CN114497426A - 一种提高钙钛矿发光二极管亮度的方法及钙钛矿发光二极管 - Google Patents
一种提高钙钛矿发光二极管亮度的方法及钙钛矿发光二极管 Download PDFInfo
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Abstract
本发明公开了一种提高钙钛矿发光二极管亮度的方法及钙钛矿发光二极管,以季膦盐为钙钛矿前驱体溶液中的一种组分,在退火过程中,季膦盐分子的亲水基团(P+)与钙钛矿晶粒表面的BX3 ‑负离子产生静电吸附作用,改变了钙钛矿晶粒生长择优取向,同时外侧的芳香环或脂肪链基团具有大的空间位阻,抑制了晶粒间的团聚,形成低缺陷的纳米晶。提升了薄膜电荷输运能力,实现钙钛矿器件高亮度发光。
Description
技术领域
本发明涉及钙钛矿发光二极管技术领域,具体涉及一种提高钙钛矿发光二极管亮度的方法及钙钛矿发光二极管。
背景技术
卤化物钙钛矿材料拥有良好的半导体特性和卓越的光电特性,在显示与照明领域具有很大的应用潜力。目前尽管通过器件优化,钙钛矿发光二极管(PeLED)的外量子效率((EQE)已经超过20%,但亮度仍然在103cd/m2的数量级范围内,远低于高亮度显示和照明应用的阈值,成为制约PeLED在高亮显示和照明领域应用的关键技术瓶颈,因此提升钙钛矿发光器件亮度性能刻不容缓。
发明内容
本发明所要解决的技术问题是针对现有技术的不足提供一种提高钙钛矿发光二极管亮度的方法及钙钛矿发光二极管。
本发明的技术方案如下:
一种提高钙钛矿发光二极管亮度的方法,钙钛矿ABX3前驱体溶液由AX、BX2、季膦盐以一定比例在溶剂中配成不同的浓度;在退火过程中,季膦盐分子的亲水基团(P+)与钙钛矿晶粒表面的BX3 -负离子产生静电吸附作用,改变了钙钛矿晶粒生长择优取向,同时外侧的芳香环或脂肪链基团具有大的空间位阻,抑制了晶粒间的团聚;最终形成低缺陷的纳米晶,提升器件电流注入,实现器件高亮度发光。
所述的方法,所述季膦盐由季膦阳离子和卤素离子构成,季膦阳离子的中心原子是膦离子P+,膦的四个未占据轨道被脂肪族官能团或芳香族官能团所占据;所述脂肪族官能团包含直链基团、脂环烃基团(-CnH2n-1);直链基团包括烷基(-CnH2n+1)、烯基(-CnH2n-1)、炔基(-CnH2n-2);所述芳香族官能团包含苯环、萘环、蒽环、咪唑环、苯并咪唑环、吡啶环、喹啉环、吲哚环以及其他稠环、五元杂环、六元杂环;卤素离子包括Cl,Br,I中的任意一种或几种。
所述的方法,所述钙钛矿为ABX3结构,其中:
A为阳离子基团,阳离子基团为Cs+、MA+、和FA+中的任意一种或两种,B为金属阳离子,包括Pb2+,Sn2+,Cu+,Cu2+,Mn2+,Eu2+,Ni2+,Co2+中的任意一种,X为卤素阴离子;AX:BX2:季膦盐摩尔比例为1~100:1~100:1~100。
所述的方法,选用的季膦盐需全部溶解于前驱体溶液中,且分子结构具有较大空间位阻,能够促进原料AX、BX2溶解。
所述的方法,所述的季膦盐结构包含芳香族官能团:苯环、萘环、蒽环、咪唑环、苯并咪唑环、吡啶环、喹啉环或吲哚环。
所述的方法,所述的季膦盐结构包含脂肪族官能团:烷基(-CnH2n+1),烯基(-CnH2n-1)和炔基(-CnH2n-2)。
所述的方法,所述的季膦盐为四苯基溴化膦(TPPB)、四苯基氯化膦(TPPCl)、四丁基溴化膦(TBPB)或四苯基碘化膦(TPPI)。
所述的方法,所述AX、BX2为CsBr、PbBr2。
所述的方法,所述钙钛矿薄膜是在玻璃、柔性基片和金属薄片中任意一种衬底上分布而成。
根据任一所述方法制备的钙钛矿发光二极管,EQE达到7.8%。器件亮度达到160,000cd/m2。
采用上述方案,本发明通过利用季膦盐分子的亲水基团(P+)与钙钛矿晶粒表面的BX3 -负离子产生静电吸附作用,改变了钙钛矿晶粒生长择优取向,同时外侧的芳香环或脂肪链基团具有大的空间位阻,抑制了晶粒间的团聚;最终形成低缺陷的纳米晶,提升器件电流注入,实现器件高亮度发光。
附图说明
图1是本发明实施例1的钙钛矿发光器件的结构示意图;
图2为本发明实施例1的钙钛矿薄膜形貌SEM图;
图3为本发明实施例1的钙钛矿薄膜光致发光光谱图;
图4为本发明实施例1的钙钛矿薄膜在不同激光强度下的荧光量子产率;
图5为本发明实施例1的器件电压-电流密度曲线图;
图6为本发明实施例1的器件的外量子效率-电流密度曲线图
图7为本发明实施例1的器件亮度-电流密度曲线图;
图8为本发明实施例2的器件亮度-电流密度曲线图;
图9为本发明实施例2的器件的外量子效率-电流密度曲线图;
图10为本发明实施例3的器件亮度-电流密度曲线图;
图11为本发明实施例3的器件的外量子效率-电流密度曲线图;
