CN102067243A - 具有fto/ito层叠体的透明导电膜 - Google Patents

具有fto/ito层叠体的透明导电膜 Download PDF

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CN102067243A
CN102067243A CN2009801235213A CN200980123521A CN102067243A CN 102067243 A CN102067243 A CN 102067243A CN 2009801235213 A CN2009801235213 A CN 2009801235213A CN 200980123521 A CN200980123521 A CN 200980123521A CN 102067243 A CN102067243 A CN 102067243A
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film
fto
ito
nesa coating
ito film
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CN102067243B (zh
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山田茂男
大芦龙也
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Nippon Soda Co Ltd
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Abstract

本发明提供一种透明导电膜，其特征在于，是用于在基材上层叠的由ITO膜和FTO膜组成的透明导电膜，FTO膜的表面的晶体结构的一部分或全部为斜方晶；还提供一种透明导电膜，其特征在于，是用于在基材上层叠的由ITO膜和FTO膜组成的透明导电膜，FTO膜的膜厚度为5nm～20nm、且FTO膜为连续膜。另外，本发明提供上述透明导电膜的制备方法，其特征是通过高温溶胶法在基材上形成ITO膜后，在ITO膜上连续地形成FTO膜。

Description

具有FTO/ITO层叠体的透明导电膜
技术领域
本发明涉及用于透明电极板等的透明导电膜，特别涉及适用于色素增感太阳能电池的透明电极等的FTO/ITO层叠膜。
本申请要求基于2008年6月24日在日本申请的特愿2008-164417号的优先权，并将其内容引用于此。
背景技术
色素增感太阳能电池是通过吸收太阳光的色素吸收光而释放出电子的方式来发电的太阳能电池。以1991年瑞士Ecole Polytechnique Federale de Lausanne(EPFL)(洛桑联邦高等理工学院)的Michael Gratzel(迈克尔格莱才尔)发表的论文为契机进行了研究。该机理是电池受到光照后，电池中的色素就会变为激发状态，释放出电子。该电子经过氧化钛(TiO2)到达透明电极，而流到外部。另一方面，释放出电子而成为阳离子的色素经由电解液中的碘(I)接收从另一方的电极供给的电子，恢复原来的状态。
作为用于这样的太阳能电池的透明电极所必需的条件，可以举出低电阻、热稳定性、化学稳定性、高透过性、耐湿性、低成本等。作为满足这样的条件的电极用的透明导电性膜，相比于一般掺杂有锡的氧化铟膜(ITO膜)，优选耐热、化学性条件强的掺杂有氟的氧化锡膜(FTO膜)。
但是，由于ITO膜的透明性、导电性优异，并且广泛使用在液晶显示元件或太阳能电池中，所以开发了在ITO膜之上层叠FTO膜的膜。作为它的一个例子，有专利文献1。
专利文献1记载了ITO膜的膜厚度为100nm～1000nm、FTO膜的膜厚度适宜为至少30nm～350nm，以及，FTO膜为该厚度时，即使在温度250～700℃下加热1小时导电性也不降低。并且，记载了FTO膜的成膜需要在ITO膜的成膜后连续进行。并记载了，因此，需要在刚形成ITO膜后的、还在400～500℃左右的玻璃板上立刻喷雾将成为FTO膜的原料化合物溶液，在ITO膜劣化之前通过喷雾热分解法(SPD法)形成FTO膜。
但是，在上述方法中存在以下不足，由于膜整体厚，所以存在成本上的问题；由于FTO膜的膜厚度厚，所以不能充分发挥ITO具有的优点等。
专利文献
专利文献1：特开2003-323818号公报
发明内容
因此，本发明的课题在于制作具有FTO/ITO层叠膜的透明导电膜，该透明导电膜可以用于太阳能电池的透明电极板等，特别是色素增感太阳能电池的透明电极等，能够发挥FTO和ITO所具有的优点，成本合适。
本发明的发明人反复进行深入研究的结果发现，通过高温溶胶(パイロゾル)法在玻璃基材上制作FTO/ITO层叠膜的情况下，通过在成膜炉中用传送带移动玻璃板期间连续地层叠ITO膜和FTO膜，使FTO膜的表面成为具有斜方晶的膜，即使在FTO膜的膜厚度为20nm以下的较薄的情况下，也可以得到耐热性优异的层叠膜，从而完成了本发明。
也就是说，本发明涉及以下的透明导电膜，
(1)一种透明导电膜，其特征在于，是用于在基材上层叠的由ITO膜和FTO膜组成的透明导电膜，FTO膜的表面的晶体结构的一部分或全部为斜方晶。
