201246575 六、發明說明： 【發明所屬之技術領域】 本發明有關太陽能電池（solar cell)用之透明導電膜 (transparent conductive film)用組成物、及透明導電膜。 詳言之，有關薄膜太陽能電池（thin film solar cell)用之透 明導電膜用組成物、及透明導電膜。 【先前技術】 現在，從環境保護之立場，在推動乾淨能源（clean energy)的硏究開發、實用化，而由於太陽能電池係作爲能 源之太陽光爲取之不盡者，且無公害等之故正受囑目。在 來，爲太陽能電池，在採用單晶砍（single crystal silicon) 或多晶砂（poly crystal silicon)的大體積太陽能電池（bulk solar cell)，惟由於大體積太陽能電池係製造成本高、生 產性亦低之故’急需開發一種經節省砂量之太陽能電池。 於是，熱烈進行採用厚度，例如在0.3至2μιη的非晶 矽（amorphous silicon)等的半導體之薄膜太陽能電池之開 發。由於此種薄膜太陽能電池，係於玻璃基板或耐熱性塑 膠基板上形成爲光電變換所需量的半導體層之構造之故， 有薄型且重量輕、低成本，容易大面積化等的優點》 薄膜太陽能電池中，有頂材構造（superstrate structure) 及底材構造（sub strate structure)構造，而頂材型構造，係 爲使太陽光從透光性基板（transmissive substrate)側入射起 見’通常採取按基板-透明電極（transparent electrode) -光 201246575 電變換層（p h 〇 t 〇 e 1 e c t r i c c ο n v e r s i ο η 1 a y e r)-後面電極（r e a r-face electrode)之順序所形成之構造。另一方面，底材型 構造，則通常採取按基板-後面電極-光電變換層-透明電極 之順序所形成之構造。 在此種薄膜太陽能電池方面，在來，電池或反射膜係 依濺鍍（sp uttering)等的真空薄膜沈積法（vacu am e deposition) 所形成者，惟一般而言，爲大型的真空薄膜沈積裝置的導 入、維持、運轉上，需要高額成本。爲改良此種缺點起見 ，揭不有一種採用透明導電膜（transparent conductive film)用組成物及導電性反射膜（conductive reflection film) 用組成物，依更低廉的製造法之濕式塗佈法（wet coating method)形成透明導電膜及導電性反射膜之技術（專利文獻 1)。 [先前技術文獻] [專利文獻] 專利文獻1 :日本專利特開2009-88489號公報 【發明內容】 [發明所欲解決之課題] 本發明，係以改良依上述濕式塗佈法中所製造之透明 導電膜作爲課題者。本發明人等發現，如改良透明導電膜 用組成物，以增大依濕式塗佈法中所用之透明導電膜的折 射率、與光電變換層的折射率之差値，即會增加在透明導 電膜-光電變換層界面的反射光，並利用該所增加之對光 -6- 201246575 電變換層的返回光（return light)，即可提升薄膜太陽能電 池之發電效率之事實。此種手法，係頂材型太陽能電池、 底材型太陽能電池以及大體積矽太陽能電池中之任一均能 適用者，特別適合於頂材型者。 [用以解決課題之手段] 本發明有關經藉由下列所示構成而解決上述課題之薄 膜太陽能電池用之透明導電膜用組成物、以及透明導電膜 〇 (1) 一種薄膜太陽能電池用之透明導電膜用組成物，其 特徵爲：含有平均粒徑1至50nm的ITO(銦錫氧化物（Indium Tin Oxide))空心粒子（hollow particle)、及黏合劑（binder) ο (2) 如上述（1)所記載之薄膜太陽能電池用之透明導電 膜用組成物，其中再含有導電性氧化物粒子（conductive oxide particle)。 (3) 如上述（1)或（2)所記載之薄膜太陽能電池用之透明 導電膜用組成物，其中黏合劑，係因加熱而硬化之聚合物 型黏合劑及/或非聚合物型黏合劑。 (4) 如上述（3)所記載之薄膜太陽能電池用之透明導電 膜用組成物，其中非聚合物型黏合劑，係選自金屬皂、金 屬錯合物、金屬烷氧化物、鹵化矽烷類、2-烷氧基乙醇、 卢，-雙酮 '以及烷基乙酸酯所成群之至少一種。 (5) —種薄膜太陽能電池用之透明導電膜，其特徵爲： 201246575 含有平均粒徑1至50nm的I TO空心粒子、及經硬化之黏 合劑，並對ΙΤΟ空心粒子和經硬化之黏合劑的合計1 00質 量份，含有ΙΤΟ空心粒子55至95質量份。 (6) 如上述（5)所記載之薄膜太陽能電池用之透明導電 膜，其中再含有導電性氧化物粒子。 (7) 如上述（5)或（6)所記載之薄膜太陽能電池用之透明 導電膜，其中黏合劑，係聚合物型黏合劑及/或非聚合物 型黏合劑。 (8) 如上述（7)所記載之薄膜太陽能電池用之透明導電 膜，其中非聚合物型黏合劑，係選自金屬皂、金屬錯合物 、金屬烷氧化物、鹵化矽烷類、2 -烷氧基乙醇、/5 -雙酮、 以及烷基乙酸酯所成群之至少一種。 (9) —種薄膜太陽能電池，係含有上述（5)至（8)之任一 項所記載之薄膜太陽能電池用之透明導電膜。 (10) —種透明導電膜之製造方法，係按順序具備基材 、透明電極層、光電變換層、以及透明導電膜之薄膜太陽 能電池之透明導電膜之製造方法，其特徵爲：於光電變換 層上，依濕式塗佈法塗佈上述（1)至（4)之任一項所記載之 透明導電膜用組成物以形成透明導電塗膜後，將具有透明 導電塗膜之基材’在130至400 °C下進行燒成，以形成厚 度0.03至0.5μιη的透明導電膜。 (11) 如上述（10)所記載之透明導電膜之製造方法，其 中濕式塗佈法，係噴霧塗佈法（spray coating)、定料分散 器塗佈法（dispenser coating)、旋轉塗佈法（spin coating)、 201246575 刮刀塗佈法（knife coating)、狹縫塗佈法（slit coating)、噴 墨塗佈法（inkjet coating)、壓模塗佈法（die coating)、網版 印刷法（screen printing)、膠版印刷法（offset printing)、或 者凹版印刷法（gravure printing)。 [發明之效果] 本發明（1)之透明導電膜用組成物，可依濕式塗佈法在 光電變換層上進行塗佈、燒成，且因ITO空心粒子之含量 而可使所得透明導電膜的折射率降低。亦即，透明導電膜 的折射率、與光電變換層的折射率之差値即增大，在透明 導電膜-光電變換層界面的反射光即增加，並藉由該所增 加之對光電變換層的返回光，即可簡便地製得能提升薄膜 太陽能電池之發電效率之透明導電膜。 如採用本發明（5)，則在透明導電膜-光電變換層界面 的反射光即增加，並藉由該所增加之對光電變換層的返回 光’即可簡便地製得經提升發電效率之薄膜太陽能電池。 如採用本發明（10)，則在不使用高價的真空設備之下 ，即能形成透明導電膜，而可簡便地，按低成本製造發電 效率高的薄膜太陽能電池。 [發明之最佳實施形態] 以下，將根據實施形態，具體說明本發明內容。在此 ，除非特別註明 '或固有數値之情形以外，％即表示質量 %之意。 ~ 9 - 201246575 [薄膜太陽能電池用之透明導電膜用組成物] 本發明之薄膜太陽能電池用之透明導電膜用組f 以下，簡稱「透明導電膜用組成物」），之特徵爲： 平均粒徑：1至50nm的ITO空心粒子、及黏合劑。 ITO(Indium Tin Oxide(銦錫氧化物））空心粒子， 均粒徑：1至50nm，如在lnm以下時，則因粒子的 性不足之故容易引起二次凝聚以致試料之製作困難， 在50nm以上時，則會阻礙導電性粒子的接觸之故不 之故。在此，平均粒徑，係從採用QUANTACHROME AUTOSORB-1之比表面積測定，假設ITO空心粒子爲 (real ball)而加以換算。ITO空心粒子的形狀而言，可 :球狀、骰子狀、有刺糖球狀等，較佳爲球狀。ITO 粒子的縱寬比（aspect ratio)(長徑/短徑），較佳爲1至 ，更佳爲1至1.2 5。ITO空心粒子，係與光電變換層 的可濕性（wettability)良好，而可降低膜厚之不均勻 可降低硬化後的透明導電膜之折射率。第1圖中，表 用本發明之透明導電膜之薄膜太陽能電池的剖面之模 。第1圖，係頂材型薄膜太陽能電池之例。薄膜電池 按順序具備有基材10、透明電極層3、光電變換層2 明導電膜1'導電性反應膜4，而太陽光則從基板10 射。所入射之多半太陽光，即被導電性反射膜4所反 而返回光電變換層2，以提升變換效率。在此，透明 膜1與光電變換層2的界面亦發生有太陽光的反射， 矣物（ 含有 係平 穩定 而如 適合 社製 正球 例舉 空心 1.4 之間 ，而 示採 式圖 ，係 、透 側入 射、 導電 惟由 -10- 201246575 於採用本發明之透明導電膜用組成物之透明導電膜1，係 折射率低之故，可使在透明導電膜1與光電變換層2的界 面之反射光增加，而提升薄膜太陽能電池之發電效率。 ITO空心粒子，如在離子液體中，使因銦錫之濺鏟所 得之銦錫奈米粒子，加以氧化即可製得。 黏合劑，如係含有因加熱而硬化之聚合物型黏合劑或 者非聚合物型黏合劑之任一或兩者之組成物則較佳。聚合 物型黏合劑而言，可例舉：丙烯酸樹脂、聚碳酸酯、聚酯 、醇酸樹脂、聚胺基甲酸酯、丙烯酸聚胺基甲酸酯、聚苯 乙烯、聚縮醛、聚醯胺、聚乙烯醇、聚醋酸乙烯酯、纖維 素、以及矽氧烷聚合物等。又，聚合物型黏合劑中，較佳 爲含有鋁 '矽、鈦、鉻 '錳、鐵、鈷、鎳、銀、銅、鋅、 鉬或者錫的金屬皂、金屬錯合物、或者金屬烷氧化物的水 解物。非聚合物型黏合劑而言，可例舉：金屬皂、金屬錯 合物、金屬烷氧化物、鹵化矽烷類、2 -烷氧基乙醇、0 -雙 酮、以及院基乙酸酯等。又，金屬巷、金屬錯合物、或金 屬烷氧化物中所含之金屬，較佳爲鋁、矽、鈦、鉻、錳、 鐵、鈷、鎳、銀、銅、鋅、鉬、錫、銦或銻，更佳爲矽、 鋁的烷氧化物（例如，四乙氧基矽烷、四甲氧基矽烷、三 乙氧基銘' 三異丙氧基鋁）。此等聚合物型黏合劑、非聚 合物型黏合劑因加熱而硬化之結果，能實現在低溫下的低 的霧狀（haze)率及體積電阻率（v〇Ume resistivity)的透明導 電膜之形成。在此，金屬烷氧化物，可爲水解物（hydrate) 1亦可爲脫水物（dehydrate)。 -11 - 201246575 當使金屬烷氧化物硬化時’較佳爲與爲引發水解反應 之用之水分一起’含有作爲觸媒之用之鹽酸、硝酸、磷酸 (H3 P 〇4 )、氟酸等的酸，或者，氨水、氫氧化鈉水溶液等 的鹼，從加熱硬化後觸媒容易揮發、不易殘留、不會殘留 鹵素、不會殘留耐水性低的P(磷）等、不會殘留Na(鈉）等 鹼金屬鹽等的觀點來看’更佳爲硝酸。又，在硝酸之情形 ，即使殘留有N(氮）以致擴散於底子的光電變換層（n型）中 ，仍然會作爲施予體（donor)發揮作用之故，光電變換層的 變換效率不致於低落，反而變換效率可能會更高。 此等黏合劑之含有比例，係對除分散介質（dispersion medium)後之透明導電膜用組成物：100質量份，較佳爲5 至50質量份、更佳爲10至30質量份。又，在作爲黏合 劑而採用金屬烷氧化物、作爲觸媒而使用硝酸之情形，如 對金屬烷氧化物：1〇〇質量份、使用硝酸〇.〇3至3質量份 時，則從黏合劑的硬化速度、硝酸的殘留量之觀點來看較 合適。再者，如作爲觸媒之硝酸的量較少時，則作爲黏合 劑之金屬烷氧化物之水解物的聚合速度變遲緩，而爲水解 所需要的水量不足時，可能難於製得堅固的透明導電膜。 又，如係採取利用燒成之硬化時聚合度高的網狀構造之水 解溶液之情形，則由於收縮時所施加之應力可能成爲補助 導電性粒子互相間之接觸之狀態之故’對金屬烷氧化物： 100重量份、水爲10至120質量份較合適。 從透明導電膜之導電性提升之觀點來看’透明導電膜 用組成物、較佳爲含有導電性氧化物粒子。導電性氧化物 -12- 201246575 粒子而言，較佳爲含有選自ITO、ATO(Antimony Tin Oxide(銻錫氧化物）：銻摻雜（doped)氧化錫）的氧化錫粉末 或A1(鋁）、Co(鈷）、Fe(鐵）、In(銦）、Sn(錫）以及Ti(鈦）所 成群之至少一種金屬之氧化鋅粉末等，其中，更佳爲ITO 、ATO、AZO(Aluminum Zinc Oxide(銘鋅氧化物）：（錦慘 雜氧化鋅）、IZO(Indium Zinc Oxide(銦鋅氧化物）：（銦摻 雜氧化鋅）、TZO (Tin Zinc Oxide (錫鋅氧化物）：（錫摻雜氧 化鋅）。又，導電性氧化物微粒子之平均粒徑，係爲在分 散介質中保持穩定性起見，較佳爲在10至l〇〇nm的範圍 內，此中，更佳爲在20至60nm的範圍內。 透明導電膜用組成物，對導電性氧化物粒子和ITO空 心粒子之合計1 00質量份，含有導竃性氧化物粒子1 0至 7〇質量份、較佳爲含有1 5至65質量份。如在上限値以上 時，則增反射（re flection increasing)之效果會降低、如在 下限値以下時，則導電性會降低之故。 透明導電膜用組成物，較佳爲按照所使用之其他成分 而添加偶合劑（conpling agent)。此乃爲提升導電性微粒子 、ITO空心粒子與黏合劑之間的結合性，及由此透明導電 膜用組成物所形成之透明導電膜與經層壓在基材上之光電 變換層或導電性反射膜之間的密貼性之故。偶合劑而言， 可例舉：矽烷偶合劑、鋁偶合劑以及鈦偶合劑等。偶合劑 的含量，係對透明導電膜用組成物中所佔之固體成分（導 電性氧化物粒子、ITO空心粒子、黏合劑、以及矽烷偶合 劑等）：100質量份，較佳爲0.2至5質量份、更佳爲0.5 -13- 201246575 至2質量份。 透明導電膜用組成物中，爲使薄膜沈積順利進行起見 ，較佳爲含有分散介質。分散介質而言，可例舉：水：甲 醇、乙醇、異丙醇、丁醇等的醇類；丙酮、甲基乙基甲酮 、環己酮、異佛爾酮等的酮類；甲苯、茬、己烷、環己烷 等的烴類；N，N-二甲基甲醯胺' N，N-二甲基乙醯胺等的醯 胺類；二甲基亞颯等的亞颯類等或乙二醇等之二醇類；乙 基纖維素等之二醇醚類。分散介質的含量，係爲獲得良好 的薄膜沈積性起見，對透明導電膜用組成物：1 00質量份 ，較佳爲65至99質量份。 又，按照所使用之成份，較佳爲添加低電阻·化劑或水 溶性纖維素衍生物等。低電阻化劑而言，較佳爲選自鈷、 鐵、銦、鎳、鉛、錫、鈦'以及鋅的無機酸鹽及有機酸鹽 所成群中之1種或2種以上。可例舉：醋酸鎳與氯化第二 鐵的混合物、環院酸鋅（Zinc naphthenate)、辛酸錫與氯化 銻的混合物、硝酸銦與醋酸鉛的混合物、乙醯醋酸鈦與辛 酸鈷的混合物等。此等低電阻化劑的含量，係對導電性氧 化物粉末：100質量份，較佳爲0.2至15質量份。水溶性 纖維素衍生物，雖係一種非離子化表面活性劑，惟較其他 表面活性劑爲即使少量之添加仍能使導電性氧化物粉末分 散之能力極高，又藉由水溶性纖維素衍生物的添加，而所 形成之透明導電膜的透明性亦會獲提升。水溶性纖維素衍 生物而言，可例舉：/9-羥基丙基纖維素、羥基丙基甲基 纖維素等。水溶性纖維素衍生物的添加量，係對導電性氧 -14- 201246575 化物粉末·· 100質量份，較佳爲0.2至5質量份。 透明導電膜用組成物，可將所需成份，依常法，利用 油漆搖動機（paint shaker)、球磨機（ball mill)、混砂機 (sand mill)、離心式磨機（centri mill)、三輕式磨機〇11166-r ο 11 m i 11)等加以混合，而使導電性氧化物粒子、i τ Ο空心 粒子等分散以製造。當然，亦可按照通常的攪拌操作製作 [薄膜太陽能電池用透明導電膜] 本發明之薄膜太陽能電池用透明導電膜（以下，簡稱 「透明導電膜」之特徵爲：含有平均粒徑·· 1至50nm的 IΤ Ο空心粒子、及經硬化之黏合劑，並對〗T 〇空心粒子和 經硬化之黏合劑的合計1 0 0質量份，含有IΤ Ο空心粒子 55至95質量份。透明導電膜，較佳爲再含有導電性氧化 物粒子。 就ITO空心粒子、導電性氧化物粒子而言，如上所述 ’經硬化之黏合劑’係使上述的黏合劑硬化者，亦即，係 上述的薄膜太陽能電池用之透明導電膜用組成物中的黏合 劑硬化者。 本發明之透明導電膜之製造方法，係按順序具備基材 、透明電極層、光電變換層、以及透明導電膜之薄膜太陽 能電池之透明導電膜之製造方法，其特徵爲：於光電變換 層上’依濕式塗佈法塗佈上述之透明導電膜用組成物以形 成透明導電塗膜後，將具有透明導電塗膜之基材，在13〇 -15- 201246575 至400 °C下進行燒成，以形成厚度0.03至0.5 μηι的透明導 電膜。 首先，基材上之光電變換層上，依濕式塗佈法塗佈上 述透明導電膜用組成物。在此之塗佈，係按燒成後之厚度 能成爲0·03至0·5 μηι、較佳爲0.05至0.2 μιη之厚度之方 式進行。將此塗膜，在溫度20至120。(：、較佳爲25至60 它下，進行1至30分鐘、較佳爲2至10分鐘之乾燥。如 此方式，形成透明導電塗膜。 上述基材，可使用玻璃、陶瓷或者由高分子材料所成 之透光性基板之任一 ’或選自玻璃、陶瓷、高分子材料、 以及矽所成群之2種以上的透光性層壓物。高分子基板而 言’可例舉：由聚醯胺或PET(莩對苯二甲酸乙二醇酯）等 的有機聚合物所形成之基板。 再者’上述濕式塗佈法，較佳爲採用噴霧塗佈法、定 料分散器塗佈法、旋轉塗佈法、刮刀塗佈法、狹縫塗佈法 、噴墨塗佈法、網版印刷法、膠版印刷法、或者壓模塗佈 法’惟並不因此等而有所限定，而可利用所有方法。 噴霧塗佈法’係將透明導電膜用組成物，使用壓縮空 氣以作成霧狀後塗佈於基板上 '或者將分散物本身加壓作 成霧狀後塗佈於基材上之方法，而定料分散器塗佈法，係 例如將透明導電膜用組成物置入注射器內，推壓該注射器 的活塞（piston)藉以從注射器前端的微細噴嘴（nozzle)吐出 分散物’以塗佈於基材上之方法。旋轉塗佈法，係將透明 導電膜用組成物滴下於在旋轉中之基材上，並將此所滴下 -16- 201246575 之透明導電膜用組成物，利用離心力擴散於基材邊緣之方 法’而刮刀塗佈法，係將刮刀的前端與空出既定間隙之基 材按能往水平方向移動之方式設置，從此刮刀供給透明導 電膜用組成物於上游側的基材上，以使基材朝向下游側水 平移動之方法。狹縫塗佈法，係使透明導電膜用組成物從 狹窄的間縫流出以塗佈於基材上之方法，而噴墨塗佈法， 係於市售之噴墨式印刷機的油墨筒（ink cartridge)內塡充 透明導電膜用組成物，並在基材上進行噴墨印刷之方法。 網版印刷法.，係作爲圖型（pattern)指示材而使用紗布，透 過其上所作之版畫像以使透明導電膜用組成物轉移於基材 上之方法。膠版印刷法，係將經附在版上之透明導電膜用 組成物，不直接附著於基材上，而從印刷版一旦轉錄於橡 膠片（rubber sheet)上，並重新從橡膠片轉移於基材上之利 用透明導電膜用組成物的撥水性之印刷方法。壓模塗佈法 ，係將經供給於壓模（die)內之透明導電膜用組成物，在岐 管（manifold)使其分配後從間縫擠出於薄膜上，並塗佈於 運行中之基材表面之方法。壓模塗佈法中，有：縫口塗佈 (slot coating)方式、或滑動塗佈（slide coating)方式、簾流 塗佈（curtain coating)方式。 最後，將具有透明導電塗膜之基材，在大氣中或者氮 或氬等的惰性氣體氣氛中在130°C至400°C下、較佳爲150 至350 °C的溫度下保持並燒成5至60分鐘、較佳爲15至 40分鐘。在此，按燒成後之透明導電膜的厚度能成爲 0.03至0.5μιη之範圍之方式塗佈透明導電膜用組成物之理 -17- 201246575 由，係如燒成後的厚度在未達0.03 μιη、或超過0.5 μιη時 ，則難於充分獲得增反射效果（reflection amplifying effect) 之故。 將具有塗膜之基材的燒成溫度作成130至400°C的範 圍之理由，係如在未達130 °C時，則會發生於複合膜之透 明導電膜之表面電阻値會成爲過高之缺點之故。又，如在 超過 400 °C時，則不能活用低溫製程之生產上的好處（ merit)，亦即，製造成本會增高以致生產性會降低。特別 是，非晶矽、微結晶矽、·或者採用此等之混雜種（hybrid) 型矽太陽能電池係耐熱性較低、因燒成過程而變換效率會 降低之故。 將具有塗膜之基材的燒成時間作成5至60分鐘的範 圍之理由，係如燒成時間在未達下限値時，則會發生於複 合膜之透明導電膜之表面電阻會成爲過高之缺點之故。如 燒成時間在超過上限値時，則過分增高製造成本以致生產 性降低’又，會發生太陽能電池元件的變換效率降低之缺 點之故。 依上述方式，即可形成本發明之透明導電膜。如此， 由於本發明之製造方法，係使用濕式塗佈法之緣故，儘可 能排除真空蒸鍍法或濺鍍法等的真空製程之故，可依更廉 價方式製造透明導電膜。 【實施方式】 [實施例] ______ •18· 201246575 以下，利用實施例，將詳細說明本發明內容，惟本發 明並不因實施例而有所限定。 按能成爲表1至3中所示組成（數値表示質量份）之方 式，合計爲60g，置入100cm3的玻璃瓶中，採用直徑 0.3 mm的氧化鉻熔珠l〇〇g，使用油漆搖動機以分散6小時 ，藉以製作實施例1至1 9、比較例1的透明導電膜組成物 。表4中，表示所用之ITO空心粒子的平均粒徑。在此， 表1的比例的欄中，簡稱導電性氧化物粒子爲導、空心 ITO粒子爲H-ITO、以及偶合劑爲偶。又，表4中，表示 所用之中空ITO粒子的平均粒徑。在此，ITO空心粒子1 至2、作爲黏合劑所用之Si02黏合劑1至7，係如下述方 式所製作者。 [ITO空心粒子1] 將1-丁基-3-甲基咪唑鐽四氟硼酸鹽（BMI-BF4)在真空 中，在120°C下乾燥後，在經於散悠電子社製濺鍍塗佈機（ 型號：SC-70HMCII)內水平所載置之玻璃板（10cm3)上，按 單面舖平之方式置入上述1-丁基-3-甲基咪唑鎗四氟硼酸 鹽 0.6 0 c m3。 將離子液體的表面，配置於從銦銀箔靶（target)(純度 :99.99%)離開20mm距離之處、在室溫下，於2.OPa(帕） 的氬氣（純度：99.99%以上）下，依濺鍍電流10mA進行濺 鍍10分鐘。 濺鍍後，從玻璃板採取含有銦錫奈米粒子之離子液體 -19- 201246575 溶液，將所得之離子液體溶液在大氣中，在250°C下實施 熱處理1小時，以製作ITO空心粒子1。 [ITO空心粒子2] 將1-烯丙基-3-乙基咪唑鎗四氟硼酸鹽（AEI-BF4))在真 空中，在120 °C下乾燥後，在經於散悠電子社製濺鏟塗佈 機（型號：SC-70HMCII)內水平所載置之玻璃板（10cm3)上 ，按單面舖平之方式置入上述1-烯丙基-3-乙基咪唑鎗四 氟硼酸鹽〇. 