掺杂聚乙烯咔唑绿光磷化铟量子点发光二极管 增强出版

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "掺杂聚乙烯咔唑绿光磷化铟量子点发光二极管" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Green InP Quantum Dot Light‑emitting Diode with PVK Blend in Emitting Layer" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "刘", "givenname": "森坤", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "LIU", "givenname": "Sen-kun", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "刘森坤(1996-)，男，江西赣州人，硕士研究生，2019年于南昌大学获得学士学位，主要从事量子点发光显示器件的研究。" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879842&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879846&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879843&type=", "width": "25.00000000", "height": "30.00000000", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "刘森坤" }, { "name": "text", "data": "(1996-)，男，江西赣州人，硕士研究生，2019年于南昌大学获得学士学位，主要从事量子点发光显示器件的研究。" } ] ] } ], "deceased": false }, { "name": [ { "lang": "zh", "surname": "罗", "givenname": "宇", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "LUO", "givenname": "Yu", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "王", "givenname": "俊杰", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "WANG", "givenname": "Jun-jie", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "郭", "givenname": "标", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "GUO", "givenname": "Biao", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "肖", "givenname": "毅", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "XIAO", "givenname": "Yi", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "王", "givenname": "璞", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "WANG", "givenname": "Pu", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "彭", "givenname": "俊彪", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "PENG", "givenname": "Jun-biao", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "corresp" ], "corresp": [ { "rid": "cor1", "lang": "en", "text": "E-mail： psjbpeng@scut.edu.cn", "data": [ { "name": "text", "data": "E-mail： psjbpeng@scut.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "彭俊彪(1962-)，男，山东宁津人，博 士，教授，博士生导师，1993 年于中国科学院长春物理研究所获得博士学位，主要从事发光显示器件与物理的研究。Email:psjbpeng@scut.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879854&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879854&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879854&type=", "width": "25.00000000", "height": "30.00000000", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "彭俊彪" }, { "name": "text", "data": "(1962-)，男，山东宁津人，博 士，教授，博士生导师，1993 年于中国科学院长春物理研究所获得博士学位，主要从事发光显示器件与物理的研究。Email:" }, { "name": "text", "data": "psjbpeng@scut.edu.cn" } ] ] } ], "email": "psjbpeng@scut.edu.cn", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "text": "华南理工大学 发光材料与器件国家重点实验室， 广东 广州 510641", "data": [ { "name": "text", "data": "华南理工大学 发光材料与器件国家重点实验室， 广东 广州 510641" } ] }, { "lang": "en", "text": "State Key Laboratory of Luminescent Materials and Devices， South China University of Technology， Guangzhou 510641， China", "data": [ { "name": "text", "data": "State Key Laboratory of Luminescent Materials and Devices， South China University of Technology， Guangzhou 510641， China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "设计了空穴传输材料聚乙烯基咔唑（PVK）与绿光无镉磷化铟（InP）量子点共混体系，改善了量子点团聚效应，减少了量子点之间相互作用产生的非辐射Förster能量转移（FRET），提高了共混无镉量子点薄膜的光致发光效率（PLQY），从24.2%提升至30.1%。同时，PVK的掺入提高了共混发光薄膜的空穴传输性能，改善了量子点电致发光器件的载流子平衡，使器件的最大外量子效率（EQE）达到5.94%，较未掺杂器件提高了32%。该聚合物掺杂方法可为研制高性能绿光InP量子点发光二极管提供参考。