CN105932088A - 一种具有钙钛矿结构的异质结薄膜光电器件及其制备方法 - Google Patents
一种具有钙钛矿结构的异质结薄膜光电器件及其制备方法 Download PDFInfo
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Abstract
一种具有钙钛矿结构的异质结薄膜光电器件，涉及一种光电器件，包括基板，以及依次层叠在基板上的下电极、p型钙钛矿型氧化物薄膜、n型钙钛矿型氧化物薄膜和上电极；其中，p型钙钛矿型氧化物薄膜为Er：Li0.1K0.4Bi0.5TiO3，掺杂的Er与Li0.1K0.4Bi0.5TiO3的摩尔比为0.005‑0.2；n型钙钛矿型氧化物薄膜为BaNbxTi1‑xO3，x的取值范围为0.05‑0.1；本发明光电器件的各薄膜层是经旋涂工艺依次涂覆在基板上后，经烘干、退火工序制成的。本发明提出了一种新的钙钛矿型异质结薄膜并应用于光电器件，能够增加异质结光电器件的光生电流，提高其光电转换效率。
Description
技术领域
本发明涉及一种光电器件，具体涉及一种具有钙钛矿结构的异质结薄膜光电器件及其制备方法。
背景技术
近年来，随着能源危机和环境恶化的日益严重，开发可再生的绿色能源成为全社会共同关注的课题。为了实现太阳能发电的经济实惠及大规模应用，探索和开发低成本、高效率的太阳能电池已迫在眉睫。近来，铁电材料的光伏效应激发了人们的研究兴趣。半导体的光生伏打效应是由宏观不均匀性造成的，产生光伏电压一般不超过半导体的禁带宽度(一般为数伏)。而铁电材料具有完全不同于半导体的反常光生伏打(APV)效应：均匀铁电晶体在均匀光照下出现稳态短路光生电流或开路电压的现象，光伏电压不受晶体禁带宽度(Eg)的限制，可比Eg高2~4个数量级，达103~105V/cm。
Brody P S.研究表明某些多晶铁电材料的光伏电压与其剩余极化强度成正比（High voltage photovoltaic effect in bariumtitanate and lead
titanate-lead zirconate ceramics. J.Solid State Chemistry.），因此，具有大的自发极化强度的铁电材料已成为研究热点。K0.5Bi0.5TiO3(KBT)作为一种钙钛矿结构铁电体被发现，但是其剩余极化强度并不是很好。需要寻找一种能够提高其剩余极化强度和铁电性的途径。
研究表明，钛酸铋作为一类压电和铁电材料，在改善其压电和铁电特性过程中发现，这类铋层状氧化物晶格中的钙钛矿层（Am-1BmO3m+1）2-的A位对许多掺杂离子具有很大的相容性，而这种相容性并不改变基质材料晶格的整体结构。这种相容性为采用稀土掺杂铋层状氧化物，设计其上转换发光特性，并在一定程度上保留或改善原有的压电和铁电性能，为开发其多功能化应用提供了可行性。
本发明致力于制备一种新型异质结光电器件，通过对铁电材料的上转换性能进行研究，以获得光电效率得到提升的光电器件，到目前为止，尚没有人采用稀土掺杂的Li0.1K0.4Bi0.5TiO3和BaNbxTi1-xO3制备异质结光电器件。
发明内容
本发明的目的是提供一种异质结光电器件及其制备方法，通过制备稀土掺杂的Li0.1K0.4Bi0.5TiO3薄膜，能够实现对光线进行上转换，进而制备稀土掺杂的Li0.1K0.4Bi0.5TiO3/BaNbxTi1-xO3异质结光电器件，提高光生电流，以提高光电转换效率。
