CN106158997B - 一种掺杂氧化锡透明导电薄膜的制备方法 - Google Patents
一种掺杂氧化锡透明导电薄膜的制备方法 Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 23
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- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- VPBPKFIZNWQANG-UHFFFAOYSA-N [F].[Sn] Chemical compound [F].[Sn] VPBPKFIZNWQANG-UHFFFAOYSA-N 0.000 description 1
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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Abstract
本发明涉及一种掺杂氧化锡透明导电薄膜的制备方法,通过多元素掺杂协同效应降低氧化锡透明导电薄膜的方块电阻,多元素掺杂形成的掺杂氧化锡透明导电薄膜的化学组成为:Sn1‑ ySbyO2‑xFxPz,其中,x=0.1‑0.8,y=0.02‑0.2,z=0.02‑0.2。制备过程包括玻璃基体上二氧化硅过渡层涂覆、掺磷氧化锡纳米溶胶制备、掺磷氧化锡凝胶薄膜制备、多孔凝胶薄膜中填充氟化锑、多元素掺杂凝胶薄膜高温烧结和致密透明导电薄膜形成六部分。本发明多元素掺杂氧化锡透明导电薄膜透光率高和方块电阻低,能够作为大面积薄膜太阳电池透明电极应用。
Description
技术领域
本发明涉及一种掺杂氧化锡透明导电薄膜的制备方法,特别是一种氟、锑、磷多元素掺杂高透光率低方块电阻氧化锡透明导电薄膜的制备方法,属于新能源材料和节能环保领域。
技术背景
透明导电氧化物(TCO)是把光学透明性与导电性复合在一体的光电材料,目前大量用作薄膜太阳电池的透明电极,还应用于液晶显示屏、光催化和建筑节能等领域,市场需求巨大。TCO玻璃是在玻璃表面通过物理或者化学方法均匀镀上一层TCO薄膜形成的。常见的TCO材料包括氧化铟基、氧化锡基和氧化锌基三类。FTO导电玻璃透光率80%以上,原料来源广,生产成本较低,热稳定性和化学稳定性好,激光刻蚀较容易。由于FTO导电玻璃的性价比优势,已作为ITO导电玻璃的替代产品成为薄膜太阳电池的重要原料和商业化应用,钙钛矿太阳电池颠覆性技术突破刺激了FTO导电玻璃市场发展。
FTO透明导电薄膜和导电玻璃制备方法主要有化学气相沉积法、喷雾热分解法、磁控溅射法和溶胶-凝胶法等,采用不同方法制备的 FTO 薄膜的微观结构和光电性质存在很大差异,共同的缺点是导电性能不够理想,薄膜表面方块电阻5-100Ω,提高FTO透明导电薄膜和导电玻璃的导电性能和降低生产成本成为应用推广的关键。
溶胶-凝胶法制备掺氟氧化锡透明导电薄膜工艺是将无机锡盐或锡酸酯水解形成氧化锡纳米溶胶,再加入氟化氢、氟化铵、氟硅酸或有机氟化合物形成掺氟氧化锡纳米溶胶,将其涂布在超白玻璃基体表面形成凝胶薄膜,经过高温热处理使氟原子进入氧化锡晶格中,形成FTO导电薄膜。也可以将含氟氧化锡纳米溶胶在100-200℃下长时间水热处理,使氟原子掺杂进入氧化锡纳米粒子晶格中,再将掺杂氧化锡纳米溶胶涂布在玻璃基体表面,加热固化形成FTO导电薄膜,从而避免采用高温热化学反应过程,在比较温和条件下实现氧化锡掺氟和改善掺氟效果。详见中国专利CN103803808(2014-02-22)公开的一种大面积制备透明导电薄膜的方法和中国专利CN101580270(2009-11-18)公开的一种纳米掺杂氧化锡溶胶的制备方法。