6 0 c m3。 將離子液體的表面，配置於從銦銀箔靶（純度： 99.99%)離開20 mm距離之處、在室溫下，於2.OPa的氬氣 (純度：99.99%以上）下，依灘鍍電流10mA進行濺鍍10分 鐘。 濺鑛後，從玻璃板採取含有銦錫奈米粒子之離子液體 溶液，將所得之離子液體溶液在大氣中，在250°C下實施 熱處理1小時，以製作ITO空心粒子2。 [Si02黏合劑1] 使用500cm3的玻璃製的四口燒瓶，添加14〇g的四乙 氧矽烷、及140g的乙醇，並在攪拌之下一次添加經將 1.7g的60%硝酸溶解於I20g的純水之溶液，然後在50°C 下反應3小時，藉以製造。 [Si02黏合劑2] -20- 201246575 使用5 00cm3的玻璃製的四口燒瓶，添加85g的四乙 氧矽烷、及l〇〇g的乙醇，並在攪拌之及室溫下’將經將 0.09叾的60%硝酸溶解於11(^的純水之溶液，使用管狀泵 (tube pump)，按耗費10至15分鐘之方式飼給。然後，於 所得混合溶液中，使用管狀泵，按耗費1 〇至1 5分鐘之方 式飼給預先所混合之45g的三第二丁氧鋁、與60g的乙醇 的混合溶液。在室溫下攪拌30分鐘後，在50°C下反應3 小時，藉以製造。 [Si02黏合劑3] 使用50cm3的玻璃製的四口燒瓶，添加115g的四乙 氧矽烷 '及175g的乙醇，並在攪拌之下一次添加經將 1.48的35°/。鹽酸溶解於11〇8的純水之溶液，然後在45艺 下反應3小時，藉以製造。 [Si02黏合劑4] 使用500cm3的玻璃製的四口燒瓶，添加130g的四乙 氧矽烷、及145g的乙醇’並在攪拌之下一次添加經將 1.25g的30%氨水溶解於124g的純水之溶液’然後在45 t下反應3小時，藉以製造。 [Si02黏合劑5] 使用500cm3的玻璃製的四口燒瓶，添加90g的四乙 氧矽烷、及l〇〇g的乙醇’並在攪拌之下於室溫的狀態下 -21 - 201246575 ，將經將〇.9g的60%硝酸溶解於1 i〇g的純水之溶液 耗費10至15分鐘之方式飼給。然後，於所得混合溶 ，按耗費1 0至1 5分鐘之方式飼給預先所混合之40g 第二丁氧鋁、與60g的乙醇的混合溶液。在室溫下攪 分鐘後’在50°C下反應3小時，藉以製造。 [Si02黏合劑6] 使用500cm3的玻璃製的四口燒瓶，添加125g的 氧矽烷、及160g的乙醇，並在攪拌之下一次添加 0.6g的60%硝酸溶解於1 15g的純水之溶液，然後在 下反應3小時，藉以製造。 [Si02黏合劑7] 使用500cm3的玻璃製的四口燒瓶’添加145g的 氧矽烷、及140g的乙醇’並在攪拌之下一次添加 0.01 5g的6 0%硝酸溶解於1 1 5g的純水之溶液，然後3 °C下反應3小時，藉以製造。 [偶合劑] 作爲矽烷偶合劑，採用乙烯基三乙氧砂院。作爲 合劑，則採用可以式（1 ): ，按 液中 的三 拌30201246575 VI. [Technical Field] The present invention relates to a composition for a transparent conductive film for a solar cell and a transparent conductive film. More specifically, a composition for a transparent conductive film for a thin film solar cell and a transparent conductive film. [Prior Art] Now, from the standpoint of environmental protection, we are promoting the development and practical use of clean energy, and the solar cells are inexhaustible as the energy of sunlight, and there is no pollution. Therefore, it is attracting attention. In the past, it is a solar cell, a bulk solar cell using single crystal silicon or poly crystal silicon, but because of the high manufacturing cost and productivity of a large-volume solar cell system. Also low is the need to develop a solar cell that saves sand. Thus, development of a thin film solar cell using a semiconductor such as amorphous silicon having a thickness of, for example, 0.3 to 2 μm is enthusiastically carried out. Since such a thin film solar cell has a structure in which a semiconductor layer required for photoelectric conversion is formed on a glass substrate or a heat-resistant plastic substrate, it has the advantages of being thin, light in weight, low in cost, and easy to be large in area. In the solar cell, there are a superstrate structure and a sub strate structure, and the top material type is configured to make sunlight from the side of the transmissive substrate. The structure formed by the order of the substrate-transparent electrode-light 201246575 electric conversion layer (ph 〇t 〇e ectricc ο nversi ο η 1 ayer)- rea r-face electrode. On the other hand, the substrate type structure is usually formed in the order of the substrate-back electrode-photoelectric conversion layer-transparent electrode. In the case of such a thin film solar cell, the battery or the reflective film is formed by a vacuum film deposition method such as sputtering, but generally, it is a large vacuum film deposition. High cost is required for the introduction, maintenance, and operation of the device. In order to improve such a defect, there is no wet coating method using a composition for a transparent conductive film and a composition for a conductive reflection film according to an inexpensive manufacturing method. (wet coating method) A technique of forming a transparent conductive film and a conductive reflective film (Patent Document 1). [Prior Art Document] [Patent Document] Patent Document 1: JP-A-2009-88489 SUMMARY OF INVENTION [Problems to be Solved by the Invention] The present invention is improved by the above-described wet coating method. The transparent conductive film is a subject. The present inventors have found that, if the composition for a transparent conductive film is modified to increase the difference between the refractive index of the transparent conductive film used in the wet coating method and the refractive index of the photoelectric conversion layer, it is increased in transparency. The fact that the conductive film-photoelectric conversion layer interface reflects light and utilizes the added return light of the light -6-201246575 electric conversion layer can improve the power generation efficiency of the thin film solar cell. This type of method is applicable to any of the top-type solar cells, the substrate-type solar cells, and the large-capacity solar cells, and is particularly suitable for the top type. [Means for Solving the Problem] The present invention relates to a composition for a transparent conductive film for a thin film solar cell which solves the above-described problems, and a transparent conductive film (1). A composition for a conductive film, comprising: ITO (Indium Tin Oxide) hollow particles having an average particle diameter of 1 to 50 nm, and a binder (2) as described above ( 1) The composition for a transparent conductive film for a thin film solar cell according to the above, further comprising a conductive oxide particle. (3) The composition for a transparent conductive film for a thin film solar cell according to the above (1) or (2), wherein the binder is a polymer type adhesive and/or a non-polymer type adhesive which is hardened by heating. Agent. (4) The composition for a transparent conductive film for a thin film solar cell according to the above (3), wherein the non-polymer type binder is selected from the group consisting of metal soaps, metal complexes, metal alkoxides, and halogenated decanes. At least one of a group consisting of 2-alkoxyethanol, lysine, -diketone', and alkyl acetate. (5) A transparent conductive film for a thin film solar cell, characterized in that: 201246575 contains I TO hollow particles having an average particle diameter of 1 to 50 nm, and a hardened binder, and a hollow particle and a hardened adhesive. A total of 100 parts by mass of the hollow particles containing 55 to 95 parts by mass. (6) The transparent conductive film for a thin film solar cell according to the above (5), which further contains conductive oxide particles. (7) The transparent conductive film for a thin film solar cell according to the above (5) or (6), wherein the binder is a polymer type binder and/or a non-polymer type binder. (8) The transparent conductive film for a thin film solar cell according to the above (7), wherein the non-polymer type binder is selected from the group consisting of metal soaps, metal complexes, metal alkoxides, halogenated decanes, 2 - At least one of a group of alkoxyethanol, /5-dione, and alkyl acetate. (9) A thin film solar cell comprising the transparent conductive film for a thin film solar cell according to any one of the items (5) to (8) above. (10) A method for producing a transparent conductive film, which is a method for producing a transparent conductive film of a thin film solar cell comprising a substrate, a transparent electrode layer, a photoelectric conversion layer, and a transparent conductive film, which is characterized in that: On the layer, the composition for a transparent conductive film according to any one of the above (1) to (4) is applied by a wet coating method to form a transparent conductive coating film, and then the substrate having a transparent conductive coating film is formed. The firing is performed at 130 to 400 ° C to form a transparent conductive film having a thickness of 0.03 to 0.5 μm. (11) The method for producing a transparent conductive film according to the above (10), wherein the wet coating method is a spray coating method, a dispenser coating method, or a spin coating method. Spin coating, 201246575 knife coating, slit coating, inkjet coating, die coating, screen printing (screen printing), offset printing, or gravure printing. [Effects of the Invention] The composition for a transparent conductive film of the invention (1) can be applied and fired on the photoelectric conversion layer by a wet coating method, and the resulting transparent conductive material can be obtained by the content of the ITO hollow particles. The refractive index of the film is lowered. That is, the difference between the refractive index of the transparent conductive film and the refractive index of the photoelectric conversion layer increases, and the reflected light at the interface of the transparent conductive film-photoelectric conversion layer increases, and the added photoelectric conversion layer By returning light, a transparent conductive film capable of improving the power generation efficiency of the thin film solar cell can be easily produced. According to the invention (5), the reflected light at the interface of the transparent conductive film-photoelectric conversion layer is increased, and the increased return power of the photoelectric conversion layer can be easily obtained to improve the power generation efficiency. Thin film solar cells. According to the invention (10), a transparent conductive film can be formed without using a high-priced vacuum device, and a thin film solar cell having high power generation efficiency can be easily manufactured at low cost. