Synthesis and Properties of Near Infrared-emitting Iridium（Ⅲ） Complexes with Auxiliary Ligand Functionalized Enhanced Publication

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "辅助配体功能化铱（Ⅲ）配合物近红外电致发光材料的合成及其性能" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Synthesis and Properties of Near Infrared-emitting Iridium（Ⅲ） Complexes with Auxiliary Ligand Functionalized" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "陈", "givenname": "俊", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "CHEN", "givenname": "Jun", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "陈俊（1995-），男，安徽合肥人，硕士研究生，2020年于南京信息工程大学获得学士学位，主要从事有机发光器件的研究。 E-mail： 1119838654@qq.com" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865490&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865500&type=", "big": 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"name": [ { "lang": "zh", "surname": "范", "givenname": "伟雪", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "FAN", "givenname": "Wei-xue", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "于", "givenname": "俊婷", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "YU", "givenname": "Jun-ting", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [ "corresp" ], "corresp": [ { "rid": "cor1", "lang": "en", "text": "E-mail： tanhua815@126.com", "data": [ { "name": "text", "data": "E-mail： tanhua815@126.com" } ] } ], "bio": [ { "lang": "zh", "text": [ "于俊婷(1987-)，女，辽宁辽阳人，博士，副教授，2014年于湘潭大学获得博士学位，主要从事有机光电功能材料的研究。 E-mail： yujuntingtt@163.com" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865503&type=", "small": 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"谭华（1984-），男，湖南衡阳人，博士，副教授，2013年于湘潭大学获得博士学位，主要从事有机光电功能材料的研究。 E-mail： tanhua815@126.com" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865513&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865520&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865516&type=", "width": "24.99999619", "height": "30.00000381", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "谭华" }, { "name": "text", "data": "（1984-），男，湖南衡阳人，博士，副教授，2013年于湘潭大学获得博士学位，主要从事有机光电功能材料的研究。 E-mail： " }, { "name": "text", "data": "tanhua815@126.com" } ] ] } ], "email": "tanhua815@126.com", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "label": "1", "text": "常州大学材料科学与工程学院 江苏省光电热能量转化材料与应用工程实验室， 江苏 常州　213164", "data": [ { "name": "text", "data": "常州大学材料科学与工程学院 江苏省光电热能量转化材料与应用工程实验室， 江苏 常州　213164" } ] }, { "lang": "en", "label": "1", "text": "Jiangsu Engineering Laboratory of Light-Electricity-Heat Energy-Converting Materials and Applications， School of Materials Science and Engineering， Changzhou University， Changzhou 213164， China", "data": [ { "name": "text", "data": "Jiangsu Engineering Laboratory of Light-Electricity-Heat Energy-Converting Materials and Applications， School of Materials Science and Engineering， Changzhou University， Changzhou 213164， China" } ] } ] }, { "id": "aff2", "intro": [ { "lang": "zh", "label": "2", "text": "湘潭大学 化学学院， 湖南 湘潭　411105", "data": [ { "name": "text", "data": "湘潭大学 化学学院， 湖南 湘潭　411105" } ] }, { "lang": "en", "label": "2", "text": "College of Chemistry， Xiangtan University， Xiangtan 411105， China", "data": [ { "name": "text", "data": "College of Chemistry， Xiangtan University， Xiangtan 411105， China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "将烷基芴（Fluorene，FL）基团通过柔性烷基链连接到吡啶甲酸（Picolinic acid，pic）上，合成了辅助配体功能化的供体‐受体（D‐A）型铱配合物近红外电致发光材料（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA‐BTz‐Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic‐FL）（TPA：Triphenylamine为三苯胺，BTz：Benzotriazole为苯并三唑，Iq：Isoquinoline为异喹啉）。