201212047 六、發明說明： 【發明所屬之技術領域】 本發明係於基板的表面上形成含有氧化銦的透明導電 層積體之具透明導電層積體之基板，以及其製造方法。 【先前技術】 從前，作爲透明導電膜之材料，有在氧化錫摻雜銻而 成的銻錫複合氧化物（ΑΤΟ )，在氧化鋅摻雜鋁而成的鋁 鋅複合氧化物（ΑΖΟ )，以及在氧化銦摻雜錫而成的銦錫 複合氧化物（ΙΤΟ)等係屬已知。其中，以ΙΤΟ膜與ΑΤΟ膜 、ΑΖΟ膜相比導電率較高，此外可見光區域之透光率很高 ，所以作爲液晶顯示元件、電致發光顯示元件等之透明電 極用材料而廣泛被使用。 然而，ΙΤΟ膜因爲銦含量很高所以會有材料成本很高 的問題，所以減低銦含量的透明導電膜受到關注檢討，例 如於日本特開平7-3 3 5 03 1號公報（專利文獻1 )，揭示著 使用燒結作爲摻雜物包含氧化錫、氧化鈦及氧化銷之中至 少1種的氧化銦系粉末，與作爲摻雜物包含氧化銻、氧化 钽及氧化鈮之中至少1種的氧化錫系粉末之混合物而得的 導電性氧化物來成膜之導電膜。 ， 然而，於專利文獻1所記載的導電膜，雖然可謀求含 銦量的減低，但是這樣的導電膜在透光性（特別是在可見 光區域的透過率是否夠大）、導電性（電阻率是否夠小） 這些點上仍是有所不足。 -5- 201212047 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開平7-3 3 503 1號公報 【發明內容】 [發明所欲解決之課題] 本發明係有鑑於前述先前技術所具有的課題而完成之 發明，目的在於提供即使減低銦含量，也有充分高的透光 性及充分低的電阻率之具透明導電層積體之基板及其製造 方法。 [供解決課題之手段] 本案之發明人，爲了達成前述目的而反覆銳意硏究的 結果，發現藉由具透明導電層積體之基板之製造方法，其 係在基板之表面上被形成含有氧化銦的透明導電層積體， 包含：於前述基板之表面上直接或間接地形成氧化銦含量 爲80〜98質量％之第一透明導電膜的步驟，及於前述第一 透明導電膜的表面上層積氧化銦含量爲45〜75質量百分比 之第二透明導電膜的步驟，及使前述第二透明導電膜在 3 5 0〜9 5 0K之溫度下進行加熱的步驟之具透明導電層積體 之基板之製造方法所得到的’具有前述第一透明導電膜及 前述第二透明導電膜有與氧化銦結晶同等的結晶構造的結 晶之具透明導電層積體之基板’即使減低銦含量’也具有 -6- 201212047 充分高的透光性及充分低的電阻率，從而完成本發明。 亦即，本發明之具透明導電層積體之基板，係於基板 之表面上被形成含有氧化銦的透明導電層積體之具透明導 電層積體之基板，其特徵爲前述透明導電層積板，具備氧 化銦含量爲80〜98質量％之第一透明導電膜與被層積於前 述第一透明導電膜的表面上之氧化銦含量爲45〜75質量百 分比之第二透明導電膜，且前述第一透明導電膜及前述第 二透明導電膜有具備與氧化銦結晶同等之結晶構造的結晶 〇 又，於本發明，所謂有具備與氧化銦結晶同等之結晶 構造的結晶，係根據銅Κ α線之X線繞射測定調查膜中的 結晶構造所得到的結果，於2 0 = 21.5度附近、30.6度附 近、35.5度附近、37.7度附近、41.8度附近、45.7度附近 、5 1.0度附近、56.0度附近、及60.7度附近所構成的群所 選擇之至少一處存在繞射峰，而前述繞射峰之S/N比爲1 以上爲較佳8 此外，相關於本發明之前述透明導電層積體，以係對 波長800〜2500nm之全區域的光的透過率爲80%以上之層 積體爲較佳。 進而，於根據銅κ α線之X線繞射測定所得到的，前 述第一透明導電膜及.前述第二透明導電膜之X線繞射圖案 ，於20 =21.5度附近、30.6度附近' 35.5度附近、51.0度 附近、及60.7度附近所構成的群所選擇之至少一處存在繞 射峰爲較佳。 201212047 此外，前述結晶係由In2〇3結晶及11145113012結晶所構 成的群所選擇之至少一結晶爲較佳。 又，於本發明，所謂「Ιη203結晶」係根據銅Κ α線之 X線繞射測定來調査膜中的結晶構造的結果，起因於氧化 銦結晶具有的立方晶系方鐵錳礦（bixbyite )構造之繞射 峰，亦即，於20 = 21.5度附近、30.6度附近、35.5度附近 、37.7度附近、41.8度附近、45.7度附近、51.0度附近、 56.0度附近、及60.7度附近所構成的群所選擇之至少一處 存在繞射峰，而前述繞射峰之S/ N比爲1以上爲較佳。此 外，所謂「In4Sn3012結晶」係根據銅Κ α線之X線繞射測 定來調查膜中的結晶構造的結果，起因於In4Sn3〇12結晶具 有的菱面體晶或六方晶系構造之繞射峰，亦即，於20 = 3 0 · 6度附近、3 5 · 5度附近（較佳爲3 5.3附近）、5 1.0度附 近、56.0度附近、及60.7度附近所構成的群所選擇之至少 —處存在繞射峰，且在20 = 30.6度附近、51.0度附近、 及60.7度附近存在分離的峰之結晶，而前述繞射峰之S/N 比爲1以上爲較佳。 此外，本發明之具透明導電層積體之基板之製造方法 ，其係於基板之表面上被形成含有氧化銦的透明導電層積 體之具透明導電層積體之基板之製造方法，其特徵爲包含 :於前述基板之表面上直接或間接地形成氧化銦含量爲8 0 〜98質量％之第一透明導電膜的步驟，及於前述第一透明 導電膜的表面上層積氧化銦含量爲45〜75質量百分比之第 二透明導電膜的步驟，及使前述第二透明導電膜在3 5 0〜 201212047 9 5 0 K之溫度下進行加熱的步驟。 加熱相關於本發明之第二透明導電膜的步驟，以如下 述之任一種方式來進行者爲較佳。 (1)加熱前述第二透明導電膜之步驟，係藉由於層 積前述第二透明導電膜之步驟，將前述基板及前述第一透 明導電膜在3 5 0〜9 5 0Κ之溫度下進行加熱而進行的。 此外’ （2 )加熱相關於本發明之第二透明導電膜之 步驟’係於層積前述第二透明導電膜的步驟之後進行的。 又’於（1)的場合，加熱前述第二透明導電膜的溫 度以3 5 0〜600Κ爲較佳。 此外，於（2 )的場合，加熱前述第二透明導電膜的 溫度以4 5 0〜9 5 0 Κ爲較佳。 此外，以相關於本發明之第一透明導電膜的厚度爲6 〜50nm，前述第二透明導電膜的厚度爲50〜150nm爲較佳 〇 進而，相關於本發明之第二透明導電膜，最好是含有 由錫、駄、錬、鉬、鐵、銘、鋅、姉、鎵、砂、銷、鎂、 鋁、金、銀、銅、鈀、鎢、及這些的氧化物所構成的群選 擇之至少1種之透明導電膜。 又，於本發明之具透明導電層積體之基板，即使減低 銦含量，也可以達成充分高的透光性及充分低的電阻率之 理由尙未有定論，但本案之發明人推測如下。亦即，本發 明之具透明導電層積體之基板，藉由把氧化銦含量低不容 易成爲結晶構造的透明導電膜，層積於氧化銦含量爲80〜 -9- 201212047 9 8質量％之容易成爲結晶構造的透明導電膜之表面上 3 5 0〜9 5 0K之溫度施以加熱等，而促進前述氧化銦含 的透明導電膜之結晶化，而成爲具有與「氧化銦結晶 同等的方鐵錳礦（bixbyite )構造。因此，推估於本 之具透明導電層積體之基板，即使減低銦含量，也可 成充分高的透光性及充分低的電阻率。 [發明之效果] 根據本發明，可以提供即使減低銦含量，也有充 的透光性及充分低的電阻率之具透明導電層積體之基 其製造方法。 【實施方式】 首先，說明本發明之具透明導電層積體之基板。 明之具透明導電層積體之基板，係於基板之表面上被 含有氧化銦的透明導電層積體之具透明導電層積體之 ，其特徵爲前述透明導電層積板，具備氧化銦含量爲 98質量％之第一透明導電膜與被層積於前述第一透明 膜的表面上之氧化銦含量爲45〜75質量百分比之第二 導電膜，且前述第一透明導電膜及前述第二透明導電 具備與氧化銦結晶同等之結晶構造的結晶。 作爲於本發明使用的基板，只要是具有高的透光 於後述之本發明的製造方法之加熱第二透明導電膜的 等不會變質的材質即可，例如可以舉出聚醯亞胺、聚 而在 量低 相」 發明 以達 分高 板及 本發 形成 基板 8 0〜 導電 透明 膜有 性， 步驟 芳醯 -10- 201212047 胺、聚苯硫醚、聚醚颯等耐熱性樹脂及玻璃。此外，基板 的厚度沒有特別限制，隨著本發明之具透明導電層積體之 基板的透光性或強度或者本發明之具透明導電層積體之基 板的使用態樣，而因應於前述材質適當選用。 於本發明使用的第一透明導電膜，係於前述基板的表 面上直接或間接形成的透明導電膜。於本發明使用的第一 透明導電膜，亦可直接層積於前述基板之表面上，爲了提 高透光率，提高反射率或者障壁性的附加爲目的而將透明 的機能膜配置於與前述基板之間亦可。 此外，作爲於本發明使用的第一透明導電膜，膜中的 氧化銦含量有必要爲8 0〜9 8質量％，以9 0〜9 7質量％爲佳 。前述氧化銦含量超過前述上限的話，於本發明使用的第 一透明導電膜中的載體密度變小所以電阻率變高，另一方 面，未達前述下限的話，很難促進後述之第二透明導電膜 的結晶化。 進而，於本發明使用的第一透明導電膜，除了氧化銦 以外，還包含其他金屬及金屬氧化物，例如可以舉出錫、 欽、錄、銷、鐵、銘、辞、姉、嫁、砂、銷、錶、錦、金 、銀、銅、鈀、鎢、及這些的氧化物，這樣的金屬及金屬 氧化物，亦可單獨或者混合2種類以上而含有於膜中。在 這樣的氧化物之中，由具有高昀導電性之作爲摻雜物的角 色以及本發明之具透明導電層積體之基板的透光性的觀點 來看，氧化錫最好是在本發明所使用的第一透明導電膜與 氧化銦共同含有爲佳。 -11 - 201212047 此外，於本發明使用的第一透明導電膜，氧化銦有必 要具結晶構造。進而，於本發明使用的第一透明導電膜， 從減低膜的電阻率的觀點來看，對於前述基板面平行地膜 狀成長爲較佳，此外膜中的氧化銦之結晶度以50〜1 00% 爲較佳。又，膜中的氧化銦之結晶度，可以藉由X線繞射 分析所得到的繞射峰強度之變化來推定。 進而，於本發明使用的第一透明導電膜，根據銅Κα 線之X線繞射測定來調査膜中的結晶構造的結果，亦即， 有必要在20 = 21.5度附近、30.6度附近、35.5度附近、 37.7度附近、41.8度附近' 45.7度附近、51.0度附近、 5 6.0度附近、及60.7度附近所構成的群所選擇之至少一處 存在繞射峰，而前述繞射峰之S/N比爲1以上爲較佳。此 外，由提高移動度，減低膜的電阻率的觀點來看，根據銅 κ α線之X線繞射測定所得到的，前述第一透明導電膜的X 線繞射圖案，以在2 0 = 21 .5度附近、30.6度附近、35.5度 附近、51.0度附近、及60.7度附近所構成的群所選擇之至 少一處存在繞射峰爲較佳，具有與於本發明使用的第一透 明導電膜具有之氧化銦結晶同等的結晶構造之結晶，最好 是由Ιη203結晶及In4Sn301;^g晶所構成的群所選擇之至少 —結晶。 此外，作爲於本發明使用的第一透明導電膜的厚度’ 以6〜50nm爲較佳，8〜15nm爲更佳。前述厚度超過削述 上限的話，本發明之具透明導電層積體之基板之製造上的 成本有變高的傾向，另一方面，未達目U述下限的3舌’膜谷 -12- 201212047 易變成在許多地方中斷而成爲島狀，所以本發明之具透明 導電層積體之基板有電阻率變高的傾向。 作爲於本發明使用的第二透明導電膜，係被層積於前 述第一透明導電膜之表面上，氧化銦含量爲45〜75質量％ ，而以45〜55質量％爲較佳。前述氧化銦含量之含有量超 過前述上限的話，本發明之具透明導電層積體之基板在製 造上的成本變高，另一方面，未達前述下限的話，第二透 明導電膜變得不容易有具有與氧化銦結晶同等的結晶構造 之結晶。進而，由本發明之具透明導電層積體之基板的製 造上減低成本的觀點來看，前述第一透明導電膜與於本發 明使用的第二透明導電膜之氧化銦含量之差以40〜50質量 %爲較佳。 此外，於本發明使用的第二透明導電膜，除了氧化銦 以外，還包含其他金屬及金屬氧化物，例如可以舉出錫、 鈦、銻、蹈、鐵、鈷、鋅、铈、鎵、矽、錐、鎂、鋁、金 、銀、銅、鈀、鎢、及這些的氧化物，這樣的金屬及金屬 氧化物，亦可單獨或者混合2種類以上而含有於膜中。在 這樣的金屬以及氧化物之中，由具有高的導電性之作爲摻 雜物的角色以及本發明之具透明導電層積體之基板的透光 性的觀點來看，以錫、鈦、銻、鉬、鐵、鋅、鎵、矽、鎂 、鋁及這些的氧化物爲佳。此外，在.把本發明之具透明導 電層積體之基板作爲太陽電池用之透明電極材料來使用的 場合，從得到沒有在紅外區域之吸收而具有高的透過率的 具透明導電層積體之基板的觀點來看，於本發明使用的第 -13- 201212047 二透明導電膜以含有錫或者氧化錫爲更佳。進而，作爲於 本發明使用的第二透明導電膜，從可以得到使體積電阻率 充分地低，波長800〜2500nm之全區域之透光率爲80%以 上之透明導電層積體的觀點來看，作爲於本發明使用之第 二透明導電膜’以膜中的氧化銦含量爲45〜55質量％，氧 化錫含量爲40〜50質量％，氧化銻之含量爲1〜1〇質量％爲 特佳。 此外，於本發明使用的第二透明導電膜，氧化銦有必 要具有結晶構造，與前述第一透明導電膜同樣，對於前述 基板面平行地膜狀成長爲較佳，此外膜中的結晶度以50〜 1 0 0 %爲較佳》 進而，於本發明使用的第二透明導電膜，根據銅Κα: 線之X線繞射測定來調査膜中的結晶構造的結果，有必要 在20 = 21.5度附近、30.6度附近、35.5度附近、37.7度附 近、41.8度附近、45.7度附近、51.0度附近、56.0度附近 、及60.7度附近所構成的群所選擇之至少一處存在繞射峰 ，而前述繞射峰之S / Ν比爲1以上爲較佳。此外，由提高 移動度，減低膜的電阻率的觀點來看，根據銅Κ α線之X 線繞射測定所得到的，前述第二透明導電膜的X線繞射圖 案，以在= 21.5度附近、30.6度附近、35.5度附近、 5 1.0度附近、及60.7度附近所構成的群所選擇之至少一處 存在繞射峰爲較佳，具有與於本發明使用的第二透明導電 膜具有之氧化銦結晶同等的結晶構造之結晶，做好是由 Ιη203結晶及In4Sn3012結晶所構成的群所選擇之至少一結 -14- 201212047 此外，作爲於本發明使用的第二透明導電膜的厚度， 以50〜150nm爲較佳。前述厚度超過前述上限的話，本發 明之具透明導電層積體之基板的透光性會有變得無法充分 地高的傾向，另一方面，未滿前述下限的話，在製作使用 了本發明的具透明導電層積體之基板的裝置時在有凹凸的 基板上會有無法得到充分的導電性之傾向。 進而，前述第一透明導電膜與前述第二透明導電膜之 合計厚度，以50〜150 nm爲佳。前述厚度超過前述上限的 話，本發明之具透明導電層積體之基板的透光性會有變得 無法充分地高的傾向，另一方面，未滿前述下限的話，在 製作使用了本發明的具透明導電層積體之基板的裝置時在 有凹凸的基板上會有無法得到充分的導電性之傾向。 其次，說明本發明之具透明導電層積體之基板之製造 方法。本發明之具透明導電層積體之基板之製造方法，其 係於前述基板之表面上被形成含有氧化銦的透明導電層積 體之具透明導電層積體之基板之製造方法，係特徵爲包含 :於前述基板之表面上直接或間接地形成前述第一透明導 電膜之步驟，及於前述第一透明導電膜的表面上層積前述 第二透明導電膜的步驟，以及把前述第二透明導電膜在 3 50〜9 5 0K之溫度下進行加熱的步驟之方痒，加熱前述第 二透明導電膜的溫度超過前述上限的話，伴隨著前述第二 透明導電膜中的載體密度之減少會使電阻率上升，另一方 面’未達前述下限的話，會起因於前述第二透明導電膜中 -15- 201212047 的非晶質構造而使移動度減少。 作爲形成相關於本發明之前述第一透明導電膜及前 第二透明導電膜的方法，可以採用濺鍍法、真空蒸鍍法 離子布植法等物理性成膜法，熱噴«法、滴下塗佈法、 CVD法等化學性成膜方法。其中，由容易形成具有充分 導電性之大面積的透明導電膜的觀點來看，以採用濺鍍 爲佳。 至於本發明之具透明導電層積體之基板之製造方法 作爲第一製造方法，加熱前述第二透明導電膜之步驟， 藉由於層積前述第二透明導電膜之步驟，將前述基板及 述第一透明導電膜在350〜950K之溫度下進行加熱而進 的方法，作爲加熱前述第二透明導電膜的溫度，以350 600K爲佳’以400〜5 5 0K爲更佳。加熱前述第二透明導 膜的溫度超過前述上限的話，伴隨著前述第二透明導電 中的載體密度的減半，電阻率有變成容易上升的傾向， 一方面’未達前述下限的話，起因於前述第二透明導電 中的非晶質構造會有移動度變得容易減少的傾向。 此外’本發明之具透明導電層積體之基板之第一製 方法’加熱前述第二透明導電膜的溫度爲523 K程度以 在比較低的溫度即可，由所得到的具透明導電層積體之 板的電阻率很低的觀點來看，可以適切地使用於製作利 透明電極用材料的平面面板顯示器等裝置的步驟。 進而，作爲第二製造方法，加熱前述第二透明導電 之步驟，係在層稹前述第二透明導電膜的步驟之後進行 述 、 及 的 法 係 刖 行 電 膜 另 膜 造 下 基 用 膜 的 -16- 201212047 方法，作爲加熱前述第二透明導電膜的溫度，以450〜 950K爲佳，以5 23〜7 23 K爲更佳。加熱前述第二透明導電 膜的溫度超過前述上限的話，伴隨著前述第二透明導電膜 中的載體密度的減半，電阻率有變成容易上升的傾向，另 —方面，未達前述下限的話，起因於前述第二透明導電膜 中的非晶質構造會有移動度變得容易減少的傾向。 此外，前述第二透明導電膜之加熱時間沒有特別限制 ，考慮到伴隨著前述第二透明導電膜中的載體密度的減少 或氧缺損導致之透光性的降低，因應於前述加熱溫度、前 述第二透明導電膜的組成、前述第二透明導電膜的厚度而 適當選擇。 進而，加熱處理中是在氧氣氣體存在下進行的，這由 可以得到透光性高的本發明之具透明導電層積體之基板的 觀點來看是較佳的。 [實施例] 以下，根據實施例、比較例更具體地說明本發明，但 本發明並不以以下之實施例爲限。 (實施例1 ) 濺鍍裝置（使用ULVAC公司製造’製品名「CS_2〇0 」），以濺鍍電力直流（DC ) 1 〇〇w ’將作爲靶材之ITO 靶材（ULVAC公司製造及三井金屬礦業公司製造，ITO中 的氧化銦含量：9 0質量％，氧化錫含量：1 〇質量％，以下 -17- 201212047 稱爲r ITO90」），在旋轉的玻璃基板（厚度：0.7mm， 長：50mm，寬：50mm’康寧公司製造，製品名「 EAGLE2000」）上，使基板加熱溫度爲523K，反應槽內 的壓力爲〇.68Pa’氬氣流量爲50sccm，氧氣流量爲 0.2sccm的條件下進行濺鍍，形成厚度12nm之ITO90所構 成的第一透明導電膜。進而’在由得到IT◦靶材（三井金 屬礦業公司製造，ITO中的氧化銦含量爲50質量％，氧化 錫含量爲50質量％ ’以下稱之爲「ITO50」）的ITO90所構 成的透明導電膜之表面上，直接以除了把氧氣流量改爲 0.3 seem以外之與前述相同的條件下進行濺鍍，形成厚度 13 8nm之ITO5 0所構成的第二透明導電膜，而得到具透明 導電層積體之玻璃基板。 又，所得到的具透明導電層積體之玻璃基板之各膜的 厚度，使用ITO膜除去加工裝置（Laserx公司製造，製品 名「LXSY-UV」）局部地剝離各膜，使用表面形狀評估系 統（SII公司製造，製品名「L-Tracell」）進行了測定。 此外，由靶材的組成及膜厚算出的，在實施例1所得到的 透明導電層積體之氧化銦含量爲5 3質量％，氧化錫含量爲 4 7質量％ » (實施例2 ) 除了替代濺鑛ITO靶材（ITO50 )，而以濺鍍電力 DC100W濺鍍ITO靶材（ITO50)，以濺鍍電力高頻（RF) 20W濺鍍氧化鈦靶材（高純度化學硏究所製造，靶材中的 -18- 201212047 氧化欽含量：99·9質量％)把氧氣氣體流量改爲0sccm同時 進行濺鍍以外’與實施例1同樣地進行而製作具透明導電 層積體之玻璃基板。所得到的具透明導電層積體之玻璃基 板，係在厚度之ITO90所構成的第一透明導電膜之表 面上，直接被層積由厚度140nm之被摻雜鈦的IT0所構成 的第二透明導電膜（以下，稱爲厂IT050 ; Ti所構成的第 二透明導電膜」）。又，由靶材的組成及膜厚算出的，在 實施例2所得到的透明導電層積體之氧化銦含量爲5 1質量 %，氧化錫含量爲4 4質量’氧化鈦含量爲5質量％。 (實施例3 ) 除了替代ITO靶材（ITO50)改用添加銻的ITO靶材（ 三井金屬礦業公司製造，ITO靶材中的氧化銦含量：50質 量％，氧化錫含量：4 5質量％ ’氧化銻含量：5質量％，以 下稱爲「ITO 5 0 ; S b」））以外與實施例1同樣地進行而 製作具透明導電層積體之玻璃基板。所得到的具透明導電 層積體之玻璃基板，係在厚度12nm之ITO90所構成的第一 透明導電膜之表面上，直接被層積由厚度13 7nm之「 ITO50 ; Sb」所構成的第二透明導電膜。又，由靶材的組 成及膜厚算出的，在實施例3所得到的透明導電層積體之 氧化銦含量爲5 3質量％，氧化錫含量爲4 2質量。/。，氧化銻 含量爲5質量％。 (比較例1〜3 ) -19- 201212047 除了不形成由ITO90所構成的膜以外’與實施例1〜3 同樣地進行而製作具透明導電膜之玻璃基板。亦即’於比 較例1所得到的透明導電膜，係由厚度153nm之ITO50所構 成之膜，膜中之氧化銦含量爲50質量％ ’氧化錫含量爲50 質量％。此外，於比較例2所得到的透明導電膜，係由厚 度150nm之「ITO5 0 ; Ti02」所構成之膜，膜中之氧化銦 含量爲47.5質量％，氧化錫含量爲47.5質量％，氧化鈦含量 爲5質量％。進而，於比較例3所得到的透明導電膜，係由 厚度150nm之「ITO50; Sb」所構成之膜，膜中之氧化銦 含量爲50質量％，氧化錫含量爲45質量％，氧化銻含量爲5 質量％。 (實施例4〜6 ) 除了不加熱基板以外，與實施例1同樣地進行，於玻 璃基板的表面上形成由ITO90所構成的透明導電膜，進而 於ITO90所構成的第一透明導電膜的表面上直接層積由 ITO 5 0所構成的第二透明導電膜》把所得到的基板、第一 透明導電膜、及第二透明導電膜進而在大氣中以5 23 K之 溫度（實施例4 ) 、623 K之溫度（實施例5 ) 、723 K之溫 度（實施例6 )加熱一小時而得具透明導電膜之玻璃基板 (實施例7〜9 ) 除了不加熱基板以外，與實施例2同樣地進行，於玻 -20- 201212047 璃基板的表面上形成由ITO90所構成的透明導電膜，進而 於ITO90所構成的第一透明導電膜的表面上直接層積由 ITO5 0-TiO2所構成的第二透明導電膜。把所得到的基板、 第一透明導電膜、及第二透明導電膜進而在大氣中以 523K之溫度（實施例7) 、623K之溫度（實施例8)、 7 23 Κ之溫度（實施例9 )加熱一小時而得具透明導電膜之 玻璃基板。 (實施例1 〇〜1 2 )[Technical Field] The present invention relates to a substrate having a transparent conductive laminate comprising a transparent conductive laminate containing indium oxide on a surface of a substrate, and a method for producing the same. [Prior Art] As a material of the transparent conductive film, there is a bismuth tin composite oxide (ΑΤΟ) which is doped with tin oxide, and an aluminum-zinc composite oxide (ΑΖΟ) which is doped with zinc oxide. And an indium tin composite oxide (yttrium) in which tin oxide is doped with tin is known. Among them, the ruthenium film has a higher conductivity than the ruthenium film and the ruthenium film, and has a high light transmittance in the visible light region. Therefore, it is widely used as a material for a transparent electrode such as a liquid crystal display element or an electroluminescence display element. However, since the ruthenium film has a high material cost due to the high indium content, the transparent conductive film having a reduced indium content has been reviewed, for example, Japanese Patent Publication No. 7-3 3 5 03 1 (Patent Document 1) An indium oxide-based powder containing at least one of tin oxide, titanium oxide, and an oxidation pin using sintering as a dopant, and oxidizing at least one of cerium oxide, cerium oxide, and cerium oxide as a dopant A conductive film formed by a conductive oxide obtained by mixing a tin-based powder. However, the conductive film described in Patent Document 1 can reduce the amount of indium contained, but such a conductive film has light transmittance (especially whether the transmittance in the visible light region is sufficiently large) and conductivity (resistivity). Is it small enough? These points are still insufficient. [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open No. Hei 7-3 3 503 1 (Summary of the Invention) [Problems to be Solved by the Invention] The present invention has been made in view of the foregoing prior art The invention has been made in an effort to provide a substrate having a transparent conductive laminate having a sufficiently high light transmittance and a sufficiently low resistivity even if the indium content is reduced, and a method for producing the same. [Means for Solving the Problem] The inventors of the present invention have found that the substrate is formed on the surface of the substrate to contain oxidation by a method of manufacturing a substrate having a transparent conductive laminate in order to achieve the above object. The transparent conductive laminate of indium includes: a step of directly or indirectly forming a first transparent conductive film having an indium oxide content of 80 to 98% by mass on the surface of the substrate, and a surface upper layer of the first transparent conductive film a step of depositing a second transparent conductive film having an indium oxide content of 45 to 75 mass%, and a step of heating the second transparent conductive film at a temperature of 3500 to 950K with a transparent conductive laminate The substrate having the transparent conductive laminate having the crystal structure of the first transparent conductive film and the second transparent conductive film having the same crystal structure as the indium oxide crystal obtained by the method of manufacturing the substrate has a reduced indium content even -6- 201212047 The present invention has been completed by sufficiently high light transmittance and sufficiently low electrical resistivity. That is, the substrate having the transparent conductive laminate of the present invention is a substrate having a transparent conductive laminate in which a transparent conductive laminate containing indium oxide is formed on the surface of the substrate, which is characterized by the aforementioned transparent conductive layer. a first transparent conductive film having an indium oxide content of 80 to 98% by mass and a second transparent conductive film having an indium oxide content of 45 to 75 mass% laminated on a surface of the first transparent conductive film, and The first transparent conductive film and the second transparent conductive film have a crystal structure having a crystal structure equivalent to that of indium oxide crystal. In the present invention, a crystal having a crystal structure equivalent to that of indium oxide crystal is based on a copper crucible. X-ray diffraction measurement of the α-line The results obtained by investigating the crystal structure in the film were around 20 = 21.5 degrees, around 30.6 degrees, around 35.5 degrees, around 37.7 degrees, around 41.8 degrees, around 45.7 degrees, and at 5 degrees. At least one of the groups selected in the vicinity, near 56.0 degrees, and around 60.7 degrees has a diffraction peak, and the S/N ratio of the diffraction peak is preferably 1 or more. Further, before the present invention The transparent conductive laminate, the transmittance of the system to the entire range of the wavelength of light is 800~2500nm the laminate of 80% or more is preferred. Further, the X-ray diffraction pattern of the first transparent conductive film and the second transparent conductive film is obtained in the vicinity of 20 = 21.5 degrees and 30.6 degrees in the X-ray diffraction measurement of the copper κ α line. It is preferable that at least one of the groups selected in the vicinity of 35.5 degrees, around 51.0 degrees, and around 60.7 degrees has a diffraction peak. Further, at least one crystal selected from the group consisting of In2〇3 crystal and 11145113012 crystal is preferable. Further, in the present invention, the "Ιη203 crystal" is a result of examining the crystal structure in the film by X-ray diffraction measurement of the copper Κα line, and is caused by the cubic bixbyite structure of the indium oxide crystal. The diffraction peak, that is, near 20 = 21.5 degrees, around 30.6 degrees, around 35.5 degrees, near 37.7 degrees, near 41.8 degrees, near 45.7 degrees, near 51.0 degrees, near 56.0 degrees, and around 60.7 degrees The diffraction peak is present in at least one of the groups selected, and the S/N ratio of the diffraction peak is preferably 1 or more. In addition, the "In4Sn3012 crystal" is a result of examining the crystal structure in the film by the X-ray diffraction measurement of the copper Κα line, and is caused by the rhombohedral crystal or the hexagonal crystal structure of the In4Sn3〇12 crystal. , that is, at least in the vicinity of 20 = 3 0 · 6 degrees, 3 5 · 5 degrees (preferably near 3 5.3), 5 1.0 degrees, 56.0 degrees, and 60.7 degrees. There is a diffraction peak, and crystals of separated peaks exist in the vicinity of 20 = 30.6 degrees, around 51.0 degrees, and around 60.7 degrees, and the S/N ratio of the above-mentioned diffraction peak is preferably 1 or more. Further, a method for producing a substrate having a transparent conductive laminate according to the present invention is a method for producing a substrate having a transparent conductive laminate in which a transparent conductive laminate containing indium oxide is formed on a surface of a substrate, and is characterized in that The method comprises the steps of: forming a first transparent conductive film having an indium oxide content of 80 to 98% by mass or directly on the surface of the substrate, and depositing an indium oxide content of 45 on the surface of the first transparent conductive film; a step of removing the second transparent conductive film by -75 mass%, and a step of heating the second transparent conductive film at a temperature of 305 to 201212047 950 K. The step of heating the second transparent conductive film according to the present invention is preferably carried out in any of the following manners. (1) a step of heating the second transparent conductive film by heating the substrate and the first transparent conductive film at a temperature of 3500 to 950° by the step of laminating the second transparent conductive film And proceed. Further, '(2) heating the step of the second transparent conductive film relating to the present invention' is performed after the step of laminating the second transparent conductive film. Further, in the case of (1), it is preferred that the temperature of the second transparent conductive film is heated to 3,500 to 600 Torr. Further, in the case of (2), it is preferred that the temperature of the second transparent conductive film is heated to 4,500 to 950 Torr. Further, the thickness of the first transparent conductive film according to the present invention is 6 to 50 nm, and the thickness of the second transparent conductive film is preferably 50 to 150 nm. Further, the second transparent conductive film of the present invention is the most It is a group selection consisting of oxides of tin, antimony, bismuth, molybdenum, iron, indium, zinc, antimony, gallium, sand, pin, magnesium, aluminum, gold, silver, copper, palladium, tungsten, and these. At least one of the transparent conductive films. Further, in the substrate having a transparent conductive laminate of the present invention, the reason why a sufficiently high light transmittance and a sufficiently low specific resistance can be achieved even if the indium content is reduced is not determined, but the inventors of the present invention presume the following. That is, the substrate having the transparent conductive laminate of the present invention is laminated on the transparent conductive film having a low indium oxide content and which is not easily crystallized, and is laminated in an indium oxide content of 80 to -9 to 201212047 9% by mass. On the surface of the transparent conductive film which is likely to be a crystal structure, the temperature of 550 to 950K is applied to the surface of the transparent conductive film, and the crystallization of the transparent conductive film contained in the indium oxide is promoted to have the same degree as the "indium oxide crystal". Since the structure of the bixbyite is estimated, it is estimated that the substrate having the transparent conductive laminate can have sufficiently high light