为实现上述发明目的，本发明的技术方案是：一种具有钙钛矿结构的异质结薄膜光电器件，包括基板，以及依次层叠在基板上的下电极、p型钙钛矿型氧化物薄膜、n型钙钛矿型氧化物薄膜和上电极；其中，p型钙钛矿型氧化物薄膜为Er：Li0.1K0.4Bi0.5TiO3，掺杂的Er与Li0.1K0.4Bi0.5TiO3的摩尔比为0.005-0.2；n型钙钛矿型氧化物薄膜为BaNbxTi1-xO3，x的取值范围为0.05-0.1。
进一步地，所述下电极和上电极均为钙钛矿型透明导电氧化物。
更进一步地，所述上电极为LaNiO3、LaCrO3、SrRuO3、CaRuO3、La1-xSrxCoO3、La1-xSrxMnO3、La1-xSrxCrO3、BaPbO3、La1-xSrxTiO3、SrIrO3中的至少一种，其中0<x<1。
所述下电极为La:SrTiO3薄膜，其制备方法为：将醋酸锶、硝酸镧溶于醋酸溶液中形成盐溶液，在 120℃下搅拌 2h；将钛酸四丁酯溶解在乙酰丙酮中，在 80℃搅拌 1h 使其混合均匀，然后将其加入上述盐溶液中，并加入稳定剂乙二醇和溶剂乙二醇甲醚，配制成澄清的1号前驱体溶液；将上述1号前驱体溶液均匀涂覆在基板上，在管式电炉中退火形成La:SrTiO3
薄膜。
所述p型钙钛矿型氧化物薄膜Er：Li0.1K0.4Bi0.5TiO3的制备方法为：将硝酸铋、醋酸钾、硝酸锂和醋酸铒按化学计量比溶解于醋酸中，加入乙二醇作为溶剂，然后加入柠檬酸，形成前驱体溶液A1；将钛酸四丁酯溶解于乙二醇中，然后加入柠檬酸，形成前驱体溶液A2；将前驱体溶液A1与前驱体溶液A2按照化学计量比进行混合，室温下搅拌均匀，从而生成2号前驱体溶液；将2号前驱体溶液涂布到下电极上，干燥后退火形成掺杂有铒的Li0.1K0.4Bi0.5TiO3薄膜。
所述n型钙钛矿型氧化物薄膜BaNbxTi1-xO3的制备方法为：将氯化铌和氢氧化钾加入乙二醇甲醚中，在氩气的保护下进行反应，过滤掉反应生成的KCl沉淀，制备得到铌的醇盐；将所得铌的醇盐与钛酸四丁酯、有机溶剂乙二醇甲醚混合，并加入乙酰丙酮作为鳌合剂，配制成前驱体溶液B1；将过量10%的硝酸钡溶于乙二醇甲醚与冰醋酸的混合液中，混合搅拌均匀，配制成前驱体溶液B2；将前驱体溶液B1和前驱体溶液B2混合均匀并静置2天，从而制备出3号前驱体溶液；将3号前驱体溶液涂布到p型钙钛矿型氧化物薄膜Er：Li0.1K0.4Bi0.5TiO3上，干燥后退火形成BaNbxTi1-xO3薄膜。
所述上电极优选为La0.8Sr0.2MnO3薄膜，其制备方法为：将硝酸镧、硝酸锶和硝酸锰按照化学计量比溶于去离子水中，然后加入柠檬酸和乙二胺四乙酸，加热搅拌，充分络合反应后，得到4号前驱体溶液；将上述4号前驱体溶液均匀涂覆于n型钙钛矿型氧化物薄膜BaNbxTi1-xO3上，干燥后退火形成La0.8Sr0.2MnO3薄膜。
所述的一种具有钙钛矿结构的异质结薄膜光电器件的制备方法，包括如下步骤：
（1）、分别采用丙酮溶液、氢氟酸清洗基板表面，再用无水乙醇和去离子水将基板表面冲洗干净，然后烘干，烘干后采用硅烷偶联剂修饰基板表面，以增强后续形成的薄膜与基板表面的附着力；
（2）、在处理过的基板上从下到上依次制备下电极、p型钙钛矿型氧化物薄膜Er：Li0.1K0.4Bi0.5TiO3、n型钙钛矿型氧化物薄膜BaNbxTi1-xO3和上电极。
本发明中的基板为玻璃、石英或硅片。
本发明与现有技术相比，具有以下有益效果：
1、钙钛矿型的Er：Li0.1K0.4Bi0.5TiO3/BaNbxTi1-xO3异质结薄膜在光电领域中为首次被提出。