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described based on embodiments. Here, % means the quality % unless it is specifically stated as 'or the inherent number.' ~ 9 - 201246575 [Composition for a transparent conductive film for a thin film solar cell] The group f for a transparent conductive film for a thin film solar cell of the present invention, hereinafter abbreviated as "a composition for a transparent conductive film", is characterized by: Diameter: 1 to 50 nm of ITO hollow particles, and a binder. ITO (Indium Tin Oxide) hollow particles, the average particle diameter: 1 to 50 nm, if it is below 1 nm, it is easy to cause secondary aggregation due to insufficient particle properties, resulting in difficulty in the preparation of the sample. When it is the above, the contact of the conductive particles is hindered. Here, the average particle diameter is measured from the specific surface area measured by QUANTACHROME AUTOSORB-1, and it is assumed that the ITO hollow particles are (real ball). The shape of the ITO hollow particles may be a spherical shape, a scorpion shape, a spurred sugar shape, or the like, and is preferably spherical. The aspect ratio (long diameter/short diameter) of the ITO particles is preferably from 1 to 1, more preferably from 1 to 1.2. The ITO hollow particles have good wettability with the photoelectric conversion layer, and can reduce the unevenness of the film thickness to lower the refractive index of the cured transparent conductive film. In Fig. 1, a section of a thin film solar cell of the transparent conductive film of the present invention is used. Fig. 1 is an example of a top-type thin film solar cell. The thin film battery is provided with the substrate 10, the transparent electrode layer 3, the photoelectric conversion layer 2, and the conductive film 1' conductive reaction film 4 in this order, and the sunlight is emitted from the substrate 10. Most of the incident sunlight is returned to the photoelectric conversion layer 2 by the conductive reflective film 4 to improve the conversion efficiency. Here, the interface between the transparent film 1 and the photoelectric conversion layer 2 also has a reflection of sunlight, and the sputum (the content of the smear is stable, and if it is suitable for a social ball, the hollow is 1.4, and the drawing is shown, The transparent conductive film 1 using the composition for a transparent conductive film of the present invention, which has a low refractive index, can be placed at the interface between the transparent conductive film 1 and the photoelectric conversion layer 2 The reflected light is increased to increase the power generation efficiency of the thin film solar cell. The ITO hollow particles, such as in an ionic liquid, can be obtained by oxidizing indium tin nanoparticles obtained by a splash of indium tin. A composition containing either or both of a polymer type binder or a non-polymer type binder which is hardened by heating is preferable, and a polymer type binder may, for example, be an acrylic resin or a polycarbonate. Polyester, alkyd resin, polyurethane, acrylic urethane, polystyrene, polyacetal, polyamine, polyvinyl alcohol, polyvinyl acetate, cellulose, and decane Polymer, etc. Among the polymer binders, metal soaps, metal complexes, or metal alkoxides containing aluminum 'niobium, titanium, chromium 'manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin are preferred. Hydrolyzate. For non-polymeric binders, metal soaps, metal complexes, metal alkoxides, halogenated decanes, 2-alkoxyethanols, 0-diketones, and hospital bases B can be exemplified. Acid, etc. Further, the metal contained in the metal lane, the metal complex, or the metal alkoxide is preferably aluminum, bismuth, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, Molybdenum, tin, indium or antimony, more preferably an alkoxide of bismuth or aluminum (for example, tetraethoxy decane, tetramethoxy decane, triethoxy dimethyl 'triisopropoxide aluminum). As a result of the hardening of the material-type binder and the non-polymer type binder by heating, the formation of a transparent conductive film having a low haze rate and a volume resistivity (v〇Ume resistivity) at a low temperature can be achieved. Thus, the metal alkoxide may be a hydrate 1 or a dehydrate. -11 - 201246575 When the alkoxide is hardened, it is preferable to contain, together with the water used for initiating the hydrolysis reaction, an acid such as hydrochloric acid, nitric acid, phosphoric acid (H3P〇4) or hydrofluoric acid as a catalyst, or ammonia water, The alkali such as an aqueous solution of sodium hydroxide is easily volatilized from the heat-hardened catalyst, does not easily remain, does not remain halogen, does not leave P (phosphorus) having low water resistance, and does not leave an alkali metal salt such as Na (sodium). From the point of view, 'it is better to be nitric acid. Also, in the case of nitric acid, even if N (nitrogen) remains so as to diffuse into the photoelectric conversion layer (n-type) of the substrate, it still acts as a donor. Therefore, the conversion efficiency of the photoelectric conversion layer is not lowered, but the conversion efficiency may be higher. The content of the binder is a composition for a transparent conductive film after removing a dispersion medium: 100 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass. In addition, when a metal alkoxide is used as a binder and nitric acid is used as a catalyst, for example, when a metal alkoxide is used in an amount of 1 part by mass, and cerium nitrate is used in an amount of 3 to 3 parts by mass, adhesion is performed. The curing rate of the agent and the residual amount of nitric acid are suitable. Further, when the amount of the nitric acid as the catalyst is small, the polymerization rate of the hydrolyzate of the metal alkoxide as the binder becomes slow, and when the amount of water required for the hydrolysis is insufficient, it may be difficult to obtain a firm transparency. Conductive film. Further, in the case of using a hydrolysis solution having a network structure having a high degree of polymerization at the time of curing by firing, the stress applied during shrinkage may become a state in which the conductive particles are in contact with each other. Oxide: 100 parts by weight and water of 10 to 120 parts by mass are suitable. The composition for a transparent conductive film preferably contains conductive oxide particles from the viewpoint of improving the conductivity of the transparent conductive film. Conductive oxide-12-201246575 particles preferably contain tin oxide powder or A1 (aluminum) selected from the group consisting of ITO, ATO (Antimony Tin Oxide: doped tin oxide) a zinc oxide powder of at least one metal, such as Co (cobalt), Fe (iron), In (indium), Sn (tin), and Ti (titanium), among which ITO, ATO, AZO (Aluminum) is more preferable. Zinc Oxide: (Zhu Zhan Zinc Oxide), IZO (Indium Zinc Oxide): (Indium-doped Zinc Oxide), TZO (Tin Zinc Oxide): Tin-doped zinc oxide. Further, the average particle diameter of the conductive oxide fine particles is preferably in the range of 10 to 10 nm in order to maintain stability in the dispersion medium, and more preferably In the range of 20 to 60 nm, the composition for a transparent conductive film contains 100 parts by mass of the conductive oxide particles and the ITO hollow particles, and contains 10 to 7 parts by mass of the conductive oxide particles, preferably. It contains 15 to 65 parts by mass. If it is above the upper limit, the effect of re-reection increases. When the temperature is lower than the lower limit 値, the conductivity is lowered. The composition for the transparent conductive film is preferably a conpling agent added to the other components used. The adhesion between the ITO hollow particles and the binder, and the adhesion between the transparent conductive film formed by the composition for the transparent conductive film and the photoelectric conversion layer or the conductive reflective film laminated on the substrate The coupling agent may, for example, be a decane coupling agent, an aluminum coupling agent, a titanium coupling agent, etc. The content of the coupling agent is a solid component (conductive oxide particles) in the composition for a transparent conductive film. , ITO hollow particles, a binder, a decane coupling agent, etc.): 100 parts by mass, preferably 0.2 to 5 parts by mass, more preferably 0.5 - 13 to 201246575 to 2 parts by mass. In the composition for a transparent conductive film, In order to facilitate the deposition of the film, it is preferred to contain a dispersion medium, and the dispersion medium may, for example, be water: alcohol such as methanol, ethanol, isopropanol or butanol; acetone or methyl ethyl ketone; Cyclohexanone a ketone such as phorone; a hydrocarbon such as toluene, hydrazine, hexane or cyclohexane; or a guanamine such as N,N-dimethylformamide as N,N-dimethylacetamide; An anthracene such as dimethyl hydrazine or a glycol such as ethylene glycol; a glycol ether such as ethyl cellulose; the content of the dispersion medium is transparent to obtain good film deposition properties. The composition for a conductive film: 100 parts by mass, preferably 65 to 99 parts by mass. Further, a low-resistance reducing agent or a water-soluble cellulose derivative or the like is preferably added depending on the component to be used. The low-resistance agent is preferably one or more selected from the group consisting of inorganic acid salts and organic acid salts of cobalt, iron, indium, nickel, lead, tin, titanium, and zinc. A mixture of nickel acetate and second iron chloride, Zinc naphthenate, a mixture of tin octoate and cerium chloride, a mixture of indium nitrate and lead acetate, a mixture of titanium acetate and cobalt octoate, etc. . The content of the low-resistance agent is 100 parts