transmittance and sufficiently low resistivity even if the indium content is reduced. [Effect of the invention] According to the present invention, it is possible to provide a method for producing a transparent conductive laminate having a light transmissive property and a sufficiently low electrical resistivity even if the indium content is reduced. [Embodiment] First, a transparent conductive laminate of the present invention will be described. The substrate of the transparent conductive layered body is a transparent conductive layered body of a transparent conductive layered body containing indium oxide on the surface of the substrate, which is characterized by the aforementioned transparent An electric laminated board comprising: a first transparent conductive film having an indium oxide content of 98% by mass; and a second conductive film having an indium oxide content of 45 to 75 mass% laminated on a surface of the first transparent film, and The first transparent conductive film and the second transparent conductive material have crystals having a crystal structure equivalent to that of the indium oxide crystal. The substrate used in the present invention is heated as long as it has high light transmission to the manufacturing method of the present invention to be described later. The transparent conductive film may be made of a material that does not deteriorate, and for example, polyimine and polypyrene may be present in a low amount. The invention is characterized in that the substrate is formed into a substrate and the conductive substrate is made of a transparent plate.芳醯-10- 201212047 Heat-resistant resin such as amine, polyphenylene sulfide or polyether oxime and glass. In addition, the thickness of the substrate is not particularly limited, and the light transmittance or strength of the substrate having the transparent conductive laminate of the present invention or the use pattern of the substrate having the transparent conductive laminate of the present invention is adapted to the above materials. Appropriate use. The first transparent conductive film used in the present invention is a transparent conductive film formed directly or indirectly on the surface of the substrate. The first transparent conductive film used in the present invention may be directly laminated on the surface of the substrate, and a transparent functional film may be disposed on the substrate in order to increase the transmittance and increase the reflectance or the barrier property. Also between. Further, as the first transparent conductive film used in the present invention, the indium oxide content in the film is preferably from 80 to 98% by mass, preferably from 90 to 97% by mass. When the indium oxide content is more than the above-mentioned upper limit, the carrier density in the first transparent conductive film used in the present invention is small, so that the electrical resistivity is high. On the other hand, if the lower limit is not reached, it is difficult to promote the second transparent conductive which will be described later. Crystallization of the film. Further, the first transparent conductive film used in the present invention contains other metals and metal oxides in addition to indium oxide, and examples thereof include tin, chin, recording, pin, iron, inscription, remarks, 姊, marry, sand. The oxides of the pin, the watch, the brocade, the gold, the silver, the copper, the palladium, the tungsten, and the like, and the metal or the metal oxide may be contained in the film alone or in combination of two or more kinds. Among such oxides, tin oxide is preferably in the present invention from the viewpoint of the role of the dopant having high bismuth conductivity and the light transmittance of the substrate having the transparent conductive laminate of the present invention. The first transparent conductive film to be used is preferably contained together with indium oxide. -11 - 201212047 Further, in the first transparent conductive film used in the present invention, indium oxide is required to have a crystal structure. Further, in the first transparent conductive film used in the present invention, it is preferable that the substrate surface is grown in parallel in a film shape from the viewpoint of reducing the resistivity of the film, and the crystallinity of indium oxide in the film is 50 to 10,000. % is better. Further, the crystallinity of indium oxide in the film can be estimated by the change in the intensity of the diffraction peak obtained by the X-ray diffraction analysis. Further, in the first transparent conductive film used in the present invention, the result of examining the crystal structure in the film based on the X-ray diffraction measurement of the copper Κα line, that is, it is necessary to be around 20 = 21.5 degrees, around 30.6 degrees, and 35.5. At least one of the groups selected by the group consisting of the vicinity of 37.7 degrees, 41.8 degrees near 45.7 degrees, 51.0 degrees, 5 6.0 degrees, and 60.7 degrees, there is a diffraction peak, and the aforementioned diffraction peak S/ It is preferred that the N ratio is 1 or more. Further, from the viewpoint of improving the mobility and reducing the resistivity of the film, the X-ray diffraction pattern of the first transparent conductive film obtained by the X-ray diffraction measurement of the copper κα line is obtained at 20 = Preferably, at least one of the groups selected from the group consisting of 21.5 degrees, 30.6 degrees, 35.5 degrees, 51.0 degrees, and 60.7 degrees is preferably a diffraction peak, and has a first transparency for use in the present invention. The crystal having a crystal structure equivalent to that of the indium oxide crystal of the conductive film is preferably at least a crystal selected from the group consisting of Ιη203 crystal and In4Sn301; Further, the thickness of the first transparent conductive film used in the present invention is preferably 6 to 50 nm, more preferably 8 to 15 nm. When the thickness exceeds the upper limit of the cutting, the cost of manufacturing the substrate having the transparent conductive laminate of the present invention tends to be high, and on the other hand, the three tongues that do not reach the lower limit are the membranes-12-201212047 Since the substrate is easily broken in many places and becomes an island shape, the substrate having the transparent conductive laminate of the present invention tends to have a high electrical resistivity. The second transparent conductive film used in the present invention is laminated on the surface of the first transparent conductive film, and has an indium oxide content of 45 to 75 mass%, preferably 45 to 55 mass%. When the content of the indium oxide content exceeds the above upper limit, the substrate having the transparent conductive laminate of the present invention has a high manufacturing cost, and on the other hand, if the lower limit is not reached, the second transparent conductive film becomes difficult. There is a crystal having a crystal structure equivalent to that of indium oxide crystal. Further, from the viewpoint of reducing the cost of manufacturing the substrate having the transparent conductive laminate of the present invention, the difference between the indium oxide content of the first transparent conductive film and the second transparent conductive film used in the present invention is 40 to 50. The mass % is preferred. Further, the second transparent conductive film used in the present invention contains, in addition to indium oxide, other metals and metal oxides, and examples thereof include tin, titanium, germanium, iron, cobalt, zinc, lanthanum, gallium, and antimony. And the oxides of the cones, magnesium, aluminum, gold, silver, copper, palladium, tungsten, and the like, and such metals and metal oxides may be contained in the film alone or in combination of two or more types. Among such metals and oxides, tin, titanium, and tantalum are used from the viewpoint of the role of the dopant having high conductivity and the light transmittance of the substrate having the transparent conductive laminate of the present invention. Molybdenum, iron, zinc, gallium, antimony, magnesium, aluminum and oxides thereof are preferred. Further, when the substrate having the transparent conductive laminate of the present invention is used as a transparent electrode material for a solar cell, a transparent conductive laminate having high transmittance without absorption in the infrared region is obtained. From the viewpoint of the substrate, the transparent conductive film of the -13 to 201212047 used in the present invention preferably contains tin or tin oxide. Further, as the second transparent conductive film used in the present invention, it is possible to obtain a transparent conductive laminate in which the volume resistivity is sufficiently low and the light transmittance in the entire region of the wavelength of 800 to 2500 nm is 80% or more. The second transparent conductive film used in the present invention has an indium oxide content of 45 to 55 mass%, a tin oxide content of 40 to 50% by mass, and a cerium oxide content of 1 to 1% by mass. good. Further, in the second transparent conductive film used in the present invention, it is necessary for the indium oxide to have a crystal structure, and similarly to the first transparent conductive film, it is preferable that the substrate surface is grown in parallel in a film shape, and the crystallinity in the film is 50. 