度，比較例9係加熱至400°C，比較例 1 0係加熱至5 5 0 °C，進行熱處理。 比較例9在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲82.4%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲9.5Ω/□、全光透過率成爲82.3%、霧度 率成爲12.0%，片電阻與霧度率未見改善。 比較例10在成膜隨後，片電阻値爲9· 9Ω/□、全光透 過率爲82.7%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲9.3Ω/□、全光透過率成爲82·2%、霧度 率成爲14.0%，片電阻與霧度率未見改善。 上述實施例1〜1 6及比較例1 ~ 1 0的結果如以下表1所 示。 -28- 201246277[Technical Field] The present invention relates to a method for producing a transparent conductive substrate having a surface electrode formed of a surface electrode film made of a transparent conductive film on a light-transmitting substrate, and a thin film solar cell. Production method. The present application is based on Japanese Patent Application No. 2010-23 51 64, filed on Jan. 20, 2010, the priority of which is incorporated herein by reference. [Prior Art] A thin-film solar cell in which light is incident on a light-transmissive substrate such as a glass substrate, and a transparent conductive glass in which a light-incident side electrode (hereinafter referred to as a "surface electrode") is formed on a light-transmitting substrate is used. Substrate. The surface electrode is formed by laminating a transparent conductive film such as tin oxide, zinc oxide or indium oxide alone or in combination. Further, the thin film solar cell utilizes a polycrystalline germanium, a microcrystalline silicon germanium crystalline germanium film or an amorphous germanium film. The development of this thin film solar cell is vigorously carried out, and the main object is to achieve high cost and high performance by forming a high-quality tantalum film on a low-cost substrate by a low-temperature process. One of the thin film solar cells has a surface electrode formed of a transparent conductive film on a light-transmitting substrate, and a photoelectric conversion semiconductor in which a P-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer are sequentially laminated. Layers, and constructors of back electrodes containing light-reflecting, metallic electrodes are well known. In this thin film solar cell, the photoelectric conversion is mainly generated in the i-type 201246277 semiconductor layer. Therefore, when the i-type semiconductor layer is thin, light in a long-wavelength region having a small light absorption coefficient is not sufficiently absorbed. In other words, the amount of photoelectric conversion is essentially limited by the film thickness of the i-type semiconductor layer. Therefore, in order to more effectively utilize the light incident on the photoelectric conversion semiconductor layer containing the i-type semiconductor layer, the surface electrode on the light incident side has a surface uneven structure, and the light is scattered into the photoelectric conversion semiconductor layer, and further on the back surface. The light reflected by the electrodes is scrambled. In the thin film solar cell, generally, the surface electrode on the light incident side is a method of forming a fluorine-doped tin oxide film by thermal decomposition of a material gas according to a thermal CVD method on a glass substrate (for example, refer to the patent document) 1) Forming a surface relief structure. However, the tin oxide film having a surface uneven structure has a high cost due to the necessity of a high temperature process of 500 ° C or higher. Further, since the specific resistance of the film is high, when the film thickness is increased, the transmittance is lowered and the photoelectric conversion efficiency is lowered. Therefore, it is proposed to form an aluminum-doped zinc oxide (AZO) film or a gallium-doped zinc oxide by sputtering on a bottom electrode composed of a tin oxide film or a tin-doped indium oxide (ITO) film. (GZO) film A method of forming a surface electrode having a surface uneven structure by etching an oxide film which is easily etched (for example, see Patent Document 2). Further, on the underlying electrode composed of a titanium-doped indium oxide (ITiO) film having excellent light transmittance in the near-infrared region, arcing or fine particles are less likely to occur at the time of film formation by sputtering. A zinc oxide (GAZO) film doped with aluminum and gallium is a method of etching a zinc oxide film-shaped 201246277 into a surface electrode having a surface uneven structure as in the technique of Patent Document 2 (see, for example, Patent Document 3). However, in the method of forming the surface uneven structure by etching, sharp protrusions are likely to be generated on the uneven film, and it is difficult to obtain a good photoelectric conversion semiconductor layer. The photoelectric conversion efficiency cannot be improved. Further, when the cleaning after etching is insufficient, the semiconductor layer is liable to cause defects, and in order to prevent this defect, a cleaning step of re-removal is required, and mass production is lacking. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2002-34232 [Problem to be Solved by the Invention] The present invention proposes a method for producing a transparent conductive substrate with a surface electrode having high photoelectric conversion efficiency and a method for producing a thin film solar cell, in view of the above-mentioned problems of the prior art. [Means for Solving the Problem] As a result of careful examination by the inventors of the present invention, it was found that a concave-convex film composed of a zinc oxide-based crystalline transparent conductive film formed by a sputtering method on a light-transmitting glass substrate was introduced into hydrogen. In the reducing atmosphere of the gas, heat treatment is performed to increase the conductivity of the transparent conductive film and also increase the haze ratio (scattering transmittance/total light transmittance) of the 201246277 index of the light-off effect. In other words, the method for producing a transparent conductive substrate with a surface electrode according to the present invention is formed on a light-transmissive substrate by a sputtering method to form a zinc oxide-based crystalline transparent conductive film having a concave-convex structure formed thereon. The transparent conductive substrate with the surface electrode attached to the surface electrode is heat-treated at 400 to 550 ° C in a hydrogen gas atmosphere of 0.1 to 100 Pa. Further, a method for producing a thin film solar cell according to the present invention is a method for producing a thin film solar cell in which a surface electrode, a photoelectric conversion semiconductor layer, and a back electrode are sequentially formed on a light-transmitting substrate, and is characterized in that light transmittance is obtained. a transparent conductive substrate having a surface electrode having a surface electrode of a zinc oxide-based crystalline transparent conductive film having a concave-convex structure formed thereon by sputtering, in a hydrogen gas atmosphere of 0.1 to 1 〇〇pa The heat treatment was carried out at 400 to 5 50 °C. [Effect of the Invention] According to the present invention, a zinc oxide-based crystalline transparent conductive film having a concave-convex structure formed on its surface is formed on a light-transmitting substrate, and then 400 to 5 5 in a hydrogen gas atmosphere of 0.1 to 100 Pa A higher haze ratio can be achieved by applying heat treatment at 0 °C. As a result, a surface electrode having a higher light-off effect can be provided, and a thin film solar cell having higher photoelectric conversion efficiency can be obtained. [Embodiment of the Invention] Hereinafter, embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail with reference to the drawings. -8 - 201246277 1. Thin film solar cell 1 -1 · Transparent conductive substrate with surface electrode 1-2. Photoelectric conversion semiconductor layer 1 - 3. Back electrode 2. Method for manufacturing thin film solar cell 2- 1 · Surface electrode Transparent conductive substrate 2-2. Photoelectric conversion semiconductor layer 2-3. Back surface electrode 3. Embodiment <1. Thin film solar cell> Fig. 1 is a cross-sectional view showing a configuration example of the thin film solar cell of the embodiment. The thin film solar cell 10 has a structure in which the surface electrode 2' photoelectric conversion semiconductor layer 3 and the back surface electrode 4 are sequentially laminated on the translucent glass substrate 1. The light to be photoelectrically converted is incident on the side of the light-transmitting glass substrate 1 as indicated by an arrow with respect to the thin film solar cell. <1-1. Transparent Conductive Substrate with Surface Electrode> The transparent conductive substrate (transparent conductive uneven film) with a surface electrode of the present embodiment is formed on the translucent glass substrate 1 to form the surface electrode 2. The transparent conductive substrate of the surface electrode has, for example, a transparent conductive substrate 11a with a surface electrode as shown in Fig. 2A or a transparent conductive substrate 1 1b with a surface electrode shown in Fig. 2B. The transparent conductive substrate 1 1 a with the surface electrode is formed on the transparent glass substrate 1 by a sputtering method to form a transparent conductive film of indium oxide system-9 - 201246277 as the underlying film 21 and a surface as the uneven film 22 A laminated film of a sequential lamination of a zinc oxide-based crystalline transparent conductive film having a concavo-convex structure. The transparent conductive substrate lib of the surface electrode is formed on the light-transmitting glass substrate 1 by the sputtering method to form the uneven film 22 as the surface electrode 2. Hereinafter, the transparent conductive substrate 1 1 a with the surface electrode and the transparent conductive substrate 1 1 b with the surface electrode are collectively referred to as "the transparent conductive substrate 1 1 with the surface electrode". (Translucent Glass Substrate) The translucent glass substrate 1 preferably has a spectrum in which sunlight is transmitted, and has a high transmittance in a wavelength range of 305 to 1 00 nm. Moreover, it is preferable to use electrical, chemical, and physical stability in consideration of the use in an outdoor environment. The light-transmitting glass substrate 1 is made of, for example, sodium carbonate-lime-silicate glass, borate glass, low alkali-containing glass, quartz glass, and various other glasses. The translucent glass substrate 1 is a surface electrode composed of a transparent conductive film that prevents ions from diffusing from the glass to the upper surface of the glass, and is intended to minimize the electrical characteristics of the film due to the type or surface state of the glass substrate. An alkaline barrier film such as a ruthenium oxide film is applied to the glass substrate. (Surface Electrode) The surface electrode 2 has a surface electrode having a surface uneven structure 2a as shown in Fig. 1 . Similarly to the translucent glass substrate 1, the surface electrode 2 preferably has a high transmittance of 80% or more for light having a wavelength of from 3 50 to 1 200 nm. Further, the surface electrode 2 is preferably 10 Ω/□ or less in resistance of the sheet -10-201246277 after heat treatment in a hydrogen atmosphere to be described later, and the haze ratio of the film is preferably 15% or more, more preferably 20%. %the above. The surface electrode 2, for example, as shown in Fig. 2B, can be composed of a single body of the uneven film 2 2 . Further, as shown in Fig. 2A, the surface electrode 2 may be composed of a laminate in which the underlayer film 21 and the uneven film 22 are laminated in this order. As shown in FIG. 2A, the surface electrode 2 is disposed between the light-transmitting glass substrate 1 and the uneven film 22, as shown in FIG. 2A, and the surface electrode 2 can be formed of a single film of the uneven film 22, The thickness of the uneven film 22 can be made thinner, and as a result, the thickness of the entire surface electrode 2 can be made thin, which is advantageous for light transmittance. Further, the underlayer film 21 is an indium oxide-based transparent conductive film as described in detail later, and has a volume resistivity smaller than that of the oxidized transparent conductive film. As a result, the thickness of the entire surface electrode 2 can be made thinner at the same specific resistance. The degree of unevenness of the surface uneven structure 2a is a haze ratio indicating an index of surface unevenness, preferably 20% or more, and the arithmetic mean roughness (Ra) is preferably 4 〇 to 12 nm. According to the surface electrode 2 having the surface unevenness structure 2a having such a haze ratio and an arithmetic mean roughness (Ra), the light-off effect is increased, and the photoelectric conversion efficiency of the thin film solar cell 10 can be improved. (Under Film) The underlayer film 21 is doped with an indium oxide-based amorphous transparent conductive film of at least one selected from the group consisting of Ti, Sn, and Ga. In the present specification, amorphous means that the diffraction peak intensity of the X-ray analysis is 20% or less of the diffraction peak intensity of the crystalline material. As such an indium oxide-based amorphous transparent conductive film, for example, an indium oxide (ITiO) film doped with titanium can be used. The light of the near-infrared region of the ITiO film is high -11 - 201246277. The amorphous film is easily formed, and the growth of the zinc oxide-based crystal formed thereon can be promoted. In the ITiO film, the amount of Ti doped is preferably 〇 5 to 2.0% by mass. Further, as the indium oxide-based amorphous transparent conductive film, an indium oxide (1 00) film doped with Sn or Ga may be used. The 1 00 film can also easily form an amorphous film. Further, the growth of the zinc oxide-based crystal formed thereon can be promoted. In the ITGO film, the amount of doping Sn and Ga is preferably 3.0 to 15 mass. /〇. As the indium oxide-based amorphous transparent conductive film, an indium oxide (ITiTO) film doped with T i or Sn can also be used. The ITiTO film can further promote the growth of zinc oxide crystals compared to the ITiO film. In the ITiTO film, the amount of Ti and Sn doped is preferably 0.01 to 2.0% by mass. The thickness of the underlayer film 21 is preferably from 1 Å to 500 nm, more preferably from 200 to 400 nm. When the film thickness is less than 100 nm, the effect of increasing the haze rate by the underlying film 21 is remarkably small, and when it exceeds 500 nm, the transmittance is decreased to cancel the light-off effect of increasing the haze ratio. (Concave-convex film) The uneven film 22 is doped with a zinc oxide-based crystalline transparent conductive film selected from at least one of A, Ga, B, In, F, Si, Ge, Ti, Zr, and Hf. Such a zinc oxide-based crystalline transparent conductive film includes, for example, a zinc oxide (GAZO) film doped with A1 and Ga, a zinc oxide (AZO) film doped with A1, and zinc oxide doped with Ga (GZO). )membrane. Among these zinc oxide films, it is more preferable that the GAZO film is less likely to cause arcing when formed by a job plating method. The amount of doping A 丨 and Ga in the GAZO film is -12-201246277, preferably 〇1~〇.5 mass%. Further, the amount of doping Ga in the GZO film is preferably 0.2 to 6 · 0% by mass. The film thickness of the uneven film 22 is preferably from 300 to 2,000 nm', more preferably from 400 to 1,600 nm. When the film thickness is less than 300 nm, the "concavities and convexities do not become large", and the haze ratio of the film may be less than 10%. Further, when the film thickness exceeds 2,000 nm, the transmittance is remarkably lowered. <1-2. Photoelectric conversion semiconductor layer> The photoelectric conversion semiconductor layer 3 is formed by sequentially laminating a P-type semiconductor layer 31, an i-type semiconductor layer 32, and an n-type semiconductor layer 33 on the surface electrode 2. The p-type semiconductor layer 31 and the n-type semiconductor layer 33 may be reversed in order, and generally, the solar cell is provided with a Ρ-type semiconductor layer on the incident side of light. The p-type semiconductor layer 31 is made of, for example, a thin film doped with microcrystalline germanium as an impurity atom bismuth (boron). Further, instead of the microcrystalline germanium, a material such as polycrystalline germanium, amorphous germanium, germanium carbide, germanium (SiGe) or the like can be used. Further, the impurity atoms are not limited to boron, and aluminum or the like may also be used. The i-type semiconductor layer 32 is composed of, for example, a film of undoped microcrystalline germanium. Further, instead of the microcrystalline germanium, a material such as polycrystalline germanium, amorphous germanium, tantalum carbide, or germanium (SiGe) may be used. Further, a weak P-type semiconductor material containing a small amount of impurities or a weak n-type semiconductor or a bismuth-based thin film material having a photoelectric conversion function can be used. The n-type semiconductor layer 33 is made of, for example, an n-type microcrystalline germanium doped with an impurity atom ρ (phosphorus). Further, instead of the microcrystalline germanium, polycrystalline germanium, amorphous germanium, tantalum carbide, niobium (Si (Je ) or the like may be used. Further, 201246277 impurity atoms are not limited to phosphorus (p), and N (nitrogen) may be used. . <1-3. Back surface electrode> The back surface electrode 4 is formed by sequentially forming a transparent conductive oxide film 41 and a light-reflective metal electrode 42 on the n-type semiconductor layer 33. The transparent conductive oxide film 41 is not necessary. However, by improving the adhesion between the n-type semiconductor layer 33 and the light-reflective metal electrode 42, the reflection efficiency of the light-reflective metal electrode 42 is improved, and the n-type semiconductor layer 33 is protected. A function that is affected by chemical changes. The transparent conductive oxide film 41 is formed of at least one selected from the group consisting of a zinc oxide film, an indium oxide film, and a tin oxide film. In particular, at least one type of aluminum (Α1) or gallium (Ga) is doped in the zinc oxide film, and at least one of Sn, Ti, W, Ce, Ga, and Mo is doped in the indium oxide film to improve conductivity. Preferably. Further, the specific resistance of the transparent conductive oxide film 41 adjacent to the n-type semiconductor layer 33 is preferably 1.5×10·3 Ω cm or less. <2. Method for Producing Thin