掺氟氧化锡透明导电薄膜对氟元素量有严格要求,只有在特定的掺氟浓度范围内掺氟氧化锡才能实现高透光率低电阻,掺氟浓度过低时载流子浓度低,而过饱和掺氟形成大量晶格缺陷,同样使导电薄膜方块电阻增大。生产原料配方的掺氟量和最终形成导电薄膜中实际掺氟量有很大差别,生产中存在氟化物挥发损失和向玻璃基体内部扩散问题,而现有技术还不能准确控制掺氟氧化锡薄膜组成达到最佳掺氟量。此外,采用溶胶-凝胶法制备的掺氟氧化锡透明导电薄膜因表面结构疏松和孔隙率高,导致薄膜表面方块电阻增大,只有表面均匀和致密的掺杂氧化锡透明薄膜才能获得优良的导电性能。
发明内容
本发明的目的是提供一种掺杂氧化锡透明导电薄膜的制备方法,其特征在于在采用溶胶-凝胶法制备的结构比较疏松的氧化锡凝胶薄膜中进一步填充掺杂磷、氟、锑的化合物,通过多元素掺杂协同效应降低氧化锡透明导电薄膜的方块电阻,多元素掺杂形成的掺杂氧化锡透明导电薄膜的化学组成为:Sn1-ySbyO2-xFxPz ,其中,x=0.1-0.8,y=0.02-0.2, z=0.02-0.2,采取的技术方案包括在太阳电池玻璃基体上涂覆二氧化硅过渡层、掺磷氧化锡纳米溶胶制备、掺磷氧化锡凝胶薄膜制备、多孔氧化锡凝胶薄膜中填充氟化锑、多元素掺杂凝胶薄膜高温烧结和致密透明导电薄膜形成六部分。
太阳电池玻璃基体上涂覆二氧化硅过渡层在太阳电池玻璃基体表面涂覆厚度为50-100nm的纳米二氧化硅过渡层,用于阻滞高温下钠钙玻璃中钠钙离子向导电薄膜中扩散,同时作为减反射层增大玻璃基体透光率和改善掺杂氧化锡透明导电薄膜在玻璃基体上的附着力。
掺磷氧化锡纳米溶胶制备方法为:(1)向四氯化锡水溶液中加入氨水使锡盐水解,将形成的沉淀洗涤至无氯离子;(2)将水合氧化锡沉淀物悬浮在去离子水中,加入掺杂剂磷酸,再加入饱和草酸水溶液,使水合氧化锡沉淀在50-60℃下完全胶溶,生成氧化锡纳米溶胶pH为0.8-1.5,氧化锡纳米溶胶的组成摩尔比为Sn(OH)4:H3PO4:H2C2O4=1:0.02-0.2:0.1-0.4;(3)向掺磷氧化锡纳米溶胶中加入聚氨酯乳液,使其质量百分浓度为0.01%-0.2%,以改善掺磷氧化锡溶胶稳定性、涂布均匀性和防止膜层干燥时开裂,掺磷氧化锡纳米溶胶中二氧化锡质量百分浓度为4%-5%。
掺磷氧化锡凝胶薄膜制备方法是在太阳电池玻璃过渡层上涂覆掺磷氧化锡溶胶2-3遍,使凝胶薄膜厚度400-800nm,在150℃下烘干得到氧化锡凝胶薄膜,掺磷氧化锡粒径10-15nm,掺磷氧化锡凝胶薄膜孔隙率25%-40%。
多孔氧化锡凝胶薄膜中填充氟化锑的方法是在掺磷氧化锡多孔凝胶薄膜上涂布质量百分浓度为5%的三氟化锑乙醇溶液2-3遍,使三氟化锑浸渍填充到薄膜孔隙中,再涂布无水乙醇使表面的三氟化锑膜层流平和填充密实均匀,控制掺杂原料的摩尔比为Sn:F:Sb=1:0.15-0.6:0.05-0.2,在150℃下烘干,掺杂氧化锡薄膜孔隙率为10%-20%。
多元素掺杂凝胶薄膜高温烧结方法是将多元素掺杂镀膜玻璃基体加热到300℃,达到350-400℃时升温速度降低到3-5℃/min,使填充的磷、锑、氟的化合物高温熔融完全掺杂,最后在500℃高温下烧结30分钟,使填充的磷、锑、氟元素均匀掺杂进入氧化锡晶格中形成透明导电薄膜,过饱和掺杂的磷、锑、氟在高温下反应形成氟磷酸锑或氟磷酸锡玻璃,以减少掺杂氧化锡晶体缺陷,掺杂氧化锡薄膜孔隙率5%-10%。
致密透明导电薄膜形成方法是将高温烧结的多元素掺杂氧化锡镀膜玻璃快速冷却,使镀膜玻璃钢化或半钢化,用去离子水清洗镀膜玻璃表面的灼烧残渣,得到高透光率低方块电阻多元素掺杂氧化锡透明导电薄膜和导电玻璃,导电玻璃可见光透光率为80%-87%,方块电阻为1-10Ω。
本发明能够降低薄膜方块电阻的原因包括几个方面:(1)通过降低掺杂氧化锡凝胶薄膜孔隙率形成致密结晶薄膜降低方块电阻;(2)发挥氟、锑、磷多元素掺杂的协同效应,进一步增加氧化锡半导体薄膜中的载流子浓度;(3)磷作为掺杂元素可以提高载流子浓度,又能结合过饱和掺杂的氟和锑原子形成氟磷酸盐玻璃,从而维持掺杂元素量在最佳掺杂浓度范围内。
