TWI391520B - 具有ｆｔｏ／ｉｔｏ積層體之透明導電膜 - Google Patents

具有ｆｔｏ／ｉｔｏ積層體之透明導電膜 Download PDF

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TWI391520B
TWI391520B TW098120798A TW98120798A TWI391520B TW I391520 B TWI391520 B TW I391520B TW 098120798 A TW098120798 A TW 098120798A TW 98120798 A TW98120798 A TW 98120798A TW I391520 B TWI391520 B TW I391520B
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film
fto
ito
transparent conductive
conductive film
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Shigeo Yamada
Tatsuya Ooashi
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Nippon Soda Co
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Description

具有FTO/ITO積層體之透明導電膜
本發明係關於一種透明電極板等所使用之透明導電膜，特別是關於適用於色素增感太陽電池之透明電極等之FTO/ITO積層膜。
本申請案係根據2008年6月24日於日本申請之日本特願2008-164417號主張優先權，而於此引用其之內容。
色素增感太陽電池係藉由吸收太陽光之色素吸收光放出電子而發電之方式的太陽電池。以1991年瑞士Ecole Polytechnique Federale de Lausanne(EPFL)之Micheal Gratzel氏所發表的論文為契機而開始研究。其之機制係當電池照到光則電池中之色素成激發狀態而放出電子。該電子經由氧化鈦(TiO2 )到達透明電極而朝外部流出。另一方面，放出電子而成為陽離子之色素係經由電解液中之碘(I)接受由另一側電極所供給之電子而回復成原本的狀態。
於如此之太陽電池所使用之透明電極的必要條件，可舉例如低電阻、熱安定性、化學安定性、高穿透性、耐濕性、低成本等。而滿足如此條件之電極用透明導電性膜方面，摻雜有熱、化學條件強之氟的氧化錫膜(FTO膜)，相較於一般摻雜有錫之氧化銦膜(ITO膜)為佳。
然而，由於ITO膜之透明性、導電性優異，故廣泛使用於液晶顯示元件或太陽電池，因此亦開發了於ITO膜上積層有FTO膜之膜。專利文獻1即為其之一例。
於專利文獻1記載：ITO膜之膜厚以100nm~1000nm、FTO膜之膜厚至少為30nm~350nm為宜；以及FTO膜若為此膜厚，則即使以溫度250~700℃加熱1小時導電性亦不會降低。又，亦記載：FTO膜之成膜必須於ITO膜之成膜後連續地進行，因此，於形成ITO膜後，必須立即將FTO膜之原料化合物溶液噴霧至持續為400~500℃左右之玻璃板，並於ITO膜劣化之前以噴霧熱裂解法(spray pyrolysis deposition，SPD法)成膜出將FTO膜。
然而，於上述方法中，有下述幾點仍不足：膜整體為厚故有成本的問題、FTO膜之膜厚為厚故無法充分活用ITO所具有之優點。
專利文獻1：日本特開2003-323818號公報
因此，本發明之課題在於製作一種透明導電膜，其可使用於太陽電池之透明電極板等、特別是色素增感太陽電池之透明電極等，且具有可活用FTO及ITO所具之優點、與成本相符之FTO/ITO積層膜。
