CN105047754B - 一种光伏电池用纳米复合导电薄膜的制备方法 - Google Patents
一种光伏电池用纳米复合导电薄膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种光伏电池用纳米复合导电薄膜的制备方法,具体为:将镀膜前驱溶液包覆的纳米光致发光陶瓷材料沉积气雾沉积在加热的基板上,即得到光伏电池用纳米复合导电薄膜。本发明采用红色荧光粉可以将太阳光的紫外光波段转变为可见光,便于光伏电池中硅器件的光电转换,提高光电转换利用率1%~1.5%;利用透明导电薄膜的导电性,提高并保持长期工作中的高透过率,提高了实际工况下的光电转换效率和利用率;利用透明导电膜红外反射特性,降低其热效应,稳定太阳能电池中硅器件的工作点,提高了其光电转换效率,从而有效改善和提高了目前太阳能电池的工程适用性,实现免维护和长周期工作。
Description
技术领域
本发明属于光电薄膜制备技术领域,涉及一种光伏电池用纳米复合导电薄膜的制备方法。
背景技术
近年来,以高透光率为特征的玻璃深加工产品在光伏电池(太阳能)电池窗口的应用表现出越来越强劲的市场需求和技术优势,形成了一个代表性的玻璃深加工产业方向。
随着太阳能光伏电池从军事领域、航天领域普及进入工业、商业、农业、通信、家用电器以及公用设施等领域,其便捷灵活性尤其适用于在边远地区、高山、沙漠、海岛和农村的地域,表现出强劲的市场需求。但是,作为其关键组件之一的窗口玻璃,主要的技术要求是在可见光和近红外区域的高透过率。目前服役中的市场化太阳能电池,主要采用超白玻璃和表面涂覆增透膜的方法来提高其透过率,但是由于窗口玻璃表面静电荷累积、导致使用过程中的窗口玻璃表面的灰尘吸附严重,直接影响其实际透光率和光电转换效率,因此,玻璃表面的防静电涂层制备对于抑制太阳能电池窗口玻璃表面灰尘静电吸附十分重要。
另外,对于太阳能电池的光电转换而言,其硅晶体的光波长吸收转换波长介于400nm~1100nm,而太阳光中的紫外波段(400nm以下)的光能不能利用,大大降低其光电转换利用率,因此利用光致发光材料,将紫外波段的太阳光能转换为可见波长的发光(593nm~703nm),对于提高太阳能电池的光电转换利用率、抑制高能量紫外线对硅晶体器件的损伤非常必要。
因此,如何拓宽太阳能光电转换波长范围、抑制表面灰尘吸附是光伏电池窗口玻璃相关镀膜产品开发和应用研究的热点领域。
发明内容
本发明的目的是提供一种光伏电池用纳米复合导电薄膜的制备方法,解决了现有单一氧化硅基增透膜涂层增透效果有限、表面静电灰尘吸附的局限,同时延宽了其吸收波长到紫外波段、稳定太阳能电池中硅器件的工作点,从根本上提高了其光电转换效率,改善和提高了目前太阳能电池的工程适用性,实现免维护和长周期工作。
本发明所采用的技术方案是,一种光伏电池用纳米复合导电薄膜的制备方法,具体按以下步骤实施:
步骤1,制备沉积气雾:
1.1将纳米光致发光陶瓷材料放入粉体定量给料器中,采用高速气流虹吸效应携带纳米光致发光陶瓷材料形成雾化气流;
1.2将镀膜前驱溶液注入雾化器中,通过上述雾化气流将镀膜前驱溶液雾化,形成镀膜前驱溶液包覆的纳米光致发光陶瓷材料沉积气雾,并将其导入雾化沉积室。
步骤2,纳米粒子复合薄膜沉积:
将基板在加热室中加热,由传送器送入雾化沉积室,沉积气雾在基板上沉积,得到光伏电池用纳米复合导电薄膜。
本发明的特点还在于,
步骤1中镀膜前驱溶液采用市售的锑掺杂氧化锡ATO、氟掺杂氧化锡FTO、锡掺杂氧化铟ITO醇基或水基溶液,pH约为5~7,浓度为10wt%~30wt%。
步骤1中纳米光致发光陶瓷材料采用市售的稀土铕掺杂的钒酸钇Eu:YVO4或稀土铕掺杂的钒磷酸钇Eu:Y(P1-xVx)O4,x=0.4~0.6红色荧光粉,纳米光致发光陶瓷材料粒径为15nm~50nm。