〜100% is preferable. Further, in the second transparent conductive film used in the present invention, the result of examining the crystal structure in the film based on the X-ray diffraction measurement of the copper Κα: line is necessary at 20 = 21.5 degrees. There is a diffraction peak in at least one of the group selected from the vicinity, the vicinity of 30.6 degrees, the vicinity of 35.5 degrees, the vicinity of 37.7 degrees, the vicinity of 41.8 degrees, the vicinity of 45.7 degrees, the vicinity of 51.0 degrees, the vicinity of 56.0 degrees, and the vicinity of 60.7 degrees. It is preferred that the above-mentioned diffraction peak has an S / Ν ratio of 1 or more. Further, from the viewpoint of improving the mobility and reducing the resistivity of the film, the X-ray diffraction pattern of the second transparent conductive film obtained by the X-ray diffraction measurement of the copper Κα line is at = 21.5 degrees. It is preferable that at least one of the groups selected in the vicinity, around 30.6 degrees, in the vicinity of 35.5 degrees, in the vicinity of 5 1.0 degrees, and in the vicinity of 60.7 degrees, a diffraction peak is preferable, and has a second transparent conductive film to be used in the present invention. At least one junction selected from the group consisting of Ιη203 crystal and In4Sn3012 crystal is prepared as a crystal having the same crystal structure as the indium oxide crystal. Further, as the thickness of the second transparent conductive film used in the present invention, It is preferably 50 to 150 nm. When the thickness exceeds the above-described upper limit, the light transmittance of the substrate having the transparent conductive laminate of the present invention tends to be insufficiently high. On the other hand, if the lower limit is not satisfied, the present invention is used. In the case of a device having a substrate of a transparent conductive laminate, sufficient conductivity may not be obtained on a substrate having irregularities. Further, the total thickness of the first transparent conductive film and the second transparent conductive film is preferably 50 to 150 nm. When the thickness exceeds the above-described upper limit, the light transmittance of the substrate having the transparent conductive laminate of the present invention tends to be insufficiently high. On the other hand, if the lower limit is not satisfied, the present invention is used. In the case of a device having a substrate of a transparent conductive laminate, sufficient conductivity may not be obtained on a substrate having irregularities. Next, a method of manufacturing a substrate having a transparent conductive laminate of the present invention will be described. A method for producing a substrate having a transparent conductive laminate according to the present invention, which is characterized in that a substrate having a transparent conductive laminate in which a transparent conductive laminate containing indium oxide is formed on a surface of the substrate is characterized in that And the step of forming the first transparent conductive film directly or indirectly on the surface of the substrate, and the step of laminating the second transparent conductive film on the surface of the first transparent conductive film, and the second transparent conductive When the film is heated at a temperature of 3 50 to 950 ° C, and the temperature of the second transparent conductive film is heated to exceed the upper limit, the decrease in the carrier density in the second transparent conductive film may cause a resistance. On the other hand, if the lower limit is not reached, the degree of mobility is reduced due to the amorphous structure of -15 to 201212047 in the second transparent conductive film. As a method of forming the first transparent conductive film and the front second transparent conductive film according to the present invention, a physical film forming method such as a sputtering method or a vacuum vapor deposition ion implantation method may be employed, and a thermal spray method may be used. A chemical film forming method such as a coating method or a CVD method. Among them, from the viewpoint of easily forming a large-sized transparent conductive film having sufficient conductivity, sputtering is preferred. The method for manufacturing a substrate having a transparent conductive laminate according to the present invention as a first manufacturing method, the step of heating the second transparent conductive film, and the step of stacking the second transparent conductive film, the substrate and the first A method in which a transparent conductive film is heated at a temperature of 350 to 950 K, as a temperature for heating the second transparent conductive film, preferably 350 600 K is more preferably 400 to 550K. When the temperature of the second transparent conductive film is increased by more than the upper limit, the resistivity tends to increase as the carrier density in the second transparent conductive is reduced. On the other hand, when the lower limit is not reached, the above-mentioned lower limit is caused. The amorphous structure in the second transparent conductive tends to be easily reduced in mobility. Further, the first method for manufacturing the substrate of the transparent conductive laminate of the present invention 'heats the second transparent conductive film to a temperature of about 523 K to be at a relatively low temperature, and the obtained transparent conductive layer is laminated. From the viewpoint of the low resistivity of the body plate, it can be suitably used in a step of manufacturing a device such as a flat panel display for a material for a transparent electrode. Further, as a second manufacturing method, the step of heating the second transparent conductive layer is performed after the step of laminating the second transparent conductive film, and the method of laminating the film for the base film is performed. 16-201212047 The method, as the temperature for heating the second transparent conductive film, is preferably 450 to 950 K, more preferably 5 23 to 7 23 K. When the temperature of the second transparent conductive film is more than the upper limit, the resistivity tends to increase as the carrier density in the second transparent conductive film is halved. On the other hand, if the lower limit is not reached, the cause is caused. The amorphous structure in the second transparent conductive film tends to be easily reduced in mobility. Further, the heating time of the second transparent conductive film is not particularly limited, and it is considered that the heating temperature is the same as the above-mentioned heating temperature, which is accompanied by a decrease in the carrier density in the second transparent conductive film or a decrease in light transmittance due to oxygen deficiency. The composition of the two transparent conductive films and the thickness of the second transparent conductive film are appropriately selected. Further, in the heat treatment, it is carried out in the presence of oxygen gas, which is preferable from the viewpoint of obtaining a substrate having a transparent conductive laminate of the present invention having high light transmittance. [Examples] Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. (Example 1) A sputtering apparatus (manufactured by ULVAC, 'product name "CS_2〇0") was used as a target ITO target by sputtering power DC (DC) 1 〇〇w ' (manufactured by ULVAC Corporation and Mitsui Co., Ltd.) Manufactured by a metal mining company, indium oxide content in ITO: 90% by mass, tin oxide content: 1 〇 mass%, below -17-201212047 called r ITO90"), on a rotating glass substrate (thickness: 0.7 mm, long) : 50mm, width: 50mm 'manufactured by Corning, product name "EAGLE2000"), the substrate heating temperature is 523K, the pressure in the reaction tank is 〇.68Pa' argon flow rate is 50sccm, oxygen flow rate is 0.2sccm Sputtering was performed to form a first transparent conductive film made of ITO 90 having a thickness of 12 nm. Further, 'the transparent conductive layer made of ITO90 which is obtained by the IT ◦ target (manufactured by Mitsui Mining and Mining Co., Ltd., having an indium oxide content of 50% by mass in ITO and a tin oxide content of 50% by mass 'hereinafter referred to as "ITO50") On the surface of the film, sputtering was performed under the same conditions as described above except that the flow rate of oxygen was changed to 0.3 seem, and a second transparent conductive film composed of ITO50 having a thickness of 13 8 nm was formed, thereby obtaining a transparent conductive layer. The glass substrate of the body. In addition, the thickness of each film of the obtained glass substrate of the transparent conductive laminated body was partially peeled off by the ITO film removal processing apparatus (product name "LXSY-UV" by Laserx Corporation), and the surface shape evaluation system was used. (The product name "L-Tracell" manufactured by SII Corporation) was measured. Further, the transparent conductive laminate obtained in Example 1 had an indium oxide content of 53% by mass and a tin oxide content of 47% by mass calculated from the composition and film thickness of the target (Example 2). Instead of splashing ITO target (ITO50), the ITO target (ITO50) was sputtered with a sputtering power of DC100W, and a high-frequency (RF) 20W sputtered titanium oxide target was sputtered (high-purity chemical research institute, -18-201212047 in the target material: 99.9% by mass) A glass substrate having a transparent conductive laminate was produced in the same manner as in Example 1 except that the oxygen gas flow rate was changed to 0 sccm and sputtering was performed. The obtained glass substrate having a transparent conductive laminate is directly laminated on the surface of the first transparent conductive film composed of ITO 90 having a thickness of 140 nm and the second transparent layer of TI0 doped with titanium. A conductive film (hereinafter referred to as a factory IT050; a second transparent conductive film made of Ti). Further, the transparent conductive laminate obtained in Example 2 had an indium oxide content of 