(2)根据(1)所述的透明导电膜，其特征在于，在350℃加热1小时后的片电阻值的变化率为1.5倍以下。
(3)根据(1)或(2)所述的透明导电膜，其特征在于，片电阻值为300Ω/□以下。
另外，本发明涉及，
(4)一种(1)至(3)中任一项所述的透明导电膜的制备方法，其特征在于，通过高温溶胶法在基材上形成ITO膜后，在ITO膜上连续地形成FTO膜。
另外，本发明涉及以下的透明导电膜，
(5)一种透明导电膜，是用于在基材上层叠的由ITO膜和FTO膜组成的透明导电膜，其特征在于，FTO膜的膜厚度为5nm～20nm、且FTO膜为连续膜。
(6)根据(5)所述的透明导电膜，其特征在于，在350℃加热1小时后的片电阻值的变化率为1.5倍以下。
(7)根据(5)或(6)所述的透明导电膜，其特征在于，片电阻值为300Ω/□以下。
另外，本发明涉及，
(8)一种(5)至(7)中任一项所述的透明导电膜的制备方法，其特征在于，通过高温溶胶法在基材上形成ITO膜后，在ITO膜上连续地形成FTO膜。
由本发明的FTO/ITO层叠膜组成的透明导电膜由于FTO膜表面的一部分或全部具有斜方晶的晶体结构，所以得到了即使膜厚度为5nm～20nm的较薄的情况下，耐热性也优异，且在350℃加热1小时后的片电阻值的变化率为1.5倍以下的良好结果。因此，不仅可以用于液晶显示元件或太阳能电池等的透明电极板等，特别是还可以作为色素增感太阳能电池的透明电极使用，这是本发明的优点。
附图说明
图1为表示实施例、比较例1和比较例2的片表面的X射线衍射结果的图。
图2为通过剖面TEM法观察实施例的层叠体的剖面结构的结果的图。
图3为通过剖面TEM法观察比较例1的层叠体的剖面结构的结果的图。
具体实施方式
(透明导电膜)
本发明的透明导电膜在基材侧设有ITO膜，其上层叠有FTO膜。FTO膜的表面的一部分或全部具有斜方晶的晶体结构。
在本发明中，表面的一部分为斜方晶是指至少为了使片电阻值的变化率为1.5倍以下，含有必要量的斜方晶的状态。晶体结构的一部分具有斜方晶的情况下，其余为正方晶或其它的晶系，通常为混晶状态。
斜方晶是指在晶体学的领域一般使用的7个晶系(立方晶、六方晶、菱形晶、正方晶、斜方晶、单斜晶、三斜晶)中，轴长的关系为a≠b≠c，轴角的关系为α＝β＝γ＝90°的晶体。晶系的鉴定通过单晶和粉末的X射线衍射、中子衍射、电子衍射等进行。
为了生成斜方晶的晶体结构，特别是通过高温溶胶法成膜的情况下，如后述，在连接了多个成膜炉的成膜炉内，在已移送到传送带上的基材上形成ITO膜后，需要在连结的成膜炉内接着连续地形成FTO膜。在这里，连续膜是指晶体没有间隙地排列的膜。在成膜炉中形成ITO膜后，暂时拿到成膜炉外后，再次在成膜炉中形成FTO膜，FTO膜的表面结构成为正方晶，同时片电阻值的变化率超过1.5倍。
另外，ITO膜和FTO膜的膜厚度只要是能够用于液晶显示元件或太阳能电池等透明电极板等就没有限制，但是，从能够发挥FTO、ITO所具有的优点，以及成本等方面考虑，FTO膜的膜厚度优选为5nm～20nm，更优选为10nm～20nm。另一方面，ITO膜的膜厚度优选为20nm～60nm，更优选为30nm～50nm。
FTO膜和ITO膜分别至少由1层组成，只要是不超过上述膜厚度，就可以层叠多层。
上述专利文献1记载的ITO膜和FTO膜的层叠膜中，ITO膜的膜厚度为100nm～1000nm，FTO膜的膜厚度为30nm～350nm。相比于在该文献中，为了保护ITO，FTO膜的膜厚度至少必需为30nm的情况，本发明的透明导电膜的特征是可以使ITO膜、FTO膜的膜厚均变薄。
本发明的透明导电膜，在FTO膜为5nm～20nm的较薄的情况下，相对于350℃以上的温度的耐热性仍优异，在350℃的温度下加热1小时后的片电阻值的变化率为1.5倍以下，优选为1.2倍以下。另外，片电阻值，特别是作为色素增感太阳能电池的透明电极使用的情况下，要求为300Ω/□以下，通过调整膜厚度可以为300Ω/□以下。
(透明电极用基材)
本发明的透明导电膜层叠在基材上。基材通常使用透明基材，不透明也可以。
透明基材具体可以举出碱性玻璃、石英玻璃等玻璃，聚碳酸酯、聚对苯二甲酸乙二醇酯、聚芳酯等聚酯，聚醚砜系树脂，非晶聚烯烃、聚苯乙烯、丙烯酸树脂等。这些材质可以根据最终使用的产品的用途适当选择最合适的。
为了防止透明导电膜中侵入碱性成分等，可以根据需要，在基材与透明导电膜之间形成无机氧化物膜。作为无机氧化物膜具体可以例示出硅氧化物(SiOx)、铝氧化物(Al2Ox)、钛氧化物(TiOx)、锆氧化物(ZrOx)、钇氧化物(Y2Ox)、镱氧化物(Yb2Ox)、镁氧化物(MgOx)、钽氧化物(Ta2Ox)、铈氧化物(CeOx)或铪氧化物(HfOx)、由有机聚硅烷化合物形成的聚硅烷膜、MgF2膜、CaF2膜、由SiOx和TiOx的复合氧化物等组成的膜。
(透明导电膜的制法)
作为透明导电膜的制造方法，只要是能够形成具有作为本发明目的的物性值的膜的方法即可，具体可以例示出溅射法、电子束法、离子镀法、丝网印刷法或化学气相沉积法(CVD法)、喷雾热分解法(SPD法)、高温溶胶法等，特别优选例示高温溶胶法。
以下，对根据高温溶胶法的本发明的制法进行具体说明。