by mass, preferably 0.2 to 15 parts by mass, based on the conductive oxide powder. A water-soluble cellulose derivative, although a non-ionic surfactant, is capable of dispersing a conductive oxide powder even when added in a small amount, and is derived from water-soluble cellulose. The addition of the substance and the transparency of the formed transparent conductive film are also improved. The water-soluble cellulose derivative may, for example, be /9-hydroxypropylcellulose or hydroxypropylmethylcellulose. The amount of the water-soluble cellulose derivative to be added is 100 parts by mass, preferably 0.2 to 5 parts by mass, based on the conductive oxygen-14-201246575. A composition for a transparent conductive film, which can use a paint shaker, a ball mill, a sand mill, a centri mill, and a third according to a usual method. The light mill 〇11166-r ο 11 mi 11) or the like is mixed to produce conductive oxide particles, i τ Ο hollow particles or the like. Of course, the transparent conductive film for a thin film solar cell of the present invention (hereinafter, simply referred to as "transparent conductive film" is characterized by containing an average particle diameter··1 to 50 nm of I Τ hollow particles, and a hardened binder, and a total of 100 parts by mass of the TT 〇 hollow particles and the hardened binder, and 55 to 95 parts by mass of the I Τ hollow particles. Transparent conductive film, Preferably, the conductive oxide particles are further contained. The ITO hollow particles and the conductive oxide particles are such that the above-mentioned "hardened adhesive" hardens the above-mentioned adhesive, that is, the above-mentioned film The method for producing a transparent conductive film of the present invention is a thin film solar cell including a substrate, a transparent electrode layer, a photoelectric conversion layer, and a transparent conductive film in this order. A method for producing a transparent conductive film, characterized in that the composition for a transparent conductive film described above is applied by a wet coating method on a photoelectric conversion layer After the transparent conductive coating film, the substrate having the transparent conductive coating film is fired at 13〇-15 to 201246575 to 400 ° C to form a transparent conductive film having a thickness of 0.03 to 0.5 μm. First, on the substrate. The composition for the transparent conductive film is applied by a wet coating method on the photoelectric conversion layer, and the thickness after the firing is 0. 03 to 0.5 μm, preferably 0.05 to The coating film is applied in a manner of a thickness of 0.2 μm. The coating film is dried at a temperature of 20 to 120 (for example, preferably 25 to 60, for 1 to 30 minutes, preferably 2 to 10 minutes). A transparent conductive coating film is formed. The substrate may be any one of glass, ceramic, or a light-transmitting substrate made of a polymer material, or selected from the group consisting of glass, ceramics, polymer materials, and strontium. In the above-mentioned light-transmitting laminate, the polymer substrate may be a substrate formed of an organic polymer such as polyamide or PET (ethylene terephthalate). The wet coating method is preferably a spray coating method, a fixed disperser coating method, The transfer coating method, the blade coating method, the slit coating method, the inkjet coating method, the screen printing method, the offset printing method, or the die coating method are not limited thereto, but may be All methods are used. The spray coating method is a method in which a composition for a transparent conductive film is applied to a substrate by using compressed air to form a mist, or the dispersion itself is pressed into a mist and then applied to a substrate. In the method of the dispersion disperser coating method, for example, a composition for a transparent conductive film is placed in a syringe, and a piston of the syringe is pushed to discharge a dispersion from a fine nozzle at the front end of the syringe to coat In the spin coating method, a composition for a transparent conductive film is dropped onto a substrate which is rotated, and a composition for a transparent conductive film of -16-465465 is dropped by a centrifugal force. In the method of the edge of the substrate, the doctor blade coating method is configured such that the front end of the doctor blade and the substrate having a predetermined gap are moved in the horizontal direction, and the blade is supplied to the base on the upstream side of the composition for the transparent conductive film. On the substrate to the method moves toward the downstream side of the water level. The slit coating method is a method in which a composition for a transparent conductive film flows out from a narrow gap to be applied to a substrate, and an inkjet coating method is used in an ink cartridge of a commercially available ink jet printer. (ink cartridge) A method of filling a composition for a transparent conductive film and performing inkjet printing on a substrate. A screen printing method is a method in which a gauze is used as a pattern indicating material, and a composition for a transparent conductive film is transferred onto a substrate by a plate image made thereon. The offset printing method is a composition for a transparent conductive film attached to a plate, which is not directly attached to a substrate, but is transcribed from a printing plate onto a rubber sheet and re-transferred from the rubber sheet to the base. A printing method using water repellency of a composition for a transparent conductive film on a material. The die coating method is a composition for a transparent conductive film supplied into a die, which is dispensed from a slit after being dispensed from a manifold, and is applied to the film during operation. The method of the surface of the substrate. Examples of the die coating method include a slot coating method, a slide coating method, and a curtain coating method. Finally, the substrate having the transparent conductive coating film is held and fired in an atmosphere of an inert gas such as nitrogen or argon at 130 ° C to 400 ° C, preferably 150 to 350 ° C. 5 to 60 minutes, preferably 15 to 40 minutes. Here, the composition for the transparent conductive film is applied in such a manner that the thickness of the transparent conductive film after firing can be in the range of 0.03 to 0.5 μm, and the thickness after firing is less than 0.03. When μιη, or more than 0.5 μm, it is difficult to sufficiently obtain the reflection amplifying effect. The reason why the firing temperature of the substrate having the coating film is in the range of 130 to 400 ° C is that if the temperature is less than 130 ° C, the surface resistance of the transparent conductive film of the composite film may become too high. The shortcomings. Further, if it exceeds 400 °C, the production merit of the low-temperature process cannot be utilized, that is, the manufacturing cost is increased so that the productivity is lowered. In particular, amorphous ruthenium, microcrystalline ruthenium, or a hybrid type solar cell using such a low heat resistance is low, and the conversion efficiency is lowered by the firing process. The reason why the firing time of the substrate having the coating film is in the range of 5 to 60 minutes is that if the firing time is less than the lower limit, the surface resistance of the transparent conductive film of the composite film may become too high. The shortcomings. If the firing time exceeds the upper limit, the manufacturing cost is excessively increased and the productivity is lowered. Further, there is a disadvantage that the conversion efficiency of the solar cell element is lowered. In the above manner, the transparent conductive film of the present invention can be formed. As described above, in the production method of the present invention, the wet coating method is used, and the vacuum process such as the vacuum deposition method or the sputtering method can be eliminated as much as possible, and the transparent conductive film can be manufactured in a more inexpensive manner. [Embodiment] [Embodiment] ______ • 18· 201246575 The following is a detailed description of the present invention, but the present invention is not limited by the embodiment. According to the composition shown in Tables 1 to 3 (the number of parts indicates the mass parts), the total amount is 60 g, placed in a 100 cm3 glass bottle, using a 0.3 mm diameter chrome oxide bead l〇〇g, using a paint shake The motive was dispersed for 6 hours to prepare the transparent conductive film compositions of Examples 1 to 19 and Comparative Example 1. In Table 4, the average particle diameter of the ITO hollow particles used is shown. Here, in the column of the ratio of Table 1, the conductive oxide particles are simply referred to as conductive, the hollow ITO particles are H-ITO, and the coupling agent is even. Further, in Table 4, the average particle diameter of the hollow ITO particles used was shown. Here, the ITO hollow particles 1 to 2, and the SiO 2 adhesives 1 to 7 used as the binder are produced as follows. [ITO Hollow Particles 1] 1-butyl-3-methylimidazolium tetrafluoroborate (BMI-BF4) was dried in a vacuum at 120 ° C, and then sputter coated by Seiko Electronics Co., Ltd. The above 1-butyl-3-methylimidazole gun tetrafluoroborate 0.6 0 c was placed on a horizontally placed glass plate (10 cm3) in a cloth machine (model: SC-70HMCII). M3. The surface of the ionic liquid was placed at a distance of 20 mm from an indium silver foil target (purity: 99.99%) at room temperature at 2.OPa (purity: 99.99% or more). Sputter was applied for 10 minutes at a sputtering current of 10 mA. After the sputtering, an ionic liquid -19-201246575 solution containing indium tin oxide particles was taken from the glass plate, and the obtained ionic liquid solution was subjected to heat treatment at 250 ° C for 1 hour in the atmosphere to prepare ITO hollow particles 1. [ITO Hollow Particles 2] 1-Allyl-3-ethylimidazole gun tetrafluoroborate (AEI-BF4)) was dried in a vacuum at 120 ° C, and then spattered by Seiko Electronics Co., Ltd. The above 1-allyl-3-ethylimidazole gun tetrafluoroborate was placed on a horizontally placed glass plate (10 cm3) in a shovel coater (model: SC-70HMCII). 