51% by mass and a tin oxide content of 44% by mass of the titanium oxide content of 5% by mass, calculated from the composition and film thickness of the target. . (Example 3) In place of the ITO target (ITO50) instead of the ITO target added with yttrium (manufactured by Mitsui Mining & Mining Co., Ltd., indium oxide content in ITO target: 50% by mass, tin oxide content: 45% by mass' A glass substrate having a transparent conductive laminate was produced in the same manner as in Example 1 except that the cerium oxide content: 5% by mass, hereinafter referred to as "ITO 5 0; S b"). The obtained glass substrate having a transparent conductive laminate was directly laminated on the surface of the first transparent conductive film made of ITO 90 having a thickness of 12 nm, and was laminated with a second layer of "ITO50; Sb" having a thickness of 13 nm. Transparent conductive film. Further, the transparent conductive laminate obtained in Example 3 had an indium oxide content of 53 mass% and a tin oxide content of 42 mass, which was calculated from the composition of the target and the film thickness. /. The cerium oxide content was 5% by mass. (Comparative Examples 1 to 3) -19-201212047 A glass substrate having a transparent conductive film was produced in the same manner as in Examples 1 to 3 except that a film made of ITO 90 was not formed. Namely, the transparent conductive film obtained in Comparative Example 1 was a film composed of ITO 50 having a thickness of 153 nm, and the content of indium oxide in the film was 50% by mass. The content of tin oxide was 50% by mass. Further, the transparent conductive film obtained in Comparative Example 2 was a film composed of "ITO50; Ti02" having a thickness of 150 nm, and the indium oxide content in the film was 47.5 mass%, and the tin oxide content was 47.5% by mass. The content is 5% by mass. Further, the transparent conductive film obtained in Comparative Example 3 was a film composed of "ITO50; Sb" having a thickness of 150 nm, and the indium oxide content in the film was 50% by mass, the tin oxide content was 45% by mass, and the cerium oxide content was It is 5 mass%. (Examples 4 to 6) A transparent conductive film made of ITO 90 was formed on the surface of the glass substrate in the same manner as in Example 1 except that the substrate was not heated, and the surface of the first transparent conductive film made of ITO 90 was further formed. Directly laminating a second transparent conductive film composed of ITO 50. The obtained substrate, the first transparent conductive film, and the second transparent conductive film are further subjected to a temperature of 5 23 K in the atmosphere (Example 4). The temperature of 623 K (Example 5) and the temperature of 723 K (Example 6) were heated for one hour to obtain a glass substrate having a transparent conductive film (Examples 7 to 9). The same procedure as in Example 2 except that the substrate was not heated. On the surface of the glass substrate, a transparent conductive film made of ITO90 is formed on the surface of the glass substrate, and the first layer of the first transparent conductive film made of ITO 90 is directly laminated with ITO5 0-TiO2. Two transparent conductive films. The obtained substrate, the first transparent conductive film, and the second transparent conductive film were further subjected to a temperature of 523 K in the atmosphere (Example 7), a temperature of 623 K (Example 8), and a temperature of 7 23 ( (Example 9) The glass substrate having a transparent conductive film is obtained by heating for one hour. (Example 1 〇~1 2 )
除了替代不加熱基板，進而濺鍍ΙΤΟ靶材（ΙΤΟ50 ) 以外，以濺鍍電力DC100W濺鍍ΙΤΟ靶材（ΙΤΟ90)，以濺 鍍電力DC45W濺鍍添加銻的氧化錫靶材（三井金屬礦業公 司製造，靶材中的氧化銻含量：10質量％，氧化錫含量90 質量％)把氧氣氣體流量改爲0.2 seem同時進行濺鍍以外， 與實施例1同樣地進行而形成第一透明導電膜及第二透明 導電膜。把所得到的基板、第一透明導電膜、及第二透明 導電膜進而在大氣中以523K之溫度（實施例1〇) 、623K 之溫度（實施例1 1 ) 、723 K之溫度（實施例12 )加熱一 小時而得具透明導電膜之玻璃基板。所得到的具透明導電 層積體之玻璃基板，係在厚度12nm之ITO90所構成的第一 透明導電膜之表面上，直接被層積由厚度13 6nm之被摻雜 氧化銻的ITO所構成的第二透明導電膜（以下，稱爲「 ITO50; Sb[2]所構成的第二透明導電膜」）。又，由靶材 的組成及膜厚算出的，在實施例1 〇〜1 2所得到的透明導電 -21 - 201212047 層積體之氧化銦含量爲52質量％，氧化錫含量爲44質量％ ，氧化銻含量爲4質量％。 (比較例4〜1 2 ) 除了不形成由ITO90所構成的膜以外，與實施例4〜12 同樣地進行而製作具透明導電膜之玻璃基板。亦即，於比 較例4〜6 (形成膜後之加熱溫度：比較例4爲523 K，比較 例5爲623 K，比較例6爲723K )所得到的透明導電膜，係 由厚度153nm之ITO50所構成之膜，膜中之氧化銦含量爲 5 0質量％，氧化錫含量爲5 0質量％。此外，於比較例7〜9 (形成膜後之加熱溫度：比較例7爲523 K，比較例8爲 623 K，比較例9爲723 K)所得到的透明導電膜，係由厚度 150nm之「ITO50 ; Ti02」所構成之膜，膜中之氧化銦含 量爲47.5質量％，氧化錫含量爲47.5質量％，氧化鈦含量爲 5質量％。進而，於比較例1 0〜1 2 (形成膜後之加熱溫度 :比較例10爲5 23K，比較例1 1爲623K，比較例12爲72 3K )所得到的透明導電膜，係由厚度151nm之「ITO50 ; Sb[2]」所構成之膜，膜中之氧化銦含量爲49質量％，氧化 錫含量爲47質量％，氧化銻含量爲4質量％。 (比較例1 3 ) 除了替代ITO50使用ITO90以外，與比較例4同樣地進 行而製作具透明導電膜之玻璃基板。亦即，於比較例1 3 ( 形成膜後的加熱溫度爲52 3 K )所得到的透明導電膜，係 -22- 201212047 由厚度152nm之ITO90所構成之膜’膜中之氧化姻含量爲 9 0質量％，氧化錫含量爲1 〇質量％。 (實施例1 3 ) 除了替代濺鍍IT 0靶材（IΤ Ο 5 0 )’而以濺鑛電力 DC100W濺鍍ITO靶材（ITO50)，以濺鍍電力高頻（RF) 2 0W濺鏟氧化鐵靶材（高純度化學硏究所製造’靶材中的 氧化鐵（Fe203 )含量：99.9質量。/。）把氧氣氣體流量改爲 0.1 seem同時進行濺鑛以外，與實施例1同樣地進行而製作 具透明導電層積體之玻璃基板。所得到的具透明導電層積 體之玻璃基板，係在厚度12nm之ITO90所構成的第一透明 導電膜之表面上，直接被層積由厚度138nm之被摻雜鐵的 ITO所構成的第二透明導電膜（以下，稱爲「ITO50 ; Fe 所構成的第二透明導電膜」）。又，由靶材的組成及膜厚 算出的，在實施例1 3所得到的透明導電層積體之氧化銦含 量爲51質量％，氧化錫含量爲44質量％，氧化鐵含量爲5質 量％。 (實施例1 4 ) 除了把濺鍍ITO50; Sb時的氧氣氣體流量改爲〇·5 seem 以外，與實施例3同樣地進行而製作具透明導電層積體之 玻璃基板。所得到的具透明導電層積體之玻璃基板，係在 厚度12 nm之ITO90所構成的第一透明導電膜之表面上，直 接被層積由厚度138nm之ITO50 ; Sb所構成的第二透明導 -23- 201212047 電膜。又，由靶材的組成及膜厚算出的，在實施例1 4所得 到的透明導電層積體之氧化銦含量爲5 3質量％，氧化錫含 量爲42質量％，氧化銻含量爲5質量％。 (比較例1 4 ) 除了把濺鍍ITO50改用ITO90，把氧氣氣體流量改爲 0.2sCCm而濺鍍以外，與比較例1同樣地進行而製作具透明 導電膜之玻璃基板。亦即，於比較例1 4所得到的透明導電 膜，係由厚度151nm之ITO90所構成之膜，膜中之氧化銦 含量爲90質量％，氧化錫含量爲1 〇質量％。 (比較例1 5 ) 除了把氧氣氣體流量改爲〇 · 5 s c c m以外，與比較例1同 樣地進行而製作具透明導電膜之玻璃基板。亦即，於比較 例1 5所得到的透明導電膜，係由厚度1 5 Onm之ITO 5 0所構 成之膜’膜中之氧化銦含量爲5 0質量％，氧化錫含量爲50 質量％。 (比較例1 6 ) 除了不形成由ITO90所構成的膜以外，與實施例2同樣 地進fT而製作具透明導電膜之玻璃基板。亦即，於比較例 16所得到的透明導電膜，係由厚度I53nm之「ΙΤΟ50; T i 02」所構成之膜，膜中之氧化銦含量爲4 7 · 5質量％，氧 化錫含量爲47.5質量％，氧化鈦含量爲5質量％。 -24- 201212047 (比較例1 7 ) 除了不形成由ITO90所構成的膜以外，與實施例13同 樣地進行而製作具透明導電膜之玻璃基板。亦即，於比較 例17所得到的透明導電膜，係由厚度151nm之「ITO50; Fe」所構成之膜，膜中之氧化銦含量爲47.5質量％，氧化 錫含量爲47.5質量％，氧化鐵含量爲5質量。/。。 (比較例1 8 ) 除了不形成由ITO90所構成的膜以外，與實施例14同 樣地進行而製作具透明導電膜之玻璃基板。亦即，於比較 例1 8所得到的透明導電膜，係由厚度1 50nm之「ITO50 ; Sb」所構成之膜，膜中之氧化銦含量爲50質量％，氧化錫 含量爲45質量％，氧化銻含量爲5質量％。 針對如此進行而得到的具透明導電層積體之玻璃基板 或具透明導電膜之玻璃基板，進行以下的評估。 (X線繞射測定） 使用X線繞射裝置（BrukerAXS公司製造、製品名「 D8DISCOVER」或者、RIGAKU公司製造、製品名「 RINT2 0 00」）以銅Κ α線爲X線源，在掃描角2 0 = 1〇〜70 度之範圍進行評估，調查20 = 21.5度、30.6度、35_5度' 37.7度、41.8 度、45.7度、51.0度、56_0度、及 60.7度附近 是否存在繞射峰，亦即是否有與氧化銦結晶同樣的結晶構 -25- 201212047 造，而針對在實施例1、實施例2、實施例10、實施例13、 實施例〗4所得到的具透明導電層積體之玻璃基板，在比較 例1、比較例2、比較例1 2所得到的具透明導電膜之玻璃基 板來進行調查。分別針對實施例1於圖1，針對比較例1於 圖2，針對實施例2於圖5，針對比較例2於圖6，針對實施 例1 0於圖1 1，針對比較例1 2於圖1 2，針對實施例1、1 3及 14於圖19及20，顯示所得到的結果此外，於表1顯示以銅 Κ α線爲X線源時於Ιη203相被確認的主要的X線繞射峰。 又，表1中「hkl」爲密勒指數，「2 0」爲繞射角，「d」 爲面間隔，「I」爲相對的繞射強度。 [表1] h k / !2^/°|d/nm / 2 1 1 I 21.5 (0.413 11 2 2 2 I 30.6 i 0.292 100 4 0 0 | 35.5 ; 0.253 31 4 4 0|51.0|0.1788 38 6 2 2 ! 60.7 10.152s 28 (根據透過型電子顯微鏡之觀察） 使用透過型電子顯微鏡（日立製作所製造、製品名「 H-9000NAR」或「H-9000UHR」），觀察實施例1、實施 例2 '實施例1 3、實施例1 4所得到的具透明導電層積體之 玻璃基板，在比較例1、比較例2所得到的具透明導電膜之 玻璃基板之各個的剖面，調查有無結晶相或非晶質層。亦 即，對於各層積體或層積膜施行機械硏磨及Ar離子硏磨’ 製作剖面觀察試片。接著，把所得到的剖面觀察試片，使 -26- 201212047 用透過型電子顯微鏡以加速電壓3 OOkV進行觀察。分別針 對實施例1於圖3，針對比較例1於圖4，針對實施例2於圖7 ，針對比較例2於圖8，針對實施例13於圖21及22，針對實 施例14於圖23及24，顯示所得到的結果。 (體積電阻率） 依據JISK7 194所記載之方法測定具透明導電層積體之 玻璃基板等之體積電阻率。亦即，把具透明導電層積體之 玻璃基板等作爲試片，使用電阻率計（三菱化學 ANALYTECH公司製造、製品名 「RO R E S T E R (音譯） GPMCP-T610」），藉由薄膜用4探針探頭，測定在實施例 1〜1 2所得到的具透明導電層積體之玻璃基板及在比較例1 〜1 3所得到的具透明導電膜之玻璃基板之體積電阻率。分 別針對實施例1〜3、比較例1〜3、及比較例1 3於圖9，針 對實施例4〜6及比較例4〜6於圖13，針對實施例7〜9及比 較例7〜9於圖14，針對實施例10〜12及比較例10〜12於圖 1 5，顯示所得到的結果。 (透過率） 使用分光光度計（日立HIGH-TECHNOLOGY公司製造 、製品名「U- 3 3 1 0」），針對實施例1〜3、實施例4、實 施例7、實施例1 0所得到的具透明導電層積體之玻璃基板 、比較例1 3所得到的具透明導電膜之玻璃基板測定200〜 9 OOnm之波長區域之光的透過率。分別針對實施例1〜3於 -27- 201212047 圖1 0，針對實施例4於圖1 6，針對實施例7於圖1 7，針對實 施例1 〇於圖1 8，顯示所得到的結果。此外，於這些圖，也 一倂顯示在比較例1 3所得到的具透明導電膜之玻璃基板以 及玻璃之透過率。 進而，使用分光光度計（日立HIGH-TECHNOLOGY公 司製造、製品名「U-4100」），以玻璃爲參考試片，針對 實施例1、實施例2、實施例1 3、及實施例1 4所得到的具透 明導電層積體之玻璃基板的透明導電層積體、以及在比較 例1 4〜1 8所得到的具透明導電膜之玻璃基板的透明導電膜 測定200〜2600nm之波長區域之光的透過率。分別針對實 施例1、2、1 3及1 4顯示於圖2 5，針對比較例1 4〜1 8所得到 的具透明導電膜之玻璃基板顯示於圖26。 由圖1所示的結果可知，確認了本發明之具透明導電 層積體之基板（實施例1 )具有氧化銦之結晶相，進而由 圖3所示之結果可知，確認了氧化銦的結晶相係由IT090所 構成的第一導電膜（圖中，白色虛線以下的區域）及 ITO 5 0所構成的第二透明導電膜（途中，白色虛線以上的 區域）全都爲氧化銦之結晶相。另一方面，於未具備相關 於本發明的ITO 90所構成之膜的具透明導電膜之基板（比 較例1 )，由圖2所示之結果可知，顯示氧化銦的結晶相的 繞射光譜強度很弱，由圖4所示之結果可知，由基板起約 至3 0 n m爲止的區域（圖中，白色虛線以下的區域）被確 認了非晶質層。此外，於實施例2及比較例2，也如圖5〜8 所示，確認了與前述同樣的結果。 -28- 201212047 此外，由圖19所示之結果可知’本發明之具透明導電 層積體之基板（實施例1、13及14 )具有氧化銦（Ιη203 ) 之結晶相，進而由圖2 0所示之結果可知’本發明之具透明 導電層積體之基板（特別是實施例1 3 )，於出現在2 0 == 3 0 · 6 °附近的X線繞射圖案，確認了起因於In4 S η3 Ο i 2的結晶 相之峰分離，確認了具有之In4Sn30 i 2結晶相。此外’由圖 2 1及圖2 2所示之結果可知，確認了不僅IT 0 9 0所構成的第 一透明導電膜（圖中「ITO90」）’由「ITO50 ; Fe」所 構成的第二透明導電膜（圖中「ITO50 : Fe」）也是與氧 化銦同等的結晶相。進而由「ITO50 ; Fe」所構成的第二 透明導電膜，相對於由ITO90所構成的第一透明導電膜明 顯進行了外延成長。此外，由圖23及圖24所示之結果可知 ，確認了不僅ITO90所構成的第一透明導電膜（圖中「 ITO90」），由「ITO50; Sb」所構成的第二透明導電膜 (圖中「ITO50: Sb」）也是與氧化銦同等的結晶相。進 而由「ITO5 0 ; Sb」所構成的第二透明導電膜，相對於由 ITO 9 0所構成的第一透明導電膜明顯進行了外延成長。 此外，由圖9所示之結果可知，本發明之具透明導電 層積體之基板（實施例1〜3 )，即使減低了銦含量，也具 有與膜中含有9 0質量％的氧化銦之具透明導電膜之基板（ 比較例I3)同等或者更低的體積電阻率。另一方面，不具 備相關於本發明的由ITO90所構成的膜，未充分具有與氧 化銦結晶同等的結晶構造的具透明導電膜之基板（比較例 1〜3)，即使同一靶材進行了基板加熱同時被濺鍍，與對 -29- 201212047 應之各個實施例1〜3相較，也在體積電阻率上呈現劣勢》 進而，由圖10所示之結果可知’本發明之具透明導電 層積體之基板（實施例1〜3 )在5 00〜900nm之波長區域 呈現約80%之透過率，即使減低了銦含量，也具有與比較 例1 3同樣高的透過率。 此外，由圖25及26所示之結果可知，本發明之具透明 導電層積體之基板（實施例1、2、13及14)之透明導電層 積體於500〜1400nm之波長區域全區域呈現80%以上之高 透過率，即使減低了銦含量，也具有與比起比較例14更寬 的波長區域，特別是在800nm以上的紅外線區域具有很高 的透過率。進而實施例14，於更寬廣的波長區域（500〜 25 00nm )之全區域具有80%以上之高透過率。亦即，本發 明之具透明導電層積體之基板，特別是具備由ITO50 ; Sb 所構成的第二透明導電膜之本發明之具透明導電層積體之 基板，明顯具有優異的紅外線透過能力。 此外，藉由與實施例1〜3、13及14不同之本發明之製 造方法所得到的具透明導電層積體之基板（實施例1 0 )， 也由圖1 1所示之結果可知，確認了具有與氧化銦結晶同等 的結晶構造。另一方面，於未具備相關於本發明的ITO90 所構成之膜的具透明導電膜之基板（比較例12)，由圖12 所示之結果可知，未被確認顯示與氧化銦結晶同等的結晶 構造之繞射光譜。 進而，由圖1 3〜圖1 5所示之結果可知，藉由與實施例 1〜3不同之本發明之製造方法所得到的本發明之具透明導 -30- 201212047 電層積體之基板（實施例4〜12) ’具備有同樣的元素組 成及元素含有率之膜，即使形成膜後在相同溫度被施以加 熱處理，也比起比較例4〜1 2之具透明導電膜之基板分別 具有更低的體積電阻率。 此外，由圖1 6及圖1 7所示之結果可知本發明之具透明 導電層積體之基板（實施例4及實施例7)在450〜900nm 之波長區域呈現約80%之透過率，由圖18所示之結果可知 本發明之具透明導電層積體之基板（實施例10)在5 00〜 900nm之波長區域呈現80%之透過率，本發明之具透明導 電層積體之基板（實施例4、實施例7及實施例1 0 )即使減 低銦含量，也具有與比較例1 3同樣高的透過率。 [產業上利用可能性] 如以上所說明的，根據本發明，可以提供即使減低銦 含量’也有充分高的透光性及充分低的電阻率之具透明導 電層積體之基板及其製造方法。 亦即’本發明之具透明導電層積體之基板，作爲構成 電駿發先顯不兀件、液晶顯不兀件、電致發光顯示元件、 太陽電池等之透明電極、紅外線吸收反射膜、防霧膜、電 磁遮蔽膜等的材料是非常有用的。 此外’根據本發明的話，可以使透明導電膜中的錫含 量增多’因而可以提供沒有在紅外線區域的吸收之高的透 過率之具透明導電層積體之基板’作爲太陽電池等之透明 電極材料特別有用。 -31 - 201212047 【圖式簡單說明】 圖1係顯示在實施例1得到的具透明導電層積體之基板 之X線繞射圖案（上部）及藉由計算得到的具有方鐵錳礦 構造的氧化銦結晶之X線繞射圖案（下部）之圖。 圖2係顯示在比較例1得到的具透明導電膜之基板之X 線繞射圖案（上部）及藉由計算得到的具有方鐵錳礦構造 的氧化銦結晶之X線繞射圖案（下部）之圖。 圖3 (a)係在實施例1所得之具透明導電層積體之基 板的透過型電子顯微鏡的照片；（b )爲以高倍率觀察（a )之透過型電子顯微鏡照片的一部分之照片。 圖4 ( a )係在比較例1所得之具透明導電膜之基板的 透過型電子顯微鏡的照片；（b )爲以高倍率觀察（a )之 透過型電子顯微鏡照片的一部分之照片。 圖5係顯示在實施例2得到的具透明導電層積體之基板 之X線繞射圖案（上部）及藉由計算得到的具有方鐡錳礦 構造的氧化銦結晶之X線繞射圖案（下部）之圖。 圖6係顯示在比較例2得到的具透明導電膜之基板之X 線繞射圖案（上部）及藉由計算得到的具有方鐵錳礦構造 的氧化銦結晶之X線繞射圖案（下部）之圖。 圖7 ( a )係在實施例2所得之具透明導電層積體之基 板的透過型電子顯微鏡的照片；（b )爲以高倍率觀察（a )之透過型電子顯微鏡照片的一部分之照片。 圖8 ( a )係在比較例2所得之具透明導電膜之基板的 -32- 201212047 透過型電子顯微鏡的照片；（b)爲以高倍率觀察（a)之 透過型電子顯微鏡照片的一部分之照片。 圖9係顯示在實施例1〜3所得到之具透明導電層積體 之基板、比較例1〜3及比較例1 3所得到的具透明導電膜之 基板的體積電阻率之圖。 圖1 0係顯示在實施例1〜3所得到之具透明導電層積體 之基板、在比較例1 3所得到的具透明導電膜之基板以及玻 璃的測定波長與透過率的關係之圖。 圖1 1係顯示在實施例1 0得到的具透明導電層積體之基 板之X線繞射圖案（上部）及藉由計算得到的具有方鐵錳 礦構造的氧化銦結晶之X線繞射圖案（下部）之圖。 圖1 2係顯示在比較例1 2得到的具透明導電膜之基板之 X線繞射圖案（上部）及藉由計算得到的具有方鐵錳礦構 造的氧化銦結晶之X線繞射圖案（下部）之圖。 圖13係顯示在實施例4〜6所得到之具透明導電層積體 之基板及在比較例4〜6所得到的具透明導電膜之基板的體 積電阻率之圖。 圖14係顯示在實施例7〜9所得到之具透明導電層積體 之基板及在比較例7〜9所得到的具透明導電膜之基板的體 積電阻率之圖。 圖1 5係顯示在實施例1 0〜1 2所得到之具透明導電層積 體之基板及在比較例1 0〜1 2所得到的具透明導電膜之基板 的體積電阻率之圖。 圖1 6係顯示在實施例4所得到之具透明導電層積體之 -33- 201212047 基板、在比較例1 3所得到的具透明導電膜之基板’以及玻 璃的測定波長與透過率的關係之圖。 圖1 7係顯示在實施例7所得到之具透明導電層積體之 基板、在比較例1 3所得到的具透明導電膜之基板’以及玻 璃的測定波長與透過率的關係之圖。 圖1 8係顯示在實施例1 〇所得到之具透明導電層積體之 基板、在比較例1 3所得到的具透明導電膜之基板，以及玻 璃的測定波長與透過率的關係之圖。 圖1 9係顯示在實施例1、1 3及1 4所得到的具透明導電 膜之基板之X線繞射圖案（上3圖案）及藉由計算得到的 具有方鐵錳礦構造的Ιη203結晶及In4Sn3012結晶之X線繞射 圖案（下2圖案）之圖。 圖20係將圖19所示之X線繞射圖案，在2 0 = 2(Γ〜40° 之範圍擴大的結果之圖。 圖2 1係在實施例1 3所得之具透明導電膜之基板的剖面 之明視野像之透過型電子顯微鏡照片。 圖22係在實施例1 3所得之具透明導電膜之基板的剖面 之高解析像，及FFT (高速傅立葉變換）解析之結果之透 過型電子顯微鏡照片。 圖23係在實施例1 4所得之具透明導電膜之基板的剖面 之明視野像之透過型電子顯微鏡照片。 圖24係在實施例1 4所得之具透明導電膜之基板的剖面 之高解析像’及FFT解析之結果之透過型電子顯微鏡照片 -34- 201212047 圖2 5係顯示在實施例1、2、13及14所得到之具透明導 電層積體之基板的透明導電層積體之測定波長與透過率的 關係之圖。 圖2 6係顯示在比較例1 4〜1 8所得到之具透明導電膜之 基板的透明導電層積膜之測定波長與透過率的關係之圖。 -35-In addition to replacing the substrate without sputtering, and sputtering the target (ΙΤΟ50), the sputtering target DC100W is sputtered with a tantalum target (ΙΤΟ90), and the tin-plated tin oxide target is sputtered by sputtering power DC45W (Mitsui Metal Mining Co., Ltd. The first transparent conductive film was formed in the same manner as in Example 1 except that the content of cerium oxide in the target was 10% by mass and the content of tin oxide was 90% by mass. A second transparent conductive film. The obtained substrate, the first transparent conductive film, and the second transparent conductive film were further subjected to a temperature of 523 K in the atmosphere (Example 1 〇), a temperature of 623 K (Example 1 1 ), and a temperature of 723 K (Example) 12) Heating for one hour to obtain a glass substrate having a transparent conductive film. The obtained glass substrate having a transparent conductive laminate was directly laminated on the surface of the first transparent conductive film composed of ITO 90 having a thickness of 12 nm, and was formed by ITO doped with yttrium oxide having a thickness of 13 nm. The second transparent conductive film (hereinafter referred to as "ITO 50; second transparent conductive film composed of Sb [2]). Further, the transparent conductive-21 - 201212047 laminate obtained in Example 1 〇 to 12 was calculated to have an indium oxide content of 52% by mass and a tin oxide content of 44% by mass, calculated from the composition and film thickness of the target. The cerium oxide content was 4% by mass. (Comparative Examples 4 to 1 2) A glass substrate having a transparent conductive film was produced in the same manner as in Examples 4 to 12 except that the film made of ITO 90 was not formed. That is, the transparent conductive film obtained in Comparative Examples 4 to 6 (heating temperature after film formation: 523 K in Comparative Example 4, 623 K in Comparative Example 5, and 723 K in Comparative Example 6) was ITO 50 having a thickness of 153 nm. In the film formed, the indium oxide content in the film was 50% by mass, and the tin oxide content was 50% by mass. Further, in Comparative Examples 7 to 9 (heating temperature after film formation: 523 K in Comparative Example 7, 623 K in Comparative Example 8, and 723 K in Comparative Example 9), the transparent conductive film was 150 nm thick. The film composed of ITO50; Ti02" had an indium oxide content of 47.5% by mass, a tin oxide content of 47.5% by mass, and a titanium oxide content of 5% by mass. Further, the transparent conductive film obtained in Comparative Examples 10 to 12 (heating temperature after film formation: 5 23 K in Comparative Example 10, 623 K in Comparative Example 1 and 72 3K in Comparative Example 12) was 151 nm in thickness. The film composed of "ITO50; Sb[2]" had an indium oxide content of 49% by mass, a tin oxide content of 47% by mass, and a cerium oxide content of 4% by mass. (Comparative Example 1 3) A glass substrate having a transparent conductive film was produced in the same manner as in Comparative Example 4 except that ITO 90 was used instead of ITO 50. That is, the transparent conductive film obtained in Comparative Example 13 (heating temperature after film formation was 52 3 K) was -22-201212047. The film having a thickness of 152 nm of ITO90 had an oxidized content of 9 in the film. 0% by mass, the tin oxide content is 1% by mass. (Example 1 3) In addition to the sputtering of the IT 0 target (IΤ Ο 50), the ITO target (ITO50) was sputtered with a splash power DC100W, and sputtered with a high frequency (RF) 20 W splash. The iron target (content of iron oxide (Fe203) in the target manufactured by the High Purity Chemical Research Institute: 99.9 mass%) was carried out in the same manner as in Example 1 except that the oxygen gas flow rate was changed to 0.1 seem and sputtering was performed. A glass substrate having a transparent conductive laminate is produced. The obtained glass substrate having a transparent conductive layered body was directly laminated on the surface of the first transparent conductive film composed of ITO 90 having a thickness of 12 nm, and was directly laminated with ITO having a thickness of 138 nm of iron doped with ITO. A transparent conductive film (hereinafter referred to as "ITO50; second transparent conductive film made of Fe"). Further, the transparent conductive laminate obtained in Example 13 had an indium oxide content of 51% by mass, a tin oxide content of 44% by mass, and an iron oxide content of 5% by mass, calculated from the composition and film thickness of the target. . (Example 1 4) A glass substrate having a transparent conductive laminate was produced in the same manner as in Example 3 except that the flow rate of the oxygen gas when the ITO 50; Sb was sputtered was changed to 〇·5 seem. The obtained glass substrate having a transparent conductive layered body is directly laminated on the surface of the first transparent conductive film composed of ITO90 having a thickness of 12 nm, and is directly laminated with ITO 50 having a thickness of 138 nm; a second transparent guide composed of Sb. -23- 201212047 Electric film. Further, the transparent conductive laminate obtained in Example 14 had an indium oxide content of 53% by mass, a tin oxide content of 42% by mass, and a cerium oxide content of 5 mass, which was calculated from the composition and film thickness of the target. %. (Comparative Example 1 4) A glass substrate having a transparent conductive film was produced in the same manner as in Comparative Example 1, except that the ITO 90 was changed to the ITO 90, and the flow rate of the oxygen gas was changed to 0.2 scc. That is, the transparent conductive film obtained in Comparative Example 14 is a film composed of ITO 90 having a thickness of 151 nm, and the indium oxide content in the film is 90% by mass, and the tin oxide content is 1% by mass. (Comparative Example 1 5) A glass substrate having a transparent conductive film was produced in the same manner as in Comparative Example 1, except that the flow rate of the oxygen gas was changed to 〇 · 5 s c c m . That is, the transparent conductive film obtained in Comparative Example 15 had an indium oxide content of 50% by mass and a tin oxide content of 50% by mass in the film formed of ITO 50 having a thickness of 15 nm. (Comparative Example 1 6) A glass substrate having a transparent conductive film was produced in the same manner as in Example 2 except that the film made of ITO 90 was not formed. That is, the transparent conductive film obtained in Comparative Example 16 was a film composed of "ΙΤΟ50; T i 02" having a thickness of I53 nm, and the indium oxide content in the film was 47.5% by mass, and the tin oxide content was 47.5. The mass% and the titanium oxide content were 5% by mass. -24-201212047 (Comparative Example 1 7) A glass substrate having a transparent conductive film was produced in the same manner as in Example 13 except that the film composed of ITO 90 was not formed. That is, the transparent conductive film obtained in Comparative Example 17 is a film composed of "ITO50; Fe" having a thickness of 151 nm, and the indium oxide content in the film is 47.5 mass%, and the tin oxide content is 47.5 mass%, iron oxide. The content is 5 mass. /. . (Comparative Example 1 8) A glass substrate having a transparent conductive film was produced in the same manner as in Example 14 except that the film composed of ITO 90 was not formed. That is, the transparent conductive film obtained in Comparative Example 18 is a film composed of "ITO50; Sb" having a thickness of 50 nm, and the indium oxide content in the film is 50% by mass, and the tin oxide content is 45% by mass. The cerium oxide content was 5% by mass. The following evaluation was carried out on the glass substrate having the transparent conductive laminate or the glass substrate having the transparent conductive film obtained in this manner. (X-ray diffraction measurement) The X-ray diffraction device (manufactured by Bruker AXS Co., Ltd., product name "D8DISCOVER" or manufactured by RIGAKU Co., Ltd., product name "RINT2 0 00") is used as the X-ray source at the scanning angle. 