CN114975837A - 一种烷基胺改性pedot:pss及基于其的钙钛矿发光二极管制备方法 - Google Patents
一种烷基胺改性pedot:pss及基于其的钙钛矿发光二极管制备方法 Download PDFInfo
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Abstract
本发明公开了一种改性PEDOT:PSS，通过采用不同链长烷基胺对空穴传输层材料PEDOT:PSS进行改性，烷基胺可以中和PEDOT:PSS中的质子，降低空穴传输层的酸性。烷基胺改性PEDOT:PSS之后，能够形成疏水层并提高其疏水性，阻碍了空穴传输层与钙钛矿发光层之间的离子迁移，所制备的钙钛矿发光二极管的工作寿命随着烷基链长的增加而增加。相比于对照器件，基于辛胺改性PEDOT:PSS的钙钛矿发光二极管，其亮度提升了2.4倍，工作稳定性提高7.1倍。本发明中的改性方法成本低廉，操作简单，效果显著并且重复性高，可适用于旋涂、刮涂、印刷以及喷墨打印等多种现行制备工艺。
Description
技术领域
本发明涉及PEDOT:PSS，尤其涉及改性PEDOT:PSS及其制备方法，和利用该改性PEDOT:PSS制备钙钛矿发光二极管。
背景技术
金属卤化物钙钛矿(Perovskite)材料由于其优异的光电性能，成为继有机半导体材料之后的下一代电致发光材料。自2014年首次在室温下报到钙钛矿发光二极管以来，在效率方面已经取得了巨大的进展，在显示和照明领域展示出很好的应用前景。但是相比之下，钙钛矿发光二极管的工作稳定性是限制其商业应用的一个严重障碍。因此如何提升钙钛矿发光二极管的工作稳定性成为科学界的重要问题，主要通过组分优化、缺陷钝化、界面改性等手段进行。
钙钛矿发光二极管通常采用氧化铟锡(ITO)/空穴传输层/钙钛矿发光层/电子传输层/氟化锂/铝电极结构。PEDOT:PSS由于其具有高透明度、低折射率、导电性可调、热稳定性好等优点，是高性能钙钛矿发光二极管常用的空穴传输层材料。然而，PEDOT:PSS中存在苯磺酸而显酸性，其中的质子会在电场偏压下迁移，破坏钙钛矿发光层，影响器件的稳定性。
发明内容
本发明所要解决的技术问题是：发光二极管的工作稳定性较低，本发明提供了解决上述问题的一种改性空穴传输层PEDOT:PSS及基于其的绿光发光二极管。
本发明通过下述技术方案实现：
改性PEDOT:PSS钙钛矿发光二极管，包括改性PEDOT:PSS和钙钛矿前驱体；
所述改性PEDOT:PSS用于钙钛矿发光二极管中，采用包括PEDOT:PSS和不同链长烷基胺混合制成，所述改性PEDOT:PSS用于作为Cs0.8FA0.2PbBr3 DMSO溶液的旋转涂膜的依附物；
所述空穴传输层为薄膜结构。
进一步地，还包括阴/阳极，分别设置ITO和LiF/Al分别作为钙钛矿发光二极管的阳极和阴极。
进一步地，还包括TPBi和Cs0.8FA0.2PbBr3；
Cs0.8FA0.2PbBr3在钙钛矿发光二极管中用于发光，为钙钛矿二极管的发光层，TPBi用于传输电子。
改性PEDOT:PSS钙钛矿发光二极管的制备方法，包括如下步骤：
步骤A，在室温下将不同链长的烷基胺分别加入到PEDOT:PSS溶液中形成混合溶液；
步骤B，将改性PEDOT:PSS采用涂覆方式制备成薄膜，所述薄膜为空穴传输层。
步骤C，在步骤B所述薄膜上旋涂钙钛矿制备成改性PEDOT:PSS钙钛矿发光二极管。
进一步地，包括如下详细步骤:
将ITO玻璃用去离子水、丙酮、异丙醇依次超声清洗10min，再用氧等离子体处理5min；
将PEDOT:PSS与不同链长烷基胺按1:200体积比共混配成改性PEDOT:PSS共混溶液，所述烷基胺为丙胺(C3)、丁胺(C4)、戊胺(C5)、己胺(C6)、庚胺(C7)、辛胺(C8)；