Film Solar Cell> Next, a method of manufacturing the thin film solar cell 10 of the present embodiment will be described. As shown in FIG. 1, the thin film solar cell 1 has a surface electrode 2, a photoelectric conversion semiconductor layer 3, and a back surface electrode 4 sequentially formed on the translucent glass substrate 1. First, a method of manufacturing the transparent conductive substrate 1 1 constituting the surface electrode of the thin film solar cell will be described. <2-1. Transparent Conductive Substrate with Surface Electrode> • 14-201246277 The transparent conductive substrate 11a with a surface electrode as shown in Fig. 2(A) first maintains the temperature of the translucent glass substrate 1 at 2. In the range of 0 to 70 ° C, the underlying film 21 made of an indium oxide-based amorphous transparent conductive film is formed by a sputtering method using, for example, a mixed gas of argon and oxygen. When the temperature of the translucent glass substrate 1 is lower than 20 ° C, an indium oxide-based amorphous transparent conductive film can be obtained. However, in the sputtering apparatus, a mechanism for cooling the translucent glass substrate is required, and the cost is increased. It is not good. Further, when the temperature of the light-transmitting glass substrate 1 exceeds 7 ° C, it is difficult to obtain an indium oxide-based amorphous transparent conductive film. The uneven film 22 in the transparent conductive substrate 11a with the surface electrode is placed in an atmosphere of an inert gas such as argon, and is deposited on the underlayer film 21 by sputtering under a high gas pressure environment in which the gas pressure of IPa or higher is adjusted. The gas pressure at the time of forming the uneven film 22 is preferably 1 to i 〇 Pa. When the gas pressure is higher than 10 Pa, the haze ratio increases and the film formation rate extremely decreases. When the gas pressure is lower than IPa, the surface of the film is less likely to have irregularities, and the haze ratio is extremely lowered. The substrate temperature at which the uneven film 22 is sputtered is 300 ° C or higher, preferably 300 - 55 0 ° C. When the upper limit of the substrate temperature is less than or equal to the softening point of the light-transmitting glass substrate 1, the maximum temperature is 800 °C. In the case of a translucent glass substrate for a solar cell, the softening point is usually 600 to 650 ° C. When the temperature exceeds 550 ° C, the softening point is approached. Therefore, the strength of the substrate is lowered, and the yield is lowered. . The transparent conductive substrate 1 1 b with the surface electrode shown in FIG. 2B is formed as a surface electrode 2 on the optical glass substrate 1 through the sputtering method in the same manner as the transparent conductive substrate 11a having the surface electrode. The uneven film 22. Next, the obtained transparent electrode substrate 1 1 with a surface electrode was subjected to heat treatment at 400 to 550 ° C in a hydrogen gas atmosphere of 0.1 to 100 Pa. Specifically, it is preferable to apply heat treatment to the transparent conductive substrate 11 with a surface electrode in the following order. Thus, in the reducing atmosphere into which the hydrogen gas is introduced, by the heat treatment, the unstable oxygen bond in the zinc oxide finish is removed to form a carrier, and the conductivity of the transparent conductive film constituting the surface electrode 2 is increased, thereby realizing High haze rate. First, in an atmosphere furnace in which the transparent conductive substrate 11 with a surface electrode is accommodated, it is replaced with an inert gas such as argon gas, and a vacuum of less than 0.1 Pa is formed in the atmosphere furnace by a vacuum pump. Next, the hydrogen gas is introduced into the atmosphere furnace, and the opening and closing of the valve between the atmosphere furnace and the vacuum pump is adjusted, and the pressure in the atmosphere furnace is maintained at ~10 Pa, and a hydrogen gas atmosphere of 0.1 to 100 Pa is obtained, and the temperature is heated to 400. Heat treatment at ~5 50 °C. When the gas pressure in the furnace exceeds 1 〇〇Pa, when the amount of hydrogen introduced is large, the concentration of hydrogen in the atmosphere furnace rises, which is not preferable. Further, when the gas pressure is less than 0.1 Pa, the reduction effect is weakened, the time required for reduction is remarkably increased, the productivity is deteriorated, and it is not practical, so it is not preferable. When the heating temperature of the heat treatment is lower than 400 ° C, there is almost no reduction effect in the hydrogen gas atmosphere, and when the sheet resistance exceeds 8 Ω / □, the effect of increasing the haze ratio of the film cannot be obtained, which is not preferable. . Further, when the heating temperature exceeds 550 ° C, the film loses transparency due to excessive reduction, and the transmittance (all-light transmittance) of light at a wavelength of 3 50 to 1 200 nm is less than 80%, which is not preferable. In the method of manufacturing a transparent conductive substrate with a surface electrode according to the present embodiment, the uneven film 22 or the underlying film 21 and the uneven film 22 are formed on the transparent glass substrate 1, and then 0.1 to 10 OP In a hydrogen gas atmosphere of a, heat treatment is carried out at 400 to 5 50 °C. Thereby, a higher haze ratio can be achieved, and as a result, the surface electrode 2 having a higher light-off effect can be provided. Fig. 3 is a graph showing the relationship between the haze ratio before and after the heat treatment of hydrogen gas introduction. Specifically, Fig. 3 is a graph showing the results of the heat treatment effect of the transparent conductive substrate 11a with the surface electrode shown in Fig. 2A, which is different in initial haze ,, at a hydrogen gas pressure of 0.1 Pa and a heat treatment temperature of 45 °C. The transparent conductive substrate 11a with the surface electrode is laminated in this order according to the GAZO film as the uneven film 22, the ITiTO film as the underlayer film 21, and the light-transmitting glass substrate 1. The horizontal axis of the graph indicates the haze ratio before the heat treatment of the transparent conductive substrate 11 with the surface electrode, and the vertical axis of the graph indicates the haze ratio after the heat treatment of the transparent conductive substrate 11 with the surface electrode. The dotted line of the graph of Fig. 3 is a reference line indicating the improvement ratio of the haze ratio before and after the thermal consideration. When there is no heat treatment effect, there is a measurement point on this dotted line. According to the results shown in FIG. 3, it is understood that the heat treatment of the transparent conductive substrate 11 with the surface electrode has an effect of increasing the haze ratio, but before the heat treatment (initial), for the haze-free transparent conductive substrate 11 with the surface electrode, There is no effect of increasing the haze rate. The transparent conductive substrate 11a with the surface electrode described above was used, and had a hydrogen gas pressure of 0.1 Pa and a heat treatment temperature of 45 °C. When the heat treatment is performed, it is preferred to use a transparent conductive substrate with a surface electrode having a haze ratio of 12% or more. Thereby, the haze ratio -17 - 201246277 of the transparent conductive substrate 1 1 with the surface electrode after heat treatment can be made 1 or more. <2-2. Photoelectric conversion semiconductor layer> Next, the photoelectric conversion semiconductor layer 3 is formed on the surface electrode 2 of the transparent conductive substrate 11 with a surface electrode using, for example, a plasma CVD (Chemical VaPr Deposition) method. This plasma CVD method can also be carried out by a conventional conventional parallel plate type RF plasma CVD' or by a plasma CVD method using a high frequency power source from an RF band of 150 MHz or less to a VHF band. The photoelectric conversion semiconductor layer 3 is formed by sequentially laminating the p-type semiconductor layer 31, the i-type semiconductor layer 32, and the n-type semiconductor layer 33. Further, if necessary, each semiconductor layer may be irradiated with pulsed laser light (laser annealing) to control the crystallization fraction or the carrier concentration. <2-3. Back surface electrode> Next, the back surface electrode 4 is formed on the photoelectric conversion semiconductor layer 3. The back surface electrode 4 is formed by laminating the sequentially-order transparent conductive oxide film 41 and the light-reflective metal electrode 42 in this order. The transparent conductive oxide film 41 is formed by a method such as vacuum deposition or sputtering, and is preferably formed of a metal oxide such as ΖηΟ 'ΙΤΟ. The light-reflective metal electrode 42 is formed by a method such as vacuum deposition 'sputtering, and is preferably one selected from the group consisting of eight §, eight \1, 八1, (11: 1 and 1), or the like. The alloy formed by the alloy is preferably -18-201246277 by vacuum evaporation at a temperature of 200 to 300%, more preferably 200 to 300 ° C. As described above, the present embodiment The manufacturing method of the thin film solar cell 10 is performed on the translucent glass substrate 1, and the uneven film 22 or the underlying film 21 and the uneven film 22 are formed as the surface electrode 2, and then in a hydrogen gas atmosphere of 0.1 to 1 〇〇Pa. The heat treatment is applied at 400 to 550 Torr to produce a transparent conductive substrate 1 1 having a surface electrode. Thereby, the surface electrode 2 composed of good irregularities can be formed without using an etching method, and a higher haze ratio can be achieved. The surface electrode 2 having a higher light-off effect is provided, and a thin film solar cell having a higher photoelectric conversion efficiency can be obtained. [Embodiment] [Embodiment] Hereinafter, the present invention will be described using an embodiment, and the present invention is not limited to the embodiments. (Example 1) manufactured by A surface electrode formed by laminating an underlayer film made of an indium oxide-based transparent conductive film and a textured film made of a zinc oxide-based crystalline transparent conductive film as shown in FIG. 2A First, the translucent glass substrate 1 uses a sodium carbonate-lime-alumina glass substrate on which the underlayer film 21 and the uneven film 22 are sequentially formed as the surface electrode 2. The underlayer film 21 is made of indium oxide. ITiTO film doped with titanium oxide 1% by mass, tin oxide bismuth, 〇1% by mass, and the uneven film 22 is made of -19 - 201246277 zinc oxide doped with gallium oxide 0 · 58 % by mass, alumina 〇. 3 2% by mass of GAZO film. 'The film formation system uses DC magnetron sputtering. The target system used is φ 6吋, and the distance between the substrate and the target is 60 mm. The temperature of the sodium carbonate-lime-alumina glass substrate is used. The ratio was set to 25. (:: The introduction gas was a mixture of argon and oxygen (argon: oxygen = 99:1), and an ITiO film having a film thickness of 200 nm was formed by sputtering. Next, sodium carbonate-lime-alumina was used. The temperature of the glass substrate is set to 30 (TC, with a sputtering power of DC400W, The inlet gas was 100% argon gas, and the gas pressure was adjusted to 7 Pa to form a GAZO film having a total film thickness of 1 200 nm. The sheet resistance of the surface electrode was measured using a surface resistance meter LORESTAAP (manufactured by Mitsubishi Chemical Corporation, MCP-T400). In addition, the haze ratio was measured using a haze meter (manufactured by Murakami Color Technology Co., Ltd., HR-2 00). The surface electrode film resistance after film formation was 9.7 Ω / □, and the total light transmittance was 8 3.4 %. The haze ratio is 14.7%. The heat treatment in the hydrogen gas reduction environment is such that the hydrogen gas flows in at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace is maintained at 0.1 Pa, and the light-transmitting glass substrate having the surface electrode is formed. The temperature was heated to 400 ° C and heat treatment was performed. As a result, after the heat treatment in the hydrogen atmosphere, the sheet resistance 値 became 6.9 Ω / 〇, the total light transmittance was 82.8%, and the haze ratio was 19.1%, which improved the sheet resistance and the haze ratio. The total light transmittance is almost unchanged. (Example 2) -20-201246277 In Example 2, the surface electrode was made transparent in the same manner as in Example 1 except that the temperature of the light-transmitting glass substrate 1 on which the surface electrode 2 was formed was heated to 450 °C. Conductive substrate. As a result, the film resistance 値 was 9.4 Ω/□, the total light transmittance was 8 3.1%, and the haze ratio was 14.5%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 6.4 Ω/□, and all light was transmitted. The rate was 82.4%, and the haze ratio was 19.8%, which improved the sheet resistance and haze ratio. The total light transmittance was hardly changed (Example 3) Example 3 was prepared in the same manner as in Example 1 except that the temperature of the light-transmitting glass substrate 1 on which the surface electrode 2 was formed was heated to 50 (T_C, heat treatment was performed). As a result of the transparent conductive substrate, the sheet resistance 値 was 9.9 Ω/□, the total light transmittance was 84.0%, and the haze ratio was 14.8%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 6.2 Ω/ □, the total light transmittance was 83.0%, and the haze ratio was 2 1.2%, and the sheet resistance and the haze ratio were improved. The total light transmittance was hardly changed. (Example 4) Example 4 was except that the surface electrode 2 was formed. A transparent conductive substrate with a surface electrode was produced in the same manner as in Example 1 except that the temperature of the light-transmissive glass substrate 1 was heated to 550 ° C and heat treatment was performed. The film resistance 随后 after the film formation was 9.9 Ω / □, When the light transmittance was 201246277 84.0% and the haze ratio was 14.5%, the sheet resistance 値 was 5.9 Ω/□, the total light transmittance was 82.9%, and the haze ratio was 21.7%. Resistance and haze rate. The total light transmittance is almost unchanged (implementation Examples 5 to 8) Examples 5 to 8 The transparent conductive film produced on the glass substrate in the same manner as in Example 1 was flowed with hydrogen gas at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was kept IPa' and formed. The temperature of the translucent glass substrate 1 having the surface electrode 2 was heated to 400 ° C in Example 5, heated to 4500 ° C in Example 6, and heated to 500 ° C in Example 7. Example 8 was heat-treated to 55 ° C and heat-treated. Example 5, after film formation, sheet resistance 値 was 9.7 Ω / □, total light transmittance was 82.5%, and haze ratio was 14.8%. After the heat treatment in the atmosphere, the sheet resistance 値 became 6.1 Ω/|□, the total light transmittance was 81.6%, and the haze ratio was 21.1%, which improved the sheet resistance and the haze ratio. Example 6 was followed by film formation. The sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 83.4%, and the haze ratio was 14.9%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.6 Ω/□, and the total light transmittance was 82.3%. The haze ratio was 22.5%, and the sheet resistance and haze ratio were improved. Example 7 After film formation, the sheet resistance 値 was 9.9 Ω/□, and the total light transmittance was S2.9%'. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.4 Ω/□, the total light transmittance was 81.5%, and the haze ratio was 23.2%, which improved sheet resistance and haze ratio. - 201246277 After the film formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 83.8%, and the haze ratio was 14.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.1 Ω/□. The total light transmittance was 82.4%, and the haze ratio was 24.1%, which improved sheet resistance and haze ratio. (Examples 9 to 12) The transparent conductive film produced on the glass substrate in the same manner as in Example 1 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 1 〇Pa, and a surface was formed. The temperature of the translucent glass substrate 1 of the electrode 2 was heated to 400 ° C in Example 9, the heating in Example 1 was 45 ° C, the heating in Example 1 was heated to 500 ° C, and the heating in Example 12 was carried out. The heat treatment was carried out at 550 °C. In Example 9, after the film formation, the sheet resistance 値 was 9.5 Ω/□, the total light transmittance was 82.9%, and the haze ratio was 14.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.4 Ω/□, The light transmittance was 81.7%, and the haze ratio was 23.3%, which improved the sheet resistance and the haze ratio. In Example 10, after sheet formation, the sheet resistance 値 was 10.0 Ω/□, the total light transmittance was 82.4%, and the haze ratio was 14.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.0 Ω/□, The light transmittance was 80.8%, and the haze ratio was 23.8%, which improved sheet resistance and haze ratio. In Example 11, after the film formation, the sheet resistance 値 was 6 Ω/□, the total light transmittance was 83.3%, and the haze ratio was 14.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.8 Ω/□, and the total light was obtained. The transmittance was 81.7%, and the haze ratio was 25.0%, which improved the sheet resistance and the haze ratio. -23- 201246277 In Example 12, after film formation, the sheet resistance 値 was 9.5 Ω/□, the total light transmittance was 83.3%, and the haze ratio was 14.6%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.5 Ω. /□, the total light transmittance is 81.5%, and the haze ratio is 26.2%, which improves the sheet resistance and the haze ratio. (Examples 1 to 3 6) Examples 13 to 16 are transparent conductive films produced on a glass substrate in the same manner as in Example 1, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained. l〇〇Pa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed, Example 1 3 was heated to 400 ° C, Example 14 was 4500 ° C, and Example 15 was heated to 5 0 0 ° C 'Example 1 6 Heated to 550 ° C and heat-treated. In Example 13, after the film formation, the sheet resistance 値 was 9.8 Ω/□, the total light transmittance was 83.3%, and the haze ratio was 14.5%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.7 Ω/□, The light transmittance was 81.5%, and the haze ratio was 24.6%, which improved the sheet resistance and the haze ratio. In Example 14, after the film formation, the sheet resistance 値 was 9.9 Ω/□, the total light transmittance was 82.8%, and the haze ratio was 14.7%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.3 Ω/□, The light transmittance was 80.8%, and the haze ratio was 26.0%, which improved the sheet resistance and the haze ratio. In Example 15, after the film formation, the sheet resistance 値 was 9.8 Ω/□, the total light transmittance was 83.7%, and the haze ratio was M.