2、采用p型钙钛矿型薄膜为Er：Li0.1K0.4Bi0.5TiO3，具有上转换功能，能够增加薄膜对光的吸收范围，从而增加异质结光电器件的光生电流。
3、采用掺有Li的钙钛矿型薄膜作为光吸收层，Li的加入能够降低薄膜的退火温度，能够降低薄膜的漏电流，同时能够降低光吸收层的带隙。
4、采用上电极和下电极都为钙钛矿型材料，使薄膜之间存在完美的晶格匹配，从而能够提高薄膜质量，进而提高器件的性能。
5、采用溶胶凝胶法制备得到三明治型光电器件，制备方法简单，容易操控。
附图说明
图1 为本发明光电器件的结构示意图；
图中标记为：1、基板、2、下电极，3、p型钙钛矿型氧化物薄膜Er：Li0.1K0.4Bi0.5TiO3，4、n型钙钛矿型氧化物薄膜BaNbxTi1-xO3，5、上电极。
具体实施方式
如图1所示，本发明的具有钙钛矿结构的异质结薄膜光电器件，其包括基板1，以及依次层叠在基板1上的下电极2、p型钙钛矿型氧化物薄膜3、n型钙钛矿型氧化物薄膜4和上电极5；其中，p型钙钛矿型氧化物薄膜为Er：Li0.1K0.4Bi0.5TiO3，掺杂的Er与Li0.1K0.4Bi0.5TiO3的摩尔比为0.005-0.2；n型钙钛矿型氧化物薄膜为BaNbxTi1-xO3，x的取值范围为0.05-0.1。
所述下电极和上电极均为钙钛矿型透明导电氧化物。比如，下电极为La:SrTiO3薄膜。上电极为LaNiO3、LaCrO3、SrRuO3、CaRuO3、La1-xSrxCoO3、La1-xSrxMnO3、La1-xSrxCrO3、BaPbO3、La1-xSrxTiO3、SrIrO3中的至少一种，其中，La1-xSrxCoO3、La1-xSrxMnO3、La1-xSrxCrO3、La1-xSrxTiO3中x的取值范围均为0<x<1。
上电极优选为La0.8Sr0.2MnO3薄膜，下面以此为例，详细说明本发明光电器件的制备方法：
（1）步骤101：基板的处理
基板可为玻璃、石英或硅片，先用丙酮溶液对基板进行超声波振荡10min，溶解基板表面的有机污染物，再用氢氟酸洗液浸泡20min去除基板表面的无机污染物，最后用无水乙醇和去离子水重复冲洗干净，放入烘箱中烘干，烘干后采用硅烷偶联剂修饰基板，以增强后续形成的薄膜与基板表面的附着力。
（2）步骤102：制备下电极
在处理过的基板上制备La:SrTiO3薄膜作为下电极； La:SrTiO3薄膜的制备方法为：利用磁力搅拌器将醋酸锶、硝酸镧溶于醋酸溶液中形成盐溶液，在 120℃下搅拌 2h；称取钛酸四丁酯溶解在乙酰丙酮中，在 80℃搅拌 1h 使混合均匀，然后将其加入上述盐溶液中，并加入乙二醇作为稳定剂，乙二醇甲醚为溶剂，乙二醇与乙二醇甲醚的体积配比为1:5，配成金属离子浓度为 0.4
mol/L 的溶液，制成澄清的1号前驱体溶液；将上述1号前驱体溶液均匀涂覆在处理过的基板上，在管式电炉中退火形成La:SrTiO3
薄膜。
上述La:SrTiO3 薄膜的形成方法为：采用多次旋涂和预处理方式。设定匀胶机参数，先在较低转速下(600 rpm)旋转 18 s，然后在 3000 rpm 的转速下旋转 30s；甩胶后将湿膜置于管式电炉中，氧气流量为 0.1 L/min。涂第一层后，以3℃/min 的速度升到 130℃，低温烘干，再升到 450 ℃，缓慢蒸发有机物，形成非晶薄膜；随后重复第一层的旋涂和加热预处理过程数次，达到所需的膜厚100-600nm，最后升到 600℃，保温 2 h，使有机物完全蒸发，然后于 650℃-750 ℃下退火 10-30分钟，生长成晶态的
La:SrTiO3 薄膜。其中，La的掺杂量为：La占La和Sr总摩尔量的0.