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "A hybrid system of polyvinylcarbazole（PVK） and green indium phosphide（InP） quantum dots was designed to produce efficient light-emitting diodes（LEDs）. PVK functions as not only disperse quantum dots well and reduce agglomeration， but also significantly reduce non-radiative Förster energy transfer（FRET） among quantum dots， and improve the film’s photoluminescence efficiency（PLQY） from 24.2% to 30.1%. Meanwhile， the incorporation of PVK can improve the hole transport performance of the QD film " }, { "name": "italic", "data": [ { "name": "text", "data": "via" } ] }, { "name": "text", "data": " the carrier balance of the devices， making the maximum external quantum efficiency（EQE） of the devices reach 5.94%， which is 32% higher than that of the devices without PVK. This method can provide a reference for the development of high performance green InP QD-LEDs." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "磷化铟量子点" } ], [ { "name": "text", "data": "聚合物掺杂" } ], [ { "name": "text", "data": "能量转移" } ], [ { "name": "text", "data": "载流子平衡" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "InP quantum dot" } ], [ { "name": "text", "data": "polymer blend" } ], [ { "name": "text", "data": "energy transfer" } ], [ { "name": "text", "data": "charge balance" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "1　引　　言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "量子点具有发射光谱窄、带隙可调、光致发光量子产率（PLQY）优良的光学特性，使其在显示领域展现出巨大的应用潜力，因而受到人们的极大关注。许多研究组通过量子点材料和器件结构的优化，在改善发光器件性能方面取得了巨大进展" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "- " }, { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。目前，镉基量子点发展较快，其红、绿、蓝量子点器件的最大外量子效率（EQE）分别达到30.9%、23.9%和19.8%。此外，红、绿器件最长寿命已经超过了百万小时" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } } ], "rid": [ "R3", "R4", "R5" ], "text": "3-5", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。然而，虽然镉基量子点含有极微量镉，但是严格来讲，这对环境和人体还会造成一定的负面影响，在一定程度上限制了其在商业应用中的长远发展。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "因此，近年来人们把目光放到了无镉量子点的研究上。其中，磷化铟（InP）量子点由于其带隙可调、发光范围涵盖整个可见光波段、不含重金属镉等优点，被认为是有发展前景的无镉基量子点材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "R6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } } ], "rid": [ "R6", "R7", "R8" ], "text": "6-8", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。三星高等技术研究院通过制备粒径均匀的InP核和高度对称的壳层，经过壳层厚度和表面配体的优化合成了高质量红光InP量子点，器件的最大EQE达到21.4%，初始亮度为100 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "50" } ] }, { "name": "text", "data": "寿命高达一百万小时" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。但是，绿光InP量子点的性能远远落后于红光量子点。由于绿光InP量子点的核尺寸远小于红光InP量子点，所以在绿光InP量子点中，电子波函数的局域性较差，容易离域到壳层，量子点表面的电子捕获会导致激子猝灭；此外，量子点薄膜的电子传输性通常优于空穴传输性，这会造成器件中载流子的不平衡，并且容易出现空穴传输材料的寄生发射。另外，较小的粒子尺寸会使量子点之间的FRET更加明显" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } }, { "name": "text", "data": "," }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } } ], "rid": [ "R10", "R11", "R12", "R13" ], "text": "10-13", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，增加发光猝灭的几率。目前，对于绿光InP量子点，主要围绕增强量子点的电子限域或减少量子点之间FRET方面展开研究。申怀彬等通过延长壳层材料的生长时间并及时补充壳层前驱体，合成了高稳定性、大粒径的厚壳层InP/GaP/ZnS//ZnS量子点，量子点直径为（7.2±1.2） nm，减少了量子点之间的FRET，制备了EQE为6.3%的绿光器件，但是其所制备的正装器件仍然存在较为严重的空穴传输层寄生发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。孙小卫等通过合成厚壳绿光量子点，将电子限制在量子点核内减少其离域，制备了无空穴层寄生发光的器件，EQE从2.2%提升至3.5%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。Chou等使用烷基二胺和卤化锌钝化修饰InP量子点，通过将1,4-丁二胺（BDA）甲苯溶液和ZnI" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "乙醇溶液混合后掺入量子点溶液中，用氨基和碘离子对量子点ZnS外壳表面的S（硫）空位进行钝化，BDA修饰不仅降低了量子点的空穴陷阱，提高了其空穴传输能力，还通过形成的界面偶极子使量子点的真空能级上移，增大了电子注入势垒，使器件注入的载流子更加平衡。通过合成Mg含量为12.5%的ZnMgO作为电子传输层，得到了EQE为16.3%的纯绿光InP器件" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "上述工作主要是基于量子点材料合成方面的研究，解决量子点器件中载流子不平衡、量子点之间存在能量转移等问题。除了设计合成量子点材料的方法外，还可以通过器件薄膜功能的设计进行调控。Chae等通过改变电子传输层ZnMgO中的Mg含量来调节其电子传输速率从而改善器件的载流子平衡，得到EQE为13.6%的纯绿光InP器件" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。Kwak等在量子点和TCTA之间插入CzSi层来阻挡空穴注入，通过调节CzSi厚度控制器件的载流子平衡，得到最大电流效率为21.6 cd/A的纯绿光InP器件" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。