CN105914243A - 一种具有铁电性能的薄膜光电器件及其制备方法 - Google Patents
一种具有铁电性能的薄膜光电器件及其制备方法 Download PDFInfo
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- H01L31/02—Details
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Abstract
一种具有铁电性能的薄膜光电器件,涉及一种光电器件,包括基板,以及从下到上依次层叠在基板上的下电极Er:SrTiO3、具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜和上电极La0.8Sr0.2MnO3。本发明光电器件的各薄膜层是采用溶胶凝胶法制备相应的前驱体溶液,涂覆后,经烘干、退火工序制成的。本发明提供了一种新的具有铁电性能的光电器件,其能够提高铁电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,具体涉及一种具有铁电性能的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。
目前,用作铁电薄膜器件底电极的材料主要为金属铂,虽然其具有较好的导电性,可是铁电薄膜在铂上的粘附性和抗疲劳性都较差,而且铂电极的制备成本较高,因此需要寻找一种能够增大铁电材料光电转换效率的电极材料。
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。
因此,迄今为止,仍然需要寻找一种合适的铁电薄膜和合适的电极材料来制备光电器件。本发明致力于制备一种新型铁电光电器件,通过对电极材料和铁电材料的研究,以获得光电效率得到提升的光电器件,到目前,尚没有人采用稀土掺杂的SrTiO3作为铁电薄膜的电极材料。
发明内容
本发明的目的是提供一种具有铁电性能的薄膜光电器件及其制备方法,通过制备具有铁电性能的钙钛矿型薄膜以及电极材料,能够实现对光线进行上转换,以提高光生电流,进而提高光电转换效率。
为实现上述发明目的,本发明的技术方案是:一种具有铁电性能的薄膜光电器件,包括基板,以及从下到上依次层叠在基板上的下电极Er:SrTiO3、具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜和上电极La0.8Sr0.2MnO3。
进一步地,所述下电极Er:SrTiO3的厚度为20-600nm,具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜的厚度为300nm-1000nm。
所述具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜的晶粒尺寸为40nm-200nm。
所述基板为玻璃、石英或蓝宝石。
上述的一种具有铁电性能的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Er:SrTiO3、具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜和上电极La0.8Sr0.2MnO3。
所述下电极Er:SrTiO3薄膜的制备方法为:将醋酸锶、醋酸铒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℃下搅拌 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掺杂有铒的SrTiO3 薄膜。
所述具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜的制备方法为:将硝酸铋、醋酸钾和硝酸锂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A;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B;将前驱体溶液A与前驱体溶液B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Li0.1K0.4Bi0.5TiO3薄膜。
所述上电极La0.8Sr0.2MnO3薄膜的制备方法为: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3号前驱体溶液;将上述3号前驱体溶液均匀涂覆于Li0.1K0.4Bi0.5TiO3薄膜上,干燥后退火形成La0.8Sr0.2MnO3薄膜。
本发明与现有技术相比,具有以下有益效果:
1、采用La0.8Sr0.2MnO3作为上电极,较通常使用的Au电极具有较大的介电常数,能够对电荷分布的屏蔽效应较弱,从而增加光生电流。
2、下电极Er:SrTiO3为透明导电氧化物,能够对可见光实现高透,采用掺杂有稀土元素的钙钛矿型导电氧化物Er:SrTiO3作为下电极,不仅能够增强SrTiO3的导电性,而且能够对不被具有铁电性能的钙钛矿型薄膜吸收的光实现上转换,转换为能够被吸收的波段的光,从而提高光生电流,进而提高铁电光电器件的光电转换效率。
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、采用的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光电器件,制备方法简单,成本低,容易操控。
附图说明
图1为本发明的光电器件的结构示意图;
图中标记为:1、基板,2、下电极Er:SrTiO3,3、Li0.1K0.4Bi0.5TiO3薄膜, 4、上电极La0.8Sr0.2MnO3。
具体实施方式
如图1所示,一种具有铁电性能的薄膜光电器件,包括基板,以及从下到上依次层叠在基板上的下电极Er:SrTiO3、具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜和上电极La0.8Sr0.2MnO3。
本发明中,下电极Er:SrTiO3的厚度为20-600nm。
具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜的厚度为300nm-1000nm,优选为600nm。Li0.1K0.4Bi0.5TiO3薄膜的晶粒尺寸为40nm-200nm,优选为60nm。该钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜在上述优选膜厚和优选晶粒尺寸下,能够确保光生电流最大化。光生电流随着膜厚减小而指数性增大,但是厚度太小,又会因为小尺寸效应导致光生电流下降,因此,薄膜具有一个优选厚度。同时,光生电流不是随着晶粒尺寸的减小而增大,而是在临界晶粒尺寸处光生电流最大,因此,优选的晶粒尺寸为薄膜的临界尺寸。
上述具有铁电性能的薄膜光电器件的制备方法,其包括如下步骤:
(1)、基板处理