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.4 Ω/□. The total light transmittance is 81.7% and the haze ratio is 27.2%, which improves the sheet resistance and haze ratio. -24- 201246277 In Example 16, after film formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 83.7%, and the haze ratio was 14.9%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.1 Ω. /□, the total light transmittance was 81.6%, and the haze ratio was 29.0%, which improved the sheet resistance and the haze ratio. (Comparative Examples 1 and 2) In Comparative Examples 1 to 2, the transparent conductive film produced on the glass substrate in the same manner as in Example 1 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at O. lPa and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed, Comparative Example 1 was heated to 3 50 ° C, and Comparative Example 2 was heated to 600 ° C, and heat treatment was performed. In Comparative Example 1, after sheet formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 83.9%, and the haze ratio was 14.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 11.7 Ω/□, The light transmittance was 84.2%, the haze ratio was 15.4%, and sheet resistance and haze ratio were not improved. In Comparative Example 2, after the film formation, the sheet resistance 値 was 9.3 Ω/□, the total light transmittance was 82.7%, and the haze ratio was 14.7%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.6 Ω/|□, The total light transmittance was 57.2%, and the haze ratio was 20.6%. Although the sheet resistance and the haze ratio were improved, the transmittance was extremely lowered, and the film became opaque. (Comparative Examples 3 to 4) Comparative Examples 3 to 4 are the transparent conductive films produced on the glass substrate in the same manner as in Example 1, and the hydrogen gas was flowed into the atmosphere of -25-201246277 in a flow rate of 2 L per minute. The pressure was maintained at IPa, and the temperature of the light-transmitting glass substrate having the surface electrode was formed. In Comparative Example 3, it was heated to 350 ° C, and Comparative Example 4 was heated to 600 ° C, and heat treatment was performed. In Comparative Example 3, after the film formation, the sheet resistance 値 was 9.7 Ω/□, the total light transmittance was 83.1%, and the haze ratio was 14.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 10.3 Ω / □, The light transmittance was 83.2%, the haze ratio was 15.7%, and sheet resistance and haze ratio were not improved. In Comparative Example 4, after the film formation, the sheet resistance 値 was 9.9 Ω/□, the total light transmittance was 83.3%, and the haze ratio was 14.5%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.7 Ω/□, The light transmittance was 57.0%, and the haze ratio was 22.4%. Although the sheet resistance and the haze ratio were improved, the transmittance was extremely lowered, and the film became opaque. (Comparative Examples 5 to 6) In Comparative Examples 5 to 6, the transparent conductive film produced on the glass substrate in the same manner as in Example 1 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 10 Torr. Pa, and the temperature of the translucent glass substrate on which the surface electrode was formed, Comparative Example 5 was heated to 350 ° C, and Comparative Example 6 was heated to 600 ° C for heat treatment. In Comparative Example 5, after the film formation, the sheet resistance 値 was 9.7 Ω/□, the total light transmittance was 83.0%, and the haze ratio was I4.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 10.9 Ω/□. The total light transmittance was 83.2%, the haze ratio was 15.7%, and the sheet resistance and the haze ratio were not improved. In Comparative Example 6, after the film formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance -26-201246277 was 82.9%, and the haze ratio was 14-7%. After the heat treatment in a hydrogen atmosphere, the sheet resistance became 4.0. Ω/□, the total light transmittance was 56.5%, and the haze ratio was 24.8%. Although the sheet resistance and the haze ratio were improved, the transmittance was extremely lowered, and the film became opaque. (Comparative Examples 7 to 8) In Comparative Examples 7 to 8, the transparent conductive film produced on the glass substrate in the same manner as in Example 1 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 100 Pa. Further, in Comparative Example 7, the temperature of the translucent glass substrate on which the surface electrode was formed was heated to 350 ° C, and Comparative Example 8 was heated to 600 ° C to carry out heat treatment. In Comparative Example 7, after the film formation, the sheet resistance 値 was 9.7 Ω/□, the total light transmittance was 82.6%, and the haze ratio was 14.7%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 10.6 Ω/□, The light transmittance was 82.8%, the haze ratio was 15.8%, and the sheet resistance and the haze ratio were not improved. In Comparative Example 8, after the film formation, the sheet resistance 値 was 9.6 Ω/□, the total light transmittance was 83.0%, and the haze ratio was 14.8%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 3.8 Ω/□, The light transmittance was 56.3%, and the haze ratio was 27.0%. Although the sheet resistance and the haze ratio were improved, the transmittance was extremely lowered, and the film became opaque. (Comparative Examples 9 to 10) Comparative Examples 9 to 10 are the transparent conductive films produced on the glass substrate in the same manner as in the first embodiment, and hydrogen gas is introduced at a flow rate of 2 L per minute to -27-201246277. The pressure inside was maintained at O.OlPa, and the temperature of the light-transmitting glass substrate having the surface electrode was formed. In Comparative Example 9, the temperature was heated to 400 ° C, and the comparative example 10 was heated to 550 ° C to carry out heat treatment. In Comparative Example 9, after the film formation, the sheet resistance 値 was 9.9 Ω/□, the total light transmittance was 82.4%, and the haze ratio was 14.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 9.5 Ω/□, The light transmittance was 82.3%, the haze ratio was 12.0%, and the sheet resistance and the haze ratio were not improved. In Comparative Example 10, after the film formation, the sheet resistance 9 was 9·9 Ω/□, the total light transmittance was 82.7%, and the haze ratio was 14.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 9.3 Ω/□. The total light transmittance was 82.2%, the haze ratio was 14.0%, and the sheet resistance and the haze ratio were not improved. The results of the above Examples 1 to 16 and Comparative Examples 1 to 10 are shown in Table 1 below. -28- 201246277

膜構成 膜 厚 (nm) 成膜後 氣 氣 體 壓 (Pa) 熱 處 理 溫 度 (°C) 熱處理後 熱處理後之改善比 表 面 電 阻 (Ω/D) 全 光 透 過 率 (*) 霧 度 (%) 表 面 電 阻 (0/□) 全 光 透 過 率 (») 霧 度 (X) 表 面 電 阻 前/後 全 光 透 過 率 wm 霧 度 後湔 實施例1 GAZO/ITITO/Glass 1200 9.7 83.4 14.7 0.1 400 6.9 82.8 19.1 1.40 0.99 1.30 實施例2 GAZO/ITiTO/Glass 1200 9.4 83.1 14.5 0.1 450 6.4 82.4 19.8 1.45 0.99 1.37 實施例3 GAZO/lTiTO/Glass 1200 9.9 84.0 14.8 0.1 500 6.2 83.0 21.2 1.60 0.99 1.43 實施例4 GAZO/ITiTO/Glass 1200 9.9 84.0 14.5 0.1 550 5.9 82.9 21.7 1.66 0.99 1.50 實施例5 GAZO/ITiTO/Glass 1200 9.7 82.5 14.8 1 400 6.1 81.6 2\Λ 1.60 0.99 1.43 實施例6 GAZO/ITiTO/Glass 1200 9.4 83.4 14.9 1 450 5.6 82.3 22.5 1.67 0.99 1.51 實施例7 GAZO/ITiTO/Glass 1200 9.9 82.9 14.8 1 500 5.4 81.5 23.2 1.83 0.98 1.57 實施例8 GAZO/ITiTO/Glass 1200 BA 83.8 14.6 1 550 5.1 82.4 24.1 1.84 0.98 1.64 實施例9 GAZO/ITiTO/Glass 1200 9.5 82.9 14.9 10 400 5.4 81.7 23.3 1.77 0.98 1.56 實施例10 GAZO/ITiTO/Glass 1200 10.0 82.4 14.6 10 450 5.0 30.8 23.8 1.Θ8 0.98 1.64 實施例11 GAZO/ITiTO/Glass 1200 9.6 83.3 14.6 10 500 4.8 81.7 25.0 1.99 0.98 1.72 實施例12 GAZO/ITiTO/Glass 1200 9.5 83.3 14.6 10 550 4.5 81.5 26.2 2.10 0.98 1.79 實施例13 GAZO/ITiTO/Glass 1200 9.8 83.3 14.5 100 400 4.7 81.5 24.6 2.09 0.98 1.69 實施例14 GAZO/ITiTO/Glass 1200 9.δ 82.8 14.7 100 450 4.3 80.8 26.0 2.33 0.98 1.77 實施例15 GAZO/ITiTO/Glass 1200 9.ίί 83.7 14.6 100 500 4.4 81.7 27.2 2.23 0.98 1.86 實施例16 GAZO/ITiTO/Glass 1200 9.4 83.7 14.9 100 650 4.1 81.6 29.0 2.28 0.98 1.94 比較例1 GAZO/ITiTO/Glass 1200 9.4 83.9 14.6 0.1 350 11.7 84.2 15.4 0.80 1.00 1.05 比較例2 GAZO/ITiTO/Glass 1200 9.3 82.7 14.7 0.1 600 5.6 57.2 20.6 1.66 0.69 1.40 比較例3 GAZO/ITiTO/Glass 1200 9.7 83.1 14.9 1 350 10.3 83.2 15.7 0.94 1.00 1.06 比較例4 GAZO/ITiTO/Glass 1200 9.9 83.3 14.5 1 600 4.7 57.0 22.4 2.11 0.68 1.54 比較例5 GAZO/ITiTO/Glass 1200 9.7 83.0 14.9 10 350 10.9 83.2 15.7 0.89 1.00 1.05 比較例6 GAZO/ITiTO/Glass 1200 9.4 82.9 14.7 10 600 4.0 56:5 24.8 2.35 0.68 1.68 比較例7 GAZCmTiTO/Glass 1200 9.7 82.6 14.7 100 350 10.6 82.8 15.8 0.92 1.00 1.07 比較例8 GAZO/ITiTO/Glass 1200 9.6 83.0 14.8 100 600 3.8 56.3 27.0 2.54 0.68 1.83 比較例9 GAZO/ITiTO/Glass 1200 9.9 82.4 14.6 0.01 400 9.5 82.3 12.0 1.04 1.00 0.82 比較例10 GAZO/lTiTO/Glass 1200 9.9 82.7 14.9 0.01 550 9.3 82.2 14.0 1.06 0.99 0.94 (實施例1 7 ) 實施例1 7係形成表面電極2之底層膜21爲使用氧化 銦中摻雜有氧化鈦1質量％的ITiO膜，凹凸膜22爲使用 在氧化鋅中摻雜有氧化鎵〇 . 5 8質量％、氧化鋁0 · 3 2質量％ 的GAZO膜。 碳酸鈉-石灰-矽土玻璃基板之溫度設定爲25°C，導入 氣體使用氬與氧的混合氣體（氬：氧=99 : 1 )，藉由濺鍍 法形成膜厚成爲2 50iim的ITiO膜。其次，碳酸鈉-石灰- -29 - 201246277 矽土玻璃基板之溫度設定爲3 00°C，濺鍍功率DC400W、 導入氣體爲氬氣體100%，氣體壓調整爲7Pa，形成總膜厚 成爲1 250nm的GAZO膜。 對於氫氣體還原環境中的熱處理係使氫氣體以每分鐘 2L的流量流入，氣氛爐內之壓力保持O.lPa，且形成有表 面電極之透光性玻璃基板的溫度加熱至40(TC，進行處理 〇 結果成膜隨後的片電阻値爲9.7Ω/□、全光透過率爲 8 3.9%、霧度率爲14.8%者在氫氣氛中之熱處理後，片電 阻値成爲6.9 Ω/□、全光透過率成爲83.2%、霧度率成爲 1 8.9%，改善了片電阻與霧度率。 (實施例1 8 ) 實施例1 8係對於與實施例1 7同樣步驟在玻璃基板上 所製作的透明導電膜，使氫氣體以每分鐘2L的流量流入 ，氣氛爐內之壓力保持O.lPa，且將形成有表面電極之透 光性玻璃基板的溫度加熱至5 5 0 °C，進行熱處理製作附表 面電極之透明導電基板1 1。 結果成膜隨後的片電阻値爲9.5Ω/□、全光透過率爲 83.4%、霧度率爲14.6 %者在氫氣氛中之熱處理後，片電 阻値成爲6.1Ω/□、全光透過率成爲82.5%、霧度率成爲 20.2%’改善了片電阻與霧度率。全光透過率幾乎未變化 -30- 201246277 (實施例19〜2 Ο ) 實施例1 9〜2 0係對於與實施例1 7同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持IPa，且將形成有表面電極之 透光性玻璃基板的溫度，在實施例1 9係加熱至400°C、實 施例20係加熱至5 50°C，進行熱處理。 實施例19在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲83.6%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲6.1 Ω/□、全光透過率成爲82.6%、霧度 率成爲19.2%，改善了片電阻與霧度率。 實施例20在成膜隨後，片電阻値爲9.5 Ω/□、全光透 過率爲83.0%、霧度率爲14·6%者在氫氣氛中之熱處理後 ，片電阻値成爲5.1 Ω/匚！、全光透過率成爲81.6%、霧度 率成爲22.2%，改善了片電阻與霧度率。 (實施例21~22 ) 實施例21〜22係對於與實施例17同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持l〇Pa，且將形成有表面電極之 透光性玻璃基板的溫度，實施例2 1係加熱至400°C，實施 例22係加熱至5 50°C，進行熱處理。 實施例21在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲82.8%、霧度率爲14.8%者在氫氣氛中之熱處理後 ，片電阻値成爲5.4Ω/Ι□、全光透過率成爲81.5%、霧度 -31 - 201246277 率成爲21.3%，改善了片電阻與霧度率。 實施例22在成膜隨後’片電阻値爲9.5Ω/□、全光透 過率爲83.6%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲4.9Ω/□、全光透過率成爲82.0%、霧度 率成爲24.7%，改善了片電阻與霧度率。 (實施例23〜24 ) 實施例23~24係對於與實施例17同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持1 OOP a，且將形成有表面電極 之透光性玻璃基板的溫度，實施例2 3係加熱至4 0 0 °C，實 施例24係加熱至5 50t，進行熱處理。 實施例23在成膜隨後，片電阻値爲10.0Ω/□、全光 透過率爲83.9%、霧度率爲14.7%者在氫氣氛中之熱處理 後，片電阻値成爲4.8Ω/□、全光透過率成爲82.1%、霧 度率成爲23.0%，改善了片電阻與霧度率。 實施例24在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲83.8%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲4.1Ω/□、全光透過率成爲81.7%、霧度 率成爲26.8%，改善了片電阻與霧度率。 (比較例1 1 ~ 1 2 ) 比較例1 1〜1 2係對於與實施例1 7同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 -32- 201246277 流入，氣氛爐內之壓力保持0.1Pa’且將形成有表面電極 之透光性玻璃基板的溫度，比較例1係加熱至3 5 0°c ’比 較例2係加熱至6 0 0 °C ’進行熱處理° 比較例1 1在成膜隨後’片電阻値爲10.0Ω/□、全光 透過率爲83.9%、霧度率爲14·6%者在氫氣氛中之熱處理 後，片電阻値成爲12· 1Ω/□、全光透過率成爲84.2%、霧 度率成爲15.4%，片電阻與霧度率未見改善。 比較例12在成膜隨後’片電阻値爲9.4Ω/□、全光透 過率爲83.2%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲5.3Ω/□、全光透過率成爲57.4%、霧度 率成爲20.9%，片電阻與霧度率雖有改善，但是透過率極 度降低，且變得非透明。 (比較例13〜14) 比較例13〜14係對於與實施例17同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持IPa，且將形成有表面電極之 透光性玻璃基板的溫度，比較例1 3係加熱至3 50°C，比較 例14係加熱至600°C，進行熱處理。 比較例13在成膜隨後，片電阻値爲9· 5Ω/□、全光透 過率爲83.3%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲9.9Ω/□、全光透過率成爲83.4%、霧度 率成爲1 5 · 3 % .，片電阻與霧度率未見改善》 比較例14在成膜隨後，片電阻値爲9.6Ω/□、全光透 -33- 201246277 過率爲82.4%、霧度率爲14.6 %者在氫氣氛中之熱處理後 ，片電阻値成爲4.8Ω/□、全光透過率成爲56.5%、霧度 率成爲22.6%，片電阻與霧度率雖有改善，但是透過率極 度降低，且變得非透明。 (比較例15〜16) 比較例15~1 6係對於與實施例17同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持l〇Pa，且將形成有表面電極之 透光性玻璃基板的溫度，比較例1 5係加熱至3 5 0 °C，比較 例16係加熱至600 °C，進行熱處理。 比較例15在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲83·7%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲10.1 Ω/□、全光透過率成爲83.8%、霧度 率成爲M.7%，片電阻與霧度率未見改善。 比較例16在成膜隨後，片電阻値爲9.7Ω/□、全光透 過率爲83.4%、霧度率爲14.8 %者在氫氣氛中之熱處理後 ’片電阻値成爲4.3Ω/□、全光透過率成爲56.9%、霧度 率成爲24.4%，片電阻與霧度率雖有改善，但是透過率極 度降低，且變得非透明。 (比較例17〜18 ) 比較例1 7〜1 8係對於與實施例1 7同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2 L的流量 -34- 201246277 流入，氣氛爐內之壓力保持l〇〇Pa，且將形成有表面電極 之透光性玻璃基板的溫度，比較例1 7係加熱至3 5 (TC，比 較例1 8係加熱至600 °C，進行熱處理。 比較例17在成膜隨後，片電阻値爲9.3 Ω/□'全光透 過率爲83.2%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲！〇.3〇/匚|、全光透過率成爲83.4%、霧度 率成爲15.2%，片電阻與霧度率未見改善。 比較例18在成膜隨後，片電阻値爲9.8 Ω/□、全光透 過率爲83.7%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲3.9Ω/□、全光透過率成爲56.9%'霧度 率成爲26.4%，片電阻與霧度率雖有改善，但是透過率極 度降低，且變得非透明。 (比較例19〜20) 比較例1 9~20係對於與實施例1 7同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持〇.〇lPa’且將形成有表面電極 之透光性玻璃基板的溫度’比較例1 9係加熱至400 °C ’比 較例2 0係加熱至5 5 0 °C ’進行熱處理。 比較例19在成膜隨後’片電阻値爲9.3 Ω/□、全光透 過率爲82.4%、霧度率爲M.7%者在氫氣氛中之熱處理後 ，片電阻値成爲13.9Ω/□、全光透過率成爲83.0%、霧度 率成爲1 3.4%，片電阻與霧度率未見改善。 比較例20在成膜隨後，片電阻値爲9.3 Ω/匚|、全光透 -35- 201246277 過率爲82.7%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲11.8Ω/|□、全光透過率成爲83.0%、霧度 率成爲15.4%，片電阻與霧度率未見改善。 實施例17〜24及比較例1 1~20的結果如下表2所示。 [表2] 膜構成 膜 厚 (nm) 成膜後 氫 氣 體 壓 (Pa) 熱 處 理 溫 度 (°C) 熱處理後 熱處理後之改善比 表 面 電 阻 (0/□) 全 光 透 過 率 (%) 霧 度 (W 表 面 電 阻 (Ω/Π) 全 光 透 過 率 (%) 霧 度 (¾) 表 面 電 阻 前/後 全 光 透 過 率 麵 霧 度 wm K施例17 GAZO/ITtO/Glass 1250 9.7 83.9 14.8 0.1 400 6.9 83.2 18.9 1.41 0.99 1.28 0施例18 GAZO/ITiO/Glass 1250 9.5 83.4 14.6 0.1 550 6.1 82.5 20.2 1.55 0.99 1.38 苡施例19 GAZO/ITiO/Glass 1250 9.9 83.6 14.6 1 400 6.1 82.6 19.2 1.62 0.99 1,32 贸施例20 GAZO/ITiO/Glass 1250 9.5 83.0 14.6 1 550 5.1 81.6 22.2 1.87 0.98 1.52 實施例21 GAZO/ITiO/Glass 1250 9.6 82.8 14.8 10 400 5.4 81.5 21.3 1.78 0.98 1.44 實施例22 GAZO/ITiO/Glass 1250 9.5 83.6 14.9 10 550 4.9 82.0 24.7 1.95 0.98 1.66 實施例23 GAZO/ITiO/Glass 1250 10.0 83.9 14.7 100 400 4.8 82.1 23.0 206 0.98 1.56 實施例24 GAZO/ITiO/Glass 1250 9.4 83.8 14.9 100 550 4.1 81.7 26.8 2.28 0.98 1.79 比較例11 GAZO/ITiO/Glass 1250 10.0 83.9 14.6 0.1 350 1Z1 84.2 15.4 0.82 1.00 1.05 比較例12 GAZO/ITiO/Glass 1250 9.4 83.2 14.9 0.1 600 5.3 57.4 20.9 1.77 0.69 1.40 比較例13 GAZO/ITiO/Glass 1250 9.5 83.3 14.9 1 350 9.9 83.4 15.3 0.96 1.00 1.02 比較例14 GAZO/ITiO/Glass 1250 9.6 82.4 14.6 1 600 4.8 56.5 22.6 zoo 0.69 1.54 比較例15 GAZO/ITiO/Glass 1250 9.4 83.7 14.7 10 350 10.1 83.8 14.7 0.93 1.00 1.00 比較例16 GAZO/ITiO/Glass 1250 9.7 83.4 14.8 10 600 4.3 56.9 24.4 2.25 0.68 1.66 比較例17 GAZO/ITiO/Glass 1250 9.3 83.2 14.7 100 350 10.3 83.4 15.2 0.91 1.00 1.03 比較例18 GAZO/m〇/Glass 1250 9.8 83.7 14.7 100 600 3.9 56.9 26.4 Z52 0.68 1.79 比較例19 GAZO/ITiO/Glass 1250 9.3 82.4 14.7 0.01 400 13.9 83.0 13.4 0.67 1.01 0.91 比較例20 GAZO/ITiO/Glass 1250 9.3 82.7 14.7 0.01 550 11.8 83.0 15.4 0.79 1.00 1.05 (實施例2 5 ) 實施例25係形成表面電極2之底層膜2 1爲使用氧化 銦中含有氧化鎵3.4質量％、氧化錫1 0質量％的I T G Ο膜 ，凹凸膜22爲使用氧化鋅中摻雜有氧化鎵0.58質量％、 氧化鋁0.32質量％的GAZO膜。 碳酸鈉-石灰-矽土玻璃基板的溫度設定爲25°C，導入 氣體爲使用氬與氧之混合氣體（氬：氧=99:1)，藉由濺 鍍法形成膜厚成爲150nm的ITGO膜。其次，將碳酸鈉- -36- 201246277 石灰-矽土玻璃基板之溫度設定爲3 00t，濺鍍功率 DC400W、導入氣體爲氬氣體1〇〇%，氣體壓調整爲7Pa， 形成總膜厚成爲1 1 50nm的GAZO膜。 氫氣體還原環境中之熱處理係將氫氣體以每分鐘2L 的流量流入，氣氛爐內之壓力保持0.1 Pa，且將形成有表 面電極之透光性玻璃基板的溫度加熱至400°C，進行處理 〇 結果成膜隨後的片電阻値爲ίο.0Ω/□、全光透過率爲 82.5%、霧度率爲14.6 %者在氫氣氛中之熱處理後，片電 阻値成爲6.4Ω/□、全光透過率成爲81.6%、霧度率成爲 18.2%，改善了片電阻與霧度率。 (實施例26) 實施例26係對於與實施例25同樣步驟在玻璃基板上 所製作的透明導電膜，使氫氣體以每分鐘2L的流量流入 ，氣氛爐內之壓力保持O.lPa’且將形成有表面電極之透 光性玻璃基板的溫度加熱至550°C，進行熱處理。 結果成膜隨後的片電阻値爲9.4Ω/□、全光透過率爲 83.9%、霧度率爲14.7%者在氫氣氛中之熱處理後，片電 阻値成爲5.4Ω/□、全光透過率成爲82.7%、霧度率成爲 2 1 .1 %，改善了片電‘阻與霧度率。全光透過率幾乎未變化 (實施例27〜28 ) -37- 201246277 實施例27〜28係對於與實施例25同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持IPa，且將形成有表面電極之 透光性玻璃基板的溫度，實施例27係加熱至400 °C，實施 例28係加熱至5 5 0°C，進行熱處理。 實施例27在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲82.4%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲6.0Ω/□、全光透過率成爲81.4%、霧度 率成爲20.5%，改善了片電阻與霧度率。 實施例28在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲83.7%、霧度率爲 M.5%者在氫氣氛中之熱處理後 ，片電阻値成爲4.8Ω/□、全光透過率成爲82.1%、霧度 率成爲23.0%，改善了片電阻與霧度率。 (實施例29〜30 ) 實施例29~30係對於與實施例25同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持l〇Pa，且將形成有表面電極之 透光性玻璃基板的溫度，實施例2 9加熱至4 0 0 °C，實施例 3 〇係加熱至5 5 0 °C，進行熱處理。 實施例29在成膜隨後，片電阻値爲9· 8Ω/匚|、全光透 過率爲82.6%、霧度率爲14.5%者在氫氣氛中之熱處理後 ’片電阻値成爲5.3Ω/□、全光透過率成爲81.2%、霧度 率成爲2 1 . 8 %，改善了片電阻與霧度率。 -38- 201246277 實施例30在成膜隨後，片電阻値爲9.7 Ω/□、全光透 過率爲82.7%、霧度率爲14.8 %者在氫氣氛中之熱處理後 ，片電阻値成爲4.3Ω/ΙΙΙ、全光透過率成爲80.6%、霧度 率成爲25.6%，改善了片電阻與霧度率。 (實施例3 1~32 ) 實施例31〜32係對於與實施例25同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持100Ρ a，且將形成有表面電極 之透光性玻璃基板的溫度，實施例3 1係加熱至40(TC，實 施例32係加熱至550°C，進行熱處理。 實施例31在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲82.6%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲4.9Ω/□、全光透過率成爲81.1%、霧度 率成爲23.9%，改善了片電阻與霧度率。 實施例32在成膜隨後，片電阻値爲9.3 Ω/□、全光透 過率爲82.7%、霧度率爲8%者在氫氣氛中之熱處理後 ’片電阻値成爲4.1Ω/□、全光透過率成爲80.6%、霧度 率成爲27.6%，改善了片電阻與霧度率。 (比較例21~22 ) 比較例21~22係對於與實施例25同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入’氣氛爐內之壓力保持O.lPa，將形成有表面電極2 -39- 201246277 之透光性玻璃基板1的溫度，比較例21係加熱至3 5 0°C， 比較例22係加熱至600°C，進行熱處理。 比較例21在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲83.8%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲11.9Ω/□、全光透過率成爲84.2%、霧度 率成爲15.5%，片電阻與霧度率未見改善。 比較例22在成膜隨後，片電阻値爲9.7Ω/□、全光透 過率爲82·7%、霧度率爲 Η.9%者在氫氣氛中之熱處理後 ，片電阻値成爲5.1 Ω/□、全光透過率成爲56.9%、霧度 率成爲20.5%，片電阻與霧度率雖有改善，但是透過率極 度降低，且變得非透明。 (比較例23〜24 ) 比較例23〜24係對於與實施例25同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持IPa，將形成有表面電極2之 透光性玻璃基板1的溫度，比較例23係加熱至3 5 0°C，比 較例24係加熱至600°C，進行熱處理。 比較例23在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲84.0%、霧度率爲14.7%者在氫氣氛中之熱處理後 ’片電阻値成爲10.6Ω/□、全光透過率成爲84.1%、霧度 率成爲15.6%，片電阻與霧度率未見改善。 比較例24在成膜隨後，片電阻値爲9.6 Ω/□、全光透 過率爲82.7%、霧度率爲14.7%者在氫氣氛中之熱處理後 -40- 201246277 ，片電阻値成爲4.6Ω/□、全光透過率成爲56.6%、霧度 率成爲2 2.3 %，片電阻與霧度率雖有改善，但是透過率極 度降低，且變得非透明。 (比較例25〜26 ) 比較例25〜26係對於與實施例25同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持10P a，將形成有表面電極2之 透光性玻璃基板1的溫度，比較例2 5係加熱至3 5 0°C，比 較例26係加熱至60(TC，進行熱處理。 比較例25在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲83.3%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲10.4Ω/□、全光透過率成爲83.5%、霧度 率成爲16.2%，片電阻與霧度率未見改善。 比較例26在成膜隨後，片電阻値爲10.0Ω/□、全光 透過率爲82.6%、霧度率爲14.9%者在氫氣氛中之熱處理 後，片電阻値成爲4.1Ω/□、全光透過率成爲56.2%、霧 度率成爲24.8%，片電阻與霧度率雖有改善，但是透過率 極度降低，且變得非透明。 (比較例27〜28 ) 比較例27~28係對於與實施例25同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持l〇〇Pa，將形成有表面電極2 -41 - 201246277 之透光性玻璃基板1的溫度，比較例27係加熱至3 50°C， 比較例28係加熱至60(TC，進行熱處理。 