本发明所用的实验原料二氧化硅溶胶、四氯化锡、氨水、磷酸、草酸、氟化锑、乙醇、聚氨酯乳液均为市售化学纯试剂;太阳电池玻璃为市售商品。
掺杂氧化锡透明导电薄膜和导电玻璃的透光率用 Lambda 920 型分光光度计测试样品在400-760nm可见光范围的透过率计算;掺杂氧化锡透明导电薄膜和导电玻璃的方块电阻用ST2258C型四探针方阻计测试;掺杂氧化锡透明导电薄膜的孔隙率通过样品扫描电镜图像截面计算。
本发明的有益效果体现在:
(1)本发明多元素掺杂氧化锡透明导电薄膜透光率高和方块电阻低,加工性能良好,能够作为大面积薄膜太阳电池透明电极应用;
(2)本发明采用溶胶凝胶法制备透明导电薄膜和导电玻璃,薄膜烧结热处理过程和玻璃基体的钢化过程可同时完成,生产成本低,安全环保,容易实现大批量工业化生产。
具体实施方式
实施例1
玻璃基体上二氧化硅过渡层涂覆:将100mm×100 mm×1mm的超白玻璃基体用清水冲洗干净,无水乙醇清洗和晾干,然后在其表面用涂布棒涂覆厚度为100nm的纳米二氧化硅镀膜溶胶,空气中晾干后形成表面均匀的镀膜玻璃过渡层,测得涂膜前后在400-760nm可见光波长范围的透光率分别为91.5%和93.5%。
掺磷氧化锡纳米溶胶制备:将无水四氯化锡26.1g(0.1mol)溶于500ml去离子水中,在搅拌下加入2mol/L的氨水,直到不再有沉淀析出和溶液pH为8-9,将水解形成的沉淀过滤,用去离子水洗涤至无氯离子。将沉淀物悬浮在200ml去离子水中,加入磷酸1.92g(0.02mol)作为掺杂磷源,再加入饱和草酸水溶液37g(0.03mol),使水合氧化锡沉淀在50-60℃下完全胶溶,加入聚氨酯乳液0.3g,得到二氧化锡质量百分浓度为5%的掺磷氧化锡纳米溶胶,溶胶pH为0.9。
掺磷氧化锡凝胶薄膜制备:在太阳电池玻璃过渡层上涂覆掺磷氧化锡溶胶3遍,使凝胶薄膜厚度为500-600nm,在150℃下烘干得到掺磷氧化锡凝胶薄膜,测得凝胶粒径10-15nm,凝胶薄膜孔隙率为30%。
多孔凝胶薄膜中填充掺杂氟化锑:在掺磷氧化锡多孔凝胶薄膜上涂布质量百分浓度为5%的三氟化锑乙醇溶液3遍,使其浸渍填充到薄膜孔隙中,再涂布无水乙醇使表面三氟化锑膜层填充均匀密实,控制掺杂原料摩尔比为Sn:F:Sb =1:0.15:0.05, 在150℃下烘干,测得薄膜孔隙率为20%。
多元素掺杂凝胶薄膜高温烧结:将多元素掺杂玻璃基体在高温炉中加热到300℃,达到350-400℃时升温速度降低到5℃/min,使磷、锑、氟化合物高温熔融掺杂,最后在500℃下高温烧结30 min形成透明导电薄膜,过饱和掺杂的磷、锑、氟高温反应形成氟磷酸锑或氟磷酸锡玻璃,测得薄膜孔隙率为10%。
致密透明导电薄膜形成:将高温烧结的多元素掺杂凝胶薄膜快速冷却,使玻璃基体钢化或半钢化,用去离子水清洗玻璃表面的灼烧残渣,得到高透光率低方块电阻掺杂氧化锡透明导电薄膜,测得可见光透光率为82.5%,方块电阻为3.5Ω。
实施例2
掺磷氧化锡凝胶薄膜制备:在太阳电池玻璃过渡层上涂布掺磷氧化锡溶胶2遍,使凝胶薄膜厚度为400-450nm,在150℃下烘干得到掺磷氧化锡凝胶薄膜,测得凝胶粒径为10-15nm,凝胶薄膜孔隙率为35%。
多孔凝胶薄膜中填充掺杂氟化锑:在掺磷氧化锡多孔凝胶薄膜上涂布质量百分浓度为5%的三氟化锑乙醇溶液2遍,使其浸渍填充到薄膜孔隙中,再涂布无水乙醇使表面三氟化锑膜层填充均匀密实,控制掺杂原料摩尔比为Sn:F:Sb =1:0.3:0.1, 在150℃下烘干,测得薄膜孔隙率为25%。