本發明人等，努力探討的結果發現，當以熔溶膠(pyrosol)法於玻璃基材上製作FTO/ITO積層膜時，於成膜爐之中，藉由於以輸送帶移動玻璃板之間連續地積層FTO膜與ITO膜，FTO膜成為表面具有斜方晶之膜，即使FTO膜之膜厚為薄的20nm以下時，亦可得耐熱性優異之積層膜，而完成本發明。
亦即，本發明係關於：
(1)一種透明導電膜，其係用以積層於基材上且由ITO膜及FTO膜所構成者，其特徵在於，FTO膜之表面之結晶構造的一部分或全部為斜方晶。
(2)如(1)所記載之透明導電膜，其以350℃加熱1小時後之片電阻值之變化率為1.5倍以下。
(3)如(1)或(2)所記載之透明導電膜，其片電阻值為300Ω/□以下。
又，本發明係關於：
(4)一種透明導電膜之製造方法，其係用以製造(1)至(3)中任一項之透明導電膜，其特徵在於，將ITO膜以熔溶膠法成膜於基材上後，連續地於ITO膜上成膜出FTO膜。
又，本發明係關於：
(5)一種透明導電膜，其係用以積層於基材上且由ITO膜及FTO膜所構成者，其特徵在於，FTO膜之膜厚為5nm~20nm、且FTO膜為連續膜。
(6)如(5)所記載之透明導電膜，其以350℃加熱1小時後之片電阻值之變化率為1.5倍以下。
(7)如(5)或(6)所記載之透明導電膜，其片電阻值為300Ω/□以下。
又，本發明係關於：
(8)一種透明導電膜之製造方法，其係用以製造(5)至(7)中任一項之透明導電膜，其特徵在於，將ITO膜以熔溶膠法成膜於基材上後，連續地於ITO膜上成膜出FTO膜。
本發明之FTO/ITO積層膜所構成之透明導電膜，由於FTO膜表面之一部分或全部具有斜方晶之結晶構造，故即使膜厚為5nm~20nm這樣薄的時候，耐熱性亦優異，可獲得以350℃加熱1小時後片電阻值之變化率為1.5倍以下的良好結果。因此，當然可使用於液晶顯示元件或太陽電池等之透明電極板等，特別是亦可使用作為色素增感太陽電池之透明電極，此乃本發明之優點。
 (透明導電膜)
本發明之透明導電膜係於基材側設置有ITO膜，而於其上積層有FTO膜。FTO膜之表面之一部分或全部具有斜方晶之結晶構造。
本發明中，所謂表面之一部分為斜方晶，係指至少含有使片電阻值之變化率為1.5倍以下所必須量之斜方晶的狀態。當結晶構造之一部分具有斜方晶時，其餘為正方晶或其他結晶系，通常為混晶狀態。
所謂斜方晶，係指結晶學的領域中一般所使用之7個結晶系(立方晶、六方晶、菱方晶、正方晶、斜方晶、單斜晶、三斜晶)中，軸長之關係為a≠b≠c、軸角之關係為α=β=γ=90°者。結晶系之鑑定係以單晶及粉末之X射線繞射、中子繞射、電子繞射等來進行。
為了生成斜方晶之結晶構造，特別是以熔溶膠法進行成膜時，如後所述，於連結有複數個成膜爐之成膜爐內，於輸送帶上所移送之基材上進行ITO膜之成膜後，必須於連結之成膜爐內連續地進行FTO膜之成膜。此處，所謂連續膜，係指結晶無間隙地排列之膜。若以成膜爐成膜出ITO膜後，先取出至成膜爐外之後，再度以成膜爐成膜出FTO膜，則FTO膜之表面構造會成為正方晶且片電阻值之變化率超過1.5倍。
又，ITO膜及FTO膜之膜厚只要是可作為液晶顯示元件或太陽電池等之透明電極板等使用即可，並無限制，但由可活用FTO、ITO所具有之優點、且於成本等之觀點考量，FTO膜之膜厚較佳為5nm~20nm、更佳為10nm~20nm。另一方面，ITO膜之膜厚較佳為20nm~60nm、更佳為30nm~50nm。
FTO膜及ITO膜分別為至少1層所構成，且只要不超過上述膜厚，可積層多層。
上述專利文獻1所記載之ITO膜與FTO膜之積層膜，ITO膜之膜厚為100nm~1000nm、FTO膜之膜厚為30nm~350nm。於該文獻中，為了保護ITO，FTO膜之膜厚至少必須為30nm，與其相比，本發明之透明導電膜之特徵在於，其膜厚方面，可將ITO膜、FTO膜共同作成較薄。
本發明之透明導電膜，FTO膜即使為5nm~20nm這樣薄的情況，對350℃以上之溫度的耐熱性亦優異，以350℃之溫度加熱1小時後之片電阻值之變化率為1.5倍以下、較佳為1.2倍以下。又，片電阻值，特別是作為色素增感太陽電池之透明電極使用時，要求為300Ω/□以下，而藉由調整膜厚可使其成為300Ω/□以下。