比較例27在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲82.6%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲10.4Ω/□、全光透過率成爲82.8%、霧度 率成爲14.3%，片電阻與霧度率未見改善。 比較例28在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲82.6%、霧度率爲14.8%者在氫氣氛中之熱處理後 ，片電阻値成爲3.7Ω/□、全光透過率成爲55.9%、霧度 率成爲26.6%，片電阻與霧度率雖有改善，但是透過率極 度降低，且變得非透明。 (比較例2 9〜3 0 ) 比較例29〜30係對於與實施例25同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持O.OlPa，且將形成有表面電極 之透光性玻璃基板的溫度，比較例29係加熱至400。(：，比 較例30係加熱至5 50°C，進行熱處理。 比較例29在成膜隨後，片電阻値爲9.5 Ω/□、全光透 過率爲83.3%、霧度率爲14.5%者在氫氣氛中之熱處理後 ’片電阻値成爲13.8Ω/□、全光透過率成爲83.8%、霧度 率成爲13.2%，片電阻與霧度率未見改善。 比較例30在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲82.8%、霧度率爲I4.6%者在氫氣氛中之熱處理後 -42 - 201246277 ，片電阻値成爲11.7Ω/□、全光透過率成爲83.1%、霧度 率成爲15.2%，片電阻與霧度率未見改善。 實施例25〜32及比較例21~30的結果如下表3所示。 [表3] 膜構成 膜 厚 (nm) 成膜後 氣 氣 體 壓 (Pa) 熱 處 理 溫 度 (°C) 熱處理後 熱處理後之改善比 表 面 電 阻 (Ω/Π) 全 光 透 過 率 (W 霧 度 (%) 表 面 電 阻 (Ω/D) 全 光 透 過 率 (%) 霧 度 (W 表 面 電 阻 前/後 全 光 透 過 率 Wm 霧 度 細 實施例25 GAZO/ITGO/Glass 1150 10.0 82.5 14.6 0.1 400 6.4 81.6 18.2 1.56 0.99 1.25 實施例26 GAZO/ITGO/Glass 1150 9.4 83.9 14.7 0.1 550 5.4 82.7 21.1 1.73 0.99 1.44 實施例27 GAZO/ITGO/Glass 1150 9.9 82.4 14.9 1 400 6.0 81.4 20.5 1.65 0.99 1.38 實施例28 GAZO/ITGO/Glass 1150 9.4 83.7 14.5 1 550 4.8 82.1 23.0 1.96 0.98 1.58 實施例29 GAZO/ITGO/Glass 1150 9.8； 82.6 14.5 \0 400 6.3 81.2 21.8 1.35 0.93 1.50 實施例30 GAZO/ITGO/Glass 1150 9.7 82.7 14.8 10 550 4.3 80.6 25.6 Z27 0.98 1.73 實施例31 GAZO/ITGO/Glass 1150 9.4 82.6 14.7 100 400 4.9 81.1 23.9 1.93 0.98 1.63 實施例32 GAZO/ITGO/Glass 1150 9.3 817 14.8 100 550 4.1 80.6 27.6 227 0.98 1.87 比較例21 GAZO/ITGO/Glass 1150 9.6 83.8 14.9 0.1 350 11.9 84.2 15.5 0.81 1.00 1.04 比較例22 GAZO/ITGO/Glass 1150 9.7 82.7 14.9 0.1 600 5.1 56.9 20.5 1.89 0.69 1.38 比較例23 GAZO/ITGO/Glass 1150 9.9 84.0 14.7 1 350 10.6 34.1 15.6 0.93 1.00 1.06 比較例24 GAZO/ITGO/Glass 1150 9.(ί 82.7 14.7 1 600 4.6 56.6 22.3 2.08 0.69 1.52 比較例25 GAZO/ITGO/Glass 1150 9Α 83.3 14.9 10 350 10.4 83.5 16.2 0.90 1.00 1.08 比較例26 GAZO/ITGO/Glass mo 10.0 82.6 14.9 10 600 4.1 56.2 24.8 2.41 0.68 1.66 比較例27 GAZO/ITGO/Glass 1150 9.4 82.6 14.6 100 350 10.4 82.8 14.3 α9〇 1.00 0.98 比較例28 GAZO/ITGO/Glass 1150 Θ.9 82.6 14.8 100 600 3.7 55.9 26.6 270 0.68 1.79 比較例29 GAZO/ITGO/Glass 1150 9.；i 83.3 14.5 0.01 400 13.8 83.8 13.2 0.69 1.01 0.91 比較例30 GAZO/ITGO/Glass 1150 BA 82.8 14.6 0.01 550 11.7 83.1 15.2 αβο 1.00 1.05 (實施例3 3 ) 實施例33係如圖2B所示，表面電極2中，不使用底 層膜21，而凹凸膜22爲使用氧化鋅中摻雜有氧化鋁2.0 質量％的AZO膜。 成膜係使用 DC磁控職鍍法（magnetron sputtering technique )，使用的靶係φ 6吋大小，且基板與靶的間隔 爲 6 0 m m。 碳酸鈉-石灰-矽土玻璃基板的溫度設定爲3 00 °C，濺 -43- 201246277 鍍功率DC400W、導入氣體爲氬氣體100%，氣體壓調整 爲7Pa，形成總膜厚成爲2400nm的AZO膜。 氫氣體還原環境中之熱處理係使氫氣體以每分鐘2L 的流量流入，氣氛爐內之壓力保持O.lPa，且將形成有表 面電極2之透光性玻璃基板1的溫度加熱至4 0 0 °C，進行 處理。 結果成膜隨後的片電阻値爲10.0Ω/□、全光透過率爲 81.3%'霧度率爲14.9%者在氣氣氛中之熱處理後，片電 阻値成爲7.2Ω/□、全光透過率成爲80.7%、霧度率成爲 18.6%，改善了片電阻與霧度率。 (實施例3 4 ) 實施例3 4係對於與實施例3 3同樣步驟在玻璃基板上 所製作的透明導電膜，使氫氣體以每分鐘2 L的流量流入 ’氣氛爐內之壓力保持O.lPa’且將形成有表面電極之透 光性玻璃基板的溫度加熱至5 50°C，進行熱處理。 結果成膜隨後的片電阻値爲9.3Ω/□、全光透過率爲 80.8%、霧度率爲M.5 %者在氫氣氛中之熱處理後，片電 阻値成爲6.3Ω /□、全光透過率成爲800%、霧度率成爲 19.2%，改善了片電阻與霧度率。全光透過率乎未變化。 (實施例3 5 ~ 3 6 ) 實施例3 5〜3 6係對於與實施例3 3同樣步驟在玻璃基 板上所製作的透明導電膜’使氫氣體以每分鐘2L的流量 -44- 201246277 流入，氣氛爐內之壓力保持IPa，將形成有表面電極2之 透光性玻璃基板1的溫度，實施例35係加熱至400它，實 施例3 6係加熱至5 5 (TC，進行熱處理。 實施例35在成膜隨後，片電阻値爲9.3 Ω/□、全光透 過率爲80.5%、霧度率爲I4.6%者在氫氣氛中之熱處理後 ，片電阻値成爲6.9Ω/□、全光透過率成爲79.9%、霧度 率成爲18.4%，改善了片電阻與霧度率。 實施例36在成膜隨後，片電阻値爲9.8Ω/□、全光透 過率爲79.9%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲5.3 Ω/□、全光透過率成爲78.6%、霧度 率成爲2 1 . 8 %，改善了片電阻與霧度率。 (實施例37〜38 ) 實施例37~38係對於與實施例33同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持l〇Pa，將形成有表面電極2之 透光性玻璃基板1的溫度，實施例37係加熱至400°C，實 施例38係加熱至550°C，進行熱處理。 實施例37在成膜隨後，片電阻値爲9.4Ω/ΙΙΙ、全光透 過率爲80.2%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲5.9Ω/□、全光透過率成爲79.3%、霧度 率成爲20.3%，改善了片電阻與霧度率。 實施例38在成膜隨後，片電阻値爲9.5 Ω/□、全光透 過率爲81.1%、霧度率爲14.6%者在氫氣氛中之熱處理後 -45- 201246277 ’片電阻値成爲5.0Ω/□、全光透過率成爲79.6%、霧度 率成爲2 3 . 1 %，改善了片電阻與霧度率。 (實施例39〜40 ) 實施例39〜40係對於與實施例33同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持1 OOP a，且將形成有表面電極 2之透光性玻璃基板1的溫度，實施例39係加熱至400°C ，實施例40係加熱至5 50°C，進行熱處理。 實施例39在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲 81.3%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲5.4Ω/□、全光透過率成爲80.1%、霧度 率成爲22.3%，改善了片電阻與霧度率。 實施例40在成膜隨後，片電阻値爲9.8Ω/□、全光透 過率爲81.2%、霧度率爲 M.7%者在氫氣氛中之熱處理後 ，片電阻値成爲4.4 Ω/口、全光透過率成爲79.2%、霧度 率成爲25.3%，改善了片電阻與霧度率。 (比較例3 1〜3 2 ) 比較例3 1〜3 2係對於與實施例3 3同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持O.lPa，且將形成有表面電極 2之透光性玻璃基板1的溫度，比較例3 1係加熱至3 5 0 °C ，比較例32係加熱至600 °C，進行熱處理。 -46- 201246277 比較例31在成膜隨後’片電阻値爲9.6Ω/ΙΙΙ、全光透 過率爲81.3%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲11.3Ω/□、全光透過率成爲81.6%、霧度 率成爲15.5%，片電阻與霧度率未見改善。 比較例32在成膜隨後’片電阻値爲9.7Ω/□、全光透 過率爲80.3%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲5.3Ω/□、全光透過率成爲55.3%、霧度 率成爲20.5%，片電阻與霧度率雖有改善，但是透過率極 度降低，且變得非透明。 (比較例3 3〜3 4 ) 比較例33~34係對於與實施例33同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持IPa，將形成有表面電極2之 透光性玻璃基板1的溫度，比較例33係加熱至3 50°C，比 較例34係加熱至600°C，進行熱處理。 比較例33在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲81.4%、霧度率爲I4.7%者在氫氣氛中之熱處理後 ’片電阻値成爲10.6Ω/□、全光透過率成爲81.5%、霧度 率成爲15.7%，片電阻與霧度率未見改善。 比較例34在成膜隨後，片電阻値爲9.6 Ω/匚]、全光透 過率爲80.2%、霧度率爲Μ.7%者在氫氣氛中之熱處理後 ’片電阻値成爲4.5Ω/□、全光透過率成爲54.9%、霧度 率成爲22.3%，片電阻與霧度率雖有改善，但是透過率極 -47- 201246277 度降低，且變得非透明。 (比較例35~36 ) 比較例35〜36係對於與實施例33同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持l〇Pa，將形成有表面電極2之 透光性玻璃基板1的溫度，比較例3 5係加熱至3 5 0 °C，比 較例36係加熱至600°C，進行熱處理。 比較例35在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲80.8%、霧度率爲 M.9%者在氫氣氛中之熱處理後 ，片電阻値成爲10.4Ω/□、全光透過率成爲81.0%、霧度 率成爲16.2%，片電阻與霧度率未見改善。 比較例36在成膜隨後，片電阻値爲10.0Ω/□、全光 透過率爲80.1%、霧度率爲14.9 %者在氫氣氛中之熱處理 後，片電阻値成爲4.3 Ω/□、全光透過率成爲54.6%、霧 度率成爲24.8%，片電阻與霧度率雖有改善，但是透過率 極度降低，且變得非透明。 (比較例37〜38 ) 比較例3 7〜3 8係對於與實施例3 3同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2 L的流量 流入，氣氛爐內之壓力保持lOOPa，且將形成有表面電極 2之透光性玻璃基板1的溫度，比較例37係加熱至3 5 0°C ，比較例38係加熱至600°C，進行熱處理。 -48- 201246277 比較例37在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲80.2%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲10.4Ω/□'全光透過率成爲80.3%、霧度 率成爲14.3%，片電阻與霧度率未見改善。 比較例38在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲80.1%、霧度率爲14.8%者在氫氣氛中之熱處理後 ，片電阻値成爲3.8Ω/□、全光透過率成爲54.3%、霧度 率成爲26.6%，片電阻與霧度率雖有改善，但是透過率極 度降低，且變得非透明。 (比較例39〜40 ) 比較例3 9〜40係對於與實施例3 3同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持O.OlPa，將形成有表面電極2 之透光性玻璃基板1的溫度，比較例39係加熱至400 °C， 比較例40係加熱至55(TC，進行熱處理。 比較例39在成膜隨後，片電阻値爲9.5 Ω/□、全光透 過率爲80.8%、霧度率爲14.5%者在氫氣氛中之熱處理後 ，片電阻値成爲13.2Ω/□、全光透過率成爲81.2%、霧度 率成爲1 3.2%，片電阻與霧度率未見改善。 比較例40在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲80.3%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲1Κ2Ω/□、全光透過率成爲80.5%、霧度 率成爲15.2%，片電阻與霧度率未見改善。 -49- 201246277 實施例3 3〜40及比較例3 1 ~4〇的結果如下表4所示。 [表4] 膜構成 膜 厚 (nm) 成膜後 氫 氣 體 壓 (Pa) 熱 處 理 溫 度 CO 熱處理後 熱處理後之改善比 表 面 電 阻 (Ω/口) 全 光 透 過 率 (¾) 霧 度 (%) 表 面 電 阻 (Ω/α) 全 光 透 過 率 (W 霧 度 (») 表 面 電 阻 前/後 全 光 透 過 率 後湔 霧 度 鋪 S施例33 A20/G!ass 2400 10.0 81.3 14.9 0.1 400 7.2 80.7 18.6 1.39 0.99 1.25 0施_ AZO/Glass 2400 9.3 80.8 14.6 0,1 550 6.3 80.0 19.2 1.48 0.99 1.32 實施例35 A20/Glass 2400 9.3 80.5 14.6 1 400 6.9 79.9 18.4 1.36 0.99 1.27 0施例36 AZO/Glass 2400 9.8 79.9 14.9 1 550 5.3 78.6 21.8 1.34 0.98 1.46 Η施例37 AZO/Glass 2400 9.4 80.2 14.7 10 400 5.9 79.3 20.3 1.59 0.99 1.38 實施例38 AZO/Glass 2400 9.5 81.1 14.6 10 550 5.0 79.6 23.1 1.89 0.98 1.59 59施_ AZO/Glass 2400 9.6 81.3 14,9 100 400 5.4 80.1 2Ζ3 1.79 0.98 1.50 S施例40 AZO/Glass 2400 9.8 81.2 14.7 100 550 4.4 79.2 25.3 2.24 0.98 1.72 比較《31 AZO/Glass 2400 9.6 81.3 14.9 0.1 350 11.3 81.6 15.5 0.85 1.00 1.04 比較例32 AZO/Glass 2400 9.7 80.3 14.9 0.1 600 5.3 55.3 20.5 1.82 0.69 1.38 比較_ AZO/Glass 2400 9.9 81.4 14.7 1 350 10.6 81.5 15.7 0.93 1.00 1.07 比較例34 AZO/Glass 2400 9.6 80.2 14.7 1 600 4.5 54,9 22.3 Ζ14 0.68 1.52 比較例35 AZO/Glass 2400 9.4 80.8 14.9 10 350 10.4 81.0 16.2 0.90 1.00 1.08 比較例36 AZO/Glass 2400 10.0 80.1 14.9 10 600 4.3 54.6 24.8 Ζ33 0.68 1.66 比較例37 AZO/Glass 2400 9.4 80.2 14.6 100 350 10.4 80.3 14.3 0.90 1.00 0.98 比較例38 AZO/Glass 2400 9.9 80.1 14.8 100 600 3.8 54.3 26.6 Ζ64 0.68 1.79 比較例39 AZO/Glass 2400 9.5 80.8 14.5 0.01 400 13.2 81.2 13.2 0.72 1.01 0.91 比較例40 AZO/Glass 2400 9.4 80.3 14.6 0.01 550 11.2 80.5 15.2 0.84 1.00 1.05 (實施例4 1 ) 實施例41係不使用底層膜21，而凹凸膜22爲使用氧 化鋅中摻雜有氧化鎵0 · 5 8質量％、氧化鋁0 · 3 2質量％的 GAZO 膜。 成膜係使用D C磁控濺鍍法，使用的靶係Φ 6吋大小 ，且基板與靶的間隔爲60mm。碳酸鈉·石灰-矽土玻璃基 板的溫度設定爲3 00°C，濺鍍功率DC400W、導入氣體爲 氬氣體 100%，氣體壓調整爲 7Pa，形成總膜厚成爲 2100nm 的 GAZO 膜。Film thickness (nm) Gas pressure after film formation (Pa) Heat treatment temperature (°C) Improvement after heat treatment Heat treatment surface resistance (Ω/D) Total light transmittance (*) Haze (%) Surface resistance (0/□) Total light transmittance (») Haze (X) Surface resistance before/after total light transmittance wm After haze Example 1 GAZO/ITITO/Glass 1200 9. 7 83. 4 14. 7 0. 1 400 6. 9 82. 8 19. 1 1. 40 0. 99 1. 30 Example 2 GAZO/ITiTO/Glass 1200 9. 4 83. 1 14. 5 0. 1 450 6. 4 82. 4 19. 8 1. 45 0. 99 1. 37 Example 3 GAZO/lTiTO/Glass 1200 9. 9 84. 0 14. 8 0. 1 500 6. 2 83. 0 21. twenty one. 60 0. 99 1. 43 Example 4 GAZO/ITiTO/Glass 1200 9. 9 84. 0 14. 5 0. 1 550 5. 9 82. 9 21. 7 1. 66 0. 99 1. 50 Example 5 GAZO/ITiTO/Glass 1200 9. 7 82. 5 14. 8 1 400 6. 1 81. 6 2\Λ 1. 60 0. 99 1. 43 Example 6 GAZO/ITiTO/Glass 1200 9. 4 83. 4 14. 9 1 450 5. 6 82. 3 22. 5 1. 67 0. 99 1. 51 Example 7 GAZO/ITiTO/Glass 1200 9. 9 82. 9 14. 8 1 500 5. 4 81. 5 23. twenty one. 83 0. 98 1. 57 Example 8 GAZO/ITiTO/Glass 1200 BA 83. 8 14. 6 1 550 5. 1 82. 4 24. 1 1. 84 0. 98 1. 64 Example 9 GAZO/ITiTO/Glass 1200 9. 5 82. 9 14. 9 10 400 5. 4 81. 7 23. 3 1. 77 0. 98 1. 56 Example 10 GAZO/ITiTO/Glass 1200 10. 0 82. 4 14. 6 10 450 5. 0 30. 8 23. 8 1. Θ8 0. 98 1. 64 Example 11 GAZO/ITiTO/Glass 1200 9. 6 83. 3 14. 6 10 500 4. 8 81. 7 25. 0 1. 99 0. 98 1. 72 Example 12 GAZO/ITiTO/Glass 1200 9. 5 83. 3 14. 6 10 550 4. 5 81. 5 26. twenty two. 10 0. 98 1. 79 Example 13 GAZO/ITiTO/Glass 1200 9. 8 83. 3 14. 5 100 400 4. 7 81. 5 24. 6 2. 09 0. 98 1. 69 Example 14 GAZO/ITiTO/Glass 1200 9. δ 82. 8 14. 7 100 450 4. 3 80. 8 26. 0 2. 33 0. 98 1. 77 Example 15 GAZO/ITiTO/Glass 1200 9. Ίί 83. 7 14. 6 100 500 4. 4 81. 7 27. twenty two. 23 0. 98 1. 86 Example 16 GAZO/ITiTO/Glass 1200 9. 4 83. 7 14. 9 100 650 4. 1 81. 6 29. 0 2. 28 0. 98 1. 94 Comparative Example 1 GAZO/ITiTO/Glass 1200 9. 4 83. 9 14. 6 0. 1 350 11. 7 84. 2 15. 4 0. 80 1. 00 1. 05 Comparative Example 2 GAZO/ITiTO/Glass 1200 9. 3 82. 7 14. 7 0. 1 600 5. 6 57. 2 20. 6 1. 66 0. 69 1. 40 Comparative Example 3 GAZO/ITiTO/Glass 1200 9. 7 83. 1 14. 9 1 350 10. 3 83. 2 15. 7 0. 94 1. 00 1. 06 Comparative Example 4 GAZO/ITiTO/Glass 1200 9. 9 83. 3 14. 5 1 600 4. 7 57. 0 22. 4 2. 11 0. 68 1. 54 Comparative Example 5 GAZO/ITiTO/Glass 1200 9. 7 83. 0 14. 9 10 350 10. 9 83. 2 15. 7 0. 89 1. 00 1. 05 Comparative Example 6 GAZO/ITiTO/Glass 1200 9. 4 82. 9 14. 7 10 600 4. 0 56:5 24. 8 2. 35 0. 68 1. 68 Comparative Example 7 GAZCmTiTO/Glass 1200 9. 7 82. 6 14. 7 100 350 10. 6 82. 8 15. 8 0. 92 1. 00 1. 07 Comparative Example 8 GAZO/ITiTO/Glass 1200 9. 6 83. 0 14. 8 100 600 3. 8 56. 3 27. 0 2. 54 0. 68 1. 83 Comparative Example 9 GAZO/ITiTO/Glass 1200 9. 9 82. 4 14. 6 0. 01 400 9. 5 82. 3 12. 0 1. 04 1. 00 0. 82 Comparative Example 10 GAZO/lTiTO/Glass 1200 9. 9 82. 7 14. 9 0. 01 550 9. 3 82. 2 14. 0 1. 06 0. 99 0. 94 (Example 1 7) Example 1 7 The underlying film 21 forming the surface electrode 2 is an ITiO film doped with 1% by mass of titanium oxide in indium oxide, and the uneven film 22 is doped with oxidation in zinc oxide. Gallium  58% by mass, alumina 0. 32% by mass of the GAZO film. The temperature of the sodium carbonate-lime-alumina glass substrate was set to 25 ° C, and the mixed gas of argon and oxygen (argon: oxygen = 99 : 1 ) was used to introduce an ITiO film having a film thickness of 2 50 μm by sputtering. . Next, sodium carbonate-lime--29 - 201246277 The temperature of the alumina glass substrate is set to 300 ° C, the sputtering power is DC400W, the introduction gas is argon gas 100%, the gas pressure is adjusted to 7Pa, and the total film thickness is 1 250nm. GAZO film. For the heat treatment in the hydrogen gas reduction environment, the hydrogen gas is flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace is maintained at O. lPa, and the temperature of the translucent glass substrate on which the surface electrode was formed was heated to 40 (TC, and the treatment was performed. 〇 The film resistance 成 after the film formation was 9. 7Ω/□, total light transmittance is 8 3. 9%, the haze rate is 14. After 8% of the heat treatment in a hydrogen atmosphere, the sheet resistance became 6. 9 Ω / □, the total light transmittance is 83. 2%, the haze rate becomes 1 8. 9%, improved sheet resistance and haze ratio. (Example 1 8) Example 1 8 is a transparent conductive film produced on a glass substrate in the same manner as in Example 17. The hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at O. lPa, and the temperature of the light-transmitting glass substrate on which the surface electrode was formed was heated to 550 ° C, and heat-treated to form a transparent conductive substrate 1 1 with a surface electrode. As a result, the sheet resistance 成 of the film formation was 9. 5Ω/□, total light transmittance is 83. 4%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 6 %, the sheet resistance became 6. 1 Ω / □, the total light transmittance is 82. 5%, the haze rate becomes 20. 2%' improved sheet resistance and haze ratio. The total light transmittance is almost unchanged -30-201246277 (Example 19 to 2 Ο) Example 1 9 to 2 0 is a transparent conductive film produced on a glass substrate in the same manner as in Example 17 to make hydrogen gas The flow rate of 2 L per minute flows in, the pressure in the atmosphere furnace is maintained at IPa, and the temperature of the translucent glass substrate on which the surface electrode is formed is heated to 400 ° C in Example 19 and heated to 5 50 in Example 20. °C, heat treatment. Example 19, after film formation, the sheet resistance 値 was 9. 9Ω/□, the total light transmittance is 83. 6%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 6%, the sheet resistance became 6. 1 Ω / □, the total light transmittance is 82. 6%, the haze rate became 19. 2%, improved sheet resistance and haze ratio. After the film formation of Example 20, the sheet resistance was 9. 5 Ω / □, the total light transmittance is 83. After heat treatment in a hydrogen atmosphere at 0% and a haze ratio of 14.6%, the sheet resistance 5 becomes 5. 1 Ω / 匚! The total light transmittance is 81. 6%, the haze rate became 22. 2%, improved sheet resistance and haze ratio. (Examples 21 to 22) In the examples 21 to 22, the transparent conductive film produced on the glass substrate in the same manner as in Example 17 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 10 Torr. Pa, and the temperature of the translucent glass substrate on which the surface electrode was formed, Example 2 1 was heated to 400 ° C, and Example 22 was heated to 550 ° C, and heat treatment was performed. After the film formation of Example 21, the sheet resistance was 9. 6Ω/□, the total light transmittance is 82. 8%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 8%, the sheet resistance became 5. 4Ω/Ι□, the total light transmittance is 81. 5%, haze -31 - 201246277 The rate became 21. 3%, improved sheet resistance and haze ratio. In Example 22, after film formation, the sheet resistance was 9. 5Ω/□, the total light transmittance is 83. 6%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 4. 9Ω/□, the total light transmittance is 82. 0%, the haze rate becomes 24. 7%, improved sheet resistance and haze ratio. (Examples 23 to 24) Examples 23 to 24 are transparent conductive films produced on a glass substrate in the same manner as in Example 17, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 1 OOP. a, and the temperature of the translucent glass substrate on which the surface electrode was formed, Example 2 3 was heated to 400 ° C, and Example 24 was heated to 5 50 t, and heat treatment was performed. Example 23, after film formation, the sheet resistance 値 was 10. 0Ω/□, all-light transmittance is 83. 9%, the haze rate is 14. After 7% of the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4. 8Ω/□, the total light transmittance is 82. 1%, the haze rate is 23. 0%, improved sheet resistance and haze ratio. Example 24, after film formation, the sheet resistance 値 was 9. 4Ω/□, the total light transmittance is 83. 8%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 4. 1Ω/□, the total light transmittance is 81. 7%, the haze rate became 26. 8%, improved sheet resistance and haze ratio. (Comparative Example 1 1 to 1 2 ) Comparative Example 1 1 to 1 2 The transparent conductive film produced on the glass substrate in the same manner as in Example 17 was allowed to flow hydrogen gas at a flow rate of 2 L per minute - 32 - 201246277 The pressure in the atmosphere furnace is maintained at 0. 1Pa' and the temperature of the light-transmissive glass substrate on which the surface electrode was formed, Comparative Example 1 was heated to 305 ° C. 'Comparative Example 2 was heated to 6,000 ° C' for heat treatment. Comparative Example 1 1 The film then has a sheet resistance of 10. 0Ω/□, all-light transmittance is 83. After heat treatment in a hydrogen atmosphere at 9% and a haze ratio of 14.6%, the sheet resistance 値 became 12·1 Ω/□, and the total light transmittance was 84. 2%, the haze rate is 15. 4%, sheet resistance and haze rate did not improve. Comparative Example 12 was filmed and then had a sheet resistance of 9. 4Ω/□, the total light transmittance is 83. 2%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 5. 3Ω/□, the total light transmittance is 57. 4%, the haze rate becomes 20. At 9%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Examples 13 to 14) In Comparative Examples 13 to 14, the transparent conductive film produced on the glass substrate in the same manner as in Example 17 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was kept at IPa. Further, the temperature of the translucent glass substrate on which the surface electrode was formed was heated to 550 ° C in Comparative Example 13 and heated to 600 ° C in Comparative Example 14 to carry out heat treatment. In Comparative Example 13, after film formation, the sheet resistance 値 was 9·5 Ω/□, and the total light transmittance was 83. 3%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 9. 9Ω/□, the total light transmittance is 83. 4%, the haze rate is 1 5 · 3 %. , sheet resistance and haze rate did not improve. Comparative Example 14 after film formation, sheet resistance 値 was 9. 6Ω/□, full light penetration -33- 201246277 The pass rate is 82. 4%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 6 %, the sheet resistance becomes 4. 8Ω/□, the total light transmittance is 56. 5%, the haze rate becomes 22. At 6%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Examples 15 to 16) Comparative Examples 15 to 16 The transparent conductive film produced on the glass substrate in the same manner as in Example 17 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained. 