多元素掺杂凝胶薄膜高温烧结:将多元素掺杂玻璃基体在高温炉中加热到300℃,达到350-400℃时升温速度降低到5℃/min,使磷、锑、氟化合物高温熔融掺杂,最后在500℃下高温烧结30 min形成透明导电薄膜,过饱和掺杂的磷、锑、氟高温反应形成氟磷酸锑或氟磷酸锡玻璃,测得薄膜孔隙率为12%。
致密透明导电薄膜形成:将高温烧结的多元素掺杂凝胶薄膜快速冷却,使玻璃基体钢化或半钢化,用去离子水清洗玻璃表面的灼烧残渣,得到高透光率低方块电阻掺杂氧化锡透明导电薄膜,测得可见光透光率为86.5%,方块电阻为6.5Ω。
对照例1
如实施例1过程操作,唯一不同是采用未掺磷的氧化锡纳米溶胶,溶胶pH为1.2,最终得到致密透明导电薄膜,测得可见光透光率为81.5%,方块电阻为53Ω。
对照例2
如实施例2过程操作,唯一不同是采用未掺磷的氧化锡纳米溶胶,溶胶pH为1.2,最终得到致密透明导电薄膜,测得可见光透光率为85.7%,方块电阻为87Ω。
Claims (5)
1. 一种掺杂氧化锡透明导电薄膜的制备方法,其特征是在采用溶胶-凝胶法制备的结构比较疏松的氧化锡凝胶薄膜中进一步填充掺杂磷、氟、锑的化合物,通过多元素掺杂协同效应降低氧化锡透明导电薄膜的方块电阻,多元素掺杂形成的掺杂氧化锡透明导电薄膜的化学组成为:Sn1-ySbyO2-xFxPz ,其中,x=0.1-0.8,y=0.02-0.2,z=0.02-0.2,采取的技术方案包括在太阳电池玻璃基体上涂覆二氧化硅过渡层、掺磷氧化锡纳米溶胶制备、掺磷氧化锡凝胶薄膜制备、多孔氧化锡凝胶薄膜中填充氟化锑、多元素掺杂凝胶薄膜高温烧结和致密透明导电薄膜形成六部分,所述多元素掺杂凝胶薄膜高温烧结为将多元素掺杂镀膜玻璃基体加热到300℃,达到350-400℃时升温速度降低到3-5℃/min,使填充的磷、锑、氟的化合物高温熔融完全掺杂,最后在500℃下烧结30分钟,使掺杂氧化锡薄膜孔隙率为5%-10%。
2.如权利要求1所述掺杂氧化锡透明导电薄膜的制备方法,其特征是掺磷氧化锡纳米溶胶制备方法为:
(1)向四氯化锡水溶液中加入氨水使锡盐水解,将形成的沉淀洗涤至无氯离子;
(2)将水合氧化锡沉淀物悬浮在去离子水中,加入掺杂剂磷酸,再加入饱和草酸水溶液,使水合氧化锡沉淀在50-60℃下完全胶溶,生成氧化锡纳米溶胶的pH为0.8-1.5,氧化锡纳米溶胶的组成摩尔比为Sn(OH)4:H3PO4 :H2C2O4=1:0.02-0.2:0.1-0.4;
(3)向掺磷氧化锡纳米溶胶中加入聚氨酯乳液,使其质量百分浓度为0.01%-0.2%,以改善掺磷氧化锡溶胶稳定性、涂布均匀性和防止膜层干燥时开裂,掺磷氧化锡纳米溶胶中二氧化锡质量百分浓度为4%-5%。
3.如权利要求1所述掺杂氧化锡透明导电薄膜的制备方法,其特征是掺磷氧化锡凝胶薄膜制备方法是在太阳电池玻璃过渡层上涂覆掺磷氧化锡溶胶2-3遍,使凝胶薄膜厚度400-800nm,在150℃下烘干得到氧化锡凝胶薄膜,掺磷氧化锡粒径为10-15nm,掺磷氧化锡凝胶薄膜孔隙率为25%-40%。
4.如权利要求1所述掺杂氧化锡透明导电薄膜的制备方法,其特征是多孔氧化锡凝胶薄膜中填充氟化锑的方法为在掺磷氧化锡多孔凝胶薄膜上涂布质量百分浓度为5%的三氟化锑乙醇溶液2-3遍,使三氟化锑浸渍填充到薄膜孔隙中,再涂布无水乙醇使表面的三氟化锑膜层流平和填充密实均匀,控制掺杂原料的摩尔比为Sn:F:Sb =1:0.15-0.6:0.05-0.2,在150℃下烘干,掺杂氧化锡薄膜孔隙率为10%-20%。
5.如权利要求1所述掺杂氧化锡透明导电薄膜的制备方法,其特征是致密透明导电薄膜形成方法为将高温烧结的多元素掺杂氧化锡镀膜玻璃快速冷却,使镀膜玻璃钢化或半钢化,用去离子水清洗镀膜玻璃表面的灼烧残渣,得到高透光率低方块电阻多元素掺杂氧化锡透明导电薄膜和导电玻璃,导电玻璃可见光透光率为80%-87%,方块电阻为1-10Ω。
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