这些工作主要是从器件结构设计方面改善载流子平衡。针对改善量子点发光层内的能量转移（FRET）问题，由于FRET对量子点间距比较敏感，薄膜状态下紧密堆积的量子点容易发生FRET" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } } ], "rid": [ "R19", "R20", "R21", "R22" ], "text": "19-22", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。陈树明等将蓝光量子点引入到红光量子点中，将蓝光量子点作为间隔物从空间上分隔红光量子点，由于红光量子点的分离，有效抑制了量子点之间的FRET，制备了EQE为21.64%的镉基红光量子点器件" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。三星高等技术研究院通过将N,N‑双（3‑甲基苯基）‑N,N‑双（苯基）‑9,9‑二辛基芴（DOFL‑TPD）空穴传输材料掺入红光InP量子点，改善了空穴注入性能，同时抑制了电子穿过发光层到达空穴传输层，减少界面复合，器件最大EQE和寿命分别达到18.6%和" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "70" } ] }, { "name": "text", "data": "@5 750 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的73.7 h，分别提高了43.1%和54.9%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在绿光InP发光二极管中，Iwasaki等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过在量子点中掺入有机电子传输材料TmPPyTz，减少了漏电流，制备了EQE为10%的绿光器件。本文将具有一定空穴传输能力的PVK通过共混引入绿光InP量子点薄膜中，调控量子点薄膜的空穴传输能力，改善发光器件的载流子平衡，同时PVK作为间隔材料可以分散其中的量子点，减少量子点之间的FRET，一定程度上改善了量子点器件的电致发光性能。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　实　　验" } ], "level": "1", "id": "s2" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.1　实验材料" } ], "level": "2", "id": "s2a" } }, { "name": "p", "data": [ { "name": "text", "data": "实验采用的氧化铟锡（Indium tin oxide，ITO）基板购于益阳华南湘城科技有限公司。氧化锌镁（ZnMgO）溶液购于广东普加福光电科技有限公司。绿光量子点的结构为InP/ZnSe/ZnS，配体为三辛基膦和十二硫醇，溶剂为甲苯，购于合肥福纳科技有限公司。PVK、三(4‑咔唑基‑9‑基苯基)胺（TCTA）、氧化钼（MoO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "）购于西安宝莱特光电科技有限公司。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2　器件制备" } ], "level": "2", "id": "s2b" } }, { "name": "p", "data": [ { "name": "text", "data": "由于本文中量子点和混合溶液所使用的甲苯溶剂会对常用的空穴传输材料（如TFB、Poly-TPD等）造成侵蚀，因此采用倒装器件结构解决溶剂侵蚀问题。器件结构如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "所示，ITO/ZnMgO（45 nm）/EML（20 nm）/TCTA(50 nm)/MoO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（8 nm）/Al，ITO和Al分别为器件的阴极和阳极。器件制备流程如下：" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "器件结构示意图" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "Diagram of device structure" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879856&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879860&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879858&type=", "width": "52.08620453", "height": "50.18125153", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "基板清洗：分别用四氢呋喃、异丙醇、洗液、去离子水和异丙醇超声清洗15 min后放至烘箱烘干备用。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "电子传输层（ZnMgO）制备：将基板进行UV处理10 min后转移至手套箱，用旋涂的方式制备ZnMgO薄膜，ZnMgO溶液浓度为30 mg/mL，旋涂转速为3 000 r/min，持续时间为30 s，然后置于加热台上以150 ℃的温度加热15 min。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "发光层制备：对于纯量子点发光层薄膜，采用浓度为15 mg/mL的量子点溶液，用旋涂的方式在ZnMgO薄膜上制膜，旋涂转速为3 000 r/min，持续时间为30 s，然后在120 ℃下加热12 min；对于混合发光层薄膜，将PVK溶于甲苯中，按照3%、5%和10%的质量比掺入量子点溶液中形成混合溶液，溶液浓度依然为15 mg/mL，然后在ZnMgO薄膜上旋涂，旋涂工艺与上述的相同。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "其他功能层都是采用真空蒸镀工艺制备的，各层材料均在2.5×10" }, { "name": "sup", "data": [ { "name": "text", "data": "-4" } ] }, { "name": "text", "data": " Pa的真空度下进行热蒸镀，其中TCTA作为空穴传输层，MoO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "作为空穴注入层。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.3　样品表征" } ], "level": "2", "id": "s2c" } }, { "name": "p", "data": [ { "name": "text", "data": "薄膜厚度测量使用台阶扫描仪（Dektak 150，Veeco公司）。薄膜及溶液的紫外-可见吸收光谱采用紫外-可见分光光度计（UV-2600，苏州岛津仪器有限公司）测试。器件光电性能表征使用四合一数字源表（Keithley2400，美国Keithley公司）和分光色度计（CS200，日本Konica Minolta公司）。荧光寿命采用时间分辨荧光寿命光谱仪（C11367⁃11，日本滨松光子学株式会社）测量。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　结果与讨论" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "选择PVK的原因主要是:（1）PVK的HUMO能级为-5.8 eV" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，与本文所用的绿光InP量子点的HUMO能级（-5.83 eV）比较匹配，不会形成势垒阻挡空穴注入，且其较浅的LUMO能级在一定程度上可以阻挡电子穿过发光层直接在空穴侧复合；（2）PVK的空穴传输性能高于QDs薄膜，因此掺入PVK可能会增加共混薄膜的空穴传输性能；（3）PVK和量子点在甲苯中溶解性都较好（浓度为15 mg/mL的甲苯溶液均很稳定），不需要使用双溶剂体系，相容性较好；（4）PVK作为宽带隙材料，自身发光比较弱，当其掺杂在量子点发光层时，产生寄生发射的可能性比较小。