〇. 6 0 c m3. The surface of the ionic liquid is placed at a distance of 20 mm from the indium silver foil target (purity: 99.99%), and at room temperature, under argon gas (purity: 99.99% or more) of 2.OPa, current is applied according to the beach. 10 mA was sputtered for 10 minutes. After the splashing, an ionic liquid solution containing indium tin nanoparticles was taken from the glass plate, and the obtained ionic liquid solution was subjected to heat treatment at 250 ° C for 1 hour in the atmosphere to prepare ITO hollow particles 2. [Si02 Binder 1] A 500 cm3 glass four-necked flask was used, 14 g of tetraethoxy decane, and 140 g of ethanol were added, and after stirring, 1.7 g of 60% nitric acid was dissolved in I20 g. A solution of pure water was then reacted at 50 ° C for 3 hours to manufacture. [Si02 Binder 2] -20- 201246575 A 500-neck glass four-necked flask was used, and 85 g of tetraethoxyoxane and 1 g of ethanol were added, and the mixture was stirred at room temperature. The 60% nitric acid of hydrazine is dissolved in a solution of 11% pure water, and is fed by a tube pump for 10 to 15 minutes. Then, in the obtained mixed solution, a tubular pump is used, and the cost is 1 The solution was mixed with 45 g of three second butoxides and 60 g of ethanol which were previously mixed for 15 minutes, stirred at room temperature for 30 minutes, and then reacted at 50 ° C for 3 hours to manufacture. [Si02 Binder 3] Using a 50 cm3 glass four-necked flask, 115 g of tetraethoxy decane' and 175 g of ethanol were added, and after stirring, a solution of 1.48 of 35 ° / hydrochloric acid was dissolved in 11 Torr. A solution of 8 pure water was then reacted for 3 hours at 45 ° to produce it. [Si02 Binder 4] Using a 500 cm3 glass four-necked flask, 130 g of tetraethoxyoxane, and 145 g of ethanol were added. Add 1.25 g of 30% ammonia water to 124 g of pure water solution with stirring under one time' The reaction was carried out at 45 t for 3 hours to produce. [Si02 Binder 5] A 500 cm3 glass four-necked flask was used, and 90 g of tetraethoxyoxane and 1 g of ethanol were added and stirred under the chamber. In the warm state, 21 - 201246575, it will be fed by dissolving 9.9g of 60% nitric acid in 1 μ〇g of pure water for 10 to 15 minutes. Then, the mixture is dissolved, and the cost is 1 A mixed solution of 40 g of second butoxide-aluminum and 60 g of ethanol previously mixed was fed in a manner of from 0 to 15 minutes, and after stirring for a minute at room temperature, it was reacted at 50 ° C for 3 hours to produce. [Si02 Adhesive 6] A 500-cm glass four-necked flask was used, 125 g of oxane, and 160 g of ethanol were added, and 0.6 g of 60% nitric acid was dissolved in a solution of 1 15 g of pure water once under stirring, and then under The reaction was carried out for 3 hours to produce. [Si02 Binder 7] A 500 cm3 glass four-necked flask was used, '145 g of oxoxane and 140 g of ethanol' were added and 0.015 g of 60% nitric acid was added at a time under stirring to dissolve. 1 1 5 g of a solution of pure water, and then reacted at 3 ° C for 3 hours to manufacture. Agent] As the silane-coupling agent, vinyl triethoxy using sand as a hospital agent is used may be of formula (1):., According to the three liquid mix 30
四乙 經將 5 0°C 四乙 經將 ί 50 鈦偶 -22- 2201246575 utn οIIc-σ4B will be 50 °C, and the fourth will pass ί 50 titanium couple -22-2201246575 utn οIIc-σ
Ti H2C—〇 Ο ΟII II / ν -ΟΡΟ p-(oc8hI7| ΟΗ ' 之二烷基焦亞磷酸酯基之鈦偶合劑。 [混合溶劑] 作爲混合溶劑1，採用異丙醇、乙醇以及Ν,Ν-二甲基 甲醯胺之混合液（質量比4 ·· 2 : 1 )，作爲混合溶劑2，則採 用乙醇與丁醇之混合液（質量比98 : 2)。 [非聚合物型黏合劑] 作爲非聚合物型黏合劑1，採用2-正丁氧乙醇與3-異 丙基-2,4-戊二酮之混合物，作爲非聚合物型黏合劑2，採 用2，2-二甲基-3,5-己二酮與異丙基乙酸酯之混合液（質量 比1 : 1 )，作爲非聚合物型黏合劑3，則採用2 - 丁氧乙醇 與2-己氧乙醇與正丙基乙酸酯之混合物（質量比4 : 1 _· 〇 [實施例1至19] 實施例1中，首先，如下列的表1所示方式，於成爲 分散介質之IPΑ(異丙醇）中，將平均粒徑8nm的ΙΤ0空心 粒子l(H-ITOl)，與作爲黏合劑之Si02黏合劑1按對IT0 空心粒子爲3 0質量％之比例混合。 5' -23- 201246575 實施例2中，於成爲分散介質之乙醇中’將平均粒徑 8 nm的I TO空心粒子1、與作爲導電性氧化物粉末之平均 粒徑30nm的I TO粉末按70對30之比例混合，又，將作 爲黏合劑之非聚合物型黏合劑1按對ΪΤΟ空心粒子和導電 性氧化物粒子合計之固體成分物粒子爲1〇質量％之比例混 合。 實施例3中，於成爲分散介質之IPA中，將平均粒徑 8nm的ITO空心粒子1、與作爲導電性氧化物粉末之平均 粒徑25nm的I TO粉末按80對20之比例混合，又，將作 爲黏合劑之Si02黏合劑2按對ITO空心粒子和導電性氧 化物粒子合計之固體成分物粒子爲30質量％之比例混合。 實施例4中，於成爲分散介質之乙醇中，將平均粒徑 15nm的ITO空心粒子2(H-IT02)、與作爲黏合劑之Si02 黏合劑7按對ITO空心粒子爲25質量％之比例混合。 實施例5中，於成爲分散介質之混合溶劑1中，將平 均粒徑1 5nm的ITO空心粒子2、與作爲導電性氧化物粉 末之平均粒徑35nm的ITO粉末按82對18之比例混合， 又，將作爲黏合劑之Si02黏合劑6按對ITO空心粒子和 導電性氧化物粒子合計之固體成分物粒子爲20質量％之比 例混合。 實施例6中，於成爲分散介質之乙醇中，將平均粒徑 15nm的ITO空心粒子2、與作爲導電性氧化物粉末之平 均粒徑40nm的ITO粉末按60對40之比例混合，又，將 作爲黏合劑之Si〇2黏合劑2按對IT0空心粒子和導電性 -24- 201246575 氧化物粒子合計之固體成分物粒子爲20質量％之比例混合 〇 實施例7中，於成爲分散介質之乙醇中，將平均粒徑 8 nm的ITO空心粒子1、與作爲導電性氧化物粉末之平均 粒徑25nm的ITO粉末按50對50之比例混合，又，將作 爲黏合劑之非聚合物型黏合劑1按對ITO空心粒子和導電 性氧化物粒子合計之固體成分物粒子爲3 0質量％，再者， 將具有可以化學式（1)表示之二烷基焦亞磷酸酯基之鈦偶合 劑按對成爲塗膜形成後的固體成分.物之ITO空心粒子和導 電性氧化物粒子以及黏合劑成分之合計之組成物質量爲 0.5質量％之比例混合。 實施例8中，於成爲分散介質之混合溶劑2中，將平 均粒徑15nm的ITO空心粒子2、與作爲導電性氧化物粉 末之平均粒徑50nm的ΑΤΟ粉末按40對60之比例混合， 又，將作爲黏合劑之非聚合物型黏合劑2按對ΙΤΟ空心粒 子和導電性氧化物粒子合計之固體成分物粒子爲30質量％ 之比例混合。 實施例9中，於成爲分散介質之混合溶劑1中，將平 均粒徑8nm的ΙΤΟ空心粒子1、與作爲導電性氧化物粉末 之平均粒徑30nm的ΑΤΟ粉末按85對15之比例混合，又 ，將作爲黏合劑之Si02黏合劑3按對ΙΤΟ空心粒子和導 電性氧化物粒子合計之固體成分物粒子爲1 5質量％之比例 混合。 實施例1 〇中，於成爲分散介質之混合溶劑2中，將 -25- 201246575 平均粒徑8nm的ITO空心粒子1、與作爲導電性氧化物粉 末之平均粒徑40nm的ΙΤΟ粉末按35對65之比例混合， 又，將作爲黏合劑之Si02黏合劑4按對ITO空心粒子和 導電性氧化物粒子合計之固體成分物粒子爲30質量％之比 例混合。 實施例11中，於成爲分散介質之混合溶劑2中，將 平均粒徑15nm的ITO空心粒子2、與作爲導電性氧化物 粉末之平均粒徑50nm的ITO粉末按80對20之比例混合 ，又，將作爲黏合劑之Si02黏合劑5按對ITO空心粒子 和導電性氧化物粒子合計之固體成分物粒子爲25質量％之 比例混合。 實施例12中，於成爲分散介質之乙醇中，將平均粒 徑8nm的ITO空心粒子1、與作爲導電性氧化物粉末之平 均粒徑30nm的ITO粉末按60對40之比例混合，又，將 作爲黏合劑之Si02黏合劑6按對ITO空心粒子和導電性 氧化物粒子合計之固體成分物粒子爲25質量％之比例混合 ，再者，將矽烷偶合劑（信越聚矽氧（股）製KBE- 1 003 )，按 對成爲塗膜形成後的固體成分物之ITO空心粒子和導電性 氧化物粒子以及黏合劑成分合計之組成物質量爲〇. 7質量 %之比例混合。 實施例13中，於成爲分散介質之IPA中，將平均粒 徑1 5nm的ITO空心粒子2、與作爲導電性氧化物粒子之 平均粒徑25 nm的IZO粉末按50對50之比例混合，又， 將作爲黏合劑之Si02黏合劑1按對ITO空心粒子和導電 -26- 201246575 性氧化物粒子合計之固體成分物粒子爲2 5質量％之比例混 合。 實施例14中，於成爲分散介質之丁醇中，將平均粒 徑8 nm的ITO空心粒子1、與作爲導電性氧化物粉末之平 均粒徑40nm的ΑΤΟ粉末按90對10之比例混合，又，將 作爲黏合劑之非聚合物型黏合劑3按對ΙΤΟ空心粒子和導 電性氧化物粒子合計之固體成分物粒子爲1 0質量％之比例 混合。 實施例15中，於成爲分散介質之ΙΡΑ中，將平均粒 徑1 5nm的ΙΤΟ空心粒子2、與作爲導電性氧化物粉末之 平均粒徑25nm的ITO粉末按95對5之比例混合，又， 將作爲黏合劑之Si02黏合劑7按對ITO空心粒子和導電 性氧化物粒子合計之固體成分物粒子爲25質量％之比例混 合。 實施例16中，於成爲分散介質之混合溶劑1中，將 平均粒徑15nm的ITO空心粒子2、與作爲導電性氧化物 粉末之平均粒徑30nm的IZO粉末按85對15之比例混合 ，又，將作爲黏合劑之Si02黏合劑5按對ITO空心粒子 和導電性氧化物粒子合計之固體成分物粒子爲30質量％之 比例混合。 [比較例1 ] ' 比較例1中，於成爲分散介質之IPA中，將作爲導電 性氧化物粉末之平均粒徑25nm的ITO粉末，又將作爲黏 -27- 201246575 合劑之Si02黏合劑1按對導電性氧化物粒子爲3 0質量％ 之比例混合。 [透明導電膜用組成物評價] 就折射率評價而言，係就實施例1至1 6、比較例1中 所示之透明導電膜用組成物，對已知光學常數之玻璃基板 上，利用濕式塗佈法（旋轉塗佈法、壓模塗佈法、噴霧塗 佈法、膠版印刷法等）進行透明電極膜之薄膜形成後，在 160至220 °C下燒成20至60分鐘，藉以形成厚度0.05至 0·2μπι的透明導電膜。對此膜，採用光譜橢圓對稱術（ spectro ellipsometry)裝置（J.A.Woollam Japan(股）製 Μ-200 0)進行測定，就透明電極膜部分解析數據以求出光學 常數。從所解析之光學常數，將63 3 nm的値作爲折射率。 將此等結果，表示於表1至表3中。 如第1圖所示，首先，將一邊的主面上形成有厚度 50nm的Si02層（未圖示）之玻璃板作爲基板1〇準備，將此 Si02層上作爲透明電極面3而形成表面具有凹凸紋理 (texture)且摻雜有 F(氟）之厚度 800nm的表面電極層 (Sn02(氧化錫）膜）3。對此透明電極層3利用雷射加工法進 行圖型構成（patterning)而作成陣列（array)狀之同時，形成 將此等按電氣性互相連接之配線。接著，於透明電極層3 上採用電漿CVD(化學汽相沈積）法，以形成光電變換層2 。在此實施例中’該光電變換層2，係從基板1 0側依順序 層壓製得由p型a-Si : H(非晶質單元矽）、I型a_ Si (非晶 -28- 201246575 質矽）以及η型pc-Si(微結晶碳化矽）所成之膜。將上述光 電變換層2，採用雷射加工法進行圖型構成。將此等利用 爲已經進展有成膜之太陽能電池元件在實施例中所示之透 明導電膜用組成物評價。 就實施例1至1 6、比較例1中所示之透明導電膜用組 成物，對已經進展有薄膜形成之太陽能電池元件，按燒成 後的厚度能成爲0.01至0·5μηι之方式利用濕式塗佈法（旋 轉塗佈法、壓模塗佈法、噴霧塗佈法、膠版印刷法）進行 塗佈後，在溫度25至60 °C的低溫下乾燥5分鐘，以形成 透明導電膜1。於表1至表3中，表示塗裝方法（coating method) ° 接著，於此透明導電膜1上，將依下述方法所調製之 導電性反射膜用組成物，按燒成後之厚度能成爲0.05至 2.0 μηι之方式依濕式塗佈法加以塗佈後，在溫度25至60 °C之低溫下乾燥5分鐘，以形成導電性反射膜。接著，在 160至220 °C下燒成20至60分鐘，藉以在太陽能電池元 件上形成複合膜。將透明導電膜1之燒成後膜厚表示於表 1至表3中。膜厚，係依使用日立高科技社製掃描式電子 顯微鏡（SEM、裝置名：S-4300、SU-8000)之剖面觀察加以 測定。在此，導電性反射膜用組成物之調製方法，係如下 述方法進行。 首先，將硝酸銀溶解於無離子水（deionized water)中 以調製金屬離子水溶液。又，將檸檬酸鈉溶解於無離子水 中以調製濃度爲26重量％之檸檬酸鈉水溶液。於該檸檬酸 -29- 201246575 鈉水溶液中，在經保持於3 5 °C之氮氣氣流中，將粒狀之硫 酸第一鐵直接添加並使其溶解，以調製按3: 2的莫耳比 含有檸檬酸離子與第一鐵離子之還原劑水溶液。接著，在 保持上述氮氣氣流爲35 °C之狀態下，將磁力攪拌器 (magnetic stirrer)之攪拌片置入還原劑水溶液中，按 lOOrpm的旋轉速度使攪拌片旋轉，並在攪拌上述還原劑 水溶液之下，對此還原劑水溶液中滴下上述金屬鹽水溶液 以進行合成。在此，對還原劑水溶液之金屬鹽水溶液的添 加量，係作成按能成爲還原劑水溶液的量之1 /1 〇之方式 調整各溶液之濃度，則即使滴下室溫之金屬鹽水溶液仍能 保持反應溫度爲40 °C之方式。又，上述還原劑水溶液與金 屬鹽水溶液的混合比例，係調整爲作爲還原劑所添加之第 一鐵、離子的當量能成爲金屬離子之3倍之方式。對還原劑 水溶液中的金屬鹽水溶液之滴下完成後，再繼續混合液之 攪拌15分鐘，藉以使混合液內部生成金屬粒子，而製得 分散有金屬粒子之金屬粒子分散液。金屬粒子分散液的 pH爲5.5、而分散液中的金屬粒子的化學理論性生成量 (stoichiometric production)，爲 5g/公升。所得之分散液 ，則放置於室溫中，以使分散液中的金屬粒子沈澱，並利 用傾析（decantation)而將所沈澱之金屬粒子的凝聚物加以 分離。所分離之金屬凝聚物中添加無離子水而作成分散體 ，並利用超濾作業（ulUafiltration)而加以脫鹽處理 (desalting)後，再使用甲醇以進行取代洗淨（sustitutional washing)之結果，將金屬（銀）的含量作成50質量％。然後 -30- 201246575 ，使用離心分離機，調整該離心分散機之離心力’以分離 粒徑在1 〇〇nm以上之較大銀粒子’按能以數平均計’含有 71 %之一次粒徑在10至50nm的範圍之銀奈米粒子之方式 加以調整。亦即，以數平均計’對所有銀奈米粒子1 00% 之一次粒徑佔有1 〇至50nm的範圍內之銀奈米粒子的比例 能成爲7 1 %之方式加以調整。所得銀奈米粒子’係經化學 改性（chemical modification)碳骨架爲3個碳數之有機主鏈 的防護劑（protective agent)者。 其次，將所得之金屬奈米粒子1 〇質量份，添加混合 於含有水、乙醇以及甲醇之混合溶液90質量份中以使其 分散。再者，對此分散液中作爲添加物而將聚乙烯基吡咯 烷酮4質量％、及檸檬酸銀1質量％、按金屬奈米粒子的 比例能成爲95質量％之方添加，而製得導電性反射膜用組 成物。將所得導電性反射膜用組成物，按燒成後之厚度能 成爲0.05至2.Ομιη之方式依濕式塗佈法塗佈於透明導電 膜1上之後，依160至220°C下20至60分鐘的熱處理條 件進行燒成，藉以在透明導電膜1上形成導電性背面反射 膜4。 接著，當作爲太陽能電池元件評價發電效率時，於導 電性反射膜上作爲補強膜，利用壓膜塗佈裝置而將補強膜 用組成物塗佈於薄膜形成已經進展至導電性反射膜之太陽 能電池元件上，並使補強膜用組成物按燒成後之厚度能成 爲350nm之方式，藉由真空乾燥而從補強膜用塗佈膜去除 溶劑後，將太陽能電池元件在180。(：下保持20分鐘於熱風 -31 - 201246575 乾燥爐內，以使補強膜用塗佈膜熱硬化，而製得導電性反 射膜用補強膜。