2 0 = 1〇~70 degree range is evaluated to investigate whether there are diffraction peaks around 20 = 21.5 degrees, 30.6 degrees, 35_5 degrees '37.7 degrees, 41.8 degrees, 45.7 degrees, 51.0 degrees, 56_0 degrees, and 60.7 degrees. That is, whether or not there is a crystal structure of the same as that of the indium oxide crystal, and a transparent conductive layer body obtained in the first embodiment, the second embodiment, the tenth embodiment, the third embodiment, and the fourth embodiment is obtained. The glass substrate was investigated in the glass substrate with a transparent conductive film obtained by the comparative example 1, the comparative example 2, and the comparative example 12. 1 for FIG. 1 , FIG. 2 for comparative example 1, FIG. 5 for embodiment 2, FIG. 6 for comparative example 2, and FIG. 1 for FIG. 1 2, the results obtained are shown in FIGS. 19 and 20 for the first, third, and fourth embodiments. Further, in Table 1, the main X-ray winding confirmed in the phase θ203 when the copper Κα line is used as the X-ray source is shown in Table 1. Shoot the peak. Further, in Table 1, "hkl" is a Miller index, "20" is a diffraction angle, "d" is a plane interval, and "I" is a relative diffraction intensity. [Table 1] hk / !2^/°|d/nm / 2 1 1 I 21.5 (0.413 11 2 2 2 I 30.6 i 0.292 100 4 0 0 | 35.5 ; 0.253 31 4 4 0|51.0|0.1788 38 6 2 2! 60.7 10.152s 28 (observation by transmission electron microscope) Using a transmission electron microscope (manufactured by Hitachi, Ltd., product name "H-9000NAR" or "H-9000UHR"), observe Example 1 and Example 2 'Implementation Example 1 3. The glass substrate having the transparent conductive laminate obtained in Example 1 and the cross section of each of the glass substrates having the transparent conductive film obtained in Comparative Example 1 and Comparative Example 2 were examined for the presence or absence of a crystal phase or a non-crystal phase. The crystal layer, that is, the mechanical honing and Ar ion honing of each layered or laminated film is used to produce a cross-sectional observation test piece. Then, the obtained cross-section observation piece is used to make the -26-201212047 transparent type. The electron microscope was observed at an acceleration voltage of 3 OO kV, respectively for FIG. 3 for Example 1, FIG. 4 for Comparative Example 1, FIG. 7 for Example 2, FIG. 8 for Comparative Example 2, and FIG. And 22, the results obtained are shown for Example 14 in Figures 23 and 24. (Volume resistance The volume resistivity of a glass substrate or the like having a transparent conductive laminate is measured by a method described in JIS K7 194. That is, a glass substrate having a transparent conductive laminate is used as a test piece, and a resistivity meter (Mitsubishi Chemical ANALYTECH) is used. A glass substrate having a transparent conductive laminate obtained in Examples 1 to 12 and a comparative example were produced by a company-produced product name "RO RESTER (GPMCP-T610)" by a 4-probe probe for a film. The volume resistivity of the glass substrate having a transparent conductive film obtained in 1 to 13 is directed to Examples 1 to 3, Comparative Examples 1 to 3, and Comparative Example 1 3, and to Examples 4 to 6 and comparisons. Examples 4 to 6 are shown in Fig. 13, and Examples 7 to 9 and Comparative Examples 7 to 9 are shown in Fig. 14, and Examples 10 to 12 and Comparative Examples 10 to 12 are shown in Fig. 15. The obtained results are shown. Transparent conductive materials obtained in Examples 1 to 3, Example 4, Example 7, and Example 10 using a spectrophotometer (manufactured by Hitachi HIGH-TECHNOLOGY, product name "U-3301") The glass substrate of the laminate and the transparent film obtained in Comparative Example 13 The glass substrate of the electric film measures the transmittance of light in a wavelength region of 200 to 900 nm. For Examples 1 to 3 to -27-201212047, FIG. 10, and for Embodiment 4, FIG. 17. The results obtained are shown for Example 1 and Figure 18. Further, in these figures, the transmittance of the glass substrate having the transparent conductive film obtained in Comparative Example 13 and the glass was also shown. Further, a spectrophotometer (manufactured by Hitachi HIGH-TECHNOLOGY, product name "U-4100") was used, and glass was used as a reference test piece, and Example 1, Example 2, Example 13 and Example 14 were used. The transparent conductive laminate of the obtained glass substrate having a transparent conductive layered body and the transparent conductive film of the glass substrate having the transparent conductive film obtained in Comparative Examples 14 to 18 were measured for light in a wavelength region of 200 to 2600 nm. Transmittance rate. The glass substrates having the transparent conductive films obtained in Comparative Examples 14 to 18 are shown in Fig. 26 for the respective embodiments 1, 2, 13 and 14 respectively. As is apparent from the results shown in Fig. 1, it was confirmed that the substrate having the transparent conductive layered body of the present invention (Example 1) had a crystal phase of indium oxide, and as a result of the results shown in Fig. 3, it was confirmed that the crystal of indium oxide was confirmed. The first conductive film (the region below the white dashed line in the figure) composed of IT090 and the second transparent conductive film (the region above the white dotted line in the middle) of ITO 50 are all the crystal phases of indium oxide. On the other hand, in the substrate (Comparative Example 1) having a transparent conductive film which is not provided with the film of the ITO 90 of the present invention, it is understood from the results shown in Fig. 2 that the diffraction spectrum of the crystal phase of indium oxide is exhibited. As a result of the results shown in FIG. 4, it was found that the amorphous layer was confirmed in a region from the substrate up to about 30 nm (in the figure, a region below the white dotted line). Further, in Example 2 and Comparative Example 2, as shown in Figs. 5 to 8, the same results as described above were confirmed. -28-201212047 In addition, as is apparent from the results shown in FIG. 19, the substrate (Examples 1, 13, and 14) having the transparent conductive laminate of the present invention has a crystal phase of indium oxide (Ιη203), and further, FIG. As a result of the above, it is understood that the substrate of the transparent conductive laminate of the present invention (particularly Example 13) exhibits an X-ray diffraction pattern appearing at around 20 == 3 0 · 6 °, confirming the cause The peak of the crystal phase of In4 S η3 Ο i 2 was separated, and the In4Sn30 i 2 crystal phase was confirmed. In addition, as a result of the results shown in Fig. 21 and Fig. 2, it was confirmed that the first transparent conductive film ("ITO90" in the figure) composed of IT 0 90 was composed of "ITO50; Fe". The transparent conductive film ("ITO50: Fe" in the figure) is also a crystal phase equivalent to indium oxide. Further, the second transparent conductive film made of "ITO50; Fe" was significantly epitaxially grown with respect to the first transparent conductive film made of ITO90. In addition, as a result of the results shown in FIG. 23 and FIG. 24, it was confirmed that the first transparent conductive film ("ITO90" in the figure) composed of ITO90 and the second transparent conductive film composed of "ITO50; Sb" were confirmed. The "ITO50: Sb" is also the same crystalline phase as indium oxide. Further, the second transparent conductive film composed of "ITO5 0 ; Sb" was significantly epitaxially grown with respect to the first transparent conductive film made of ITO 90. Further, as is apparent from the results shown in Fig. 9, the substrate (Examples 1 to 3) having the transparent conductive laminate of the present invention has 90% by mass of indium oxide in the film even if the indium content is reduced. The substrate having the transparent conductive film (Comparative Example I3) had an equivalent or lower volume resistivity. On the other hand, a film having a transparent conductive film which does not have a crystal structure equivalent to that of indium oxide crystals (Comparative Examples 1 to 3) is not provided in the film made of ITO 90 according to the present invention, and even the same target is used. The substrate is simultaneously sputtered and has a disadvantage in volume resistivity as compared with the respective Examples 1 to 3 of -29 to 201212047. Further, from the results shown in Fig. 10, the transparent conductive material of the present invention is known. The substrate of the laminate (Examples 1 to 3) exhibited a transmittance of about 80% in the wavelength region of 500 to 900 nm, and had a transmittance higher than that of Comparative Example 13 even if the indium content was reduced. Further, as is apparent from the results shown in FIGS. 25 and 26, the transparent conductive laminate of the substrate (Examples 1, 2, 13, and 14) having the transparent conductive laminate of the present invention is in the entire region of the wavelength region of 500 to 1400 nm. The high transmittance of 80% or more is exhibited, and even if the indium content is reduced, it has a wavelength region wider than that of Comparative Example 14, and particularly has a high transmittance in an infrared region of 800 nm or more. Further, in Example 