作为用于ITO膜形成溶液的铟化合物，优选热分解而成为氧化铟的物质，具体可以例示三乙酰丙酮合铟(In(CH3COCHCOCH3)3)、三苯甲酰基苯乙酮铟(In(C6H5COCHCOC6H5)3)、三氯化铟(InCl3)、硝酸铟(In(NO3)3)、三异丙氧基铟(In(OPr-i)3)等。
另外，作为锡化合物可以优选使用热分解为氧化锡的物质，具体可以举出氯化锡、二甲基二氯化锡、二丁基二氯化锡、四丁基锡、辛酸亚锡(Sn(OCOC7H15)2)、马来酸二丁基锡、二乙酸二丁基锡、双乙酰丙酮合二丁基锡等。
另外，上述铟化合物和锡化合物之外，作为第3成分添加Mg、Ca、Sr、Ba等元素周期表第ⅡA族元素，Sc、Y等第ⅢB族元素，La、Ce、Nd、Sm、Gd等镧系，Ti、Zr、Hf等第ⅣB族元素，V、Nb、Ta等第ⅤB族元素、Cr、Mo、W等第ⅥB族元素、Mn等第ⅦB族元素，Co等Ⅷ族元素(第9族元素)，Ni、Pd、Pt等第Ⅷ族元素(第10族元素)、Cu、Ag等第I B族元素、Zn、Cd等第ⅡB族元素，B、Al、Ga等第ⅢA族元素，Si、Ge、Pb等第ⅣA族元素、P、As、Sb等第ⅤA族元素，Se、Te等第ⅥA族元素等的单体或者它们的化合物来形成ITO膜。
作为用于FTO膜形成溶液的氟化合物，可以举出氟化氢、氟化钠、三氟乙酸、二氟乙烷、三氟一溴甲烷等。另外，作为锡化合物可以使用用于制造上述ITO膜的锡化合物。
将上述化合物溶解在甲醇、乙醇等醇类，丙酮、甲基丁基酮、乙酰丙酮等酮类等的有机溶剂中，调制FTO膜形成溶液和FTO膜形成溶液。
如下进行通过高温溶胶法在透明基材上形成ITO膜和FTO膜。
将多座预先加热至400～750℃、优选为400～550℃的传送式成膜炉进行连结，将基材投入炉内。在第1座炉中吹入ITO膜形成溶液、在第2座炉中吹入FTO膜形成溶液，将它们分别用超声波制成雾滴状并以空气作为载气吹入传送炉中，通过与基材的表面接触而热分解来制作膜。膜厚度可以通过改变传送带的速度来进行调整。
通过连结3座以上的成膜炉，可以将ITO膜、FTO膜的至少任意一种制成多层膜。另外，在第一座中还可以形成SiO2膜等其它的无机氧化物膜。
实施例
以下，对实施例进行表示，但是本发明的技术范围不限于此。
实施例1 玻璃/SiO2/ITO/FTO层叠体(连续成膜)
将3座(炉(1)～(3))加热至500℃的传送炉进行连结，将碱石灰玻璃基材(320×420×0.7mm)投入传送炉内，在第1座中吹入SiO2膜形成溶液(四乙氧基硅烷(溶液Ⅰ))、在第2座中吹入ITO膜形成溶液(含有5摩尔％氯化锡和0.2摩尔/L乙酰丙酮铟的乙酰丙酮溶液(溶液Ⅱ))、在第3座中吹入FTO膜形成溶液(含150摩尔％氟和0.5摩尔/L二乙酸二丁基锡的乙醇溶液(溶液Ⅲ))，将它们用超声波制成雾滴状并以空气作为载气吹入传送炉中，通过与玻璃基材的表面接触而热分解来连续地制作层叠体。得到的层叠体为玻璃/SiO2膜(40nm)/ITO膜(40nm)/FTO膜(13nm)。
比较例1 玻璃/SiO2/ITO/FTO层叠体(非连续成膜法)
为了比较，在玻璃基材上形成与实施例相同组成的ITO膜后，暂且取出玻璃基材，然后再次将玻璃基材投入成膜炉中，在ITO膜上形成FTO膜，制作与实施例大致相同的膜厚度的层叠体。
在第1次的成膜中，除了将2座(炉(1)～(2))加热至500℃的传送炉进行连结，将碱石灰玻璃基材(320×420×0.7mm)投入传送炉内，在第1座中吹入SiO2膜形成溶液(四乙氧基硅烷(溶液Ⅰ))、在第2座中吹入ITO膜形成溶液(含有5摩尔％氯化锡和0.2摩尔/L乙酰丙酮铟的乙酰丙酮溶液(溶液Ⅱ))以外，按照与实施例1相同的方法制作层叠体。得到的层叠体为玻璃/SiO2膜(40nm)/ITO膜(40nm)。
在第2次的成膜中，除了使用1座加热至500℃的传送炉，将第一次中得到的玻璃/SiO2/ITO层叠体投入传送炉内，使用FTO膜形成溶液(含150摩尔％氟和0.5摩尔/L二乙酸二丁基锡的乙醇溶液(溶液Ⅲ))以外，按照与实施例1相同的方法制作层叠体。得到的层叠体为玻璃/SiO2膜(40nm)/ITO膜(40nm)/FTO膜(17nm)。
(比较例2)玻璃/SiO2/ITO/FTO层叠体
第1次的成膜是按照与比较例1相同的方法制作层叠体。得到的层叠体为玻璃/SiO2膜(40nm)/ITO膜(40nm)。
第2次的成膜除了除了搬运速度相比于比较例1慢以外，按照相同的方法制作层叠体。得到的层叠体为玻璃/SiO2膜(40nm)/ITO膜(40nm)/FTO膜(54nm)。
对上述实施例1、比较例1和比较例2进行膜厚度、在350℃加热1小时前后的片电阻值、变化率、可见光透射率、FTO膜的晶系、剖面结构的评价，结果如表1和图1所示。
另外，膜厚度是用偏振光椭圆率测量仪(IMEC公司制造的SE800)评价，片电阻值是通过四端子法评价，可见光透射率(550nm)是用分光光度计(日立公司制造的U4000)评价，晶系是用片评价用试样水平型X射线衍射装置(日本理学株式会社制造的SmartLab)评价，剖面结构是通过剖面TEM法评价。
其结果，本发明与以往的产品相比较，可知，虽然FTO膜厚度较薄，但是耐热性提高(表1)。
另外，可知，本发明的FTO膜的晶系为斜方晶，与以往的FTO膜的晶系(正方晶)不同(图1)。进一步可知，虽然本发明的FTO膜的表面有微细的凹凸，但是表面平坦性良好(图2)，而以往的FTO膜的表面有凹凸，且表面平弹性差(图3)。
表1