图12为本发明实施例4的器件亮度-电流密度曲线图;
图13为本发明实施例4的器件的外量子效率-电流密度曲线图;
图14为本发明实施例1、4、5、6的钙钛矿薄膜电致发光光谱图;
图15为本发明实施例5的器件的亮度-电流密度曲线图;
图16为本发明实施例5的器件的外量子效率-电流密度曲线图;
图17为本发明实施例6的器件的亮度-电流密度曲线图;
图18为本发明实施例6的器件的外量子效率-电流密度曲线图;
具体实施方式
以下结合具体实施例,对本发明进行详细说明。
溶液配制方法:
钙钛矿ABX3前驱体溶液由AX,BX2,季膦盐以一定比例在溶剂中配成不同的浓度。其中A为阳离子基团(包括甲脒阳离子、甲胺阳离子、Cs+),B为第四主族金属(Pb2+,Sn2+)或过渡金属离子(Cu2+,Ni2+,Co2+,Fe2+,Mn2+,Eu2+),X为卤族元素(Cl,Br,I)。其中AX:BX2:季膦盐比例为1~100:1~100:1~100,溶剂是指二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、γ-丁内酯中的任意一种。其中浓度是指溶质(钙钛矿ABX3和季膦盐)占溶质与溶剂总质量的百分比,为0.1%~99.9%。
器件制备方法如下:
钙钛矿发光器件结构如图1所示,包括阴极层透明导电衬底,衬底上依次设有空穴传输-电子阻挡层、钙钛矿发光层、电子传输-空穴阻挡层、电极修饰层、铝电极。
①衬底为氧化铟锡(ITO)导电玻璃,ITO膜的方块电阻为15Ω/□,膜厚为20-200nm。分别利用丙酮溶液、乙醇溶液对透明导电衬底ITO玻璃进行超声清洗两次,处理后用干燥氮气吹干,将ITO转移至氧等离子清洗机内,在真空条件下对其进行氧等离子清洗。
②空穴传输层的制备,将购买的PEDOT:PSS(Al4083)溶液用水溶性的过滤头过滤之后,通过旋涂的方式涂覆于处理过的ITO导电玻璃上,150℃退火15min后形成一层致密的PEDOT:PSS薄膜。
③钙钛矿层的制备,在氮气手套箱中,取钙钛矿前驱体溶液采用一步旋涂法,转速为4000rpm,时间为45s,得到的钙钛矿薄膜在加热板上100℃退火25min,冷却至室温。
④电子传输层的制备,将上述制备好的钙钛矿薄膜转移到真空蒸发室中进行电子传输层TmPyPB的制备,气压为6×10-7Torr,蒸发速率控制在0.02~0.05nm/s,厚度为30~50nm,蒸镀速率及厚度由膜厚仪监控。
⑤电极修饰层、电极的制备,在真空蒸发室中,继续制备电极修饰层(LiF)和电极(Al)。在蒸镀电极修饰层时,蒸发速率控制在0.01nm/s以下,厚度为1.2nm,电极的蒸发速率保持在0.1nm/s,厚度为100nm。
测试器件的电流-电压-辐射强度等特性,同时测试器件的发光光谱参数。
实施例1
钙钛矿CsPbBr3前驱体溶液由CsBr和PbBr2和四苯基溴化膦(TPPB)以摩尔比为1.8:1:0.1,质量分数为7wt%溶于溶剂二甲基亚砜(DMSO)。常温下搅拌12h,得到澄清透明的无色钙钛矿前驱体溶液。整个器件结构描述为:玻璃衬底/ITO/PEDOT:PASS/CsPbBr3/TmPyPB/LiF/Al。参照上述器件制备方法,分别制备得到不含和含有TPPB的PeLED器件,在手套箱中进行器件性能测试。
图2a为钙钛矿薄膜形貌图,图2b为截面图,季膦盐的作用下钙钛矿形成高质量纳米晶粒。图3是钙钛矿薄膜的荧光光谱图,可以看出,季膦盐的作用下薄膜的荧光强度显著提升。图4是光强依赖下的荧光量子效率(PLQE)图,掺杂季膦盐的钙钛矿的PLQE得到明显的提高,说明缺陷降低。图5为钙钛矿器件电压-电流关系曲线图,显示纳米晶钙钛矿器件在启亮前漏电流降低了一个数量级,启亮电压减小0.4V,启亮后器件电流更好的注入。图6为钙钛矿器件外量子效率(EQE)-电流密度的关系曲线图。显示纳米晶钙钛矿器件EQE达到7.8%。器件亮度从1500cd/m2提高到160,000cd/m2(图7)。
实施例2
本实施例与实施例1不同的是前驱体溶液组分CsBr和PbBr2和四苯基溴化膦(TPPB)摩尔比为2:1:0.2,器件制备方法参照实施例1。
如图8所示,CsPbBr3发光器件的亮度达到159,000cd/m2,器件亮度与实施例1器件性能基本不变,而且器件的外量子效率8.5%(图9)。
实施例3
本实施例与实施例1不同的是前驱体溶液组分CsBr和PbBr2和四苯基溴化膦(TPPB)摩尔比为1.5:1:0.3,器件制备方法参照实施例1。
如图10所示,CsPbBr3发光器件的亮度达到125,000cd/m2,亮度略有下降,外量子效率达到7.9%(图11)。
实施例4
本实施例与实施例1不同的是采用四苯基氯化膦(TPPCl)作为添加剂,器件制备方法参照实施例1。