将改性PEDOT:PSS溶液以4000r.p.m的速度旋涂到ITO玻璃上，持续60s，然后再150℃下退火5min，形成改性空穴传输层；
将Cs0.8FA0.2PbBr3 DMSO溶液旋涂在上述制备成的薄膜上，得到ITO/空穴传输层/Cs0.8FA0.2PbBr3薄膜；
将上述得到的ITO/空穴传输层/Cs0.8FA0.2PbBr3薄膜传入真空系统，采用真空蒸镀工艺制备钙钛矿发光二极管。
本发明的优点和积极效果
(1)本发明的改性材料成本低廉，改性PEDOT:PSS的方法操作简单，改性前后不影响器件结构和制备工艺，并且重复性好；
(2)本发明所改性的PEDOT:PSS，能够适用于旋涂、刮涂、印刷以及喷墨打印技术工艺，适用于工业上制备大面积钙钛矿光电器件；
(3)本发明的改性材料不同链长烷基胺，能够中和PEDOT:PSS里面的质子，降低离子迁移和酸性，并能不同程度地钝化钙钛矿缺陷，平衡空穴和电子之间的注入。所制备的钙钛矿发光二极管的亮度和工作稳定性得到不同程度的提升。
附图说明
图1为PEDOT:PSS及所涉及的烷基胺的分子结构；
图2为掺杂不同链长烷基胺前后的傅里叶红外光谱变化(a)和PEDOT:PSS与烷基胺之间的相互作用示意图(b)；
图3为PEDOT:PSS与不同链长烷基胺改性PEDOT:PSS液滴在玻璃上的接触角测试；
图4为在PEDOT:PSS和改性PEDOT:PSS上制备的Cs0.8FA0.2PbBr3钙钛矿薄膜的扫描电子显微镜图；
图5为在PEDOT:PSS和改性PEDOT:PSS上制备的Cs0.8FA0.2PbBr3钙钛矿薄膜的原子力显微镜图；
图6为在PEDOT:PSS和改性PEDOT:PSS上制备的Cs0.8FA0.2PbBr3钙钛矿薄膜的XRD图(a)，紫外可见吸收光谱图(b)和光致发光光谱图(c)；
图7为原始和改性的PEDOT:PSS上钙钛矿发光层的缺陷密度图；
图8为原始和改性的PEDOT:PSS上制备的钙钛矿发光二极管的电压-电流密度图；
图9为原始和改性的PEDOT:PSS上制备的钙钛矿发光二极管的电压-亮度图；
图10为原始和改性的PEDOT:PSS上制备的钙钛矿发光二极管的电流密度-外量子效率图；
图11为基于原始PEDOT:PSS和改性PEDOT:PSS的纯空穴器件与纯电子器件的电流密度与电压关系图。
图12为原始和改性的PEDOT:PSS上制备的钙钛矿发光二极管的电致发光光谱图；
图13为原始和改性的PEDOT:PSS上制备的钙钛矿发光二极管在约1000cd/m-2下的初始发光亮度随时间衰减的曲线。
具体实施方式
为使发明的目的、技术方案和优点更加清楚明白，下面结合实施例和附图，对本发明作进一步的详细说明，本发明的示意性实施方式及其说明仅用于解释本发明，并不作为对本发明的限定。
实施例
本发明烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管的制备过程具体包括如下几个步骤：
1)ITO玻璃的清洗处理
首先将ITO玻璃用去离子水清洗干净，接着用丙酮和异丙醇依次超声10min，最后用烘箱烘干；
2)改性PEDOT:PSS的制备
首先将不同链长烷基胺丙胺、丁胺、戊胺、己胺、庚胺、辛胺分别按体积比1:200加入到PEDOT:PSS(Clevios P VP AI 4083)溶液配置成混合溶液。
3)空穴传输层的制备
将步骤1中清洗干净的ITO玻璃放于紫外臭氧清洗仪器灯下处理5min，然后将步骤2中制备的改性PEDOT:PSS溶液旋涂在ITO基底上，旋转速度为4000r.p.m，持续60s，然后在150℃干燥10min，待冷却到室温之后转移到手套箱。
4)发光层的制备