〇Pa, and the temperature of the light-transmitting glass substrate on which the surface electrode was formed, Comparative Example 15 was heated to 350 ° C, and Comparative Example 16 was heated to 600 ° C to perform heat treatment. In Comparative Example 15, after film formation, the sheet resistance 値 was 9. 4Ω/□, the total light transmittance is 83.7%, and the haze ratio is 14. After heat treatment in a hydrogen atmosphere of 7%, the sheet resistance becomes 10. 1 Ω / □, the total light transmittance is 83. 8%, the haze rate becomes M. 7%, sheet resistance and haze rate did not improve. In Comparative Example 16, after film formation, the sheet resistance 値 was 9. 7Ω/□, the total light transmittance is 83. 4%, haze rate is 14. After 8 % of the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4. 3Ω/□, the total light transmittance is 56. 9%, the haze rate became 24. At 4%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Examples 17 to 18) Comparative Example 1 7 to 18 The transparent conductive film produced on the glass substrate in the same manner as in Example 17 was allowed to flow in a flow rate of 2 L per minute -34 - 201246277. The pressure in the atmosphere furnace was maintained at 100 Pa, and the temperature of the translucent glass substrate on which the surface electrode was formed was heated to 3 5 (TC in Comparative Example 1 and heated to 600 ° C in Comparative Example 18). Heat treatment. Comparative Example 17 was followed by film formation, and the sheet resistance was 9. 3 Ω / □ 'total light transmission rate of 83. 2%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 7%, the sheet resistance becomes !! Hey. 3〇/匚|, the total light transmittance is 83. 4%, the haze rate becomes 15. 2%, sheet resistance and haze rate did not improve. In Comparative Example 18, after film formation, the sheet resistance 値 was 9. 8 Ω / □, the total light transmittance is 83. 7%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 7%, the sheet resistance becomes 3. 9Ω/□, the total light transmittance is 56. 9% 'haze rate became 26. At 4%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Examples 19 to 20) Comparative Example 1 9 to 20 The transparent conductive film produced on the glass substrate in the same manner as in Example 17 was allowed to flow in a hydrogen gas at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained. Hey. 〇lPa' and the temperature of the light-transmitting glass substrate on which the surface electrode was formed were heated to 400 °C by the comparative example 197, and the heat treatment was performed by heating to 550 °C. In Comparative Example 19, film formation was followed by a sheet resistance of 9. 3 Ω / □, the total light transmittance is 82. 4%, haze rate is M. After heat treatment in a hydrogen atmosphere of 7%, the sheet resistance became 13. 9Ω/□, the total light transmittance is 83. 0%, the haze rate becomes 1 3. 4%, sheet resistance and haze rate did not improve. In Comparative Example 20, after film formation, the sheet resistance 値 was 9. 3 Ω / 匚 |, full light penetration -35- 201246277 The pass rate is 82. 7%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 7%, the sheet resistance became 11. 8Ω/|□, the total light transmittance is 83. 0%, the haze rate becomes 15. 4%, sheet resistance and haze rate did not improve. The results of Examples 17 to 24 and Comparative Examples 1 to 20 are shown in Table 2 below. [Table 2] Film composition film thickness (nm) Hydrogen gas pressure (Pa) after film formation Heat treatment temperature (°C) Improvement after heat treatment heat treatment surface resistance (0/□) Total light transmittance (%) Haze ( W Surface resistance (Ω/Π) Total light transmittance (%) Haze (3⁄4) Surface resistance before/after total light transmittance Surface haze wm K Example 17 GAZO/ITtO/Glass 1250 9. 7 83. 9 14. 8 0. 1 400 6. 9 83. 2 18. 9 1. 41 0. 99 1. 28 0 Example 18 GAZO/ITiO/Glass 1250 9. 5 83. 4 14. 6 0. 1 550 6. 1 82. 5 20. twenty one. 55 0. 99 1. 38 苡Example 19 GAZO/ITiO/Glass 1250 9. 9 83. 6 14. 6 1 400 6. 1 82. 6 19. twenty one. 62 0. 99 1,32 Trade Example 20 GAZO/ITiO/Glass 1250 9. 5 83. 0 14. 6 1 550 5. 1 81. 6 22. twenty one. 87 0. 98 1. 52 Example 21 GAZO/ITiO/Glass 1250 9. 6 82. 8 14. 8 10 400 5. 4 81. 5 21. 3 1. 78 0. 98 1. 44 Example 22 GAZO/ITiO/Glass 1250 9. 5 83. 6 14. 9 10 550 4. 9 82. 0 24. 7 1. 95 0. 98 1. 66 Example 23 GAZO/ITiO/Glass 1250 10. 0 83. 9 14. 7 100 400 4. 8 82. 1 23. 0 206 0. 98 1. 56 Example 24 GAZO/ITiO/Glass 1250 9. 4 83. 8 14. 9 100 550 4. 1 81. 7 26. 8 2. 28 0. 98 1. 79 Comparative Example 11 GAZO/ITiO/Glass 1250 10. 0 83. 9 14. 6 0. 1 350 1Z1 84. 2 15. 4 0. 82 1. 00 1. 05 Comparative Example 12 GAZO/ITiO/Glass 1250 9. 4 83. 2 14. 9 0. 1 600 5. 3 57. 4 20. 9 1. 77 0. 69 1. 40 Comparative Example 13 GAZO/ITiO/Glass 1250 9. 5 83. 3 14. 9 1 350 9. 9 83. 4 15. 3 0. 96 1. 00 1. 02 Comparative Example 14 GAZO/ITiO/Glass 1250 9. 6 82. 4 14. 6 1 600 4. 8 56. 5 22. 6 zoo 0. 69 1. 54 Comparative Example 15 GAZO/ITiO/Glass 1250 9. 4 83. 7 14. 7 10 350 10. 1 83. 8 14. 7 0. 93 1. 00 1. 00 Comparative Example 16 GAZO/ITiO/Glass 1250 9. 7 83. 4 14. 8 10 600 4. 3 56. 9 24. 4 2. 25 0. 68 1. 66 Comparative Example 17 GAZO/ITiO/Glass 1250 9. 3 83. 2 14. 7 100 350 10. 3 83. 4 15. 2 0. 91 1. 00 1. 03 Comparative Example 18 GAZO/m〇/Glass 1250 9. 8 83. 7 14. 7 100 600 3. 9 56. 9 26. 4 Z52 0. 68 1. 79 Comparative Example 19 GAZO/ITiO/Glass 1250 9. 3 82. 4 14. 7 0. 01 400 13. 9 83. 0 13. 4 0. 67 1. 01 0. 91 Comparative Example 20 GAZO/ITiO/Glass 1250 9. 3 82. 7 14. 7 0. 01 550 11. 8 83. 0 15. 4 0. 79 1. 00 1. 05 (Example 2 5) Example 25 is the formation of the surface electrode 2 of the underlying film 2 1 using indium oxide containing gallium oxide 3. 4% by mass, tin oxide 10% by mass of I T G ruthenium film, the uneven film 22 is doped with zinc oxide 0. 58% by mass, alumina 0. 32% by mass of GAZO film. The temperature of the sodium carbonate-lime-alumina glass substrate was set to 25 ° C, and the introduction gas was a mixed gas of argon and oxygen (argon: oxygen = 99:1), and an ITGO film having a film thickness of 150 nm was formed by sputtering. . Next, the temperature of the sodium carbonate--36-201246277 lime-alumina glass substrate is set to 300 t, the sputtering power is DC 400 W, the introduction gas is argon gas 1%, the gas pressure is adjusted to 7 Pa, and the total film thickness is 1 1 50 nm GAZO film. The heat treatment in the hydrogen gas reduction environment flows hydrogen gas at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace is maintained at 0. 1 Pa, and the temperature of the light-transmissive glass substrate on which the surface electrode was formed was heated to 400 ° C for treatment. 〇 The film resistance 成 after film formation was ίο. 0Ω/□, the total light transmittance is 82. 5%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 6 %, the sheet resistance became 6. 4Ω/□, the total light transmittance is 81. 6%, the haze rate is 18. 2%, improved sheet resistance and haze ratio. (Example 26) Example 26 is a transparent conductive film produced on a glass substrate in the same manner as in Example 25, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at O. The temperature of the light-transmitting glass substrate on which the surface electrode was formed was heated to 550 ° C, and heat treatment was performed. As a result, the sheet resistance 成 of the film formation was 9. 4Ω/□, total light transmittance is 83. 9%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 7%, the sheet resistance became 5. 4Ω/□, the total light transmittance is 82. 7%, the haze rate becomes 2 1 . 1%, improved the film's resistance and haze rate. The total light transmittance was hardly changed (Examples 27 to 28) -37-201246277 Examples 27 to 28 are transparent conductive films produced on a glass substrate in the same manner as in Example 25, so that hydrogen gas was 2 L per minute. The flow rate was inflow, the pressure in the atmosphere furnace was maintained at IPa, and the temperature of the translucent glass substrate on which the surface electrode was formed was heated to 400 ° C in Example 27, and heated to 550 ° C in Example 28, and heat treatment was performed. . Example 27, after film formation, the sheet resistance 値 was 9. 9Ω/□, the total light transmittance is 82. 4%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 6. 0Ω/□, the total light transmittance is 81. 4%, the haze rate becomes 20. 5%, improved sheet resistance and haze ratio. Example 28, after film formation, the sheet resistance 値 was 9. 4Ω/□, the total light transmittance is 83. 7%, the haze ratio is M. After heat treatment in a hydrogen atmosphere of 5%, the sheet resistance 値 becomes 4. 8Ω/□, the total light transmittance is 82. 1%, the haze rate becomes 23. 0%, improved sheet resistance and haze ratio. (Examples 29 to 30) In the examples 29 to 30, the transparent conductive film produced on the glass substrate in the same manner as in Example 25 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 10 Torr. Pa, and the temperature of the light-transmitting glass substrate on which the surface electrode was formed was heated to 40 ° C in Example 29, and the lanthanide was heated to 550 ° C in Example 3, and heat-treated. In Example 29, after film formation, the sheet resistance 値 was 9·8 Ω/匚|, and the total light transmittance was 82. 6%, the haze rate is 14. After 5% of the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5. 3Ω/□, the total light transmittance is 81. 2%, the haze rate becomes 2 1 .  8 %, improved sheet resistance and haze ratio. -38- 201246277 Example 30, after film formation, the sheet resistance 値 was 9. 7 Ω / □, the total light transmittance is 82. 7%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 8 %, the sheet resistance becomes 4. 3Ω/ΙΙΙ, the total light transmittance is 80. 6%, the haze rate became 25. 6%, improved sheet resistance and haze ratio. (Examples 3 to 32) Examples 31 to 32 are transparent conductive films produced on a glass substrate in the same manner as in Example 25, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 100 Torr. a, and the temperature of the translucent glass substrate on which the surface electrode is formed, Example 31 is heated to 40 (TC, and Example 32 is heated to 550 ° C, and heat treatment is performed. Example 31 is formed after film formation, The resistance 値 is 9. 4Ω/□, the total light transmittance is 82. 6%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 7%, the sheet resistance 値 became 4. 9Ω/□, the total light transmittance is 81. 1%, the haze rate becomes 23. 9%, improved sheet resistance and haze ratio. In Example 32, after film formation, the sheet resistance was 9. 3 Ω / □, the total light transmittance is 82. 7%, the haze ratio of 8% after heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4. 1 Ω / □, the total light transmittance is 80. 6%, the haze rate became 27. 6%, improved sheet resistance and haze ratio. (Comparative Examples 21 to 22) Comparative Examples 21 to 22 are the transparent conductive films produced on the glass substrate in the same manner as in Example 25, and the pressure of the hydrogen gas flowing into the atmosphere furnace at a flow rate of 2 L per minute was maintained. lPa, the temperature of the translucent glass substrate 1 having the surface electrode 2 - 39 - 201246277 was formed, Comparative Example 21 was heated to 350 ° C, and Comparative Example 22 was heated to 600 ° C, and heat treatment was performed. In Comparative Example 21, after film formation, the sheet resistance 値 was 9. 6Ω/□, the total light transmittance is 83. 8%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 11.1. 9Ω/□, the total light transmittance is 84. 2%, the haze rate becomes 15. 5%, sheet resistance and haze rate did not improve. In Comparative Example 22, after film formation, the sheet resistance 値 was 9. 7Ω/□, the total light transmittance is 82.7%, and the haze ratio is Η. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 5. 1 Ω / □, the total light transmittance is 56. 9%, the haze rate became 20. 5%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Examples 23 to 24) In Comparative Examples 23 to 24, the transparent conductive film produced on the glass substrate in the same manner as in Example 25 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was kept at IPa. The temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 550 ° C in Comparative Example 23, and heated to 600 ° C in Comparative Example 24, and heat treatment was performed. In Comparative Example 23, after film formation, the sheet resistance 値 was 9. 9Ω/□, the total light transmittance is 84. 0%, haze rate is 14. After 7% of the heat treatment in a hydrogen atmosphere, the sheet resistance became 10. 6Ω/□, the total light transmittance is 84. 1%, the haze rate becomes 15. 6%, sheet resistance and haze rate did not improve. In Comparative Example 24, after film formation, the sheet resistance 値 was 9. 6 Ω / □, the total light transmittance is 82. 7%, the haze rate is 14. After 7% of the heat treatment in a hydrogen atmosphere -40-201246277, the sheet resistance becomes 4. 6Ω/□, the total light transmittance is 56. 6%, the haze rate becomes 2 2. At 3 %, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes opaque. (Comparative Examples 25 to 26) Comparative Examples 25 to 26 are the transparent conductive films produced on the glass substrate in the same manner as in Example 25, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 10 Pa. The temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 550 ° C in Comparative Example 2, and heated to 60 (TC in Comparative Example 26, and heat treatment was performed. Comparative Example 25 was formed after film formation. , the sheet resistance 値 is 9. 4Ω/□, the total light transmittance is 83. 3%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 10. 4Ω/□, the total light transmittance is 83. 5%, the haze rate became 16. 2%, sheet resistance and haze rate did not improve. In Comparative Example 26, after film formation, the sheet resistance 値 was 10. 0Ω/□, all-light transmittance is 82. 6%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 4. 1 Ω / □, the total light transmittance is 56. 2%, the haze rate becomes 24. At 8%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Examples 27 to 28) Comparative Examples 27 to 28 are the transparent conductive films produced on the glass substrate in the same manner as in Example 25, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 10 Torr. 〇Pa, the temperature of the translucent glass substrate 1 on which the surface electrodes 2 -41 - 201246277 were formed, Comparative Example 27 was heated to 3 50 ° C, and Comparative Example 28 was heated to 60 (TC, heat treatment was performed. Comparative Example 27 After film formation, the sheet resistance 値 was 9. 4Ω/□, the total light transmittance is 82. 6%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 6%, the sheet resistance becomes 10. 4Ω/□, the total light transmittance is 82. 8%, the haze rate became 14. 3%, sheet resistance and haze rate did not improve. In Comparative Example 28, after film formation, the sheet resistance 値 was 9. 9Ω/□, the total light transmittance is 82. 6%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 8%, the sheet resistance became 3. 7Ω/□, the total light transmittance is 55. 9%, the haze rate became 26. At 6%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Example 2 9 to 3 0 ) Comparative Examples 29 to 30 are the transparent conductive films produced on the glass substrate in the same manner as in Example 25, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained. O. The temperature of the translucent glass substrate on which the surface electrode was formed was OlPa, and Comparative Example 29 was heated to 400. (: Comparative Example 30 was heated to 550 ° C and heat-treated. Comparative Example 29, after film formation, sheet resistance 9 was 9. 5 Ω / □, the total light transmittance is 83. 3%, the haze rate is 14. After 5% of the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 13. 8Ω/□, the total light transmittance is 83. 8%, the haze rate became 13. 2%, sheet resistance and haze rate did not improve. In Comparative Example 30, after film formation, the sheet resistance 値 was 9. 4Ω/□, the total light transmittance is 82. 8%, the haze ratio is I4. After 6% of the heat treatment in a hydrogen atmosphere -42 - 201246277, the sheet resistance 値 became 11. 7Ω/□, the total light transmittance is 83. 1%, the haze rate becomes 15. 2%, sheet resistance and haze rate did not improve. The results of Examples 25 to 32 and Comparative Examples 21 to 30 are shown in Table 3 below. [Table 3] Film composition film thickness (nm) Gas pressure after film formation (Pa) Heat treatment temperature (°C) Improvement after heat treatment heat treatment surface resistance (Ω/Π) Total light transmittance (W haze (%) Surface resistance (Ω/D) Total light transmittance (%) Haze (W Surface resistance before/after total light transmittance Wm) Fine haze Example 25 GAZO/ITGO/Glass 1150 10. 0 82. 5 14. 6 0. 1 400 6. 4 81. 6 18. twenty one. 56 0. 99 1. 25 Example 26 GAZO/ITGO/Glass 1150 9. 4 83. 9 14. 7 0. 1 550 5. 4 82. 7 21. 1 1. 73 0. 99 1. 44 Example 27 GAZO/ITGO/Glass 1150 9. 9 82. 4 14. 9 1 400 6. 0 81. 4 20. 5 1. 65 0. 99 1. 38 Example 28 GAZO/ITGO/Glass 1150 9. 4 83. 7 14. 5 1 550 4. 8 82. 1 23. 0 1. 96 0. 98 1. 58 Example 29 GAZO/ITGO/Glass 1150 9. 8; 82. 6 14. 5 \0 400 6. 3 81. 2 21. 8 1. 35 0. 93 1. 50 Example 30 GAZO/ITGO/Glass 1150 9. 7 82. 7 14. 8 10 550 4. 3 80. 6 25. 6 Z27 0. 98 1. 73 Example 31 GAZO/ITGO/Glass 1150 9. 4 82. 6 14. 7 100 400 4. 9 81. 1 23. 9 1. 93 0. 98 1. 63 Example 32 GAZO/ITGO/Glass 1150 9. 3 817 14. 8 100 550 4. 1 80. 6 27. 6 227 0. 98 1. 87 Comparative Example 21 GAZO/ITGO/Glass 1150 9. 6 83. 8 14. 9 0. 1 350 11. 9 84. 2 15. 5 0. 81 1. 00 1. 04 Comparative Example 22 GAZO/ITGO/Glass 1150 9. 7 82. 7 14. 9 0. 1 600 5. 1 56. 9 20. 5 1. 89 0. 69 1. 38 Comparative Example 23 GAZO/ITGO/Glass 1150 9. 9 84. 0 14. 7 1 350 10. 6 34. 1 15. 6 0. 93 1. 00 1. 06 Comparative Example 24 GAZO/ITGO/Glass 1150 9. (ί 82. 7 14. 7 1 600 4. 6 56. 6 22. 3 2. 08 0. 69 1. 52 Comparative Example 25 GAZO/ITGO/Glass 1150 9Α 83. 3 14. 9 10 350 10. 4 83. 5 16. 2 0. 90 1. 00 1. 08 Comparative Example 26 GAZO/ITGO/Glass mo 10. 0 82. 6 14. 9 10 600 4. 1 56. 2 24. 8 2. 41 0. 68 1. 66 Comparative Example 27 GAZO/ITGO/Glass 1150 9. 4 82. 6 14. 6 100 350 10. 4 82. 8 14. 3 α9〇 1. 00 0. 98 Comparative Example 28 GAZO/ITGO/Glass 1150 Θ. 9 82. 6 14. 8 100 600 3. 7 55. 9 26. 6 270 0. 68 1. 79 Comparative Example 29 GAZO/ITGO/Glass 1150 9. ;i 83. 3 14. 5 0. 01 400 13. 8 83. 8 13. 2 0. 69 1. 01 0. 