如图12所示,虽然TPPCl-CsPbBr3的器件的亮度达到60,000cd/m2,而且器件的外量子效率6%(图13)。器件的驱动电压基本不变。另外,TPPCl-CsPbBr3器件的电致发光光谱与TPPCl-CsPbBr3器件相一致(图14,520nm)。
实施例5
本实施例与实施例1不同的是采用四丁基溴化膦(TBPB)作为添加剂,器件制备方法参照实施例1。
如图15,虽然TBPB-CsPbBr3的器件的亮度相比于实施例1有所下降,但器件亮度也可以达到27000cd/m2,器件的外量子效率3.6%(图16)。器件的驱动电压基本不变。另外,TBPB-CsPbBr3器件的电致发光光谱与TBPB-CsPbBr3器件相一致(图14,520nm)。
实施例6
本实施例与实施例1不同的是采用四苯基碘化膦(TPPI)作为添加剂,器件制备方法参照实施例1。
如图17所示,虽然TPPI-CsPbBr3的器件的亮度相比于实施例1有所下降,但是其未优化的器件亮度也可以达到58000cd/m2,而且器件的驱动电压基本不变,器件的外量子效率4.6%(图18)。另外TPPI-CsPbBr3器件的电致发光光谱与TBPB-CsPbBr3器件相一致(图14,520nm)。
应当理解的是,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,而所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (10)
1.一种提高钙钛矿发光二极管亮度的方法,其特征在于,钙钛矿ABX3前驱体溶液由AX、BX2、季膦盐以一定比例在溶剂中配成不同的浓度;在退火过程中,季膦盐分子的亲水基团P+与钙钛矿晶粒表面的BX3 -负离子产生静电吸附作用,改变了钙钛矿晶粒生长择优取向,同时外侧的芳香环或脂肪链基团具有大的空间位阻,抑制了晶粒间的团聚;最终形成低缺陷的纳米晶,提升器件电流注入,实现器件高亮度发光。
2.根据权利要求1所述的方法,其特征在于,所述季膦盐由季膦阳离子和卤素离子构成,季膦阳离子的中心原子是膦离子P+,膦的四个未占据轨道被脂肪族官能团或芳香族官能团所占据;所述脂肪族官能团包含直链基团、脂环烃基团(-CnH2n-1);直链基团包括烷基(-CnH2n+1)、烯基(-CnH2n-1)、炔基(-CnH2n-2);所述芳香族官能团包含苯环、萘环、蒽环、咪唑环、苯并咪唑环、吡啶环、喹啉环、吲哚环以及其他稠环、五元杂环、六元杂环;卤素离子包括Cl,Br,I中的任意一种或几种。
3.根据权利要求1所述的方法,其特征在于,所述钙钛矿为ABX3结构,其中:
A为阳离子基团,阳离子基团为Cs+、MA+、和FA+中的任意一种或两种,B为金属阳离子,包括Pb2+,Sn2+,Cu+,Cu2+,Mn2+,Eu2+,Ni2+,Co2+中的任意一种,X为卤素阴离子;AX:BX2:季膦盐摩尔比例为1~100:1~100:1~100。
4.根据权利要求1所述的方法,其特征在于,选用的季膦盐需全溶解于前驱体溶液中,且分子结构具有较大空间位阻,能够促进原料AX、BX2溶解。
5.根据权利要求1所述的方法,其特征在于,所述的季膦盐结构包含芳香族官能团:苯环、萘环、蒽环、咪唑环、苯并咪唑环、吡啶环、喹啉环或吲哚环。
6.根据权利要求1所述的方法,其特征在于,所述的季膦盐结构包含脂肪族官能团:烷基(-CnH2n+1),烯基(-CnH2n-1)和炔基(-CnH2n-2)。
7.根据权利要求1所述的方法,其特征在于,所述的季膦盐为四苯基溴化膦(TPPB)、四苯基氯化膦(TPPCl)、四丁基溴化膦(TBPB)或四苯基碘化膦(TPPI)。
8.根据权利要求7所述的方法,其特征在于,所述AX、BX2为CsBr、PbBr2。
9.根据权利要求1所述的方法,其特征在于,所述钙钛矿薄膜是在玻璃、柔性基片和金属薄片中任意一种衬底上分布而成。
10.根据权利要求1-9任一所述方法制备的钙钛矿发光二极管。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4380335A1 (en) * | 2022-11-30 | 2024-06-05 | CSEM Centre Suisse d'Electronique et de Microtechnique SA - Recherche et Développement | Method of manufacturing a perovskite photovoltaic cell |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060255722A1 (en) * | 2005-05-16 | 2006-11-16 | Yasuo Imanishi | Organic electroluminescence device and organic electroluminescence system |