步骤1.1中所述雾化气流气源为过滤干燥的压缩空气、氮气、氧气。
步骤1.2中粉体定量给料器给料速度为0.1g/min~2g/min,高速气流流量为1L/min~7L/min。
步骤2中加热温度为480℃~650℃,气雾沉积时间为5~30s。
制备得到的光伏电池用纳米复合导电薄膜厚度为50nm~200nm。
本发明的有益效果是,
1、通过纳米粒子的红色荧光粉可以将太阳光的220nm~328nm波段内紫外光波段转变为593nm~704nm波段内的可见光,便于光伏电池中硅器件的光电转换,提高光电转换利用率1%~1.5%;
2、通过ATO、FTO、ITO的导电性,去除表面的静电累积,避免静电吸尘,提高并保持长期工作中的高透过率,实现免清洁,同时提高实际工况下的光电转换效率和利用率;
3、ATO、FTO、ITO透明导电膜具有可见光透过和红外反射特性,可以反射太阳光中的红外波段,降低其热效应,有利于稳定太阳能电池中硅器件的工作点,提高其光电转换效率。
因此,本发明能够从根本上有效改善和提高目前太阳能电池的工程适用性,实现免维护和长周期工作,同时大幅度提高其实际光电转换效率和光电转换利用率。
附图说明
图1是本发明光伏电池用纳米复合导电薄膜的制备方法工艺流程图;
图2是本发明制备得到的纳米复合导电薄膜结构示意图;
图3是本发明实施例2制备得到稀土铕掺杂钒酸钇(Eu:YVO4)纳米粒子复合FTO薄膜的SEM照片;
图4是本发明实施例3制备得到的稀土铕掺杂钒酸钇(Eu:YVO4)纳米粒子复合ATO薄膜紫外激发可见光光谱图;
图5是本发明实施例4制备得到的稀土铕掺杂钒磷酸钇(Eu:Y(P0.5,V0.5)O4)纳米粒子复合ITO薄膜紫外激发可见光光谱图;
图6是本发明实施例5制备得到的稀土铕掺杂钒酸钇(Eu:YVO4)纳米粒子复合ITO薄膜紫外-可见光透光率曲线。
图中,1.光致发光纳米粒子,2.透明导电膜,3.基板。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明提供了一种光伏电池用纳米复合导电薄膜的制备方法,如图1所示,具体按以下步骤实施:
步骤1,制备沉积气雾:
1.1将纳米光致发光陶瓷材料放入粉体定量给料器中,控制给料速度为0.1g/min~2g/min,采用高速气流虹吸负压使纳米光致发光陶瓷材料形成雾化气流,控制气流流量为1L/min~7L/min;
雾化用气流采用过滤干燥的压缩空气、氮气、氧气等气源。
1.2将镀膜前驱溶液注入雾化器中,通过上述雾化气流将镀膜前驱溶液雾化,形成镀膜前驱溶液包覆的纳米光致发光陶瓷材料沉积气雾,并将其导入到雾化沉积室中。
其中镀膜前驱溶液采用市售商品化的锑掺杂氧化锡ATO、氟掺杂氧化锡FTO、锡掺杂氧化铟ITO醇基或水基溶液,pH约为5~7,浓度为10wt%~30wt%;锑掺杂氧化锡ATO、氟掺杂氧化锡FTO、锡掺杂氧化铟ITO醇基溶液为锑掺杂氧化锡ATO、氟掺杂氧化锡FTO、锡掺杂氧化铟ITO与异丙醇混合而成。
纳米光致发光陶瓷材料采用市售商品化的稀土铕掺杂的钒酸钇(Eu:YVO4)或钒磷酸钇(Eu:Y(P1-xVx)O4,x=0.4~0.6)红色荧光粉,纳米光致发光陶瓷材料粒径为15nm~50nm。
步骤2,纳米粒子复合薄膜沉积:
将基板在加热室中加热至480℃~650℃,通过传送器送入雾化沉积室,使沉积气雾在基板上沉积5~30s,得到厚度为50nm~200nm的光伏电池用纳米复合导电薄膜,如图2所示。
基板采用光伏电池用超白玻璃基板,基板采用红外加热器、或红外加热窑炉加热。
本发明的技术原理是:
1、利用高速气流的虹吸负压原理,通过给料装置将光致发光陶瓷材料的纳米粒子按按设定比例携带混入,形成混合有光致发光陶瓷材料的雾化气流。