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "制备了器件结构为ITO/PEDOT/PVK或QDs/TCTA/MoO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "/Al的 PVK和量子点的单空穴器件（PVK和量子点薄膜的厚度相同，约20 nm），PVK和量子点薄膜的表面粗糙度分别为1.68 nm和1.73 nm，如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（a）所示，它们表面粗糙度的差别不大。PVK的单空穴器件电流密度高于量子点的单空穴器件电流密度，说明PVK的空穴传输性能要优于量子点的空穴传输性能，如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（b）所示。" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "是掺杂PVK前后量子点薄膜的AFM图，可以发现PVK和量子点混合后成膜比较均匀，掺杂PVK后薄膜的粗糙度略微增加，从1.71 nm上升至1.86 nm，没有发生明显的团聚现象，说明PVK和量子点共混分散比较均匀。粗糙度的增加可能是因为聚合物和球形量子点混合后，长链的聚合物在表面形成凹陷区和凸起区使得粗糙度轻微增大。掺杂5%（wt） PVK器件的截面SEM见图S1，可以发现器件各功能层的界面均比较清晰。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "（a）PVK和QDs薄膜表面粗糙度；（b）PVK和QDs单空穴器件的" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "-" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "text", "data": "曲线。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "（a）Surface roughness of PVK and QDs films. （b）Current density-voltage graphs for the hole only devices." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879861&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879866&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879863&type=", "width": "133.25152588", "height": "51.80633545", "fontsize": "" } ] } }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "未掺杂PVK（a）和掺杂5%（wt）PVK（b）的AFM图" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "AFM images of quantum dot film. （a）Before 5% PVK blended. （b）After 5% PVK blended." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879868&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879872&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879869&type=", "width": "130.16024780", "height": "52.27218628", "fontsize": "" } ] } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　掺杂PVK的量子点发光二极管器件" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "量子点电致发光器件能级结构如" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（a）所示，PVK的HUMO能级不会在量子点和空穴传输层（TCTA）层之间形成势垒。为探究最优的PVK掺杂比例，分别在量子点中掺入了0%、3%、5%和10%的PVK，制备了电致发光器件。发现各掺杂比例器件的电致发光光谱均未出现PVK的寄生发射，如" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（b）。器件的电流密度和亮度随电压变化（" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "-" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "text", "data": "-" }, { "name": "italic", "data": [ { "name": "text", "data": "L" } ] }, { "name": "text", "data": "）特性以及电流效率曲线如" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（c）~（d）所示。从" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（c）中可以看到，启亮之前，与未掺杂的器件相比，掺杂3%和5% PVK器件的漏电流有不同程度的下降，可能是因为PVK填充于量子点间隙中减少了漏电流；而掺杂10% PVK的器件漏电流则有所提升，根据薄膜的AFM图（如图S2），发现掺杂10% PVK的量子点薄膜粗糙度为2.85 nm，这可能是掺杂过量，长链聚合物进一步加剧了量子点薄膜表面的粗糙度，导致器件漏电流轻微提升。与未掺杂量子点发光器件相比，除了10%的掺杂比例外，其余掺杂器件的电流密度均有一定程度的提升。通过对比器件亮度和最大电流效率可以发现PVK的最优掺杂比例是5%，此时器件的最大亮度从2 799 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "提升至3 855 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": ", 器件的最高电流效率从18.2 cd/A提升至24.2 cd/A，与未掺杂的器件相比，掺杂5% PVK器件的最大亮度和最大电流效率分别提高37.7%和32.9%。各掺杂比例器件的性能数据汇总在" }, { "name": "xref", "data": { "text": "表1", "type": "table", "rid": "T1", "data": [ { "name": "text", "data": "表1" } ] } }, { "name": "text", "data": "中。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "（a）掺杂PVK的器件能级示意图；不同PVK掺杂浓度的器件电致发光光谱（b）、器件" }, { "name": "italic", "data": [ { "name": "text", "data": "J⁃V⁃L" } ] }, { "name": "text", "data": "特性（c）、CE-" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "特性（d）。