在此，補強膜用組成物之調製方法係如下 述方式進行。 首先，混合：作爲導電性氧化物微粒子之平均粒徑 2 5 nm的ITO粒子8質量％、作爲偶合劑之具有二烷基焦亞 磷酸酯基之鈦偶合劑2質量％、作爲分散介質之乙醇與丁 醇的混合液（質量比：98 : 2)90質量％之後，在室溫下依 800rpm的旋轉速度攪拌1小時。接著，將此混合物60g 置入lOOcc的玻璃瓶內，採用直徑〇.3mm的氧化鉻熔珠 l〇〇g並在油漆搖動機內分散6小時，藉以調製ITO粒子 的分散液。在此，具有二烷基焦亞磷酸酯基之鈦偶合劑， 係如上述化學式（1)所示者。又，Si02黏合劑，係與上述 Si〇2黏合劑1同樣方式所調整者。其次，將ITO粒子的分 散液4質量％、與作爲分散介質之乙醇86質量％混合後， 將Si02黏合劑1再混合1 0質量％，而製得補強膜用組成 物的基礎液體（base liquid)後，將此基礎液體95質量％、 與作爲添加劑之霧狀二氧化矽（fumed silica)分散液5質量 %加以混合，並使用超音波振動器在室溫下進行分散混合 10分鐘以使混合物融和於全體，以調製作爲補強膜用組成 物之塗佈液。 / 經形成至導電性反射膜用補強膜之太陽能電池元件， 係將光電變換層2以及經於其上薄膜形成之透明導電膜1 、導電性反射膜4、以及導電性反射膜用補強膜，利用雷 射加工法而實施圖型構成。 -32- 201246575 太陽能電池元件之評價方法而言’於經利用雷射加工 法所實施圖型構成之加工後的基板上實施導線（lead wire) 配線，將確認IV特性曲線時的輸出特性及屬於短路電流 (short-circuit current)之（Jsc)的値，採用與實施例同樣的 製造方法所得之光電變換層，實施將透明導電膜、導電性 反射膜、補強膜全部經依濺鍍法所形成之太陽能電池元件 作爲100時的相對輸出評價。將此等結果，表示於表1至 表3中。 在此，全部經依濺鏟法所形之太陽能電池元件，係指 如第1圖所示，首先將一邊的主面形成有厚度50nm的 Si〇2層（未圖示）之玻璃基板作爲基板10準備，將此Si02 層上作爲透明電極面3而形成表面具有凹凸紋理且摻雜有 v F (氟）之厚度800nrn的表面電極層（Sn02膜）3。對此透明電 極層3利用雷射加工法進行圖型構成而作成陣列狀之同時 ’形成將此等按電氣性互相連接之配線。接著，於透明電 極層3採用電漿CVD法，以形成光電變換層2。在此實施 例中，該光電變換層2，係從基板1 0側依順序層壓製得由 P型a-Si : H(非晶質單元矽）、i型a-Si(非晶質矽）以及n 型με-Si (微結晶碳化矽）所成之膜。將上述光電變換層2， 採用雷射加工法進行圖型構成後，採用磁控管直線排列式 灑鍍（m a g n e t r ο n i η -1 i n e t y p e s p u 11 e r n i n g )裝置，於光電變 換層2上，順序形成厚度80nm的透明導電膜（ZnO)(氧化 鋅）層）1及厚度20nm的導電性反射膜（銀電極層）4者之意 -33- 201246575 [表1] 實施例1 寊施例2 寶施例3 實施例4 實施例5 資施例6 平均粒徑(nm) 8 8 8 15 15 15 空心ΓΓΟ 粒子 獅 Η-ΓΤ01 H-IT01 H-IT01 Η-ΓΓ02 H-IT02 Η-ΓΓ02 比例(％) 100 70 80 75 82 60 mm - ΠΌ ΙΤ0 — ΠΌ IT0 導電性氧 化物粒子 平均粒徑(nm) - 30 25 - 35 40 比例W 一 30 20 一 18 40 黏合劑 _ Si〇2黏合劑 弈聚合物 型黏合劑 Si〇2黏合劑 Si02黏合劑 Si02黏合劑 S〇s黏合劑 比率(％)對(導+ Η.ΠΌ+黏合劑> 30 10 30 25 20 20 觸媒 觀 60%硝酸 - 60¾硝酸 60¾硝酸 60S硝酸 60¾硝酸 比率(％)對金 思烷氧化物 - 0.1 0.01 0.5 0.1 分散介質 _ IPA Et-〇H IPA Et-OH 混合溶劑1 Et-OH 比率(％)對 組成物 72.3 85 72.3 88 93.9 85 偶合劑 - - - — — - 比率(％)對(導 +Η-ΠΌ+黏合 刺+偁合劑） - - - - - - 薄膜形成 塗裝方法 旋轉塗佈法 旋轉塗佈法 旋轉塗佈法 旋轉塗佈法 壓模塗佈法 旋轉塗佈法 mmmm (“m) 0.1 0.1 0,15 0.13 0.1 0.1 折射率 1.53 1.58 1.55 1.54 1.58 1.59 評價 相對發電效率W 115 118 119 120 116 118 相對短路笛 流密度(％) 103 104 103 107 105 104 -34- 201246575 阴AJ 實施例7 實施例3 實施例9 實施例10 實施例11 實施例12 空心ΠΌ 粒子 平均粒徑(nm> 8 15 8 8 15 8 mm Η-ΓΓ01 Η-ΓΤ02 Η-ΓΤ01 Η-ΓΤ01 Η-ΓΤ02 Η-ΠΌ1 比例(%) 50 40 85 35 80 60 導電性氧 化物粒子 mm ΙΤ0 ΑΤΟ ΑΤΟ ΙΤ0 ITO ΙΤ0 平均粒徑(nm) 25 50 30 40 50 30 比例(%) 50 60 15 65 20 40 黏合劑 觀 非聚合物 型黏合劑 非聚合物 型黏合劑 印〇2黏合劑 Si〇a黏合劑 黏合劑 Si〇2黏合劑 比率(％)對傅+ Η-ΓΓΟ+黏合 _ 30 30 15 30 25 25 觸媒 mm . - - 35Ϊ强酸 30¾氨 60*硝酸 60¾搬 比率(％)對金 馬烷氧化物 - — 1.2 1.0 1.0 0.5 分散介質 mm Et-〇N 混合溶劑2 混雜劑1 混合溶劑2 混合溶剤2 Et-OH 比率(％)對 組成物 86 81 69 81 90 88 偶合劑 面 鈦偶合劑 — - - - 矽烷偶合劑 比率(％)對(導 +Η-ΓΓ0+黏合 劑+偶合劑） 0.5 - - — — 0.7 塗裝方法 旋轉塗佈法 旋轉塗佈法 網版印刷法 旋轉塗佈法 壓模塗佈法 壓搜塗佈法 燒成後膜厚 (βτη) 0,13 0.1 0.15 0.07 0.07 0.1 折射率 1.65 1.66 1.59 1.67 1.57 1.60 評價 相對發電效率W 117 118 121 119 117 116 相對短路電 流密度(％) 104 104 104 105 105 104 -35- 201246575 1^1 實施例13 實施例14 實施例15 實施例16 比較例1 平均粒徑(nm) 15 8 15 15 — 空心ΓΓΟ 粒子 mm Η-ΠΌ2 Η-ΓΓ01 Η-ΓΓ02 Η-ΠΌ2 - 比例(％) 50 90 95 85 - mm 1ΖΟ ΑΤΟ ΙΤ0 120 IT0 導電性氧 化物粒子 平均粒徑(nm) 25 40 25 30 25 50 10 5 15 100 黏合劑 mm Si〇2黏合劑 非聚合物 型黏合劑 Si〇2黏合劑 SiOz黏合劑 Si〇2黏合劑 比率(％)對(導+ Η-ΓΓΟ+黏合節 25 10 25 30 30 觸媒 mm 60¾硝酸 - 60¾硝酸 60%硝酸 60¾硝酸 比率(％)對金 恩烷氧化物 1.2 - 0.01 1 1.2 分散介質 mm IPA 丁醇 IPA 混合溶劑1 1PA 比率(％)對 組成物 89 90.5 88 86 72.3 偶合劑 麵 一 一 - 一 - 比率(％)對(導 +Η-ΓΓΟ+黏合 劑+偶合劑） - 一 — — - 薄膜形成 塗裝方法 旋轉塗佈法 屋模塗佈法 膠版印刷法 膠版印刷法 旋轉塗佈法 燒成後膜厚 (βΛ) 0.07 0.1 0.15 0.1 0,1 折射率 1.61 1.55 1.56 1.59 2.05 評價 相對發電效率(％) 118 119 120 118 99 相對短路電 流密度(％) 104 105 106 104 100 [表4]Ti H2C - 〇Ο Ο II II / ν - ΟΡΟ p - (oc8hI7| ΟΗ ' dialkyl pyrophosphite-based titanium coupling agent. [Mixed solvent] As a mixed solvent 1, using isopropanol, ethanol and hydrazine, A mixture of hydrazine-dimethylformamide (mass ratio 4 ·· 2 : 1 ), as a mixed solvent 2, a mixture of ethanol and butanol (mass ratio 98 : 2). [Non-polymer type bonding] As a non-polymeric binder 1, a mixture of 2-n-butoxyethanol and 3-isopropyl-2,4-pentanedione is used as the non-polymeric binder 2, and 2,2-two is used. a mixture of methyl-3,5-hexanedione and isopropyl acetate (mass ratio 1:1), and as a non-polymeric binder 3, 2-butoxyethanol and 2-hexyloxyethanol Mixture with n-propyl acetate (mass ratio 4:1 _· 〇 [Examples 1 to 19] In Example 1, first, as shown in Table 1 below, IP Α (isopropyl) as a dispersion medium In the alcohol), ΙΤ0 hollow particles 1 (H-ITO1) having an average particle diameter of 8 nm and SiO 2 binder 1 as a binder were mixed at a ratio of 30% by mass to the IOT hollow particles. 5' -23- 201246575 example 2, in the ethanol to be a dispersion medium, 'I TO hollow particles 1 having an average particle diameter of 8 nm and I TO powder having an average particle diameter of 30 nm as a conductive oxide powder are mixed at a ratio of 70 to 30, and The non-polymeric binder 1 as a binder is mixed at a ratio of 1% by mass to the total solid particles of the total of the hollow particles and the conductive oxide particles. In Example 3, in the IPA which becomes a dispersion medium ITO hollow particles 1 having an average particle diameter of 8 nm and I TO powder having an average particle diameter of 25 nm as a conductive oxide powder were mixed at a ratio of 80 to 20, and SiO 2 adhesive 2 as a binder was pressed against ITO. The solid component particles in total of the hollow particles and the conductive oxide particles were mixed at a ratio of 30% by mass. In Example 4, ITO hollow particles 2 (H-IT02) having an average particle diameter of 15 nm were formed in ethanol as a dispersion medium. And the SiO 2 binder 7 as a binder is mixed at a ratio of 25% by mass to the ITO hollow particles. In Example 5, the ITO hollow particles having an average particle diameter of 15 nm are mixed in the mixed solvent 1 serving as a dispersion medium. And as a conductive The ITO powder having an average particle diameter of 35 nm of the oxide powder is mixed at a ratio of 82 to 18, and the SiO 2 binder 6 as a binder is 20 parts by mass of the solid component particles of the ITO hollow particles and the conductive oxide particles. In Example 6, in the ethanol to be a dispersion medium, the ratio of the ITO hollow particles 2 having an average particle diameter of 15 nm to the ITO powder having an average particle diameter of 40 nm as the conductive oxide powder was 60 to 40. In addition, the Si 2 bonding agent 2 as a binder is mixed in a ratio of 20% by mass to the solid component particles of the total of the IT0 hollow particles and the conductive-24-201246575 oxide particles. In the ethanol to be a dispersion medium, the ITO hollow particles 1 having an average particle diameter of 8 nm and the ITO powder having an average particle diameter of 25 nm as the conductive oxide powder are mixed at a ratio of 50 to 50, and the non-adhesive agent is used. The polymer binder 1 is 30% by mass based on the total solid particles of the ITO hollow particles and the conductive oxide particles, and further has a dialkyl pyrophosphite represented by the formula (1). The mixing ratio of the titanium coupling agent according to become% of the solid component coating film is formed. The hollow particles and the ITO composition the total composition and the electrically conductive oxide particles of binder component was 0.5 mass mass. In Example 8, in the mixed solvent 2 to be a dispersion medium, ITO hollow particles 2 having an average particle diameter of 15 nm and cerium powder having an average particle diameter of 50 nm as a conductive oxide powder were mixed at a ratio of 40 to 60, and The non-polymeric binder 2 as a binder was mixed at a ratio of 30% by mass of the solid component particles of the total of the hollow particles and the conductive oxide particles. In the mixed solvent 1 which is a dispersion medium, the tantalum hollow particles 1 having an average particle diameter of 8 nm and the tantalum powder having an average particle diameter of 30 nm as the conductive oxide powder are mixed at a ratio of 85 to 15, and The SiO 2 adhesive 3 as a binder was mixed at a ratio of 15% by mass to the solid component particles of the total of the hollow particles and the conductive oxide particles. Example 1 In a mixed solvent 2 to be a dispersion medium, ITO hollow particles 1 having an average particle diameter of 8 nm of -25,465,465,075, and cerium powder having an average particle diameter of 40 nm as a conductive oxide powder were 35 to 65. In addition, the SiO 2 adhesive 4 as a binder was mixed at a ratio of 30% by mass to the solid component particles in total of the ITO hollow particles and the conductive oxide particles. In the mixed solvent 2 which is a dispersion medium, the ITO hollow particles 2 having an average particle diameter of 15 nm and the ITO powder having an average particle diameter of 50 nm as the conductive oxide powder are mixed at a ratio of 80 to 20 in the mixed solvent 2, The SiO 2 adhesive 5 as a binder was mixed at a ratio of 25% by mass to the total solid particles of the ITO hollow particles and the conductive oxide particles. In Example 12, ITO hollow particles 1 having an average particle diameter of 8 nm and ITO powder having an average particle diameter of 30 nm as a conductive oxide powder were mixed in a ratio of 60 to 40 in ethanol to be a dispersion medium, and further, The SiO 2 adhesive 6 as a binder is mixed at a ratio of 25% by mass to the total solid particles of the ITO hollow particles and the conductive oxide particles, and further, a decane coupling agent (KBE of Shin-Etsu Chemical Co., Ltd.) And the composition of the total mass of the ITO hollow particles, the conductive oxide particles, and the binder component which are solid components after the formation of the coating film is 〇. 7 mass%. In Example 13, in the IPA to be a dispersion