通过对其紫外‐可见吸收光谱和光致发光光谱研究发现，由于主配体中强D‐A作用的CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA‐BTz结构，配合物具有强分子内电荷转移跃迁（Charge transfer transition，ICT）吸收峰和720 nm左右的光致发光峰。与此同时，（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA‐BTz‐Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic‐FL）分子中柔性烷基链和高荧光量子效率芴基团的引入，可以提高材料光致发光效率，改善材料的溶解性能和器件成膜性能，提高电致发光效率。以配合物为发光掺杂剂制备的有机电致发光器件其最大发射峰位于722 nm左右的近红外区域，最大外量子效率（EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "）为0.92%，是其母体配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA‐BTz‐Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "‐Irpic器件效率的2.24倍（EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "为0.41%@723 nm）。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "In this paper， a novel auxiliary ligand functionalized donor-acceptor（D-A） type near infrared-emitting iridium（Ⅲ） complex （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL） was synthesized by connecting alkylfluorene（FL） to picolinic acid（pic）. Through the study of UV-Vis absorption and photoluminescence spectrum， the complex has a strong intramolecular charge transfer transition （ICT） absorption peak and a photoluminescence peak about 720 nm due to the strong D-A effect of the CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq ligand. Furthermore， the photoluminescence and electroluminescent properties of （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL） were improved by introducing alkyl chains and FL group with high fluorescence quantum efficiency， good solubility and film forming performance. In （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir‐（pic-FL）-based OLEDs， a maximum external quantum efficiency （EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "） of 0.92% at 722 nm was obtained， which is much superior than that of the （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Irpic-based OLEDs （0.41% at 723 nm）." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "铱（Ⅲ）配合物" } ], [ { "name": "text", "data": "芴" } ], [ { "name": "text", "data": "供体-受体" } ], [ { "name": "text", "data": "近红外" } ], [ { "name": "text", "data": "电致发光" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "iridium（Ⅲ） complex" } ], [ { "name": "text", "data": "fluorene" } ], [ { "name": "text", "data": "donor-acceptor" } ], [ { "name": "text", "data": "near infrared" } ], [ { "name": "text", "data": "electroluminescence" } ] ] } ], "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": "近红外（Near infrared，NIR）发光材料具有穿透力强、背景干扰少和对生物组织伤害较小等优点，在光纤通信、夜视显示、信息安全和医疗诊断等方面有着非常广泛的应用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } } ], "rid": [ "R1", "R2", "R3", "R4", "R5", "R6", "R7", "R8", "R9" ], "text": "1-9", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。铱（Ⅲ）配合物因其较短的磷光寿命、较大的耦合常数以及理论上可以达到100%内量子效率等优点，成为NIR电致发光材料最重要的研究课题之一" }, { "name": "sup", "data": [ { "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": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } } ], "rid": [ "R10", "R11", "R12", "R13", "R14", "R15", "R16", "R17", "R18", "R19", "R20", "R21", "R22" ], "text": "10-22", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。环金属配体的结构对于近红外环金属铱（Ⅲ）配合物的影响至关重要。