14, the transmittance was 80% or more in the entire region of the wider wavelength region (500 to 255 nm). That is, the substrate having the transparent conductive laminate of the present invention, particularly the substrate having the transparent conductive laminate of the present invention comprising the second transparent conductive film composed of ITO50; Sb, has excellent infrared transmission capability. . Further, the substrate having the transparent conductive laminate obtained by the production method of the present invention which is different from Examples 1 to 3, 13 and 14 (Example 10) can also be seen from the results shown in Fig. 11. It was confirmed that it has a crystal structure equivalent to that of indium oxide crystal. On the other hand, in the substrate (Comparative Example 12) having a transparent conductive film which is not provided with the film of the ITO 90 of the present invention, as shown by the results shown in Fig. 12, it was confirmed that crystals equivalent to those of indium oxide crystals were not confirmed. The diffraction spectrum of the structure. Further, from the results shown in FIGS. 13 to 15 , the substrate of the present invention having the transparent conductive layer -30-201212047 obtained by the manufacturing method of the present invention which is different from the first to third embodiments can be seen. (Examples 4 to 12) 'A film having the same elemental composition and elemental content ratio, even if a film is formed and then heat-treated at the same temperature, compared with the substrate of the transparent conductive film of Comparative Examples 4 to 12. Each has a lower volume resistivity. Further, as is apparent from the results shown in FIGS. 16 and 17 , the substrate having the transparent conductive laminate of the present invention (Example 4 and Example 7) exhibits a transmittance of about 80% in a wavelength region of 450 to 900 nm. From the results shown in FIG. 18, it is understood that the substrate having the transparent conductive laminate of the present invention (Example 10) exhibits a transmittance of 80% in the wavelength region of 500 to 900 nm, and the substrate having the transparent conductive laminate of the present invention. (Example 4, Example 7 and Example 10) The transmittance was as high as that of Comparative Example 13 even when the indium content was reduced. [Industrial Applicability] As described above, according to the present invention, it is possible to provide a substrate having a transparent conductive laminate having sufficiently high light transmittance and sufficiently low resistivity even if the indium content is reduced, and a method for producing the same . That is, the substrate having the transparent conductive laminate of the present invention is used as a transparent electrode, an infrared absorbing and reflecting film, etc., which constitutes an electric spring, a liquid crystal display element, an electroluminescence display element, a solar cell, or the like. Materials such as antifogging films and electromagnetic shielding films are very useful. Further, according to the present invention, it is possible to increase the tin content in the transparent conductive film, and it is possible to provide a substrate having a transparent conductive laminate having a high transmittance without absorption in the infrared region as a transparent electrode material for a solar cell or the like. Particularly useful. -31 - 201212047 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an X-ray diffraction pattern (upper portion) of a substrate having a transparent conductive laminate obtained in Example 1 and oxidation obtained by calculation of a bixbyite structure. A diagram of the X-ray diffraction pattern (bottom) of indium crystals. 2 is a view showing an X-ray diffraction pattern (upper portion) of a substrate having a transparent conductive film obtained in Comparative Example 1 and an X-ray diffraction pattern (lower portion) of indium oxide crystal having a bixbyite structure obtained by calculation. Figure. Fig. 3 (a) is a photograph of a transmission electron microscope of the substrate having the transparent conductive laminate obtained in Example 1, and (b) is a photograph of a part of the transmission electron microscope photograph of (a) observed at a high magnification. Fig. 4 (a) is a photograph of a transmission electron microscope of a substrate having a transparent conductive film obtained in Comparative Example 1, and (b) is a photograph of a part of a transmission electron microscope photograph of (a) observed at a high magnification. 5 is an X-ray diffraction pattern (upper portion) showing a substrate having a transparent conductive laminate obtained in Example 2, and an X-ray diffraction pattern of indium oxide crystal having a stellite structure having a calculated structure (lower portion) ) The map. 6 is an X-ray diffraction pattern (upper portion) showing a substrate having a transparent conductive film obtained in Comparative Example 2, and an X-ray diffraction pattern (lower portion) of indium oxide crystal having a bixbyite structure obtained by calculation. Figure. Fig. 7 (a) is a photograph of a transmission electron microscope of the substrate having the transparent conductive laminate obtained in Example 2; (b) is a photograph of a part of the transmission electron microscope photograph of (a) observed at a high magnification. 8( a ) is a photograph of a transmission electron microscope of -32 to 201212047 which is a substrate having a transparent conductive film obtained in Comparative Example 2; (b) is a part of a transmission electron microscope photograph of (a) observed at a high magnification. photo. Fig. 9 is a graph showing the volume resistivity of the substrate having the transparent conductive film obtained in Examples 1 to 3 and the substrates having the transparent conductive film obtained in Comparative Examples 1 to 3 and Comparative Example 13. Fig. 10 is a graph showing the relationship between the measurement wavelength and the transmittance of the substrate having the transparent conductive laminate obtained in Examples 1 to 3, the substrate having the transparent conductive film obtained in Comparative Example 13, and the glass. 11 is an X-ray diffraction pattern (upper portion) showing a substrate having a transparent conductive laminate obtained in Example 10, and an X-ray diffraction pattern of indium oxide crystal having a bixbyite structure calculated by calculation. (bottom) map. Fig. 1 is a view showing an X-ray diffraction pattern (upper portion) of a substrate having a transparent conductive film obtained in Comparative Example 12 and an X-ray diffraction pattern of indium oxide crystal having a bixbyite structure (bottom portion) ) The map. Fig. 13 is a view showing the volume resistivity of the substrate having the transparent conductive laminate obtained in Examples 4 to 6 and the substrate having the transparent conductive film obtained in Comparative Examples 4 to 6. Fig. 14 is a view showing the volume resistivity of the substrate having the transparent conductive laminate obtained in Examples 7 to 9 and the substrate having the transparent conductive film obtained in Comparative Examples 7 to 9. Fig. 15 is a graph showing the volume resistivity of the substrate having the transparent conductive layer obtained in Examples 10 to 12 and the substrate having the transparent conductive film obtained in Comparative Examples 10 to 12. Fig. 1 is a graph showing the relationship between the measurement wavelength and the transmittance of the substrate of the transparent conductive film obtained in Example 4, which was obtained in Example 4, and the substrate of the transparent conductive film obtained in Comparative Example 13. Picture. Fig. 1 is a graph showing the relationship between the measurement wavelength and the transmittance of the substrate with the transparent conductive laminate obtained in Example 7, the substrate with the transparent conductive film obtained in Comparative Example 13, and the glass. Fig. 1 is a graph showing the relationship between the measurement wavelength and the transmittance of the substrate having the transparent conductive laminate obtained in Example 1 and the substrate having the transparent conductive film obtained in Comparative Example 13 and the glass. FIG. 19 shows an X-ray diffraction pattern (upper 3 pattern) of the substrate having a transparent conductive film obtained in Examples 1, 13 and 14 and a Ιη203 crystal having a bixbyite structure calculated and A diagram of the X-ray diffraction pattern (lower 2 pattern) of In4Sn3012 crystal. Fig. 20 is a view showing the result of expanding the X-ray diffraction pattern shown in Fig. 19 at a range of 20 = 2 (Γ~40°). Fig. 21 is a substrate having a transparent conductive film obtained in Example 13. Fig. 22 is a high-resolution image of a cross section of a substrate having a transparent conductive film obtained in Example 13 and a transmission electron obtained as a result of FFT (High Speed Fourier Transform) analysis. Fig. 23 is a transmission electron micrograph of a clear field of view of a cross section of a substrate having a transparent conductive film obtained in Example 14. Fig. 24 is a cross section of a substrate having a transparent conductive film obtained in Example 14. Transmission electron micrograph of the result of the high-resolution image and the FFT analysis - 34 - 201212047 FIG. 2 is a transparent conductive layer showing the substrate having the transparent conductive laminate obtained in Examples 1, 2, 13 and 14. Fig. 2 shows the relationship between the measurement wavelength and the transmittance of the transparent conductive laminated film of the substrate having the transparent conductive film obtained in Comparative Example 14 to 18. Fig. -35-