5mol%-10mol%，La和Sr总摩尔量即为醋酸锶和硝酸镧两者的总和。
（3）步骤103：制备钙钛矿型异质结薄膜
A、制备p型钙钛矿型Er：Li0.1K0.4Bi0.5TiO3薄膜
将硝酸铋Bi(NO3)3、醋酸钾KOOCCH3、硝酸锂LiNO3和醋酸铒Er(OOCCH3)3按照化学计量比5:4:1:x溶解于醋酸中，其中x为铒的掺杂量，取值范围为0.05~2，并加入适量的乙二醇作为溶剂，然后加入适量的柠檬酸，使乙二醇、柠檬酸与金属离子的摩尔比为5:1.5:1，形成前驱体溶液A1；将钛酸四丁酯C16H36O4Ti溶解于乙二醇中，加入柠檬酸，使乙二醇、柠檬酸与金属离子的摩尔比为5:1.5:1，形成前驱体溶液A2；将前驱体溶液A1与前驱体溶液A2按照化学计量比进行混合，室温下搅拌均匀，从而生成2号前驱体溶液；将2号前驱体溶液涂布到下电极薄膜上，干燥后退火形成掺杂有铒的Li0.1K0.4Bi0.5TiO3薄膜。
上述掺杂有铒的Li0.1K0.4Bi0.5TiO3薄膜的形成方法为：设定匀胶机参数，控制转速为1000rpm甩胶10秒，然后在3800rpm转速下甩胶30秒；甩胶结束后将带有2号前驱体湿膜的基板在热板上先200℃烘干3分钟，然后在350℃煅烧5分钟；然后重复上述甩胶和热处理过程，直到膜厚达到所需的300-1200nm，最后在氢气气氛下通过快速退火炉烧结5-30分钟，通过控制退火过程的升温速率和降温速率使钙钛矿型薄膜的晶粒尺寸为40-200nm，其中退火温度600-1000℃，优选800℃，最后降温形成掺杂有铒的Li0.1K0.4Bi0.5TiO3薄膜。
B、制备n型钙钛矿型BaNbxTi1-xO3薄膜，x的取值范围为0.05-0.1
将化学计量比1:5的氯化铌 ( NbCl5)和氢氧化钾（KOH）加入乙二醇甲醚中，在保护性气体氩气下进行反应，80℃以上过滤掉反应生成的氯化钾(KCl)沉淀，制备得到铌的醇盐；将所得铌醇盐与钛酸四丁酯 ( C16H36O4Ti)、乙二醇甲醚混合，并加入少量乙酰丙酮作为鳌合剂，搅拌 2h 配制成前驱体溶液B1；将称量好的过量10%的硝酸钡( Ba(NO3) 2)溶于乙二醇甲醚与冰醋酸 (体积配比为3∶1)的混合液中，其中冰醋酸起稳定剂的作用，混合搅拌2h，制备获得前驱体溶液B2；将前驱体溶液B1和前驱体溶液B2按照化学计量比混合搅拌并静置 2 天左右，制备出3号前驱体溶液；将3号前驱体溶液涂布到p型钙钛矿型氧化物薄膜Er：Li0.1K0.4Bi0.5TiO3上，干燥后退火形成BaNbxTi1-xO3薄膜。
BaNbxTi1-xO3薄膜的形成方法为：设定匀胶机参数，控制转速为600rpm甩胶10秒，然后在3000rpm转速下甩胶30秒；甩胶结束后将带有3号前驱体湿膜的基板在热板上先200℃烘干3分钟，然后在350℃煅烧5分钟；然后重复上述甩胶和热处理过程，直到所需的膜厚达到300-1200nm，最后通过快速退火炉在600-1000℃下烧结5-30分钟，优选850℃，最后形成BaNbxTi1-xO3薄膜。
（4）步骤104：制备上电极
在n型钙钛矿型BaNbxTi1-xO3薄膜上制备La0.8Sr0.2MnO3薄膜作为上电极，La0.8Sr0.2MnO3薄膜的制备方法为：按照化学计量比将硝酸镧La(NO3)3·6H2O，硝酸锶Sr(NO3)2和硝酸锰 Mn(NO3)2溶于去离子水中搅拌均匀，将其配成金属离子总浓度为 0.5mol/L 的溶液；然后将柠檬酸和乙二胺四乙酸（EDTA）用作络合剂加入到上述混合溶液中，使得溶液中的金属离子总浓度：柠檬酸浓度：EDTA 浓度为 1:1.5:1；通过滴加浓氨水将混合溶液的 pH 值调节到 8 后，将其转移至 80℃恒温水浴磁力搅拌器中加热搅拌 24 h，确保络合剂与金属阳离子充分络合，得到4号前驱体溶液；将上述4号前驱体溶液均匀涂覆于n型钙钛矿型氧化物薄膜BaNbxTi1-xO3上，涂覆后将其在烘箱中250℃条件下干燥5min，再经600℃预烧 10min，最后在600℃-700℃煅烧10分钟，随炉冷却形成厚度为100-600nm的La0.8Sr0.2MnO3薄膜。
Claims (10)