91 Comparative Example 30 GAZO/ITGO/Glass 1150 BA 82. 8 14. 6 0. 01 550 11. 7 83. 1 15. 2 αβο 1. 00 1. 05 (Example 3 3) Example 33 is shown in Fig. 2B. In the surface electrode 2, the underlayer film 21 is not used, and the uneven film 22 is doped with zinc oxide in the zinc oxide. 0% by mass of AZO film. The film formation system uses a magnetron sputtering technique, and the target system is φ 6 吋 in size, and the distance between the substrate and the target is 60 m. The temperature of the sodium carbonate-lime-alumina glass substrate is set to 300 °C, the sputtering-43-201246277 plating power DC400W, the introduction gas is argon gas 100%, the gas pressure is adjusted to 7Pa, and the AZO film having a total film thickness of 2400 nm is formed. . The heat treatment in the hydrogen gas reduction environment causes the hydrogen gas to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace is maintained at O. lPa, and the temperature of the light-transmitting glass substrate 1 on which the surface electrode 2 was formed was heated to 400 ° C for processing. As a result, the subsequent sheet resistance of the film formation was 10. 0Ω/□, total light transmittance is 81. 3% 'haze rate is 14. After 9% of the heat treatment in the gas atmosphere, the sheet resistance became 7. 2 Ω / □, the total light transmittance is 80. 7%, the haze rate is 18. 6%, improved sheet resistance and haze ratio. (Example 3 4) Example 3 4 The transparent conductive film produced on the glass substrate in the same manner as in Example 3 3 was allowed to flow into the atmosphere of the atmosphere furnace at a flow rate of 2 L per minute. The heat treatment was carried out by heating the temperature of the light-transmitting glass substrate on which the surface electrode was formed to 550 °C. As a result, the sheet resistance 成 of the film formation was 9. 3Ω/□, the total light transmittance is 80. 8%, the haze ratio is M. After heat treatment in a hydrogen atmosphere of 5 %, the sheet resistance became 6. 3 Ω / □, the total light transmittance is 800%, and the haze ratio is 19. 2%, improved sheet resistance and haze ratio. The total light transmission rate has not changed. (Example 3 5 to 3 6 ) Example 3 5 to 3 6 The transparent conductive film 'made on the glass substrate in the same procedure as in Example 3 3 was made to flow hydrogen gas at a flow rate of 2 L per minute - 44 - 201246277 The pressure in the atmosphere furnace was maintained at IPa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated, and Example 35 was heated to 400, and Example 36 was heated to 5 5 (TC) for heat treatment. Example 35, after film formation, the sheet resistance 値 was 9. 3 Ω / □, the total light transmittance is 80. 5%, haze rate is I4. After heat treatment in a hydrogen atmosphere of 6%, the sheet resistance became 6. 9Ω/□, the total light transmittance is 79. 9%, the haze rate became 18. 4%, improved sheet resistance and haze ratio. Example 36, after film formation, the sheet resistance 値 was 9. 8Ω/□, the total light transmittance is 79. 9%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 5. 3 Ω / □, the total light transmittance is 78. 6%, the haze rate becomes 2 1 .  8 %, improved sheet resistance and haze ratio. (Examples 37 to 38) In Examples 37 to 38, the transparent conductive film produced on the glass substrate in the same manner as in Example 33 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 10 Torr. Pa, the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 400 ° C in Example 37, and heated to 550 ° C in Example 38, and heat treatment was performed. Example 37, after film formation, the sheet resistance 値 was 9. 4Ω/ΙΙΙ, the total light transmittance is 80. 2%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 7%, the sheet resistance becomes 5. 9Ω/□, the total light transmittance is 79. 3%, the haze rate became 20. 3%, improved sheet resistance and haze ratio. In Example 38, after film formation, the sheet resistance was 9. 5 Ω / □, the total light transmittance is 81. 1%, haze rate is 14. After 6% of the heat treatment in a hydrogen atmosphere -45-201246277 ‘the sheet resistance 値 becomes 5. 0Ω/□, the total light transmittance is 79. 6%, the haze rate is 2 3 .  1%, improved sheet resistance and haze ratio. (Examples 39 to 40) Examples 39 to 40 are transparent conductive films produced on a glass substrate in the same manner as in Example 33, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 1 OOP. a, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed, Example 39 was heated to 400 ° C, and Example 40 was heated to 550 ° C, and heat treatment was performed. Example 39, after film formation, the sheet resistance 値 was 9. 6Ω/□, the total light transmittance is 81. 3%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 5. 4Ω/□, the total light transmittance is 80. 1%, the haze rate becomes 22. 3%, improved sheet resistance and haze ratio. After the film formation of Example 40, the sheet resistance was 9. 8Ω/□, the total light transmittance is 81. 2%, haze rate is M. After heat treatment in a hydrogen atmosphere of 7%, the sheet resistance 値 became 4. 4 Ω / port, the total light transmittance is 79. 2%, the haze rate becomes 25. 3%, improved sheet resistance and haze ratio. (Comparative Example 3 1 to 3 2 ) Comparative Example 3 1 to 3 2 The transparent conductive film produced on the glass substrate in the same manner as in Example 3 3 was allowed to flow in a flow rate of 2 L per minute in an atmosphere furnace. The pressure remains O. lPa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed, Comparative Example 31 was heated to 350 ° C, and Comparative Example 32 was heated to 600 ° C to carry out heat treatment. -46- 201246277 Comparative Example 31 was formed into a film followed by a sheet resistance of 9. 6Ω/ΙΙΙ, the total light transmittance is 81. 3%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 11.1. 3Ω/□, the total light transmittance is 81. 6%, the haze rate became 15. 5%, sheet resistance and haze rate did not improve. Comparative Example 32 was filmed and then had a sheet resistance of 9. 7Ω/□, the total light transmittance is 80. 3%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 5. 3Ω/□, the total light transmittance is 55. 3%, the haze rate became 20. 5%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Example 3 3 to 3 4 ) Comparative Examples 33 to 34 are the transparent conductive films produced on the glass substrate in the same manner as in Example 33, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained. In IPa, the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated, Comparative Example 33 was heated to 3 50 ° C, and Comparative Example 34 was heated to 600 ° C to perform heat treatment. In Comparative Example 33, after film formation, the sheet resistance 値 was 9. 9Ω/□, the total light transmittance is 81. 4%, haze rate is I4. After 7% of the heat treatment in a hydrogen atmosphere, the sheet resistance became 10. 6Ω/□, the total light transmittance is 81. 5%, the haze rate became 15. 7%, sheet resistance and haze rate did not improve. In Comparative Example 34, after film formation, the sheet resistance 値 was 9. 6 Ω / 匚], the total light transmittance is 80. 2%, haze rate Μ. After 7% of the heat treatment in a hydrogen atmosphere, the sheet resistance 4 became 4. 5Ω/□, the total light transmittance is 54. 9%, the haze rate became 22. At 3%, although the sheet resistance and haze ratio are improved, the transmittance is extremely low at -47 to 201246277 degrees, and becomes non-transparent. (Comparative Examples 35 to 36) In Comparative Examples 35 to 36, the transparent conductive film produced on the glass substrate in the same manner as in Example 33 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 10 Torr. Pa, the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 550 ° C in Comparative Example 35, and heated to 600 ° C in Comparative Example 36, and heat treatment was performed. In Comparative Example 35, after film formation, the sheet resistance 値 was 9. 4Ω/□, the total light transmittance is 80. 8%, haze rate is M. After heat treatment in a hydrogen atmosphere of 9%, the sheet resistance became 10. 4Ω/□, the total light transmittance is 81. 0%, the haze rate became 16. 2%, sheet resistance and haze rate did not improve. In Comparative Example 36, after film formation, the sheet resistance 値 was 10. 0Ω/□, all-light transmittance is 80. 1%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 9 %, the sheet resistance became 4. 3 Ω / □, the total light transmittance is 54. 6%, the haze rate became 24. At 8%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Examples 37 to 38) Comparative Example 3 7 to 3 8 The transparent conductive film produced on the glass substrate in the same manner as in Example 3 3 was allowed to flow in a flow rate of 2 L per minute in an atmosphere furnace. The pressure was maintained at 100 Pa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 550 ° C in Comparative Example 37, and heated to 600 ° C in Comparative Example 38, and heat treatment was performed. -48- 201246277 Comparative Example 37, after film formation, the sheet resistance 値 was 9. 4Ω/□, the total light transmittance is 80. 2%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 6%, the sheet resistance becomes 10. 4Ω/□' total light transmittance is 80. 3%, the haze rate became 14. 3%, sheet resistance and haze rate did not improve. In Comparative Example 38, after film formation, the sheet resistance 値 was 9. 9Ω/□, the total light transmittance is 80. 1%, haze rate is 14. After heat treatment in a hydrogen atmosphere of 8%, the sheet resistance became 3. 8Ω/□, the total light transmittance is 54. 3%, the haze rate became 26. At 6%, although the sheet resistance and haze ratio are improved, the transmittance is extremely lowered and becomes non-transparent. (Comparative Examples 39 to 40) Comparative Example 3 9 to 40 The transparent conductive film produced on the glass substrate in the same manner as in Example 3 3 was allowed to flow in a hydrogen gas at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained. O. OlPa, the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed, Comparative Example 39 was heated to 400 ° C, and Comparative Example 40 was heated to 55 (TC, heat treatment was performed. Comparative Example 39 was formed after film formation. The resistance 値 is 9. 5 Ω / □, the total light transmittance is 80. 8%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 5%, the sheet resistance 13 became 13. 2Ω/□, the total light transmittance is 81. 2%, the haze rate becomes 1 3. 2%, sheet resistance and haze rate did not improve. In Comparative Example 40, after film formation, the sheet resistance 値 was 9. 4Ω/□, the total light transmittance is 80. 3%, the haze rate is 14. After heat treatment in a hydrogen atmosphere of 6%, the sheet resistance 値 becomes 1 Κ 2 Ω / □, and the total light transmittance becomes 80. 5%, the haze rate became 15. 2%, sheet resistance and haze rate did not improve. -49-201246277 Example 3 3 to 40 and Comparative Example 3 The results of 1 to 4 are shown in Table 4 below. [Table 4] Film composition film thickness (nm) Hydrogen gas pressure (Pa) after film formation Heat treatment temperature CO Improvement after heat treatment heat treatment Surface resistance (Ω/port) Total light transmittance (3⁄4) Haze (%) Surface Resistance (Ω/α) Total light transmittance (W haze (») Surface resistance before/after total light transmittance after haze spread S Example 33 A20/G!ass 2400 10. 0 81. 3 14. 9 0. 1 400 7. 2 80. 7 18. 6 1. 39 0. 99 1. 25 0 Shi _ AZO/Glass 2400 9. 3 80. 8 14. 6 0,1 550 6. 3 80. 0 19. twenty one. 48 0. 99 1. 32 Example 35 A20/Glass 2400 9. 3 80. 5 14. 6 1 400 6. 9 79. 9 18. 4 1. 36 0. 99 1. 27 0Example 36 AZO/Glass 2400 9. 8 79. 9 14. 9 1 550 5. 3 78. 6 21. 8 1. 34 0. 98 1. 46 37例37 AZO/Glass 2400 9. 4 80. 2 14. 7 10 400 5. 9 79. 3 20. 3 1. 59 0. 99 1. 38 Example 38 AZO/Glass 2400 9. 5 81. 1 14. 6 10 550 5. 0 79. 6 23. 1 1. 89 0. 98 1. 59 59 Shi _ AZO/Glass 2400 9. 6 81. 3 14,9 100 400 5. 4 80. 1 2Ζ3 1. 79 0. 98 1. 50 S Example 40 AZO/Glass 2400 9. 8 81. 2 14. 7 100 550 4. 4 79. 2 25. 3 2. 24 0. 98 1. 72 Compare "31 AZO/Glass 2400 9. 6 81. 3 14. 9 0. 1 350 11. 3 81. 6 15. 5 0. 85 1. 00 1. 04 Comparative Example 32 AZO/Glass 2400 9. 7 80. 3 14. 9 0. 1 600 5. 3 55. 3 20. 5 1. 82 0. 69 1. 38 comparison_ AZO/Glass 2400 9. 9 81. 4 14. 7 1 350 10. 6 81. 5 15. 7 0. 93 1. 00 1. 07 Comparative Example 34 AZO/Glass 2400 9. 6 80. 2 14. 7 1 600 4. 5 58, 22. 3 Ζ14 0. 68 1. 52 Comparative Example 35 AZO/Glass 2400 9. 4 80. 8 14. 9 10 350 10. 4 81. 0 16. 2 0. 90 1. 00 1. 08 Comparative Example 36 AZO/Glass 2400 10. 0 80. 1 14. 9 10 600 4. 3 54. 6 24. 8 Ζ33 0. 68 1. 66 Comparative Example 37 AZO/Glass 2400 9. 4 80. 2 14. 6 100 350 10. 4 80. 3 14. 3 0. 90 1. 00 0. 98 Comparative Example 38 AZO/Glass 2400 9. 9 80. 1 14. 8 100 600 3. 8 54. 3 26. 6 Ζ 64 0. 68 1. 79 Comparative Example 39 AZO/Glass 2400 9. 5 80. 8 14. 5 0. 01 400 13. 2 81. 2 13. 2 0. 72 1. 01 0. 91 Comparative Example 40 AZO/Glass 2400 9. 4 80. 3 14. 6 0. 01 550 11. 2 80. 5 15. 2 0. 84 1. 00 1. 05 (Example 4 1) In Example 41, the underlayer film 21 was not used, and the uneven film 22 was a GAZO film doped with gallium oxide at 0. 58 % by mass and 0. 32 % by mass of alumina. The film formation system uses D C magnetron sputtering, and the target system used is Φ 6 吋 in size, and the distance between the substrate and the target is 60 mm. The temperature of the sodium carbonate-lime-alumina glass substrate was set to 300 ° C, the sputtering power was DC 400 W, the introduction gas was 100% argon gas, and the gas pressure was adjusted to 7 Pa to form a GAZO film having a total film thickness of 2100 nm.

氫氣體還原環境中之熱處理係使氫氣體以每分鐘2L 的流量流入，氣氛爐內之壓力保持〇 . 1 P a，且將形成有表 -50- 201246277 面電極之透光性玻璃基板的溫度加熱至4〇〇°C ’進行處理 〇 結果成膜隨後的片電阻値爲9.9Ω/□、全光透過率爲 81.3%、霧度率爲14.6 %者在氫氣氛中之熱處理後’片電 阻値成爲7.9Ω/□、全光透過率成爲80.9%、霧度率成爲 1 8.4 %，改善了片電阻與霧度率。 (實施例42 ) 實施例42係對於與實施例4 1同樣步驟在玻璃基板上 所製作的透明導電膜使氫氣體以每分鐘2L的流量流入 ，氣氛爐內之壓力保持〇.1 Pa，將形成有表面電極2之透 光性玻璃基板1的溫度加熱至5 50 °C，進行熱處理。 結果成膜隨後的片電阻値爲9.9Ω/□、全光透過率爲 80.5%、霧度率爲14.8 %者在氫氣氛中之熱處理後，片電 阻値成爲6.2Ω/□、金光透過率成爲79.6%、霧度率成爲 19.6%，改善了片電阻與霧度率。全光透過率幾乎未變化 (實施例43〜44 ) 實施例43〜44係對於與實施例41同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持IPa’將形成有表面電極2之 透光性玻璃基板1的溫度，實施例43係加熱至400 °C ,實 施例44係加熱至5 50°C，進行熱處理。 -51 - 201246277 實施例43在成膜隨後’片電阻値爲9.5 Ω/□、全光透 過率爲80.4%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲6.8Ω/1ΙΙ、全光透過率成爲79.8%、霧度 率成爲18.8%，改善了片電阻與霧度率。 實施例44在成膜隨後，片電阻値爲9.9Ω/C]、全光透 過率爲80.1%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲5.7Ω/□、全光透過率成爲78.9%、霧度 率成爲21.4%，改善了片電阻與霧度率。 (實施例45〜46) 實施例45〜46係對於與實施例41同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持l〇Pa，將形成有表面電極2之 透光性玻璃基板1的溫度，實施例45係加熱至400°C，實 施例46係加熱至5 50°C，進行熱處理。 實施例45在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲81.4%、霧度率爲14.8 %者在氫氣氛中之熱處理後 ，片電阻値成爲5.7Ω/□、全光透過率成爲80.3%、霧度 率成爲20.4%，改善了片電阻與霧度率。 實施例46在成膜隨後，片電阻値爲9.7Ω/□、全光透 過率爲80.4%、霧度率爲14.7 %者在氫氣氛中之熱處理後 ，片電阻値成爲4.8 Ω/□、全光透過率成爲78.8 %、霧度 率成爲2 3 . 3 %，改善了片電阻與霧度率。 -52- 201246277 (實施例47〜48 ) 實施例47〜48係對於與實施例41同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持100pa，將形成有表面電極2 之透光性玻璃基板1的溫度’實施例47係加熱至400°C ’ 實施例4 8係加熱至5 5 0 °C，進行熱處理。 實施例47在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲80.1%、霧度率爲I4.9%者在氫氣氛中之熱處理後 ，片電阻値成爲5.2Ω/□、全光透過率成爲78·7%、霧度 率成爲22.3%，改善了片電阻與霧度率。 實施例48在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲81.2%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲4.4Ω/□、全光透過率成爲79.3%、霧度 率成爲25.0%，改善了片電阻與霧度率。 (比較例41〜42 ) 比較例41~42係對於與實施例41同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持O.lPa，將形成有表面電極2 之透光性玻璃基板1的溫度，比較例41係加熱至3 50°C， 比較例42係加熱至6 00 °C，進行熱處理。 比較例41在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲81.3%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲12·3Ω/□、全光透過率成爲81.7%、霧度 -53- 201246277 率成爲15.5%，片電阻與霧度率未見改善。 比較例42在成膜隨後，片電阻値爲9.7Ω/□、全光透 過率爲80.3%、霧度率爲14_9 %者在氫氣氛中之熱處理後 ，片電阻値成爲5.1Ω/□、全光透過率成爲55.2%、霧度 率成爲20.5%，片電阻與霧度率雖有改善，但是透過率極 度降低，且變成非透明。 (比較例43~44) 比較例43~44係對於與實施例41同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持IPa，將形成有表面電極2之 透光性玻璃基板1的溫度，比較例43係加熱至3 50°C，比 較例44係加熱至600 °C，進行熱處理。 比較例43在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲81·4%、霧度率爲Μ.7%者在氫氣氛中之熱處理後 ’片電阻値成爲10.6Ω/□、全光透過率成爲81.5%、霧度 率成爲15.8%，片電阻與霧度率未見改善。 比較例44在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲80.2%、霧度率爲14.7%者在氫氣氛中之熱處理後 ’片電阻値成爲4.8Ω/□、全光透過率成爲55.0%、霧度 率成爲22.3%’片電阻與霧度率雖有改善，但是透過率極 度降低’且變成非透明。 (比較例4 5〜4 6 ) -54- 201246277 比較例4 5 ~4 6係對於與實施例4 1同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入’氣氛爐內之壓力保持10Pa，將形成有表面電極2之 透光性玻璃基板1的溫度，比較例45係加熱至3 5 0。<3，比 較例46係加熱至600 °C，進行熱處理。 比較例45在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲80·8%、霧度率爲I4.9%者在氫氣氛中之熱處理後 ，片電阻値成爲1 0.4Ω/□、全光透過率成爲8 1.0%、霧度 率成爲1 6 · 2 %，片電阻與霧度率未見改善。 比較例46在成膜隨後，片電阻値爲10.0Ω/□、全光 透過率爲80.1%、霧度率爲I4.9%者在氫氣氛中之熱處理 後，片電阻値成爲4.1 Ω/□、全光透過率成爲54.5%、霧 度率成爲24.8%，片電阻與霧度率雖有改善，但是透過率 極度降低，且膜變成非透明。 (比較例47〜48 ) 比較例47〜48係對於與實施例41同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持lOOPa，將形成有表面電極2 之透光性玻璃基板1的溫度，比較例47係加熱至3 50°C， 比較例48係加熱至600°C，進行熱處理。 比較例47在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲80.2%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲10.4Ω/□、全光透過率成80.3%、霧度率 -55- 201246277 成爲14.3%，片電阻與霧度率未見改善。 比較例48在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲80.1%、霧度率爲14.8%者在氫氣氛中之熱處理後 ，片電阻値成爲3.7Ω/□、全光透過率成爲54.2%、霧度 率成爲26.6%，片電阻與霧度率雖有改善，但是透過率極 度降低，且膜變成非透明。 (比較例4 9 ~ 5 0 ) 比較例49〜50係對於與實施例41同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持O.OlPa，將形成有表面電極2 之透光性玻璃基板1的溫度，比較例49係加熱至400 °C， 比較例50係加熱至5 5 0°C，進行熱處理。 比較例49在成膜隨後，片電阻値爲9.5 Ω/□、全光透 過率爲80.8%、霧度率爲14.5%者在氫氣氛中之熱處理後 ，片電阻値成爲12.9Ω/□、全光透過率成爲81.2%、霧度 率成爲13.2%，片電阻與霧度率未見改善。 比較例50在成膜隨後，片電阻値爲9.4Ω/E]、全光透 過率爲80.3%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲11.1 Ω/□、全光透過率成爲80.5%、霧度 率成爲15.2%，片電阻與霧度率未見改善。 實施例41〜48及比較例41〜50的結果如下表5所示。 -56- 201246277 [表5] 膜構成 膜 厚 (nm) 成膜後 氫 氣 體 壓 (Pa) 熱 處 理 溫 度 (°〇 熱處理後 熱處理後之改善比 表 面 電 阻 (Ω/α) 全 光 透 過 率 (%) 霧 度 (S) 表 面 電 阻 (Ω/Π) 全 光 透 過 率 (%) 霧 度 (%) 表 面 電 阻 前/後 全 光 透 過 率 Wm 霧 度 ma 實施例41 GAZO/Glass 2100 9.9 81.3 14.6 0.1 400 7-9 80.9 18.4 1.25 0.99 1.26 實施例42 GAZO/G!ass 2100 Θ.9 80.5 14.8 0.1 550 6.2 79.6 19.6 1.59 0.99 1.32 實施例43 GAZO/Glass 2100 9.5 80.4 14.9 1 400 6.8 79.8 18.8 1.40 0.99 1.27 實施例44 GAZO/Glass 2100 9.9 80.1 14.7 1 550 5.7 78.9 21.4 1.72 0.99 1.45 實施例45 GAZO/Glass 2100 9.4 81.4 14.8 10 400 5.7 80.3 20.4 1,66 0.99 1.38 實施例46 GAZO/Glass 2100 9.7 80.4 14.7 10 550 4.8 78.8 23.3 Z00 0.98 1.59 實施例47 GAZO/Glass 2100 9.9 80.1 14.9 100 400 5.2 78.7 2Z3 189 0.98 1.50 實施例48 GAZO/Glass 2100 9.9 81.2 14.6 100 550 4.4 79.3 25.0 224 0.98 1.72 比較_ GAZO/Glass 2100 9.6 81.3 14.9 0.1 350 12.3 81.7 15.5 0.78 1.00 1.04 比較例42 GAZO/Glass 2100 9.7 80.3 14.9 0.1 600 5.1 55.2 20.5 1.90 0.69 1.38 比較例43 GAZO/Glass 2100 9.9 81.4 14.7 1 350 J0,6 81.5 15.8 0.93 1.00 1.0S 比較例44 GAZO/Glass 2100 9.6 80.2 14.7 1 600 4.8 55.0 22.3 2·00 0.69 1.52 比較例45 GAZO/Glass 2100 9.4 80.8 14.9 10 350 10.4 81.0 16.2 α9〇 1.00 1.08 比較例46 GAZO/Glass 2100 10.0 80.1 14.9 10 600 4.1 54.5 24.8 2*46 0.68 1.66 比較例47 GAZO/Glass 2100 9.4 80.2 14.6 100 350 10.4 80.3 14,3 0.90 1.00 0.98 比較_ GAZO/Glass 2100 9.9 80.1 14.8 100 600 3.7 54.2 26.6 270 0.68 1.79 比較例49 GAZO/Glass 2100 9.5 80.8 14.5 0.01 400 1Z9 81.2 13.2 0.74 1.01 0.91 比較例50 GAZO/Glass 2100 9.4 80.3 14.6 0.01 550 11.1 80.5 15.2 0.84 1.00 1.05 (實施例49 ) 實施例49係表面電極2中’不使用底層膜21’而凹 凸膜22爲使用氧化鋅中摻雜有氧化鎵〇·6質量％的GZO 膜。 