环金属配体主要分为C^N配体和辅助配体" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，对于大多数同质Ir（C^N）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "型" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "," }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "或异质 Ir（C^N）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（L^X）型" }, { "name": "sup", "data": [ { "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": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } } ], "rid": [ "R10", "R11", "R12", "R13", "R14", "R15", "R16" ], "text": "10-16", "type": "bibr" } }, { "name": "text", "data": "," }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } } ], "rid": [ "R18", "R19", "R20", "R21" ], "text": "18-21", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "近红外发光配合物，环金属C^N配体在其光物理性质方面占主导地位。相比之下，同质环金属铱（Ⅲ）配合物比异质铱（Ⅲ）配合物具有更好的化学稳定性和更高的量子效率" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。然而，同质配合物通常需要更复杂的合成过程，因此，关于同质铱（Ⅲ）配合物NIR-OLEDs的报道很少。对于异质环金属铱（Ⅲ）配合物，常见的非发色团型辅助配体对其光物理性质影响较小，更多的是通过辅助配体功能化来改善材料溶解性能和载流子传输性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "," }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。为了获得高效的近红外发光材料，研究者把研究重点集中在主配体的设计上，通过扩展共轭和/或用缺电子/富电子的杂原子/环取代苯环，从而降低发射三重态的能级，获得“更红”的发射。2006年，Williams等率先报道了一种基于双（1-芘基-异喹啉基-N,C'）乙酰丙酮的铱（Ⅲ）配合物，并在720 nm处获得了0.1%的最大外量子效率（External quantum efficiency，EQE）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。此后到现在近15年的时间，基于环金属铱（Ⅲ）配合物的近红外电致发光（Electroluminescence，EL）材料不断涌现，我国研究者更有大量相关的高质量报道。2015年，武汉大学杨楚罗课题组报道了（thdpqx）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（acac） NIR铱（Ⅲ）配合物，在二苯基喹喔啉（dpqx）配体的外围引入芴基或噻吩基扩展π共轭，降低能隙，以聚乙烯咔唑（PVK）和2-（4'-叔丁苯基）-5-（4'-联苯基）-1,3,4-噁二唑（PBD）为主体材料（PVK∶PBD=40∶60）的器件最大发射峰位于702 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "为1.9%。随后，通过增加1,3,5-三（N-苯基苯并咪唑-2-基）-苯（TPBi）作为电子传输层和空穴阻挡层，其电致发光器件效率有了明显提升，优化后的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "达到3.4%，为当时溶液加工型近红外电致发光器件（NIR-OLEDs）的最高值" }, { "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": "。2017年，清华大学乔娟课题组报道了一种NIR发光的同质环金属铱（Ⅲ）配合物Ir（Ftbpa）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，通过引入三氟甲基/氟原子，提高其光致发光量子效率（Photoluminescence quantum yield，PLQY），从而获得高的NIR-OLEDs效率，其以12-（4,6-二苯基-1,3,5-三嗪-2-基）-11-苯基吲哚并[2,3-a]咔唑（DIC-TRZ）为主体材料的真空蒸镀器件在760 nm处获得了EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "为 4.5%的器件效率" }, { "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": "。2018年，中国香港浸会大学黄维扬课题组报道了一种NIR铱（Ⅲ）配合物（BCF" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "-ptq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（acac），通过在配合物中引入CF" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "以及[1,2,5]噻二唑并[3,4-c]" }, { "name": "text", "data": "吡啶，降低了其HOMO与LUMO能隙（" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "）和三线态能级（" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "T" } ] }, { "name": "text", "data": "），并以1,3-二咔唑苯（mCP）为主体材料制备了真空蒸镀器件，在715 nm处实现了4.0%的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "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": "。2020年，五邑大学陈钊课题组报道了一种结构简单、高效NIR发光的铱（Ⅲ）配合物Ir（tiqCN）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（acac），引入较强吸电子氰基基团有利于降低铱（Ⅲ）配合物的LUMO能级，降低能隙，获得长波长发射。以4,4'-二（9-咔唑）联苯（CBP）为主体材料的真空蒸镀器件最大发射波长为706 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "高达9.59%，且器件稳定性良好" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。同年，常州大学朱卫国课题组设计合成了一系列新颖高效的核‐壳型近红外发光铱（Ⅲ）配合物，这类配合物通过刚性稠杂环单元二苯并[a,c]酚嗪刚性内核、己基噻吩和三苯胺柔性外壳构筑，基于配合物（3,6-DTPA-DBPz）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（acac）以CBP为主体材料的可溶液加工型器件在708 nm处获得了13.72%的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "，为目前铱（Ⅲ）配合物近红外电致发光材料最高值" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "目前，获得高效电致发光的方式不外乎两种，一是从器件的角度出发，优化器件结构和制备工艺，合理设置功能层；二是从材料本身着手，设计合成出性能优异的发光材料。