(透明電極用基材)
本發明之透明導電膜係積層於基材上。基材通常係使用透明基材，但亦可為非透明。
透明基材具體而言可舉例如鹼玻璃、石英玻璃等玻璃、聚碳酸酯、聚對苯二甲酸乙二醇酯、全芳香族聚酯(polyarylate)等聚酯、聚醚碸系樹脂、無定形聚烯烴、聚苯乙烯、丙烯酸樹脂等。該等材質可視最終使用其之製品的用途適當選擇最佳者。
為了防止鹼成分等侵入透明導電膜，於基材與透明導電膜之間可視需要形成無機氧化物膜。無機氧化物膜具體而言可例示如矽酸氧化物(SiOx )、鋁氧化物(Al2 Ox )、鈦氧化物(TiOx )、鋯氧化物(ZrOx )、釔氧化物(Y2 Ox )、鐿氧化物(Yb2 Ox )、鎂氧化物(MgOx )、鉭氧化物(Ta2 Ox )、鈰氧化物(CeOx )或鉿氧化物(HfOx )、有機聚矽烷化合物所形成之聚矽烷膜、MgF2 膜、CaF2 膜、SiOx 與 TiOx 之複合氧化物等所構成之膜。
(透明導電膜之製法)
透明導電膜之製造方法只要可成膜出具有本發明所要之物性值之膜的方法即可，具體而言，可例示如濺鍍法、電子束法、離子沉積法、網版印刷法或化學氣相沉積法(CVD法)、噴霧熱裂解法(SPD法)、熔溶膠法等，特佳可例示如熔溶膠法。
以下，具體說明藉熔溶膠法之本發明之製法。
ITO膜形成溶液中所使用之銦化合物較佳為經熱裂解會成為銦之物質，具體而言可例示如三乙醯丙酸銦(In(CH3 COCHCOCH3 )3 )、三苯甲醯甲酸銦(indium trisbenzoyl methanate，In(C6 H5 COCHCOC6 H5 )3 )、三氯化銦(InCl3 )、硝酸銦(In(NO3 )3 )、三異丙氧化銦(In(OPr-i)3 )等。
又，錫化合物較佳可使用經熱裂解會成為二氧化錫者，具體而言可舉例如二氯化錫、二甲基二氯化錫、二丁基二氯化錫、四丁基錫、辛酸錫(stannous octoate，Sn(OCOC7 H15 )2 )、二丁基馬來酸錫、二丁基乙酸錫、二丁基雙乙醯丙酸錫等。
又，除上述銦化合物及錫化合物之外，作為第三成分亦可添加Mg、Ca、Sr、Ba等週期表第2族元素、Sc、Y等第3族元素、La、Ce、Nd、Sm、Gd等類鑭元素、Ti、Zr、Hf等第4族元素、V、Nb、Ta等第5族元素、Cr、Mo、W等第6族元素、Mn等第7族元素、Co等第9族元素、Ni、Pd、Pt等第10族元素、Cu、Ag等第11族元素、Zn、Cd等第12族元素、B、Al、Ga等第13族元素、Si、Ge、Pb等第14族元素、P、As、Sb等第15族元素、Se、Te等第16族元素等單體或該等之化合物來形成ITO膜。
FTO膜形成溶液所使用之氟化合物可舉例如氟化氫、氟化鈉、三氟乙酸、二氟乙烷、溴三氟甲烷等。又，錫化合物，可使用上述ITO膜之製造中所使用之錫化合物。
將上述化合物溶解於甲醇、乙醇等醇類、丙酮、甲基丁基酮、乙醯丙酮等酮類等有機溶劑來調製ITO膜形成溶液及FTO膜形成溶液。
藉熔溶膠法於透明基材上成膜出ITO膜及FTO膜，係如以下方進行。
連結複數個事先加熱至400~750℃(較佳為400~550℃)之輸送帶式成膜爐，將基材置入爐內。於第1爐內、及第2爐內，分別將ITO膜形成溶液及FTO膜形成溶液以超音波作成霧滴狀、將空器作為載體氣體吹入輸送帶爐之中，使其與基材表面接觸而熱裂解，藉此製作膜。膜厚可藉由改變輸送帶之速度來調整。
藉由連結3個以上成膜爐，可將ITO膜、FTO膜之至少其一作成為多層膜。又，亦可於第1爐成膜出SiO2 膜等其他無機氧化物膜。
【實施例】
以下，顯示實施例，但本發明之技術範圍並不限於其。