2、携带有光致发光材料的纳米粒子的雾化气流作为雾化气源,在雾化器内将注入的镀膜前驱溶液(ATO、FTO、ITO醇基或水基溶液)进行雾化,形成由前驱溶液包覆的光致发光纳米粒子的沉积气雾,并将其导入到雾化沉积室。
3、雾化沉积室中,当一定温度(480℃~650℃)的玻璃基板匀速进入后,在基板的高温作用下,沉积气雾发生热分解反应,形成包裹有纳米级光致发光陶瓷材料的连续的透明导电ATO或FTO或ITO薄膜。
4、通过调节前驱溶液浓度和粉体定量给料器给料速度,可以控制纳米粒子分散程度和比例;控制雾化气流量可以控制雾化沉积速率或膜厚生长速度,从而得到复合比例和不同膜厚的纳米粒子复合透明导电膜。
实施例1
步骤1,制备沉积气雾:
1.1将铕掺杂钒磷酸钇纳米陶瓷粉料(Eu:YPxV(1-x)O4,x=0.4~0.6,市售,15nm~20nm)放入粉体定量给料器中,控制给料速度为0.1g/min~0.22g/min,采用高速气流虹吸负压使纳米光致发光陶瓷材料形成雾化气流,控制气流流量为1L/min~1.5L/min;
1.2雾化气流将雾化器中水体系的ATO(锑掺杂氧化锡)溶液(浓度:10wt%~12wt%)雾化,形成沉积气雾,并将其通入雾化沉积室。
步骤2,纳米粒子复合薄膜沉积:
将光伏电池用超白玻璃基板在加热室中加热至480℃~500℃,通过传送器送入雾化沉积室,使沉积气雾在基板上沉积25~30s,得到厚度为50nm~600nm的光伏电池用纳米复合导电薄膜,薄膜方阻4000Ω/sq~5000Ω/sq,相对透过率≥95%。
实施例2
步骤1,制备沉积气雾:
1.1将铕掺杂钒酸钇纳米陶瓷粉料(Eu:YVO4,市售,30nm~40nm)放入粉体定量给料器中,控制给料速度为1.8g/min~2g/min,采用高速气流虹吸负压使纳米光致发光陶瓷材料形成雾化气流,控制气流流量为6L/min~7L/min;
1.2雾化气流将雾化器中水体系的FTO(氟掺杂氧化锡)溶液(浓度:15wt%~20wt%)雾化,形成沉积气雾,并将其通入雾化沉积室。
步骤2,纳米粒子复合薄膜沉积:
将光伏电池用超白玻璃基板在加热室中加热至500℃~520℃,通过传送器送入雾化沉积室,使沉积气雾在基板上沉积5~10s,得到厚度为150nm~170nm的光伏电池用纳米复合导电薄膜,薄膜方阻500Ω/sq~1000Ω/sq,相对透过率≥95%。其SEM照片如图3所示,Eu:YVO4纳米粒子在FTO薄膜表面弥散分布。
实施例3
步骤1,制备沉积气雾:
1.1将铕掺杂钒酸钇纳米陶瓷粉料(Eu:YVO4,市售,20nm~30nm)放入粉体定量给料器中,控制给料速度为0.5g/min~0.8g/min,采用高速气流虹吸负压使纳米光致发光陶瓷材料形成雾化气流,控制气流流量为4L/min~5L/min;
1.2雾化气流将雾化器中异丙醇体系的ATO(锑掺杂氧化锡)溶液(浓度:15wt%~17wt%)雾化,形成沉积气雾,并将其通入雾化沉积室。
步骤2,纳米粒子复合薄膜沉积:
将光伏电池用超白玻璃基板在加热室中加热至640℃~650℃,通过传送器送入雾化沉积室,使沉积气雾在基板上沉积18~20s,得到厚度为120nm~150nm的光伏电池用纳米复合导电薄膜,薄膜方阻1500Ω/sq~2000Ω/sq,相对透过率≥95%,其Eu:YVO4纳米粒子复合ATO薄膜紫外激发和可见光发射光谱如图4所示,紫外激发波段主要为280nm~325nm,特征发射光谱波段主要集中在618nm、614nm、593nm、698nm、704nm。
实施例4
步骤1,制备沉积气雾:
1.1将铕掺杂钒磷酸钇纳米陶瓷粉料(Eu:YPxV(1-x)O4,x=0.4~0.6,市售,40nm~50nm)放入粉体定量给料器中,控制给料速度为0.8g/min~1g/min,采用高速气流虹吸负压使纳米光致发光陶瓷材料形成雾化气流,控制气流流量为3L/min~4L/min;