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "（a）Energy level diagram of QD-LED comprising PVK blended QD EML. （b）EL spectra of the devices blended with different ratio of PVK. " }, { "name": "italic", "data": [ { "name": "text", "data": "J⁃V⁃L" } ] }, { "name": "text", "data": " characteristics（c） and CE-" }, { "name": "italic", "data": [ { "name": "text", "data": "J " } ] }, { "name": "text", "data": "characteristics（d） for QD" }, { "name": "italic", "data": [ { "name": "text", "data": "⁃" } ] }, { "name": "text", "data": "LEDs with QD-only EML and PVK blended QD EML." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879873&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879878&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879876&type=", "width": "120.74591064", "height": "87.93122864", "fontsize": "" } ] } }, { "name": "table", "data": { "id": "T1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "表1" } ], "title": [ { "name": "text", "data": "不同PVK掺杂浓度器件的性能汇总表" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Tab.1" } ], "title": [ { "name": "text", "data": "Device performance of the QD-LED by blending different ratios of PVK" } ] } ], "note": [], "table": [ { "head": [ [ { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "text", "data": "PVK掺杂量/%" } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "p", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "on" } ] }, { "name": "text", "data": "/" } ] }, { "name": "p", "data": [ { "name": "text", "data": "V" } ] } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "p", "data": [ { "name": "text", "data": "CE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "/" } ] }, { "name": "p", "data": [ { "name": "text", "data": "（cd·A" }, { "name": 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"name": "text", "data": "10" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "2.7" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "17.2" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "2 571" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "4.21" } ] } ] ], "foot": [] } ], "graphics": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879881&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879880&type=", "width": "77.69583893", "height": "30.51803589", "fontsize": "" } } }, { "name": "p", "data": [ { "name": "text", "data": "PVK掺杂量子点形成的共混发光层使器件性能得到了明显改善。为了进一步理解PVK在其中的作用，针对PVK最优掺杂比例（5%）的器件进一步探究了PVK对共混薄膜光学性能以及器件电学性能的影响。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　PVK掺杂对量子点间能量转移的影响" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "text", "data": "对于紧密堆积的量子点，小粒径量子点中的激子能量可以通过FRET转移到大粒径的量子点中" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } } ], "rid": [ "R26", "R27" ], "text": "26-27", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。而在转移过程中，激子有一定概率会在含有缺陷的量子点上解离，从而产生发光猝灭，降低发光效率。该过程通常发生在短距离（10 nm）的给受体之间，PVK的掺杂可能在一定程度上增大量子点之间的距离，减少量子点之间的能量转移。量子点溶液的PLQY为51.6%（如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（b）），其薄膜的PLQY下降为24.5%；而当掺入PVK后，量子点薄膜的PLQY提升至30.2%，在ZnMgO薄膜上的量子点PLQY也从掺杂前的13.1%提升至掺杂后的16.2%。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "（a）量子点粒径分布图；（b）量子点光致发光效率。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "（a）Size distribution of InP QDs. （b）PLQY of InP QDs." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879883&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879885&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879884&type=", "width": "144.42401123", "height": "52.66769409", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "本实验所用InP量子点的粒径分布如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（a）所示，其平均粒径为6.2 nm。由于量子点的粒径分布不均匀，在量子点紧密堆积的薄膜中，稍小的量子点的能量有几率转移到稍大的量子点上，所以波长较短的光被猝灭，波长较长的光被增强，导致发射峰发生红移" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，具体示意图见图S3。为了验证量子点之间的能量转移情况，测量了量子点溶液及PVK掺杂前后的量子点薄膜的荧光光谱和时间分辨荧光光谱（TRPL），其中激发波长为350 nm，溶液的监测波长为526 nm，薄膜的监测波长为536 nm。