Claims (8)

1.一种透明导电膜，其特征在于，是用于在基材上层叠的由ITO膜和FTO膜组成的透明导电膜，FTO膜的表面的晶体结构的一部分或全部为斜方晶。
2.根据权利要求1所述的透明导电膜，其特征在于，在350℃加热1小时后的片电阻值的变化率为1.5倍以下。
3.根据权利要求1或2所述的透明导电膜，其特征在于，片电阻值为300Ω/□以下。
4.一种权利要求1～3中任一项所述的透明导电膜的制备方法，其特征在于，通过高温溶胶法在基材上形成ITO膜后，在ITO膜上连续地形成FTO膜。
5.一种透明导电膜，其特征在于，是用于在基材上层叠的由ITO膜和FTO膜组成的透明导电膜，FTO膜的膜厚度为5nm～20nm、且FTO膜为连续膜。
6.根据权利要求5所述的透明导电膜，其特征在于，在350℃加热1小时后的片电阻值的变化率为1.5倍以下。
7.根据权利要求5或6所述的透明导电膜，其特征在于，片电阻值为300Ω/□以下。
8.一种权利要求5～7中任一项所述的透明导电膜的制备方法，其特征在于，通过高温溶胶法在基材上形成ITO膜后，在ITO膜上连续地形成FTO膜。
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