US20070085470A1 (en) * | 2003-10-30 | 2007-04-19 | Japan Science and Technology Agency, Kawaguchi-shi | Electroluminescent material and electroluminescent element using the same |
CN101636796A (zh) * | 2007-03-19 | 2010-01-27 | 旭硝子株式会社 | 导电体的制造方法 |
CN105237745A (zh) * | 2015-10-13 | 2016-01-13 | 华南理工大学 | 含季膦盐基团共轭聚电解质及其在有机光电器件中的应用 |
US20160254472A1 (en) * | 2015-02-26 | 2016-09-01 | Nanyang Technological University | Perovskite thin films having large crystalline grains |
CN108305937A (zh) * | 2017-01-11 | 2018-07-20 | 南京工业大学 | 一种三维钙钛矿薄膜纳米尺度晶粒的调控方法及其应用和器件 |
CN108630831A (zh) * | 2017-03-23 | 2018-10-09 | 南京工业大学 | 一种提高钙钛矿发光器件寿命的方法及钙钛矿发光器件 |
CN109980095A (zh) * | 2017-12-27 | 2019-07-05 | 南京工业大学 | 一种有效提升发光器件效率的钙钛矿膜层、器件和制备方法 |
-
2020
- 2020-10-28 CN CN202011172056.7A patent/CN114497426A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070085470A1 (en) * | 2003-10-30 | 2007-04-19 | Japan Science and Technology Agency, Kawaguchi-shi | Electroluminescent material and electroluminescent element using the same |
US20060255722A1 (en) * | 2005-05-16 | 2006-11-16 | Yasuo Imanishi | Organic electroluminescence device and organic electroluminescence system |
CN101636796A (zh) * | 2007-03-19 | 2010-01-27 | 旭硝子株式会社 | 导电体的制造方法 |
US20160254472A1 (en) * | 2015-02-26 | 2016-09-01 | Nanyang Technological University | Perovskite thin films having large crystalline grains |
CN105237745A (zh) * | 2015-10-13 | 2016-01-13 | 华南理工大学 | 含季膦盐基团共轭聚电解质及其在有机光电器件中的应用 |
CN108305937A (zh) * | 2017-01-11 | 2018-07-20 | 南京工业大学 | 一种三维钙钛矿薄膜纳米尺度晶粒的调控方法及其应用和器件 |
CN108630831A (zh) * | 2017-03-23 | 2018-10-09 | 南京工业大学 | 一种提高钙钛矿发光器件寿命的方法及钙钛矿发光器件 |
CN109980095A (zh) * | 2017-12-27 | 2019-07-05 | 南京工业大学 | 一种有效提升发光器件效率的钙钛矿膜层、器件和制备方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4380335A1 (en) * | 2022-11-30 | 2024-06-05 | CSEM Centre Suisse d'Electronique et de Microtechnique SA - Recherche et Développement | Method of manufacturing a perovskite photovoltaic cell |
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