测试结果采用双指数或三指数拟合，指数衰减公式和平均荧光寿命计算公式如下：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（1）" } ], "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879888&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879887&type=", "width": "46.65133286", "height": "9.90600014", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF1" } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（2）" } ], "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879890&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879889&type=", "width": "69.17266846", "height": "9.90600014", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF2" } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（3）" } ], "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879893&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879891&type=", "width": "55.11800003", "height": "12.19200039", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF3" } }, { "name": "p", "data": [ { "name": "text", "data": "一般认为" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": " 、" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "分别表示短寿命、中寿命和长寿命成分，其中短寿命对应电子直接复合辐射的特征时间，而中寿命和长寿命表示电子经过中间态（例如量子点本身的缺陷态、与周围物质的能量转移等）后再跃迁回基态复合辐射的特征时间，所以寿命相对较长；" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "、" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "分别表示对应寿命所占的比例" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。测试结果如" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "所示，根据公式（" }, { "name": "xref", "data": { "text": "1", "type": "disp-formula", "rid": "DF1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "）、（" }, { "name": "xref", "data": { "text": "2", "type": "disp-formula", "rid": "DF2", "data": [ { "name": "text", "data": "2" } ] } }, { "name": "text", "data": "）、（" }, { "name": "xref", "data": { "text": "3", "type": "disp-formula", "rid": "DF3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "）拟合得到的结果如" }, { "name": "xref", "data": { "text": "表2", "type": "table", "rid": "T2", "data": [ { "name": "text", "data": "表2" } ] } }, { "name": "text", "data": "所示。与量子点溶液相比，量子点薄膜的荧光发射峰位从526 nm红移至536 nm，与文献报道一致，同时平均瞬态荧光寿命也从44.4 ns减少到31.1 ns。由于测试采用的量子点浓度仅为0.5 mg/mL，浓度较低，可以认为溶液中的量子点间距较大，不会产生FRET，因此溶液中量子点之间几乎没有能量转移； 而薄膜状态下光谱发生红移以及荧光寿命的减少说明紧密堆积的量子点之间存在能量转移" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": ", " }, { "name": "xref", "data": { "text": "29", "type": "bibr", "rid": "R29", "data": [ { "name": "text", "data": "29" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。掺杂5% PVK后，共混薄膜的荧光发射峰位为535 nm（" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（a）），而掺杂3%和10% PVK的共混薄膜荧光发射峰位分别为536 nm和534 nm（如图S4所示），掺杂量越多，光谱越蓝移，发光峰就越靠近稀溶液光谱，说明PVK掺杂可以抑制紧密堆积的量子点之间的相互作用。同时，掺杂5% PVK后量子点的平均瞬态荧光寿命也从31.3 ns提升至36.5 ns（其他掺杂比例的瞬态荧光寿命如表S1所示），说明掺入PVK之后，量子点之间的相互作用导致的非辐射复合在一定程度上得到了抑制。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "量子点薄膜的光致发光特性。 （a）量子点荧光光谱；（b）瞬态荧光衰减曲线。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 6" } ], "title": [ { "name": "text", "data": "Fluorescence spectra（a） and transient PL decay curves（b） before and after PVK blended" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879895&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879899&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879897&type=", "width": "133.73010254", "height": 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"data": [ { "name": "text", "data": "122.9" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "2.1" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "36.5" } ] } ] ], "foot": [] } ], "graphics": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879905&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879902&type=", "width": "162.79995728", "height": "21.33966064", "fontsize": "" } } }, { "name": "p", "data": [ { "name": "text", "data": "此外，可以通过" }, { "name": "xref", "data": { "text": "公式（4）", "type": "disp-formula", "rid": "DF4", "data": [ { "name": "text", "data": "公式（4）" } ] } }, { "name": "text", "data": "进一步计算能量转移效率：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（4）" } ], "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879910&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879908&type=", "width": "23.19866753", "height": "8.72066593", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF4" } }, { "name": "p", "data": [ { "name": "text", "data": "其中" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "DA" } ] }, { "name": "text", "data": "表示给体和受体都存在时的平均荧光寿命，" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "D" } ] }, { "name": "text", "data": "为不存在受体时的平均荧光寿命" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。假设量子点溶液中不存在能量转移，这里的" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "DA" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "D" } ] }, { "name": "text", "data": "分别代表薄膜和溶液的平均荧光寿命。所以，与未掺杂PVK的薄膜相比，掺杂PVK后能量传递效率从29.5%降低至17.8%，说明PVK抑制了量子点之间的能量转移，使量子点薄膜的PLQY也从24.5%提升至30.2%。" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": " 说明了激子的扩散和猝灭过程，当量子点紧密堆积时，量子点之间相互作用会发生能量转移，由于量子点中缺陷的存在，在激子能量转移过程中无辐射几率会增加，这将会导致发光效率降低。而当掺入了PVK后，PVK填充于量子点之间，可以一定程度上减少量子点之间的FRET过程，从而减少激子能量转移过程中的非辐射复合几率。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "量子点薄膜中激子扩散和猝灭过程示意图 （绿点、灰点和黑色线条分别表示绿光量子点、发生能量转移的量子点和PVK）" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "Schematic illustration of exciton diffusion and quenching processes in the QD film（green， gray dots and black curve represent QDs， QDs with energy transfer and PVK， respectively）" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879912&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879916&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879914&type=", "width": "140.15344238", "height": "20.62266541", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "当然，根据量子点和PVK的紫外吸收和荧光发射光谱（如图S5所示），发现理论上PVK和量子点之间存在能量转移，这会影响量子点的平均瞬态寿命。为了验证PVK和量子点之间是否存在能量转移，使用430 nm的激发光源（该波长无法激发PVK），只激发量子点发光，测量共混薄膜中量子点的瞬态荧光寿命。如果此时量子点的寿命与之前一致，说明PVK和量子点之间不存在能量转移。测试结果如图S6所示，拟合结果如表S2所示。当使用430 nm激发光、监测波长为536 nm时，量子点的平均寿命与使用350 nm激发光时的（如表S1所示）非常接近，所以量子点和PVK之间几乎不存在能量转移，掺杂PVK后量子点瞬态荧光寿命的提高主要是因为减少了它们之间的能量转移。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.3　PVK掺杂对量子点器件载流子传输的影响" } ], "level": "2", "id": "s3c" } }, { "name": "p", "data": [ { "name": "text", "data": "为了探究PVK掺杂对器件载流子平衡的影响，制备了单空穴和单电子器件，单空穴器件结构为ITO/PEDOT∶PSS/EML/TCTA/MoO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "/Al，单电子器件结构为ITO/ZnMgO/EML/TPBi/LiF/Al，测试结果如" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "所示。在驱动电压为8 V时，掺入PVK和未掺入PVK的单空穴器件的电流密度分别为0.78 mA/cm" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "和1.90 mA/cm" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，说明PVK可以提高混合发光层的空穴传输能力。在电压为8 V时，掺杂PVK和未掺杂PVK的单电子器件的电流密度分别为19.4 mA/cm" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "和14.9 mA/cm" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，说明PVK的浅LUMO能级可以增加电子注入势垒，一定程度上减少电子电流密度。当不掺杂PVK时，由于绿光InP量子点电子限域能力弱，量子点层中电子比较容易从ZnMgO中传输到另一侧量子点，空穴则不容易从TCTA中传输到另一侧量子点，如" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "（a）所示；当掺杂PVK后，PVK链分布于量子点之间，空穴可以通过PVK链从TCTA中传输到另一侧量子点中，同时对量子点之间的电子传输起一定阻挡作用，如" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "（b）所示。所以在掺杂PVK前后，单载流子器件中空穴电流密度会增大，电子电流密度会减小，PVK掺杂可一定程度平衡器件的载流子。 此外，采用阻抗法测试了掺杂前后QLEDs器件的" }, { "name": "italic", "data": [ { "name": "text", "data": "C⁃V" } ] }, { "name": "text", "data": "（电容-电压）特性曲线，测试偏压为0~4 V，调制频率为100 Hz，正弦幅值为50 mV，如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "所示。在0~2 V偏压内，器件的电容值基本不变，该阶段电容是器件的体电容，与各功能层材料性质有关；当偏压在2 V左右时，电子开始注入，此时器件还未启亮，随着偏压的提高，电子会堆积在ZnMgO和量子点界面，导致器件电容逐渐增加；随着偏压的进一步增大，空穴开始注入并与电子复合发光，电容随之下降" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } } ], "rid": [ "R30", "R31" ], "text": "30-31", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。