1.一种具有钙钛矿结构的异质结薄膜光电器件，其特征在于：包括基板，以及依次层叠在基板上的下电极、p型钙钛矿型氧化物薄膜、n型钙钛矿型氧化物薄膜和上电极；其中，p型钙钛矿型氧化物薄膜为Er：Li0.1K0.4Bi0.5TiO3，掺杂的Er与Li0.1K0.4Bi0.5TiO3的摩尔比为0.005-0.2；n型钙钛矿型氧化物薄膜为BaNbxTi1-xO3，x的取值范围为0.05-0.1。
2.如权利要求1所述的一种具有钙钛矿结构的异质结薄膜光电器件，其特征在于：所述下电极和上电极均为钙钛矿型透明导电氧化物。
3.如权利要求1所述的一种具有钙钛矿结构的异质结薄膜光电器件，其特征在于：所述上电极为LaNiO3、LaCrO3、SrRuO3、CaRuO3、La1-xSrxCoO3、La1-xSrxMnO3、La1-xSrxCrO3、BaPbO3、La1-xSrxTiO3、SrIrO3中的至少一种，其中，0<x<1。
4.如权利要求1所述的一种具有钙钛矿结构的异质结薄膜光电器件，其特征在于：所述下电极为La:SrTiO3薄膜。
5.如权利要求1所述的一种具有钙钛矿结构的异质结薄膜光电器件，其特征在于：所述基板为玻璃、石英或硅片。
6.如权利要求1所述的一种具有钙钛矿结构的异质结薄膜光电器件的制备方法，其特征在于，包括如下步骤：
（1）、分别采用丙酮溶液、氢氟酸清洗基板表面，再用无水乙醇和去离子水将基板表面冲洗干净，然后烘干，烘干后采用硅烷偶联剂修饰基板表面，以增强后续形成的薄膜与基板表面的附着力；
（2）、在处理过的基板上从下到上依次制备下电极、p型钙钛矿型氧化物薄膜Er：Li0.1K0.4Bi0.5TiO3、n型钙钛矿型氧化物薄膜BaNbxTi1-xO3和上电极。
7.如权利要求6所述的一种具有钙钛矿结构的异质结薄膜光电器件的制备方法，其特征在于：所述下电极为La:SrTiO3薄膜，其制备方法为：
将醋酸锶、硝酸镧溶于醋酸溶液中形成盐溶液，在 120℃下搅拌 2h；将钛酸四丁酯溶解在乙酰丙酮中，在 80℃搅拌 1h 使其混合均匀，然后将其加入上述盐溶液中，并加入稳定剂乙二醇和溶剂乙二醇甲醚，配制成澄清的1号前驱体溶液；将上述1号前驱体溶液均匀涂覆在基板上，在管式电炉中退火形成La:SrTiO3 薄膜。
8.如权利要求6所述的一种具有钙钛矿结构的异质结薄膜光电器件的制备方法，其特征在于：所述p型钙钛矿型氧化物薄膜Er：Li0.1K0.4Bi0.5TiO3的制备方法为：
将硝酸铋、醋酸钾、硝酸锂和醋酸铒按化学计量比溶解于醋酸中，加入乙二醇作为溶剂，然后加入柠檬酸，形成前驱体溶液A1；将钛酸四丁酯溶解于乙二醇中，然后加入柠檬酸，形成前驱体溶液A2；将前驱体溶液A1与前驱体溶液A2按照化学计量比进行混合，室温下搅拌均匀，从而生成2号前驱体溶液；将2号前驱体溶液涂布到下电极上，干燥后退火形成掺杂有铒的Li0.1K0.4Bi0.5TiO3薄膜。
9.如权利要求6所述的一种具有钙钛矿结构的异质结薄膜光电器件的制备方法，其特征在于：所述n型钙钛矿型氧化物薄膜BaNbxTi1-xO3的制备方法为：
将氯化铌和氢氧化钾加入乙二醇甲醚中，在氩气的保护下进行反应，过滤掉反应生成的KCl沉淀，制备得到铌的醇盐；将所得铌的醇盐与钛酸四丁酯、有机溶剂乙二醇甲醚混合，并加入乙酰丙酮作为鳌合剂，配制成前驱体溶液B1；将过量10%的硝酸钡溶于乙二醇甲醚与冰醋酸的混合液中，混合搅拌均匀，配制成前驱体溶液B2；将前驱体溶液B1和前驱体溶液B2混合均匀并静置2天，从而制备出3号前驱体溶液；将3号前驱体溶液涂布到p型钙钛矿型氧化物薄膜Er：Li0.1K0.4Bi0.5TiO3上，干燥后退火形成BaNbxTi1-xO3薄膜。
10.如权利要求6所述的一种具有钙钛矿结构的异质结薄膜光电器件的制备方法，其特征在于：所述上电极为La0.8Sr0.2MnO3薄膜，其制备方法为：将硝酸镧、硝酸锶和硝酸锰按照化学计量比溶于去离子水中，然后加入柠檬酸和乙二胺四乙酸，加热搅拌，充分络合反应后，得到4号前驱体溶液；将上述4号前驱体溶液均匀涂覆于n型钙钛矿型氧化物薄膜BaNbxTi1-xO3上，干燥后退火形成La0.8Sr0.2MnO3薄膜。
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