根据公式" }, { "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": " " }, { "name": "italic", "data": [ { "name": "text", "data": "η" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EQE" } ] }, { "name": "text", "data": "=" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865527&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865523&type=", "width": "29.46400070", "height": "4.65666676", "fontsize": "" } } } ] }, { "name": "text", "data": "，我们可以从以下几方面来提高器件效率：（1）通过引入电子和空穴传输基团来平衡电荷迁移率，进而提高复合载流子与注入载流子之比（" }, { "name": "italic", "data": [ { "name": "text", "data": "γ" } ] }, { "name": "text", "data": "）来改善OLED的EQE；（2）采用磷光材料，如Ir（Ⅲ）和Pt（Ⅱ）配合物，因为理论上磷光材料中的辐射激子产生效率（" }, { "name": "italic", "data": [ { "name": "text", "data": "η" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "r" } ] }, { "name": "text", "data": "）为100%；（3）增加刚性结构，引入能提高材料量子效率的基团，提高材料的光致发光效率（" }, { "name": "italic", "data": [ { "name": "text", "data": "Φ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "PL" } ] }, { "name": "text", "data": "）；（4）抑制发光客体材料与主体材料的相分离，优化器件结构，有助于得到最优的" }, { "name": "italic", "data": [ { "name": "text", "data": "η" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "out" } ] }, { "name": "text", "data": "为光输出耦合因子（与材料成膜性及器件结构有关）。基于此及上述科研成果的启发，我们设计并合成了一种辅助配体功能化的D-A型铱（Ⅲ）配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL），其中三苯胺（Triphenylamine，TPA）衍生物作为空穴传输基团和电子供体（D）单元，苯并三唑（Benzotriazole，BTz）衍生物用作电子传输基团和电子受体（A）单元；烷基芴（Fluorene，FL）基团由于其刚性结构及良好的热和光化学稳定性" }, { "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": "，用于提高材料的发光量子效率；烷（氧）基的引入可以提高配合物溶解性，改善材料的成膜性能。与此同时，鉴于三重态-三重态湮灭（Triplet-triplet annihilation，TTA）容易导致材料在高电流密度下严重的效率下降，使用非平面CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA单元可以避免聚集诱导的发光猝灭效应。将配合物作为发光掺杂客体制备溶液加工型OLEDs，测得EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "为0.92%，EL最大发射峰值为722 nm，与之前报道的母体铱（Ⅲ）配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Irpic" }, { "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": "相比，基于（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的OLEDs可以将EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "提高2.24倍。" } ] } ] }, { "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　试剂、仪器与测试条件" } ], "level": "2", "id": "s2a" } }, { "name": "p", "data": [ { "name": "text", "data": "所有化学原料直接从安耐吉化学等试剂公司购买，所有溶剂均从天津市科密欧化学试剂有限公司购买，纯度为分析纯。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "热重分析（TGA）通过Perkin Elmer TGA 7仪器以10 ℃·min" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "的加热速率在干燥氮气流下测得；紫外-可见吸收光谱（UV-Vis）采用型号为CARY 100的分光光度计测得；光致发光光谱（PL）采用型号为Perkin-Elmer LS50B的荧光光谱仪测得；荧光量子效率（PLQY）以Ru（byp）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（PF" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "为参比（" }, { "name": "italic", "data": [ { "name": "text", "data": "Ф" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "PL" } ] }, { "name": "text", "data": "=6.2%），采用相对法在二氯甲烷溶液中测试；采用爱丁堡FLS1000光谱仪测试了配合物的发光衰减特性；电化学性能采用CHI 600E电化学工作站，扫描速率为100 mV·s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，以0.1 mol/L四丁基六氟磷酸铵（Bu" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "NPF" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "）的乙腈溶液作为电解质溶液，二茂铁（Fc/Fc" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "）为内标，在氩气流排氧 15 min后测定循环伏安（CV）曲线，其中铂盘、铂丝和Ag/AgCl电极分别用作工作电极、对电极和参比电极。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "OLEDs器件的制备：首先，在超声波浴中分别用丙酮、异丙醇、清洁剂、去离子水和异丙醇清洗ITO涂层玻璃基板，并在100 ℃紫外线臭氧处理15 min，将PEDOT∶PSS作为空穴注入层涂覆在ITO基板，并在手套箱中150 ℃下干燥15 min。其中，器件Ⅰ是将主体材料4,4',4'-三（N-3-甲基苯基-N-苯基氨基）三苯胺（m-MTDATA）与溶于氯苯溶液的铱（Ⅲ）配合物混合，旋涂40 nm作为发光层，在手套箱中60 ℃下退火10 min制备。器件Ⅱ是引入聚[双（4-苯基）（4-丁基苯基）胺]（poly-TPD）作为空穴传输层，在120 ℃下退火15 min，然后分别制备PVK与OXD-7氯苯溶液，按70∶30的比例混合作为主体，再混合客体铱（Ⅲ）配合物，旋涂60 nm作为发光层。最后，在2×10" }, { "name": "sup", "data": [ { "name": "text", "data": "-5" } ] }, { "name": "text", "data": " Pa的压力下依次蒸镀3,3'-[5'-[3-（3-吡啶基）苯基]（TmPyPB）、Liq和Al分别作为电子传输层、电子注入层和阴极电极。