当掺杂PVK时，电容在2.7 V时开始下降，此时已经有空穴开始和电子复合发光，而未掺杂的器件则在2.8 V，说明掺杂后的器件空穴注入更容易。从" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（a）中的能级图也可得知，PVK的HUMO能级和TCTA几乎相同，当PVK掺入量子点中有利于空穴注入量子点发光层内部，使器件空穴注入更加容易。掺杂之后的器件由于载流子更加平衡，其寿命也有所提高，器件具体的亮度衰减曲线如图S7所示。可以发现未掺杂PVK时，器件在初始亮度" }, { "name": "italic", "data": [ { "name": "text", "data": "L" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "为361 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "时，" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "50" } ] }, { "name": "text", "data": "寿命为172 s；掺杂PVK后，器件在初始亮度" }, { "name": "italic", "data": [ { "name": "text", "data": "L" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "为391 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "时，" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "50" } ] }, { "name": "text", "data": "寿命为308 s，换算成初始亮度为100 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "下的寿命，可以得到掺杂PVK之前器件寿命为" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "50" } ] }, { "name": "text", "data": "@100 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "=1 734 s，掺杂PVK之后器件寿命为" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "50" } ] }, { "name": "text", "data": "@100 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "=3 585 s。提高了一倍。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "单载流子器件" }, { "name": "italic", "data": [ { "name": "text", "data": "I⁃V" } ] }, { "name": "text", "data": "特性曲线。 （a）单空穴；（b）单电子。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "Comparison of" }, { "name": "italic", "data": [ { "name": "text", "data": " I⁃V" } ] }, { "name": "text", "data": " characteristic curves. （a）The hole only device. （b）The electron only device." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879917&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879920&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879919&type=", "width": "144.11163330", "height": "52.95333862", "fontsize": "" } ] } }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "载流子传输过程示意图。 （a）纯量子点发光器件；（b）PVK掺杂量子点发光器件。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.9" } ], "title": [ { "name": "text", "data": "Schematic diagram of carrier transport process in the devices with pure QDs（a） and QDs with PVK（b）" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879922&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879926&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879924&type=", "width": "140.57550049", "height": "45.98425293", "fontsize": "" } ] } }, { "name": "fig", "data": { "id": "F10", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图10" } ], "title": [ { "name": "text", "data": "器件的电容-电压特性曲线" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.10" } ], "title": [ { "name": "text", "data": "Capacitance-voltage（" }, { "name": "italic", "data": [ { "name": "text", "data": "C⁃V" } ] }, { "name": "text", "data": "） characteristics of QLEDs before and after PVK blended" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879927&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879931&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35879929&type=", "width": "64.68572998", "height": "52.26789856", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　结　　论" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "本文通过将PVK掺入量子点中形成混合发光层，改善了发光性能，主要原因是减少了非辐射Förster共振能量转移，同时提高了空穴传输性，使量子点发光器件的载流子更加平衡。通过调节掺杂比例，得到5%掺杂的器件性能最优，掺杂后器件的启亮电压为2.6 V，最大亮度为3 855 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，最高电流效率为24.2 cd/A，最大EQE为5.92%，相比于未掺杂器件，最大亮度和效率分别提高37.7%和32.9%。" } ] }, { "name": "p", "data": [ { "name": "text", 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