medium, ITO hollow particles 2 having an average particle diameter of 15 nm and IZO powder having an average particle diameter of 25 nm as conductive oxide particles were mixed at a ratio of 50 to 50, and The SiO 2 adhesive 1 as a binder was mixed at a ratio of 25 mass % of the solid component particles of the ITO hollow particles and the conductive -26-201246575 oxide particles. In Example 14, in the butanol to be a dispersion medium, ITO hollow particles 1 having an average particle diameter of 8 nm and cerium powder having an average particle diameter of 40 nm as a conductive oxide powder were mixed at a ratio of 90 to 10, The non-polymeric binder 3 as a binder was mixed at a ratio of 10% by mass of the solid component particles of the total of the hollow particles and the conductive oxide particles. In Example 15, in the crucible to be a dispersion medium, the crucible hollow particles 2 having an average particle diameter of 15 nm and the ITO powder having an average particle diameter of 25 nm as the conductive oxide powder were mixed at a ratio of 95 to 5, The SiO 2 adhesive 7 as a binder was mixed at a ratio of 25% by mass to the total solid particles of the ITO hollow particles and the conductive oxide particles. In Example 16, in the mixed solvent 1 which is a dispersion medium, the ITO hollow particles 2 having an average particle diameter of 15 nm and the IZO powder having an average particle diameter of 30 nm as the conductive oxide powder were mixed at a ratio of 85 to 15, and The SiO 2 adhesive 5 as a binder was mixed at a ratio of 30% by mass to the total solid particles of the ITO hollow particles and the conductive oxide particles. [Comparative Example 1] In Comparative Example 1, an ITO powder having an average particle diameter of 25 nm as a conductive oxide powder and an SiO 2 adhesive 1 as a viscous -27-201246575 mixture were used in the IPA to be a dispersion medium. The conductive oxide particles were mixed at a ratio of 30% by mass. [Evaluation of Composition for Transparent Conductive Film] For the evaluation of the refractive index, the compositions for transparent conductive films shown in Examples 1 to 16 and Comparative Example 1 were used on a glass substrate having a known optical constant. After forming a thin film of a transparent electrode film by a wet coating method (a spin coating method, a die coating method, a spray coating method, an offset printing method, or the like), it is baked at 160 to 220 ° C for 20 to 60 minutes. Thereby, a transparent conductive film having a thickness of 0.05 to 0.2 μm is formed. This film was measured by a spectro ellipsometry apparatus (J.A. Woollam Japan Co., Ltd. - 200 0), and data was analyzed for the transparent electrode film portion to determine an optical constant. From the resolved optical constant, 63 3 nm 値 is used as the refractive index. These results are shown in Tables 1 to 3. As shown in Fig. 1, first, a glass plate having a SiO 2 layer (not shown) having a thickness of 50 nm formed on one main surface is prepared as a substrate 1 , and the SiO 2 layer is formed as a transparent electrode surface 3 to have a surface. The surface texture layer (Sn02 (tin oxide) film) 3 having a thickness of 800 nm of F (fluorine) was doped. On the other hand, the transparent electrode layer 3 is patterned by a laser processing method to form an array, and wirings which are electrically connected to each other are formed. Next, a plasma CVD (Chemical Vapor Deposition) method is employed on the transparent electrode layer 3 to form the photoelectric conversion layer 2. In this embodiment, the photoelectric conversion layer 2 is sequentially pressed from the substrate 10 side by p-type a-Si: H (amorphous unit 矽), type I a_Si (amorphous -28-201246575矽) and a film made of n-type pc-Si (microcrystalline niobium carbide). The above-described photoelectric conversion layer 2 is patterned by a laser processing method. These were evaluated as a composition for a transparent conductive film shown in Examples by using a solar cell element which has been developed into a film. In the composition for a transparent conductive film shown in Examples 1 to 16 and Comparative Example 1, the solar cell element in which the film formation has progressed is wetted so that the thickness after firing can be 0.01 to 0.5 μm. After coating by a coating method (a spin coating method, a die coating method, a spray coating method, or an offset printing method), it is dried at a low temperature of 25 to 60 ° C for 5 minutes to form a transparent conductive film 1 . . In Tables 1 to 3, a coating method is shown. Next, on the transparent conductive film 1, the composition for a conductive reflective film prepared by the following method is subjected to a thickness after firing. After coating to a wet coating method of 0.05 to 2.0 μm, it is dried at a low temperature of 25 to 60 ° C for 5 minutes to form a conductive reflective film. Next, it is fired at 160 to 220 ° C for 20 to 60 minutes to form a composite film on the solar cell element. The film thickness after firing of the transparent conductive film 1 is shown in Tables 1 to 3. The film thickness was measured by a cross-sectional observation using a scanning electron microscope (SEM, device name: S-4300, SU-8000) manufactured by Hitachi High-Technologies Corporation. Here, the method of preparing the composition for a conductive reflective film is carried out by the following method. First, silver nitrate is dissolved in deionized water to prepare an aqueous metal ion solution. Further, sodium citrate was dissolved in deionized water to prepare a sodium citrate aqueous solution having a concentration of 26% by weight. In the citric acid -29-201246575 sodium aqueous solution, the granular first iron of sulfuric acid was directly added and dissolved in a nitrogen gas stream maintained at 35 ° C to prepare a molar ratio of 3:2. An aqueous solution of a reducing agent containing citrate ions and a first iron ion. Next, while maintaining the nitrogen gas flow at 35 ° C, a magnetic stirrer stirring piece was placed in the reducing agent aqueous solution, the stirring piece was rotated at a rotation speed of 100 rpm, and the reducing agent aqueous solution was stirred. Next, the above aqueous metal salt solution is dropped into the aqueous solution of the reducing agent to carry out synthesis. Here, the addition amount of the metal salt aqueous solution of the reducing agent aqueous solution is adjusted so that the concentration of each solution can be adjusted to be 1 / 1 Torr of the amount of the reducing agent aqueous solution, and the metal salt aqueous solution can be maintained even if it is dropped at room temperature. The reaction temperature is 40 °C. Further, the mixing ratio of the reducing agent aqueous solution and the metal salt aqueous solution is adjusted so that the equivalent amount of the first iron and ions added as the reducing agent can be three times that of the metal ion. After the dropwise addition of the aqueous metal salt solution in the aqueous solution of the reducing agent was completed, the mixture was further stirred for 15 minutes to form metal particles inside the mixed liquid to obtain a metal particle dispersion in which metal particles were dispersed. The pH of the metal particle dispersion was 5.5, and the stoichiometric production of the metal particles in the dispersion was 5 g/liter. The resulting dispersion was allowed to stand at room temperature to precipitate metal particles in the dispersion, and the agglomerates of the precipitated metal particles were separated by decantation. The separated metal condensate is added with deionized water to form a dispersion, and desalting is performed by ultrafiltration (ulUafiltration), and then methanol is used for the result of the substitutional washing. The content of (silver) was 50% by mass. Then -30-201246575, using a centrifugal separator, adjusting the centrifugal force of the centrifugal disperser to separate larger silver particles having a particle size above 1 〇〇 nm, which can contain a primary particle size of 71% The silver nanoparticles in the range of 10 to 50 nm are adjusted in such a manner. In other words, the ratio of the number of silver nanoparticles in the range of 1 〇 to 50 nm of the primary particle diameter of 100% of all silver nanoparticles is adjusted to be 7 1 %. The obtained silver nanoparticle " is a protective agent whose chemical modification carbon skeleton is an organic backbone of three carbon numbers. Then, 1 part by mass of the obtained metal nanoparticles are added and mixed in 90 parts by mass of a mixed solution containing water, ethanol and methanol to disperse them. Further, in the dispersion liquid, 4% by mass of polyvinylpyrrolidone and 1% by mass of silver citrate and 95% by mass of metal nanoparticles are added as an additive to obtain conductivity. A composition for a reflective film. The composition for a conductive reflective film obtained is applied to the transparent conductive film 1 by a wet coating method in a thickness of 0.05 to 2. Ομηη after firing, and is 20 to 160 ° C at 220 ° C. The conductive back surface reflective film 4 is formed on the transparent conductive film 1 by firing in a heat treatment condition for 60 minutes. Next, when the power generation efficiency is evaluated as a solar cell element, the reinforcing film is applied as a reinforcing film on the conductive reflective film, and the composition for the reinforcing film is applied to the film to form a solar cell which has progressed to the conductive reflective film. On the