成膜係使用D C磁控濺鍍法’使用的靶係Φ 6吋大小 ，且基板與靶的間隔爲60mm。 碳酸鈉-石灰-矽土玻璃基板的溫度設定爲3 00°C ’濺 鍍功率DC400W、導入氣體爲氬氣體1〇〇%，氣體壓調整 爲7Pa，形成總膜厚成爲2200nm的GZO膜。 氫氣體還原環境中之熱處理係使氫氣體以每分鐘2L 的流量流入，氣氛爐內之壓力保持〇.1Pa，將形成有表面 -57- 201246277 電極2之透光性玻璃基板1的溫度加熱至400°C，進行處 理。 結果成膜隨後的片電阻値爲9.5Ω/□、全光透過率爲 81.2%、霧度率爲14.7%者在氫氣氛中之熱處理後，片電 阻値成爲7.5Ω/□、全光透過率成爲80.8%、霧度率成爲 18.4%，改善了片電阻與霧度率。 (實施例5 0 ) 實施例5 0係對於與實施例49同樣步驟在玻璃基板上 所製作的透明導電膜，使氫氣體以每分鐘2L的流量流入 ，氣氛爐內之壓力保持〇」Pa，將形成有表面電極2之透 光性玻璃基板1的溫度加熱至5 50°C，進行熱處理。 結果成膜隨後的片電阻値爲9.7Ω/□、全光透過率爲 81.0%、霧度率爲15.0%者在氫氣氛中之熱處理後，片電 阻値成爲6.4Ω/ΙΙ]、全光透過率成爲80.2%、霧度率成爲 20.1%，改善了片電阻與霧度率。全光透過率幾乎未變化 (實施例51〜52 ) 實施例5 1〜52係對於與實施例49同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持IPa，將形成有表面電極2之 透光性玻璃基板1的溫度，實施例5 1係加熱至40CTC，實 施例52係加熱至5 5 0°C進行熱處理。 -58- 201246277 實施例51在成膜隨後，片電阻値爲9.7Ω/□、全光透 過率爲80.3%、霧度率爲14.6%者在氫氣氛中之熱處理後 ，片電阻値成爲6.7Ω/□、全光透過率成爲79.5%、霧度 率成爲1 8.8 %，改善了片電阻與霧度率。 實施例52在成膜隨後，片電阻値爲9.8Ω/□、全光透 過率爲80.1%、霧度率爲14.8%者在氫氣氛中之熱處理後 ，片電阻値成爲5.8Ω/□、全光透過率成爲79.0%、霧度 率成爲22.0%，改善了片電阻與霧度率。 (實施例5 3 ~ 5 4 ) 實施例53~54係對於與實施例49同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持l〇Pa，且將形成有表面電極之 透光性玻璃基板的溫度，實施例53係加熱至400°C，實施 例5 4係加熱至5 5 0 °C，進行熱處理。 實施例53在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲80.9%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲6.1Ω/□、全光透過率成爲80.0%、霧度 率成爲2 0.9 %，改善了片電阻與霧度率。 實施例54在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲80.6%、霧度率爲14.8%者在氫氣氛中之熱處理後 ，片電阻値成爲5.2 Ω/□、全光透過率成爲79.3%、霧度 率成爲2 3.9 %，改善了片電阻與霧度率。 -59- 201246277 (實施例55〜56 ) 實施例55〜56係對於與實施例49同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2 L的流量 流入，氣氛爐內之壓力保持l〇〇Pa，將形成有表面電極2 之透光性玻璃基板1的溫度，實施例55係加熱至400 °C， 實施例56係加熱至550°C，進行熱處理。 實施例55在成膜隨後，片電阻値爲10.0Ω/□、全光 透過率爲81.0%、霧度率爲14.6%者在氫氣氛中之熱處理 後，片電阻値成爲5.3 Ω/□、全光透過率成爲79.6%、霧 度率成爲22.3%，改善了片電阻與霧度率。 實施例56在成膜隨後，片電阻値爲9.8 Ω/□、全光透 過率爲80.1%、霧度率爲14.8%者在氫氣氛中之熱處理後 ，片電阻値成爲4.4Ω/□、全光透過率成爲78.2%、霧度 率成爲25.8%，改善了片電阻與霧度率。 (比較例5 1〜5 2 ) 比較例51〜52係對於與實施例49同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2 L的流量 流入，氣氛爐內之壓力保持O.lPa，將形成有表面電極2 之透光性玻璃基板1的溫度，比較例5 1係加熱至350 °C， 比較例52係加熱至600°C，進行熱處理。 比較例51在成膜隨後，片電阻値爲9.9Ω/□、全光透 過率爲80.2%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲11.7Ω/□、全光透過率成爲80.4%、霧度 -60- 201246277 率成爲14.8%，片電阻與霧度率未見改善。 比較例52在成膜隨後，片電阻値爲9.5 Ω/Ε]、全光透 過率爲81.1%、霧度率爲I4.6 %者在氫氣氛中之熱處理後 ，片電阻値成爲5.3Ω /□、全光透過率成爲55.9%、霧度 率成爲20.1%，片電阻與霧度率雖有改善，但是透過率極 度降低，且膜變成非透明。 (比較例53〜54) 比較例53〜54係對於與實施例49同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持IPa，將形成有表面電極2之 透光性玻璃基板1的溫度，比較例5 3係加熱至3 5 (TC，比 較例54係加熱至60(TC，進行熱處理。 比較例53在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲80.5%、霧度率爲14.5%者在氫氣氛中之熱處理後 ，片電阻値成爲10.4Ω/□、全光透過率成爲80.7%、霧度 率成爲14.3%，片電阻與霧度率未見改善。 比較例54在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲81.4%、霧度率爲14.8%者在氫氣氛中之熱處理後 ，片電阻値成爲4.5Ω/□、全光透過率成爲55.7%、霧度 率成爲22.5%，片電阻與霧度率雖有改善，但是透過率極 度降低，且膜變成非透明。 (比較例55〜56 ) -61 - 201246277 比較例55〜56係對於與實施例49同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入，氣氛爐內之壓力保持10P a，將形成有表面電極2之 透光性玻璃基板1的溫度，比較例5 5係加熱至3 5 0 °C ’比 較例56係加熱至600°C，進行熱處理。 比較例55在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲81.0%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲10.4Ω/□、全光透過率成爲81.1%、霧度 率成爲15.2%，片電阻與霧度率未見改善。 比較例5 6在成膜隨後，片電阻値爲9.3 Ω/□、全光透 過率爲80.6%、霧度率爲14.7%者在氫氣氛中之熱處理後 ，片電阻値成爲4.1 Ω/□、全光透過率成爲55.0%、霧度 率成爲24.3%，片電阻與霧度率雖有改善，但是透過率極 度降低，且膜變成非透明。 (比較例57~58 ) 比較例5 7〜5 8係對於與實施例49同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2L的流量 流入’氣氛爐內之壓力保持lOOPa，將形成有表面電極2 之透光性玻璃基板1的溫度，比較例5 7係加熱至3 5 0。(：， 比較例58係加熱至600 °C，進行熱處理。 比較例57在成膜隨後，片電阻値爲9· 4Ω/□、全光透 過率爲80.4%、霧度率爲14.6%者在氫氣氛中之熱處理後 ’片電阻値成爲10.5Ω/□、全光透過率成爲80.5%、霧度 -62- 201246277 率成爲14.2%，片電阻與霧度率未見改善。 比較例58在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲80.2%、霧度率爲14.5%者在氫氣氛中之熱處理後 ，片電阻値爲3.8Ω/□、全光透過率爲54.5%、霧度率爲 26.1 %，片電阻與霧度率雖有改善，但是透過率極度降低 ，且變得非透明。 (比較例5 9 ~ 6 0 ) 比較例59〜60係對於與實施例49同樣步驟在玻璃基 板上所製作的透明導電膜，使氫氣體以每分鐘2 L的流量 流入，氣氛爐內之壓力保持O.OlPa，將形成有表面電極2 之透光性玻璃基板1的溫度，比較例59係加熱至400°C， 比較例60係加熱至5 50°C，進行熱處理。 比較例59在成膜隨後，片電阻値爲9.4Ω/□、全光透 過率爲79.9%、霧度率爲1 4.7%者在氫氣氛中之熱處理後 ，片電阻値成爲13.8 Ω/□、全光透過率成爲80.4%、霧度 率成爲13.4%，片電阻與霧度率未見改善。 比較例60在成膜隨後，片電阻値爲9.6Ω/□、全光透 過率爲80.8%、霧度率爲14.9%者在氫氣氛中之熱處理後 ，片電阻値成爲10.9Ω/□、全光透過率成爲81.0%、霧度 率成爲1 5.7 %，片電阻與霧度率未見改善。 實施例49〜56及比較例51~60的結果如下表6所示》 -63- 201246277 [表6] 膜構成 膜 厚 (nm) 成膜後 氫 氣 體 壓 (Pa) 熱 處 理 溫 度 CC) 熱處理後 熱處理後之改善比 表 面 電 阻 (Ω/Π) 全 光 透 過 率 (%) 霧 度 (%) 表 面 電 阻 (0/□) 全 光 透 過 率 (») m 度 (%) 表 面 電 阻 前/後 全 光 透 過 率 後湔 霧 度 後湔 實施例49 GZO/Glass 2200 9.5 81.2 14.7 0.1 400 7.5 80.8 18.4 1.26 1.00 1.26 實施例50 GZO/Glass 2200 9.7 81.0 14.9 0.1 550 6.4 80.2 20.1 1.51 0.99 1.35 實施例51 GZO/Glass 2200 9.7 80.3 14.6 1 400 6.7 79.5 18.8 1.45 0.99 1.29 S施例52 GZO/Glass 2200 9.8 80.1 14.8 1 550 5.8 79.0 22.0 1.69 0.99 1.48 實施例53 GZO/Glass 2200 9.4 80.9 14.9 10 400 6.1 80.0 20.9 1.56 0.99 1.40 實施例54 GZO/Glass 2200 9.6 80.6 14.8 10 550 5.2 79.3 23.9 1.84 0.98 1.61 實施例55 GZO/Glass 2200 10.0 81.0 14.6 100 400 5.3 79.6 22.3 1.88 0.98 1.52 實施例56 GZO/Glass 2200 9.8 80.1 14.8 100 550 4.4 78.2 25.8 2.23 0.98 1.75 比較例51 GZO/Glass 2200 9.9 80.2 14.9 0.1 350 11.7 80.4 14.8 0.85 1.00 0.99 比較例52 GZO/Glass 2200 9.5 81.1 14.6 0.1 600 5.3 55.9 20.1 1.80 0.69 1.38 比較例53 GZO/Glass 2200 9.6 80.5 14.5 1 350 10.4 80.7 14.3 0.92 1.00 0.99 比較例54 GZO/Glass 2200 9.4 81.4 14.8 1 600 4.5 55.7 22.5 Z10 0.68 1.52 比較例55 GZO/Glass 2200 9.6 81.0 14.9 10 350 10.4 81.1 15.2 0.92 1.00 1.02 比較例56 GZO/Glass 2200 9.3 80.6 14.7 10 600 4.1 55.0 24.3 Z30 0.68 1.66 比較例57 GZO/Glass 2200 9.4 80.4 14.6 100 350 10.5 80.5 14.2 0.90 1.00 0.97 比較例58 GZO/Glass 2200 9.6 80.2 14.5 100 600 3.8 54.5 26.1 Z56 0.68 1.79 比較例59 GZO/Glass 2200 9.4 79.9 14.7 0.01 400 13.8 80.4 13.4 0.69 1.01 0.91 比較例60 GZO/Glass 2200 9.6 80.8 14.9 0.01 550 10.9 81.0 15.7 0.86 1.00 1.05 如表1〜6及圖3所示，實施例1〜5 6係將附表面電極 之透明導電基板在1〜1 OOP a之氫氣體氣氛下，藉由以 400〜5 5 0°C施予熱處理，在熱處理之前後可提高1.25倍以 上霧度率。 如以上說明，實施例1 ~56係將附表面電極之透明導 電基板在0.1〜lOOPa之氫氣體氣氛下，藉由以400〜5 5 0°C 進行熱處理，可改善片電阻與霧度率。又，表面電極（透 明導電膜）之透明度雖有若干降低的傾向，但是實用上沒 有問題。 【圖面之簡單說明】 64- 201246277 [圖〗]圖1係表示本發明之一實施形態之薄膜太陽能 電池之構成例的剖面圖。 [圖2]圖2係表示本發明之一實施形態之薄膜太陽能 電池用之附表面電極之透明導電基板之構成例的剖面圖， 圖2A係於透光性玻璃基板上依序層合作爲表面電極之氧 化銦系之透明導電膜與表面形成有凹凸構造之氧化鋅系之 結晶質透明導電膜的剖面圖，圖2B係於透光性玻璃基板 上形成作爲表面電極之表面形成有凹凸構造之氧化鋅系之 結晶質透明導電膜的剖面圖。 [圖3]表示氣氣體導入之熱處理前後之霧度率的關係 圖。The heat treatment in the hydrogen gas reduction environment causes hydrogen gas to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace is maintained at P1 Pa, and the temperature of the light-transmitting glass substrate having the surface electrode of Table-50-201246277 is formed. After heating to 4 ° ° C 'processed, the film resistance 値 was 9.9 Ω / □, the total light transmittance was 81.3%, and the haze ratio was 14.6%. The heat resistance after heat treatment in a hydrogen atmosphere値 is 7.9 Ω/□, the total light transmittance is 80.9%, and the haze ratio is 18.4%, which improves the sheet resistance and the haze ratio. (Example 42) Example 42 is a transparent conductive film produced on a glass substrate in the same manner as in Example 41, wherein hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 11 Pa. The temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 550 ° C, and heat treatment was performed. As a result, the sheet resistance 値 of the film formation was 9.9 Ω/□, the total light transmittance was 80.5%, and the haze ratio was 14.8%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 6.2 Ω/□, and the golden light transmittance became 79.6%, the haze rate was 19.6%, which improved the sheet resistance and haze ratio. The total light transmittance was hardly changed (Examples 43 to 44). In Examples 43 to 44, the transparent conductive film produced on the glass substrate in the same manner as in Example 41 was allowed to flow at a flow rate of 2 L per minute. The pressure in the furnace was maintained at IPa' to form the temperature of the translucent glass substrate 1 of the surface electrode 2, in Example 43, it was heated to 400 °C, and in Example 44, it was heated to 550 °C, and heat treatment was performed. -51 - 201246277 In Example 43, after the film formation, the sheet resistance 値 was 9.5 Ω/□, the total light transmittance was 80.4%, and the haze ratio was 14.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 6.8 Ω. /1ΙΙ, the total light transmittance is 79.8%, and the haze ratio is 18.8%, which improves the sheet resistance and haze ratio. In Example 44, after the film formation, the sheet resistance 値 was 9.9 Ω/C], the total light transmittance was 80.1%, and the haze ratio was 14.7%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.7 Ω/□. The total light transmittance was 78.9%, and the haze ratio was 21.4%, which improved sheet resistance and haze ratio. (Examples 45 to 46) In Examples 45 to 46, the transparent conductive film produced on the glass substrate in the same manner as in Example 41 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 10 Torr. Pa, the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 400 ° C in Example 45, and heated to 550 ° C in Example 46, and heat treatment was performed. In Example 45, after the film formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 81.4%, and the haze ratio was 14.8%, and the sheet resistance 値 became 5.7 Ω/□ after heat treatment in a hydrogen atmosphere. The light transmittance was 80.3%, and the haze ratio was 20.4%, which improved the sheet resistance and the haze ratio. In Example 46, after the film formation, the sheet resistance 値 was 9.7 Ω/□, the total light transmittance was 80.4%, and the haze ratio was 14.7%, and the sheet resistance 値 became 4.8 Ω/□ after heat treatment in a hydrogen atmosphere. The light transmittance was 78.8 %, and the haze ratio was 23.3%, which improved the sheet resistance and the haze ratio. -52-201246277 (Examples 47 to 48) Examples 47 to 48 are transparent conductive films produced on a glass substrate in the same manner as in Example 41, and hydrogen gas was flowed at a flow rate of 2 L per minute. The pressure was maintained at 100 Pa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 400 ° C in the example 47. The example 4 was heated to 550 ° C and heat-treated. In Example 47, after the film formation, the sheet resistance 値 was 9.9 Ω/□, the total light transmittance was 80.1%, and the haze ratio was I4.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.2 Ω/□. The total light transmittance was 78.7%, and the haze ratio was 22.3%, which improved the sheet resistance and the haze ratio. In Example 48, after film formation, the sheet resistance 値 was 9.9 Ω/□, the total light transmittance was 81.2%, and the haze ratio was 14.6%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.4 Ω/□, The light transmittance was 79.3%, and the haze ratio was 25.0%, which improved sheet resistance and haze ratio. (Comparative Examples 41 to 42) Comparative Examples 41 to 42 are the transparent conductive films produced on the glass substrate in the same manner as in Example 41, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at O. lPa, the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed, Comparative Example 41 was heated to 3 50 ° C, and Comparative Example 42 was heated to 600 ° C, and heat treatment was performed. In Comparative Example 41, after sheet formation, the sheet resistance 値 was 9.6 Ω/□, the total light transmittance was 81.3%, and the haze ratio was 14.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 12·3 Ω/□. The all-light transmittance was 81.7%, the haze-53-201246277 rate was 15.5%, and the sheet resistance and haze ratio were not improved. In Comparative Example 42, after sheet formation, the sheet resistance 値 was 9.7 Ω/□, the total light transmittance was 80.3%, and the haze ratio was 14-9 %. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.1 Ω/□, The light transmittance was 55.2%, the haze ratio was 20.5%, and the sheet resistance and the haze ratio were improved, but the transmittance was extremely lowered and became non-transparent. (Comparative Examples 43 to 44) In Comparative Examples 43 to 44, the transparent conductive film produced on the glass substrate in the same manner as in Example 41 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was kept at IPa. The temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 325 ° C in Comparative Example 43, and the comparative example 44 was heated to 600 ° C to carry out heat treatment. In Comparative Example 43, after sheet formation, the sheet resistance 値 was 9.9 Ω/□, the total light transmittance was 81·4%, and the haze ratio was 7%.7%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 10.6 Ω. /□, the total light transmittance was 81.5%, the haze ratio was 15.8%, and the sheet resistance and haze ratio were not improved. In Comparative Example 44, after the film formation, the sheet resistance 値 was 9.6 Ω/□, the total light transmittance was 80.2%, and the haze ratio was 14.7%, and the sheet resistance 値 became 4.8 Ω/□ after heat treatment in a hydrogen atmosphere. The light transmittance was 55.0%, and the haze ratio was 22.3%. Although the sheet resistance and the haze ratio were improved, the transmittance was extremely lowered and became non-transparent. (Comparative Example 4 5 to 4 6 ) -54 - 201246277 Comparative Example 4 5 to 4 6 The transparent conductive film produced on the glass substrate in the same manner as in Example 4 1 was allowed to flow hydrogen gas at a flow rate of 2 L per minute. The pressure in the atmosphere furnace was maintained at 10 Pa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated, and Comparative Example 45 was heated to 350. <3, Comparative Example 46 was heated to 600 ° C and heat-treated. In Comparative Example 45, after the film formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 80·8%, and the haze ratio was I4.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 10.4. Ω/□, the total light transmittance was 8 1.0%, the haze ratio was 16.2%, and the sheet resistance and the haze ratio were not improved. In Comparative Example 46, after the film formation, the sheet resistance 値 was 10.0 Ω/□, the total light transmittance was 80.1%, and the haze ratio was I4.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.1 Ω/□. The total light transmittance was 54.5%, and the haze ratio was 24.8%. Although the sheet resistance and the haze ratio were improved, the transmittance was extremely lowered, and the film became non-transparent. (Comparative Examples 47 to 48) In Comparative Examples 47 to 48, the transparent conductive film produced on the glass substrate in the same manner as in Example 41 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 100 Pa. The temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 550 ° C in Comparative Example 47, and heated to 600 ° C in Comparative Example 48, and heat treatment was performed. In Comparative Example 47, after the film formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 80.2%, and the haze ratio was 14.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 10.4 Ω/□, The light transmittance was 80.3%, the haze rate was -55-201246277, which was 14.3%, and the sheet resistance and haze ratio were not improved. In Comparative Example 48, after the film formation, the sheet resistance 値 was 9.9 Ω/□, the total light transmittance was 80.1%, and the haze ratio was 14.8%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 3.7 Ω/□, The light transmittance was 54.2%, the haze ratio was 26.6%, and the sheet resistance and the haze ratio were improved, but the transmittance was extremely lowered, and the film became non-transparent. (Comparative Example 4 9 to 50) Comparative Examples 49 to 50 are the transparent conductive films produced on the glass substrate in the same manner as in Example 41, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained. O.OlPa, the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 400 °C in Comparative Example 49, and heated to 550 °C in Comparative Example 50, and heat treatment was performed. In Comparative Example 49, after the film formation, the sheet resistance 値 was 9.5 Ω/□, the total light transmittance was 80.8%, and the haze ratio was 14.5%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 12.9 Ω/□, The light transmittance was 81.2%, the haze ratio was 13.2%, and the sheet resistance and the haze ratio were not improved. In Comparative Example 50, after the film formation, the sheet resistance 値 was 9.4 Ω/E], the total light transmittance was 80.3%, and the haze ratio was 14.