首先将0.10214g的溴化铯(CsBr)、0.01499g甲脒溴(FABr)和0.22g溴化铅(PbBr2)溶解在3ml的二甲基甲酰胺(DMSO)中，超声直至完全溶解，钙钛矿前驱体使用之前用0.45μm聚四氟乙烯(PTFE)过滤器过滤。将70μL的钙钛矿前驱体溶液滴在步骤3所制备的空穴层上，并以5000r.p.m的速度旋转涂覆60s。20s后，将200μL含有10mg/mL三苯基氧膦(TPPO)的氯仿溶液缓慢滴在钙钛矿基底上，然后80℃下干燥5min。然后放入真空蒸镀系统，抽至高真空(5～7*10-5Pa)。
5)电子传输层的制备
在步骤4的基片上以1A s-1的蒸镀速率真空蒸镀80nm的1,3,5-三(1-苯基-1H-苯并咪唑-2-苯-基)苯(TPBi)。
6)电子注入层和阴极层制备
在步骤5的基础上依次蒸镀1nm氟化锂(LiF)和100nm金属铝，氟化锂和金属铝的蒸镀速率分别为0.1A s-1和2A s-1，从而制备出改性PEDT:PSS钙钛矿发光二极管。
图1所示的是PEDOT:PSS及所涉及的烷基胺的分子结构示意图，依次包括PEDOT:PSS、丙胺、丁胺、戊胺、己胺、庚胺和辛胺。
图2a所示的是纯PEDOT:PSS以及本发明所涉及的不同链长烷基胺改性的PEDOT:PSS中羟基峰波数位置。改性PEDOT:PSS相比于纯PEDOT:PSS的羟基峰波数明显减小，可能是由于氨基与羟基之间形成了氢键，图2b展示了PEDOT:PSS与烷基胺之间的相互作用示意图。
图3所示的是纯PEDOT:PSS以及本发明所涉及的不同链长烷基胺改性的PEDOT:PSS在玻璃表面的接触角。改性PEDOT:PSS在玻璃表面的接触角随着烷基链长度的增加而增加，因为烷基链本质上是疏水链，随着烷基链的增加会使分子的对称性更好，形成低极性的表面，空穴传输层的亲水性逐渐减低，有利于增强器件的工作稳定性。
图4所示的是在纯PEDOT:PSS和本发明所涉及的改性PEDOT:PSS上钙钛矿薄膜的扫描电子显微镜图。与对照相比，基于C3改性的钙钛矿薄膜存在大量针孔，基于C4、C5、C6改性的钙钛矿薄膜具有相似的形貌，存在少量针孔，基于C7、C8制备的钙钛矿薄膜致密且存在少量针孔。
图5所示的是在纯PEDOT:PSS和本发明所涉及的改性PEDOT:PSS上钙钛矿薄膜的原子力显微镜图。基于纯PEDOT:PSS和本发明涉及的烷基胺改性的PEDOT:PSS上制备的钙钛矿薄膜都非常光滑均匀，具有1nm左右的粗糙度。因此，改性PEDOT:PSS不会影响钙钛矿薄膜的粗糙度。
图6a所示的是在纯PEDOT:PSS和本发明所涉及的改性PEDOT:PSS上钙钛矿薄膜的XRD图。所有钙钛矿薄膜均出现(100)和(200)晶面，改性PEDOT:PSS上制备的钙钛矿薄膜未出现衍射峰偏移，烷基胺改性PEDOT:PSS不会影响钙钛矿层的晶体取向和结构。图6b所示的是在PEDOT:PSS和改性PEDOT:PSS上制备的钙钛矿薄膜的紫外可见吸收光谱，与对照相比，基于烷基胺改性PEDOT:PSS上制备的所有钙钛矿薄膜都显示出轻微的红移，图6c显示，基于烷基胺改性PEDOT:PSS上制备的所有钙钛矿薄膜的光致发光峰也显示出轻微的红移。
图7所示的是原始和改性的PEDOT:PSS上钙钛矿发光层的缺陷密度图。基于C3、C4、C5改性的PEDOT:PSS上制备的钙钛矿薄膜显示出降低的缺陷密度，从C6到C8缺陷密度呈上升趋势。基于C5改性PEDOT:PSS之制备的钙钛矿显示出最低的缺陷密度为3.09×1015cm-3。
图8所示为电流密度与电压之间的关系。从C3到C7改性的器件，钙钛矿发光二极管的电流密度逐渐增大，C8改性的器件电流密度减小。C3改性的器件电流密度低于原始PEODT:PSS的器件。