1.2雾化气流将雾化器中异丙醇体系的ITO(锡掺杂氧化铟)溶液(浓度:25wt%~30wt%)雾化,形成沉积气雾,并将其通入雾化沉积室。
步骤2,纳米粒子复合薄膜沉积:
将光伏电池用超白玻璃基板在加热室中加热至550℃~570℃,通过传送器送入雾化沉积室,使沉积气雾在基板上沉积10~15s,得到厚度为170nm~200nm的光伏电池用纳米复合导电薄膜,薄膜方阻100Ω/sq~200Ω/sq,相对透过率≥93%,其紫外激发和可见光发射光谱如图5所示,紫外激发波段主要为220nm~328nm,特征发射光谱波段主要集中在619nm、614nm、593nm、698nm、703nm。
实施例5
步骤1,制备沉积气雾:
1.1将铕掺杂钒酸钇纳米陶瓷粉料(Eu:YVO4,市售,15nm~20nm)放入粉体定量给料器中,控制给料速度为0.5g/min~0.7g/min,采用高速气流虹吸负压使纳米光致发光陶瓷材料形成雾化气流,控制气流流量为3L/min~4L/min;
1.2雾化气流将雾化器中异丙醇体系的ITO(锡掺杂氧化铟)溶液(浓度:10wt%~12wt%)雾化,形成沉积气雾,并将其通入雾化沉积室。
步骤2,纳米粒子复合薄膜沉积:
将光伏电池用超白玻璃基板在加热室中加热至600℃~620℃,通过传送器送入雾化沉积室,使沉积气雾在基板上沉积25~30s,得到厚度为100nm~120nm的光伏电池用纳米复合导电薄膜,薄膜方阻500Ω/sq~900Ω/sq,相对透过率≥98%,其紫外-可见光透光率光谱如图6所示,在可见光400nm~800nm波段内。
Claims (7)
1.一种光伏电池用纳米复合导电薄膜的制备方法,其特征在于,具体按以下步骤实施:
步骤1,制备沉积气雾:
1.1将纳米光致发光陶瓷材料放入粉体定量给料器中,采用高速气流虹吸效应携带纳米光致发光陶瓷材料形成雾化气流;
1.2将镀膜前驱溶液注入雾化器中,通过上述雾化气流将镀膜前驱溶液雾化,形成镀膜前驱溶液包覆的纳米光致发光陶瓷材料沉积气雾,并将其导入雾化沉积室;
步骤2,纳米粒子复合薄膜沉积:
将基板在加热室中加热,由传送器送入雾化沉积室,沉积气雾在基板上沉积,得到光伏电池用纳米复合导电薄膜。
2.根据权利要求1所述的一种光伏电池用纳米复合导电薄膜的制备方法,其特征在于,步骤1中所述镀膜前驱溶液采用锑掺杂氧化锡ATO、氟掺杂氧化锡FTO、锡掺杂氧化铟ITO醇基或水基溶液,pH为5~7,浓度为10wt%~30wt%。
3.根据权利要求1所述的一种光伏电池用纳米复合导电薄膜的制备方法,其特征在于,步骤1中所述纳米光致发光陶瓷材料采用稀土铕掺杂的钒酸钇Eu:YVO4或稀土铕掺杂的钒磷酸钇Eu:Y(P1-xVx)O4,x=0.4~0.6红色荧光粉,纳米光致发光陶瓷材料粒径为15nm~50nm。
4.根据权利要求1所述的一种光伏电池用纳米复合导电薄膜的制备方法,其特征在于,步骤1.1中所述雾化气流气源为过滤干燥的压缩空气、氮气、氧气。
5.根据权利要求1所述的一种光伏电池用纳米复合导电薄膜的制备方法,其特征在于,步骤1.2中所述粉体定量给料器给料速度为0.1g/min~2g/min,步骤1.1中所述雾化气流流量为1L/min~7L/min。
6.根据权利要求1所述的一种光伏电池用纳米复合导电薄膜的制备方法,其特征在于,步骤2中所述加热温度为480℃~650℃,气雾沉积时间为5~30s。
7.根据权利要求1所述的一种光伏电池用纳米复合导电薄膜的制备方法,其特征在于,制备得到的光伏电池用纳米复合导电薄膜厚度为50nm~200nm。
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