element, the thickness of the composition for the reinforcing film was 350 nm, and the solvent was removed from the coating film for the reinforcing film by vacuum drying, and then the solar cell element was 180. (: The reinforced film for the reinforced film is prepared by heat-hardening the film for the reinforced film with a coating film for 20 minutes in a hot air-31 - 201246575 drying furnace. First, mixing: 8% by mass of ITO particles having an average particle diameter of 25 nm as conductive oxide fine particles, and 2% by mass of a titanium coupling agent having a dialkyl pyrophosphite group as a coupling agent, After the mixture of ethanol and butanol as a dispersion medium (mass ratio: 98:2) was 90% by mass, the mixture was stirred at a rotation speed of 800 rpm for 1 hour at room temperature. Then, 60 g of this mixture was placed in a 100 cc glass bottle. a dispersion of ITO particles is prepared by dispersing a chrome oxide bead having a diameter of 33 mm and dispersing in a paint shaker for 6 hours. Here, a titanium coupling agent having a dialkyl pyrophosphite group, The SiO 2 adhesive is adjusted in the same manner as the Si 2 binder 1 described above. Next, 4% by mass of the dispersion of the ITO particles and ethanol as a dispersion medium are used. After mixing 86% by mass, The SiO 2 adhesive 1 was further mixed with 10% by mass, and after the base liquid of the composition for reinforcing the film was obtained, 95% by mass of the base liquid was dispersed with the fumed silica as an additive. 5 mass% of the liquid was mixed, and dispersion-mixing was carried out for 10 minutes at room temperature using an ultrasonic vibrator to melt the mixture to the whole to prepare a coating liquid as a composition for a reinforcing film. / After being formed into a conductive reflective film In the solar cell element of the reinforced film, the photoelectric conversion layer 2, the transparent conductive film 1 formed on the thin film, the conductive reflective film 4, and the reinforcing film for the conductive reflective film are imaged by a laser processing method. In the evaluation method of the solar cell element, the lead wire is wired on the substrate after the processing by the laser processing method, and the output is confirmed when the IV characteristic curve is confirmed. The characteristics and the J of the short-circuit current (Jsc) are carried out by using the photoelectric conversion layer obtained by the same manufacturing method as the embodiment, and the transparent conductive film is implemented. The conductive reflective film and the reinforced film were all evaluated for relative output when the solar cell element formed by the sputtering method was used as 100. The results are shown in Tables 1 to 3. Here, all the splatter method is used. In the solar cell element, as shown in Fig. 1, a glass substrate having a Si 〇 2 layer (not shown) having a thickness of 50 nm is formed on the main surface as a substrate 10, and the SiO 2 layer is used as the substrate. The surface of the transparent electrode surface 3 was formed to have a surface electrode layer (Sn02 film) 3 having a concave-convex texture and having a thickness of 800 nrn of v F (fluorine). On the other hand, the transparent electrode layer 3 is patterned by a laser processing method to form an array, and the wirings which are electrically connected to each other are formed. Next, a plasma CVD method is employed in the transparent electrode layer 3 to form the photoelectric conversion layer 2. In this embodiment, the photoelectric conversion layer 2 is sequentially pressed from the substrate 10 side to obtain P-type a-Si: H (amorphous unit 矽), i-type a-Si (amorphous 矽). And a film formed of n-type με-Si (microcrystalline niobium carbide). After the photoelectric conversion layer 2 is patterned by a laser processing method, a magnetron linear arrangement sputtering (magnetr οni η -1 inetypes pu 11 erning) device is used to sequentially form a thickness on the photoelectric conversion layer 2. 80 nm transparent conductive film (ZnO) (zinc oxide) layer 1 and conductive film (silver electrode layer) having a thickness of 20 nm - 33 - 201246575 [Table 1] Example 1 Example 2 Example 2 3 Example 4 Example 5 Example 6 Average particle size (nm) 8 8 8 15 15 15 Hollow ΓΓΟ Particle Griffon-ΓΤ01 H-IT01 H-IT01 Η-ΓΓ02 H-IT02 Η-ΓΓ02 Proportion (%) 100 70 80 75 82 60 mm - ΠΌ ΙΤ0 — ΠΌ IT0 Conductive oxide particles average particle size (nm) - 30 25 - 35 40 Proportion W - 30 20 - 18 40 Adhesive _ Si〇2 adhesive polymer bond Agent Si〇2 Adhesive SiO2 Adhesive SiO2 Adhesive S〇s Binder Ratio (%) Pair (Conduit + Η.ΠΌ+Binder> 30 10 30 25 20 20 Catalyst View 60% Nitric Acid - 603⁄4 Nitric Acid 603⁄4 Nitric Acid 60S nitric acid 603⁄4 nitric acid ratio (%) to gold alkyl oxide - 0.1 0.01 0.5 0.1 dispersion _ IPA Et-〇H IPA Et-OH mixed solvent 1 Et-OH ratio (%) to composition 72.3 85 72.3 88 93.9 85 coupling agent - - - - - - ratio (%) pair (guide + Η - ΠΌ + Adhesive thorn + chelating agent) - - - - - - Film formation coating method Rotary coating method Rotary coating method Rotary coating method Rotary coating method Press molding method Rotary coating method mmmm ("m) 0.1 0.1 0 , 15 0.13 0.1 0.1 Refractive index 1.53 1.58 1.55 1.54 1.58 1.59 Evaluation of relative power generation efficiency W 115 118 119 120 116 118 Relative short circuit flute density (%) 103 104 103 107 105 104 -34- 201246575 Yin AJ Example 7 Example 3 Example 9 Example 10 Example 11 Example 12 Hollow crucible Particle average particle diameter (nm > 8 15 8 8 15 8 mm Η-ΓΓ01 Η-ΓΤ02 Η-ΓΤ01 Η-ΓΤ01 Η-ΓΤ02 Η-ΠΌ1 ratio (%) 50 40 85 35 80 60 Conductive oxide particles mm ΙΤ0 ΑΤΟ ΑΤΟ ΙΤ0 ITO ΙΤ0 Average particle size (nm) 25 50 30 40 50 30 Ratio (%) 50 60 15 65 20 40 Adhesive agent non-polymer type adhesive Polymer type adhesive stamp 2 adhesive Si〇a adhesive adhesive Si〇2 adhesive Rate (%) vs. Fu+Η-ΓΓΟ+bonding_ 30 30 15 30 25 25 Catalyst mm. - - 35 Strong acid 303⁄4 ammonia 60*Nitric acid 603⁄4 moving ratio (%) to gold-mamadane oxide - 1.2 1.0 1.0 0.5 Dispersion Medium mm Et-〇N Mixed Solvent 2 Hybrid 1 Mixed Solvent 2 Mixed Solvent 2 Et-OH Ratio (%) vs. Composition 86 81 69 81 90 88 Coupler Surface Titanium Coupling Agent - - - - Decane Coupler Ratio (% ) (guide + Η - ΓΓ 0 + binder + coupling agent) 0.5 - - - — 0.7 Coating method Rotary coating method Rotary coating method Screen printing method Rotary coating method Compression molding method Pressure search coating method Film thickness after formation (βτη) 0,13 0.1 0.15 0.07 0.07 0.1 Refractive index 1.65 1.66 1.59 1.67 1.57 1.60 Evaluation of relative power generation efficiency W 117 118 121 119 117 116 Relative short-circuit current density (%) 104 104 104 105 105 104 -35- 201246575 1^1 Example 13 Example 14 Example 15 Example 16 Comparative Example 1 Average particle diameter (nm) 15 8 15 15 — Hollow ΓΓΟ Particles mm Η-ΠΌ2 Η-ΓΓ01 Η-ΓΓ02 Η-ΠΌ2 - Proportion (% ) 50 90 95 85 - mm 1ΖΟ ΑΤΟ ΙΤ0 120 IT0 Conductive oxide particles Average particle size (nm) 25 40 25 30 25 50 10 5 15 100 Adhesive mm Si〇2 Adhesive Non-polymeric binder Si〇2 Adhesive SiOz Adhesive Si〇2 Binder ratio (%) Pair (guide) + Η-ΓΓΟ+bonding section 25 10 25 30 30 Catalyst mm 603⁄4 Nitric acid - 603⁄4 Nitric acid 60% Nitric acid 603⁄4 Nitric acid ratio (%) to Jinen alkoxide 1.2 - 0.01 1 1.2 Dispersing medium mm IPA Butanol IPA Mixed solvent 1 1PA ratio (%) to composition 89 90.5 88 86 72.3 Coupler surface - one - ratio (%) to (guide + Η - ΓΓΟ + binder + coupling agent) - one - - - film formation coating method rotation Coating method, coating method, offset printing, offset printing, spin coating, film thickness after sintering (βΛ) 0.07 0.1 0.15 0.1 0,1 Refractive index 1.61 1.55 1.56 1.59 2.05 Evaluation of relative power generation efficiency (%) 118 119 120 118 99 Relative short-circuit current density (%) 104 105 106 104 100 [Table 4]
No. H-IT01 H-IT02 平均粒徑(nm) 8 15 從表1至表3可知，在實施例1至1 6之全部，係折 射率低、相對發電效率爲如1 1 5至1 2 1 %之顯著地高、相 對短路電流亦爲如1 〇 3至1 0 7 %之高。相對之，在不含有 ITO空心粒子之比較例1中，折射率高、相對於發電效率 、相對短路電流密度均爲略1 〇〇%。 -36- 201246575 如上所述，本發明之透明導電膜用組成物，係可依濕 式塗佈法而塗佈於光電變換層上，並加以燒成’藉由IT〇 空心粒子之添加，而可調整所得透明導電膜之折射率。因 而可知，可簡便地製得能提升薄膜太陽能電池之發電效率 之透明導電膜之事實。 【圖式簡單說明】 第1圖：採用本發明之透明導電膜之薄膜太陽能電池 的剖面之模式圖。 【主要元件符號說明】 1〇 :基材 1 :透明導電膜 2 :光電變換層 3 :透明電極層 4 :導電性反射膜 -37-No. H-IT01 H-IT02 Average particle diameter (nm) 8 15 As shown in Tables 1 to 3, all of Examples 1 to 16 have a low refractive index and a relative power generation efficiency of, for example, 1 15 to 1 2 . 1% is significantly higher, and the relative short-circuit current is also as high as 1 〇3 to 107%. On the other hand, in Comparative Example 1 which does not contain ITO hollow particles, the refractive index is high, and the relative short-circuit current density is slightly 1%%. -36-201246575 As described above, the composition for a transparent conductive film of the present invention can be applied onto a photoelectric conversion layer by a wet coating method and fired by adding IT hollow particles. The refractive index of the obtained transparent conductive film can be adjusted. Therefore, it is understood that the fact that the transparent conductive film capable of improving the power generation efficiency of the thin film solar cell can be easily obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a cross section of a thin film solar cell using a transparent conductive film of the present invention. [Description of main component symbols] 1〇: Substrate 1 : Transparent conductive film 2 : Photoelectric conversion layer 3 : Transparent electrode layer 4 : Conductive reflective film -37-