图9所示为亮度与电压之间的关系与电流密度与电压之间的关系一致。基于C7改性PEDOT:PSS器件的亮度相比于原始PEDOT:PSS器件的亮度提升了2.4倍。
图10所示为原始和改性的PEDOT:PSS上制备的钙钛矿发光二极管的电流密度-外量子效率图。外量子效率从C3到C5改性的器件逐渐增加,C6到C8改性的器件外量子效率逐渐降低，这与缺陷密度相匹配。
图11为纯电子器件与纯空穴器件的电流密度与电压之间的关系。所有纯空穴器件的电流密度比纯电子器件的电流密度大很多。然而，基于烷基胺改性PEDOT:PSS可以使纯空穴器件与纯电子器件有更加接近的电流，可以平衡载流子的注入。烷基胺改性PEDOT:PSS电导率的下降可能与空穴传输层表面的烷基层有关。
图12为原始和改性的PEDOT:PSS上制备的钙钛矿发光二极管的电致发光光谱图。所有器件显示出位于515nm相似的发光峰位置，具有19-22nm的最大半峰宽。
图13为原始和改性的PEDOT:PSS上制备的钙钛矿发光二极管在初始发光亮度随时间衰减的曲线。随着链长的增加，钙钛矿发光二极管的工作稳定性得到提升。在100cd/m-2初始亮度下，基于C7改性的PEDOT:PSS制备的器件显示出36.4h的半衰期，相比于原始PEDOT:PSS制备的5.1h，稳定性得到了7.1倍的提升。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (6)
1.一种烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管，其特征在于，所述烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管的空穴传输层为不同链长烷基胺改性PEDOT:PSS。
2.根据权利要求1所述烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管，其特征在于，所述基于改性PEDOT:PSS及基于其的钙钛矿发光二极管还包括绿光钙钛矿发光层、电子传输层、阳极和阴极。
3.根据权利要求1所述烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管，其特征在于，所述烷基胺为丙胺、丁胺、戊胺、己胺、庚胺、辛胺。
4.根据权利要求1所述烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管，其特征在于，将烷基胺与PEDOT:PSS溶液按照1:200的体积比混合，得到改性的PEDOT:PSS溶液，再将改性的PEDOT:PSS溶液制备成膜，作为烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管的空穴传输层。
5.根据权利要求1所述烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管，其特征在于，烷基胺改性的PEDOT:PSS的空穴传输层厚度为20nm～40nm，绿光钙钛矿发光层厚度为20nm～25nm。
6.根据权利要求1所述烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管，其特征在于，包括以下步骤，将烷基胺加入到PEDOT:PSS溶液中，得到改性的PEDOT:PSS溶液，然后将改性的PEDOT:PSS溶液旋涂与ITO玻璃阳极表面，退火处理，得到空穴传输层，再制备绿光钙钛矿发光层、电子传输层和阴极，得到烷基胺改性PEDOT:PSS及基于其的钙钛矿发光二极管。
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