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 11.1 Ω/□. The total light transmittance was 80.5%, the haze ratio was 15.2%, and the sheet resistance and the haze ratio were not improved. The results of Examples 41 to 48 and Comparative Examples 41 to 50 are shown in Table 5 below. -56- 201246277 [Table 5] Film composition film thickness (nm) Hydrogen gas pressure (Pa) after film formation Heat treatment temperature (° improvement after heat treatment after heat treatment Specific surface resistance (Ω/α) Total light transmittance (%) Haze (S) Surface resistance (Ω/Π) Total light transmittance (%) Haze (%) Surface resistance before/after total light transmittance Wm Haze ma Example 41 GAZO/Glass 2100 9.9 81.3 14.6 0.1 400 7 -9 80.9 18.4 1.25 0.99 1.26 Example 42 GAZO/G!ass 2100 Θ.9 80.5 14.8 0.1 550 6.2 79.6 19.6 1.59 0.99 1.32 Example 43 GAZO/Glass 2100 9.5 80.4 14.9 1 400 6.8 79.8 18.8 1.40 0.99 1.27 Example 44 GAZO/Glass 2100 9.9 80.1 14.7 1 550 5.7 78.9 21.4 1.72 0.99 1.45 Example 45 GAZO/Glass 2100 9.4 81.4 14.8 10 400 5.7 80.3 20.4 1,66 0.99 1.38 Example 46 GAZO/Glass 2100 9.7 80.4 14.7 10 550 4.8 78.8 23.3 Z00 0.98 1.59 Example 47 GAZO/Glass 2100 9.9 80.1 14.9 100 400 5.2 78.7 2Z3 189 0.98 1.50 Example 48 GAZO/Glass 2100 9.9 81.2 14.6 100 550 4.4 79.3 25.0 224 0.98 1.72 Comparison _ GAZO/Glass 2100 9.6 81.3 14.9 0.1 350 12 .3 81.7 15.5 0.78 1.00 1.04 Comparative Example 42 GAZO/Glass 2100 9.7 80.3 14.9 0.1 600 5.1 55.2 20.5 1.90 0.69 1.38 Comparative Example 43 GAZO/Glass 2100 9.9 81.4 14.7 1 350 J0,6 81.5 15.8 0.93 1.00 1.0S Comparative Example 44 GAZO /Glass 2100 9.6 80.2 14.7 1 600 4.8 55.0 22.3 2·00 0.69 1.52 Comparative Example 45 GAZO/Glass 2100 9.4 80.8 14.9 10 350 10.4 81.0 16.2 α9〇1.00 1.08 Comparative Example 46 GAZO/Glass 2100 10.0 80.1 14.9 10 600 4.1 54.5 24.8 2*46 0.68 1.66 Comparative Example 47 GAZO/Glass 2100 9.4 80.2 14.6 100 350 10.4 80.3 14,3 0.90 1.00 0.98 Comparison _ GAZO/Glass 2100 9.9 80.1 14.8 100 600 3.7 54.2 26.6 270 0.68 1.79 Comparative Example 49 GAZO/Glass 2100 9.5 80.8 14.5 0.01 400 1Z9 81.2 13.2 0.74 1.01 0.91 Comparative Example 50 GAZO/Glass 2100 9.4 80.3 14.6 0.01 550 11.1 80.5 15.2 0.84 1.00 1.05 (Example 49) Example 49 is a surface electrode 2 in which 'the underlying film 21' is not used. The film 22 is a GZO film in which zinc oxide is doped with 6 mass% of zinc oxide. The film formation system used the target system Φ 6 吋 size used in the D C magnetron sputtering method, and the distance between the substrate and the target was 60 mm. The temperature of the sodium carbonate-lime-alumina glass substrate was set to 300 ° C. The sputtering power was DC 400 W, the introduction gas was 1% by volume of argon gas, and the gas pressure was adjusted to 7 Pa to form a GZO film having a total film thickness of 2200 nm. The heat treatment in the hydrogen gas reduction environment causes the hydrogen gas to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace is maintained at 11 Pa, and the temperature of the translucent glass substrate 1 on which the surface-57-201246277 electrode 2 is formed is heated to The treatment was carried out at 400 °C. As a result, after the film formation, the sheet resistance 値 was 9.5 Ω/□, the total light transmittance was 81.2%, and the haze ratio was 14.7%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 7.5 Ω/□, and the total light transmittance was 175 Ω/□. It became 80.8% and the haze ratio was 18.4%, which improved sheet resistance and haze ratio. (Example 50) Example 5 The transparent conductive film produced on the glass substrate in the same manner as in Example 49 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 〇Pa. The temperature of the light-transmitting glass substrate 1 on which the surface electrode 2 was formed was heated to 550 ° C, and heat treatment was performed. As a result, after sheet formation, the sheet resistance 値 was 9.7 Ω/□, the total light transmittance was 81.0%, and the haze ratio was 15.0%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 6.4 Ω/ΙΙ], and all light was transmitted. The rate was 80.2%, and the haze ratio was 20.1%, which improved sheet resistance and haze ratio. The total light transmittance was hardly changed (Examples 51 to 52). Example 5 1 to 52 The transparent conductive film produced on the glass substrate in the same manner as in Example 49 was allowed to flow at a flow rate of 2 L per minute. The pressure in the atmosphere furnace was maintained at IPa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated, and Example 51 was heated to 40 CTC, and Example 52 was heated to 550 °C for heat treatment. -58- 201246277 In Example 51, after film formation, the sheet resistance 値 was 9.7 Ω/□, the total light transmittance was 80.3%, and the haze ratio was 14.6%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 6.7 Ω. /□, the total light transmittance is 79.5%, and the haze ratio is 18.8%, which improves the sheet resistance and haze ratio. In Example 52, after sheet formation, the sheet resistance 値 was 9.8 Ω/□, the total light transmittance was 80.1%, and the haze ratio was 14.8%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.8 Ω/□, The light transmittance was 79.0%, and the haze ratio was 22.0%, which improved sheet resistance and haze ratio. (Examples 5 to 5 4) Examples 53 to 54 are transparent conductive films produced on a glass substrate in the same manner as in Example 49, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained. l〇Pa, and the temperature of the translucent glass substrate on which the surface electrode was formed, Example 53 was heated to 400 ° C, and Example 5 was heated to 550 ° C to perform heat treatment. In Example 53, after the film formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 80.9%, and the haze ratio was 14.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 6.1 Ω/□, The light transmittance was 80.0%, and the haze ratio was 20.9 %, which improved sheet resistance and haze ratio. In Example 54, after the film formation, the sheet resistance 値 was 9.6 Ω/□, the total light transmittance was 80.6%, and the haze ratio was 14.8%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.2 Ω/□, The light transmittance was 79.3%, and the haze ratio was 23.9 %, which improved the sheet resistance and the haze ratio. -59-201246277 (Examples 55 to 56) Examples 55 to 56 are transparent conductive films produced on a glass substrate in the same manner as in Example 49, and hydrogen gas was flowed at a flow rate of 2 L per minute in an atmosphere furnace. The pressure was maintained at 100 Pa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 400 ° C in Example 55, and heated to 550 ° C in Example 56, and heat treatment was performed. In Example 55, after the film formation, the sheet resistance 値 was 10.0 Ω/□, the total light transmittance was 81.0%, and the haze ratio was 14.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.3 Ω/□, The light transmittance was 79.6%, and the haze ratio was 22.3%, which improved the sheet resistance and the haze ratio. In Example 56, after film formation, the sheet resistance 値 was 9.8 Ω/□, the total light transmittance was 80.1%, and the haze ratio was 14.8%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.4 Ω/□, The light transmittance was 78.2%, and the haze ratio was 25.8%, which improved the sheet resistance and the haze ratio. (Comparative Example 5 1 to 5 2 ) Comparative Examples 51 to 52 are the transparent conductive films produced on the glass substrate in the same manner as in Example 49, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was While holding O.lPa, the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 350 °C in Comparative Example 51, and heated to 600 °C in Comparative Example 52, and heat treatment was performed. In Comparative Example 51, after the film formation, the sheet resistance 値 was 9.9 Ω/□, the total light transmittance was 80.2%, and the haze ratio was 14.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 11.7 Ω/□, The light transmittance was 80.4%, the haze-60-201246277 rate was 14.8%, and the sheet resistance and haze ratio were not improved. In Comparative Example 52, after the film formation, the sheet resistance 値 was 9.5 Ω/Ε], the total light transmittance was 81.1%, and the haze ratio was I4.6%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 5.3 Ω / □, the total light transmittance is 55.9%, the haze ratio is 20.1%, and the sheet resistance and the haze ratio are improved, but the transmittance is extremely lowered, and the film becomes opaque. (Comparative Examples 53 to 54) In Comparative Examples 53 to 54, the transparent conductive film produced on the glass substrate in the same manner as in Example 49 was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was kept at IPa. The temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 3 5 (TC in Comparative Example 153, and heated to 60 (TC in Comparative Example 54), and heat treatment was performed. Comparative Example 53 was formed after film formation. When the resistance 値 is 9.6 Ω/□, the total light transmittance is 80.5%, and the haze ratio is 14.5%, the sheet resistance 値 becomes 10.4 Ω/□, and the total light transmittance becomes 80.7%, and the haze is after heat treatment in a hydrogen atmosphere. The rate was 14.3%, and the sheet resistance and the haze ratio were not improved. In Comparative Example 54, after sheet formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 81.4%, and the haze ratio was 14.8% in the hydrogen atmosphere. After the heat treatment, the sheet resistance 値 was 4.5 Ω/□, the total light transmittance was 55.7%, and the haze ratio was 22.5%. The sheet resistance and the haze ratio were improved, but the transmittance was extremely lowered, and the film became non-transparent. (Comparative Examples 55 to 56) -61 - 201246277 Comparative Examples 55 to 56 are the same as in the embodiment 49. The transparent conductive film produced on the glass substrate was allowed to flow at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was maintained at 10 Pa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was compared. 5 series was heated to 350 ° C. 'Comparative Example 56 was heated to 600 ° C and heat-treated. Comparative Example 55, after film formation, sheet resistance 値 was 9.6 Ω / □, total light transmittance was 81.0%, haze When the heat treatment in a hydrogen atmosphere was 14.9%, the sheet resistance 値 became 10.4 Ω/□, the total light transmittance was 81.1%, the haze ratio was 15.2%, and the sheet resistance and the haze ratio were not improved. 6 After film formation, the sheet resistance 値 was 9.3 Ω/□, the total light transmittance was 80.6%, and the haze ratio was 14.7%. After heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 4.1 Ω/□, and all light was transmitted. The ratio was 55.0%, the haze ratio was 24.3%, and the sheet resistance and the haze ratio were improved, but the transmittance was extremely lowered, and the film became opaque. (Comparative Examples 57 to 58) Comparative Example 5 7 to 5 8 The transparent conductive film formed on the glass substrate in the same manner as in Example 49 was allowed to make hydrogen gas every minute. The flow rate of 2 L flowed into the atmosphere furnace was maintained at a pressure of 100 Pa, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated, and Comparative Example 57 was heated to 305. (:, Comparative Example 58 was heated to 600. The heat treatment was carried out at ° C. In Comparative Example 57, after the film formation, the sheet resistance 9 was 9·4 Ω/□, the total light transmittance was 80.4%, and the haze ratio was 14.6%, and the sheet resistance was 热处理 after heat treatment in a hydrogen atmosphere. The film resistance was 10.5 Ω/□, the total light transmittance was 80.5%, and the haze-62-201246277 rate was 14.2%, and the sheet resistance and the haze ratio were not improved. In Comparative Example 58, after film formation, the sheet resistance 値 was 9.6 Ω/□, the total light transmittance was 80.2%, and the haze ratio was 14.5%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 was 3.8 Ω/□, The light transmittance was 54.5%, the haze ratio was 26.1%, and the sheet resistance and the haze ratio were improved, but the transmittance was extremely lowered and became non-transparent. (Comparative Example 5 9 to 60) Comparative Examples 59 to 60 are the transparent conductive films produced on the glass substrate in the same manner as in Example 49, and hydrogen gas was flowed at a flow rate of 2 L per minute, and the pressure in the atmosphere furnace was O.OlPa was maintained, and the temperature of the translucent glass substrate 1 on which the surface electrode 2 was formed was heated to 400 ° C in Comparative Example 59, and heated to 550 ° C in Comparative Example 60, and heat treatment was performed. In Comparative Example 59, after sheet formation, the sheet resistance 値 was 9.4 Ω/□, the total light transmittance was 79.9%, and the haze ratio was 14.7%, and the sheet resistance 値 became 13.8 Ω/□ after heat treatment in a hydrogen atmosphere. The total light transmittance was 80.4%, the haze ratio was 13.4%, and sheet resistance and haze ratio were not improved. In Comparative Example 60, after sheet formation, the sheet resistance 値 was 9.6 Ω/□, the total light transmittance was 80.8%, and the haze ratio was 14.9%. After the heat treatment in a hydrogen atmosphere, the sheet resistance 値 became 10.9 Ω/□, The light transmittance was 81.0%, the haze ratio was 15.7%, and the sheet resistance and the haze ratio were not improved. The results of Examples 49 to 56 and Comparative Examples 51 to 60 are shown in Table 6 below. -63-201246277 [Table 6] Film thickness (nm) Hydrogen gas pressure (Pa) after film formation Heat treatment temperature CC) Heat treatment after heat treatment After-imaging ratio surface resistance (Ω/Π) Total light transmittance (%) Haze (%) Surface resistance (0/□) Total light transmittance (») m degree (%) Surface resistance before/after full light transmission After the rate of haze, Example 49 GZO/Glass 2200 9.5 81.2 14.7 0.1 400 7.5 80.8 18.4 1.26 1.00 1.26 Example 50 GZO/Glass 2200 9.7 81.0 14.9 0.1 550 6.4 80.2 20.1 1.51 0.99 1.35 Example 51 GZO/Glass 2200 9.7 80.3 14.6 1 400 6.7 79.5 18.8 1.45 0.99 1.29 S Example 52 GZO/Glass 2200 9.8 80.1 14.8 1 550 5.8 79.0 22.0 1.69 0.99 1.48 Example 53 GZO/Glass 2200 9.4 80.9 14.9 10 400 6.1 80.0 20.9 1.56 0.99 1.40 Example 54 GZO/Glass 2200 9.6 80.6 14.8 10 550 5.2 79.3 23.9 1.84 0.98 1.61 Example 55 GZO/Glass 2200 10.0 81.0 14.6 100 400 5.3 79.6 22.3 1.88 0.98 1.52 Example 56 GZO/Glass 2200 9.8 80.1 14.8 100 550 4.4 78.2 25.8 2.23 0.98 1.75 Comparative Example 51 GZO/Glass 2200 9.9 80.2 14.9 0.1 350 11.7 80.4 14.8 0.85 1.00 0.99 Comparative Example 52 GZO/Glass 2200 9.5 81.1 14.6 0.1 600 5.3 55.9 20.1 1.80 0.69 1.38 Comparative Example 53 GZO/Glass 2200 9.6 80.5 14.5 1 350 10.4 80.7 14.3 0.92 1.00 0.99 Comparative Example 54 GZO/Glass 2200 9.4 81.4 14.8 1 600 4.5 55.7 22.5 Z10 0.68 1.52 Comparative Example 55 GZO/Glass 2200 9.6 81.0 14.9 10 350 10.4 81.1 15.2 0.92 1.00 1.02 Comparative Example 56 GZO/Glass 2200 9.3 80.6 14.7 10 600 4.1 55.0 24.3 Z30 0.68 1.66 Comparative Example 57 GZO/Glass 2200 9.4 80.4 14.6 100 350 10.5 80.5 14.2 0.90 1.00 0.97 Comparative Example 58 GZO/Glass 2200 9.6 80.2 14.5 100 600 3.8 54.5 26.1 Z56 0.68 1.79 Comparative Example 59 GZO /Glass 2200 9.4 79.9 14.7 0.01 400 13.8 80.4 13.4 0.69 1.01 0.91 Comparative Example 60 GZO/Glass 2200 9.6 80.8 14.9 0.01 550 10.9 81.0 15.7 0.86 1.00 1.05 As shown in Tables 1 to 6 and Figure 3, Examples 1 to 5 6 The transparent conductive substrate with the surface electrode is subjected to heat treatment at 400 to 550 ° C under a hydrogen gas atmosphere of 1 to 1 OOP a , and can be improved by 1.25 after the heat treatment. Double the upper haze rate. As described above, in Examples 1 to 56, the sheet-resistance and haze ratio were improved by heat-treating at 400 to 550 ° C in a hydrogen gas atmosphere of 0.1 to 100 Pa under a hydrogen gas atmosphere of 0.1 to 100 Pa. Further, although the transparency of the surface electrode (transparent conductive film) tends to be somewhat lowered, there is no problem in practical use. [Brief Description of the Drawings] Fig. 1 is a cross-sectional view showing a configuration example of a thin film solar cell according to an embodiment of the present invention. [ Fig. 2] Fig. 2 is a cross-sectional view showing a configuration example of a transparent conductive substrate with a surface electrode for a thin film solar cell according to an embodiment of the present invention, and Fig. 2A is a surface layer on a transparent glass substrate. A cross-sectional view of a transparent conductive film of an indium oxide-based electrode and a zinc oxide-based crystalline transparent conductive film having a concavo-convex structure formed on the surface thereof, and FIG. 2B is formed on the surface of the translucent glass substrate to have a concavo-convex structure as a surface electrode. A cross-sectional view of a zinc oxide-based crystalline transparent conductive film. Fig. 3 is a graph showing the relationship between the haze ratio before and after the heat treatment of gas gas introduction.

Claims (1)

201246277 七、申請專利範圍： 1.一種附表面電極之透明導電基板之製造 徵係將於透光性基板上，藉由濺鍍法形成有具 有凹凸構造之氧化鋅系之結晶質透明導電膜之 附表面電極的透明導電基板，在0.1〜lOOPa之 下，以400〜5 50°C施予熱處理。 2 .如申請專利範圍第1項之附表面電極之 板之製造方法，其中前述表面電極係於前述透 ，藉由濺鍍法依序層合氧化銦系之透明導電膜 形成有凹凸構造之氧化鋅系的結晶質透明導電, 3 ·如申請專利範圍第1或2項之附表面電 電基板之製造方法，其中前述表面形成有凹凸 鋅系之結晶質透明導電膜爲由摻雜有選自 A1、 、F、Si、Ge、Ti、Zr、Hf之至少1種的氧化 ο 4 ·如申請專利範圍第2項之附表面電極之 板之製造方法，其中前述氧化銦系之透明導電 有選自Ti、Sn、Ga之至少1種的氧化銦所構试 5 .如申請專利範圍第3項之附表面電極之 板之製造方法，其中前述氧化銦系之透明導電 有選自Ti、Sn、Ga之至少1種的氧化銦所構成 6.—種薄膜太陽能電池之製造方法，其係 板上，依序形成表面電極、光電轉換半導體層 之薄膜太陽能電池的製造方法，其特徵係將於 方法，其特 有表面形成 表面電極之 氫氣體氣氛 透明導電基 光性基板上 及前述表面 摸者。 極之透明導 構造之氧化 G a、B、I η 鋅所構成者 透明導電基 膜爲由摻雜 :者。 透明導電基 膜爲由摻雜 :者。 於透光性基 、背面電極 前述透光性 -66- 201246277 基板上，藉由濺鍍法形成有具有表面形成有凹凸構造之氧 化鋅系之結晶質透明導電膜之前述表面電極之附表面電極 的透明導電基板，在 0.1 ~1 OOP a之氫氣體氣氛下，以 400〜55 0°C施予熱處理。 7.如申請專利範圍第6項之薄膜太陽能電池之製造方 法，其中前述表面電極係於前述透光性基板上，藉由濺鍍 法依序層合氧化銦系之透明導電膜及前述表面形成有凹凸 構造之氧化鋅系的結晶質透明導電膜者。 -67-201246277 VII. Patent application scope: 1. A manufacturing method of a transparent conductive substrate with a surface electrode is formed on a light-transmitting substrate by a sputtering method to form a zinc oxide-based crystalline transparent conductive film having a concave-convex structure. The transparent conductive substrate with the surface electrode is subjected to heat treatment at 400 to 5 50 ° C under 0.1 to 100 Pa. 2. The method of manufacturing a surface electrode-attached sheet according to the first aspect of the invention, wherein the surface electrode is oxidized by the indium oxide-based transparent conductive film by sputtering method to form an uneven structure. The zinc-based crystalline transparent conductive material, wherein the surface-formed electro-optical substrate according to claim 1 or 2, wherein the surface is formed with a concave-convex zinc-based crystalline transparent conductive film which is doped with a selected from A1. And a method for producing a surface electrode with a surface electrode according to the second aspect of the invention, wherein the transparent indium oxide-based transparent conductive material is selected from the group consisting of The method for producing a plate having a surface electrode according to the third aspect of the invention, wherein the indium oxide-based transparent conductive material is selected from the group consisting of Ti, Sn, and Ga A method for producing a thin film solar cell comprising at least one type of indium oxide, wherein a method for producing a thin film solar cell in which a surface electrode and a photoelectric conversion semiconductor layer are sequentially formed on a tie plate is characterized by a method, Its special surface forms a hydrogen gas atmosphere of the surface electrode on the transparent conductive substrate on the optical substrate and the aforementioned surface. The oxidation of the extremely transparent structure G a, B, I η zinc constitutes a transparent conductive film is doped: . The transparent conductive substrate is doped by : . a surface electrode of the surface electrode having a zinc oxide-based crystalline transparent conductive film having a concavo-convex structure formed on the surface of the light-transmitting substrate and the back electrode of the light-transmitting-66-201246277 substrate The transparent conductive substrate is heat-treated at 400 to 55 ° C under a hydrogen gas atmosphere of 0.1 to 1 OOP a . 7. The method of manufacturing a thin film solar cell according to claim 6, wherein the surface electrode is on the light-transmitting substrate, and the indium oxide-based transparent conductive film is sequentially laminated by sputtering and the surface is formed. A zinc oxide-based crystalline transparent conductive film having a concavo-convex structure. -67-
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