基板可为玻璃、石英或蓝宝石,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)、制备下电极Er:SrTiO3
在处理过的基板上制备掺杂有稀土元素Er的SrTiO3薄膜作为下电极。下电极Er:SrTiO3薄膜的制备方法为:利用磁力搅拌器将一定化学计量比的醋酸锶、醋酸铒溶于醋酸溶液中形成盐溶液,在 120℃下搅拌 2h;同时称取一定量的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,并加入乙二醇作为稳定剂,乙二醇甲醚为溶剂,其中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,从而制成澄清的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Er:SrTiO3薄膜。
Er:SrTiO3薄膜的涂覆及成膜方法为: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 30 s;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预处理过程数次,达到所需的膜厚20~600nm,最后升温到 600 ℃,保温 30min,使有机物完全蒸发,然后于 750 ℃下退火10-60分钟,最后生长成晶态的 Er: SrTiO3 薄膜。其中,Er的掺杂量为:Er占Sr和Er总摩尔量的0.5mol%-10mol%,Sr和Er的总摩尔量即为醋酸锶和醋酸铒两者摩尔量的总和。
(3)、制备具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜
在下电极上制备Li0.1K0.4Bi0.5TiO3薄膜,该薄膜具有铁电性能;Li0.1K0.4Bi0.5TiO3薄膜的制备方法包括以下步骤:
①、采用化学计量比为5:4:1的硝酸铋Bi(NO3)3、醋酸钾KOOCCH3 和硝酸锂LiNO3溶解于醋酸中,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A;
②、将钛酸四丁酯C16H36O4Ti溶解于乙二醇中,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B,将前驱体溶液A与前驱体溶液B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;
③、利用甩胶机将2号前驱体溶液涂布到下电极上,控制转速为1000rpm甩胶10秒,然后在3000~4000rpm转速下甩胶30秒;甩胶结束后将带有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加热预处理过程,直到达到所需的膜厚300nm-1000nm;最后在氢气气氛下通过快速退火炉烧结5分钟,通过控制退火过程的升温速率和降温速率使Li0.1K0.4Bi0.5TiO3薄膜的晶粒尺寸为40nm-200nm,其中退火温度600~800℃,最后降温形成Li0.1K0.4Bi0.5TiO3薄膜。
(4)、制备上电极
在钙钛矿型Li0.1K0.4Bi0.5TiO3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,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 的混合溶液;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3号前驱体溶液;将上述3号前驱体溶液均匀涂覆于Li0.1K0.4Bi0.5TiO3薄膜上,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700℃煅烧10-60分钟,最后随炉冷却形成厚度为100-600
nm的La0.8Sr0.2MnO3薄膜。其中,涂覆方式可以为喷墨打印,丝网印刷等常用的薄膜涂覆方法。
Claims (8)
1.一种具有铁电性能的薄膜光电器件,其特征在于:包括基板,以及从下到上依次层叠在基板上的下电极Er:SrTiO3、具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜和上电极La0.8Sr0.2MnO3。
2.如权利要求1所述的一种具有铁电性能的薄膜光电器件,其特征在于:所述下电极Er:SrTiO3的厚度为20-600nm,具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜的厚度为300nm-1000nm。
3.如权利要求1所述的一种具有铁电性能的薄膜光电器件,其特征在于:所述具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜的晶粒尺寸为40nm-200nm。
4.如权利要求1所述的一种具有铁电性能的薄膜光电器件,其特征在于:所述基板为玻璃、石英或蓝宝石。
5.如权利要求1所述的一种具有铁电性能的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Er:SrTiO3、具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜和上电极La0.8Sr0.2MnO3。
6.如权利要求5所述的一种具有铁电性能的薄膜光电器件的制备方法,其特征在于,所述下电极Er:SrTiO3薄膜的制备方法为:将醋酸锶、醋酸铒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℃下搅拌 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掺杂有铒的SrTiO3 薄膜。
7.如权利要求5所述的一种具有铁电性能的薄膜光电器件的制备方法,其特征在于,所述具有铁电性能的钙钛矿型Li0.1K0.4Bi0.5TiO3薄膜的制备方法为:将硝酸铋、醋酸钾和硝酸锂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A;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B;将前驱体溶液A与前驱体溶液B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Li0.1K0.4Bi0.5TiO3薄膜。
8.如权利要求5所述的一种具有铁电性能的薄膜光电器件的制备方法,其特征在于,所述上电极La0.8Sr0.2MnO3薄膜的制备方法为: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3号前驱体溶液;将上述3号前驱体溶液均匀涂覆于Li0.1K0.4Bi0.5TiO3薄膜上,干燥后退火形成La0.8Sr0.2MnO3薄膜。
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