(實施例1)玻璃/SiO2 /ITO/FTO積層體(連續成膜)連結3個(爐(1)~(3))加熱至500℃之輸送帶爐，將鈉鈣玻璃(Soda Lime Glass)基材(320×420×0.7mm)置入輸送帶爐內，於第1爐、第2爐、第3爐中，分別使用SiO2 膜形成溶液(四乙氧矽烷(溶液I))、ITO膜形成溶液(含有含5莫耳%二氧化錫之銦乙醯丙酮0.2莫耳/L之乙醯丙酮溶液(溶液II))、FTO膜形成溶液(含有含150莫耳%氟之二丁基乙酸錫0.5莫耳/L之乙醇溶液(溶液III))，以超音波作成霧滴狀而將空器作為載體氣體吹入輸送帶爐之中，使其與玻璃基材表面接觸而熱裂解，藉此連續地製作積層體。所得之積層體係玻璃/SiO2 膜(40nm)/ITO膜(40nm)/FTO膜(13nm)。
(比較例1)玻璃/SiO2 /ITO/FTO積層體(非連續成膜法)
為了比較，將與實施例相同組成之ITO膜成膜於玻璃基材上後，先將玻璃基材取出，之後再度將玻璃基材置入成膜爐中以於ITO膜上成膜出FTO膜，製作成與實施例大致相同膜厚之積層體。
第1次之成膜係連結2個(爐(1)~(2))加熱至500℃之輸送帶爐，將鈉鈣玻璃基材(320×420×0.7mm)置入輸送帶爐內，於第1爐、第2爐中，分別使用SiO2 膜形成溶液(四乙氧矽烷(溶液I))、ITO膜形成溶液(含有含5莫耳%二氧化錫之銦乙醯丙酮0.2莫耳/L之乙醯丙酮溶液(溶液II))，除此之外，以與實施例相同之方法製作積層體。所得之積層體係玻璃/SiO2 膜(40nm)/ITO膜(40nm)。
第2次之成膜係使用1個加熱至500℃之輸送帶爐，將第1次成膜所得之玻璃/SiO2 /ITO積層體置入輸送帶爐內，使用FTO膜形成溶液(含有含150莫耳%氟之二丁基乙酸錫0.5莫耳/L之乙醇溶液(溶液III))，除此之外，以與實施例相同之方法製作積層體。所得之積層體，係玻璃/SiO2 膜(40nm)/ITO膜(40nm)/FTO膜(17nm)。
(比較例2)玻璃/SiO2 /ITO/FTO積層體
第1次之成膜係與比較例1以相同方法製作積層體。所得之積層體係玻璃/SiO2 膜(40nm)/ITO膜(40nm)。
第2次之成膜，除搬送速度較比較例1慢以外，係以相同方法製作積層體。所得之積層體係玻璃/SiO2 膜(40nm)/ITO膜(40nm)/FTO膜(54nm)。
對上述實施例1、比較例1及比較例2，進行膜厚、以350℃加熱1小時前後之片電阻值、變化率、可見光穿透率、FTO膜之結晶系、截面構造之評價，結果示於表1及圖1。
又，膜厚係使用橢圓偏光計(艾麥克公司製SE800)，片電阻值係藉4端子法，可見光穿透率(550nm)係使用分光光度計(日立公司製U4000)，結晶系係使用薄膜評價用試樣水平型X射線繞射裝置(理學公司製SmartLab)，截面構造係使用截面TEM法來評價。
其之結果可知，本發明品與以往品相比，不僅FTO膜厚較薄，耐熱性亦提昇(表1)。
又，本發明品之FTO膜之結晶系為斜方晶，可知與以往品之FTO膜之結晶系(正方晶)不同(圖1)。再者，本發明品之FTO膜表面雖具有微細之凹凸，但表面平坦性良好(圖2)，而以往品之FTO膜表面具有表面凹凸，可知表面平坦性不佳(圖3)。
圖1，係顯示實施例、比較例1及比較例2之薄膜表面之X射線繞射結果之圖。
圖2，係顯示實施例之積層體之以截面TEM法所得之截面構造觀察結果之圖。
圖3，係顯示比較例1之積層體之以截面TEM法所得之截面構造觀察結果之圖。

Claims (5)

  1. 一種透明導電膜，其係用以積層於基材上且由ITO膜及FTO膜所構成者，其特徵在於，該FTO膜之膜厚為5nm~20nm，該FTO膜之表面之結晶構造的一部分或全部為斜方晶。
  2. 如申請專利範圍第1項之透明導電膜，其以350℃加熱1小時後之片電阻值之變化率為1.5倍以下。
  3. 如申請專利範圍第1或2項之透明導電膜，其片電阻值為300Ω/□以下。
  4. 如申請專利範圍第1或2項之透明導電膜，其中，FTO膜為連續膜。
  5. 一種透明導電膜之製造方法，其係用以製造申請專利範圍第1至4項中任一項之透明導電膜，其將ITO膜以熔溶膠法成膜於基材上後，連續地於ITO膜上成膜出FTO膜。
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