该器件在手套箱中氮气氛围下用可固化UV树脂进行封装. 通过PR-735 SpectraScan光谱辐射计（Photo Research）与Keithley 2400 Source Meter装置结合，使用定制软件进行控制，可以同时确定EL光谱（在密闭黑暗条件下测得）和电流电压发光强度特性。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2　辅助配体及配合物的合成" } ], "level": "2", "id": "s2b" } }, { "name": "p", "data": [ { "name": "text", "data": "辅助配体及配合物的合成路线如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "所示。化合物1和主配体CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq的合成参考相关文献中的方法" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } } ], "rid": [ "R25", "R26" ], "text": "25-26", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "功能化辅助配体FL-pic和铱（Ⅲ）配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的合成路线" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "Synthetic routes of functionalized auxiliary ligand FL-pic and iridium（Ⅲ） complex （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865532&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865540&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865536&type=", "width": "163.00001526", "height": "60.61868286", "fontsize": "" } ] } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2.1　化合物3‐（6‐（9‐辛基‐9H‐芴‐9‐基）己基）氧基）吡啶甲酸甲酯（2）的合成" } ], "level": "3", "id": "s2b1" } }, { "name": "p", "data": [ { "name": "text", "data": "在100 mL三口瓶中，依次加入1.00 g化合物1（2.27 mmol）、173 mg（1.13 mmol）3-羟基吡啶甲酸甲酯、0.78 g（5.65 mmol）碳酸铯、50 mL N,N-二甲基甲酰胺，氮气保护下80 ℃反应12 h。停止反应，加水淬灭，冷却至室温。二氯甲烷萃取，有机层无水MgSO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "干燥。过滤，减压蒸馏除去溶剂，粗产品以石油醚∶乙酸乙酯=1∶1（" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "text", "data": "）为洗脱剂，柱层析分离，得到淡黄色粘稠固体482 mg，产率83%。" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR（400 MHz，CDCl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "）, " }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "（10" }, { "name": "sup", "data": [ { "name": "text", "data": "-6" } ] }, { "name": "text", "data": "）: 8.30（s，1H），7.73（d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=15.4 Hz，2H）, 7.38~7.27（m，8H），4.06~3.85（m，5H），2.01（s，4H），1.35~0.95（m，14H），0.95~0.77（m，4H），0.65（s，5H）。" }, { "name": "sup", "data": [ { "name": "text", "data": "13" } ] }, { "name": "text", "data": "C NMR（75 MHz，CDCl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "），" }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "（10" }, { "name": "sup", "data": [ { "name": "text", "data": "-6" } ] }, { "name": "text", "data": "）:165.21，154.98，150.48，141.07，140.75，138.92，127.00，126.91，126.72，122.78，120.88，119.63，77.48，77.26，77.05，76.63，68.93，54.93，53.44，52.46，40.37，40.23，31.76，30.00，29.54，29.19，28.72，25.41，23.69，23.64，22.57，14.07。Anal.calcd for C" }, { "name": "sub", "data": [ { "name": "text", "data": "34" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "43" } ] }, { "name": "text", "data": "‐NO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": ": C, 79.49; H, 8.44; N, 2.73; O, 9.34；found: C, 79.51； H, 8.43； N, 2.77; O, 9.29。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2.2　化合物3‐（6‐（9‐辛基‐9H‐芴‐9‐基）己基）氧基）吡啶甲酸（3）（FL‐pic）的合成" } ], "level": "3", "id": "s2b2" } }, { "name": "p", "data": [ { "name": "text", "data": "在100 mL单口瓶中，依次加入400 mg（0.78 mmol）化合物2、8 mL 5%的NaOH溶液、8 mL甲醇、8 mL四氢呋喃，在氮气保护下70 ℃反应4 h。 停止反应，冷却至室温，将反应液倒入50 mL蒸馏水中，用稀硫酸调节pH=2，静置过夜。抽滤，固体用蒸馏水洗涤，得到白色固体294 mg，产率76%。" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR（400 MHz，CDCl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "），" }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "（10" }, { "name": "sup", "data": [ { "name": "text", "data": "-6" } ] }, { "name": "text", "data": "）: 8.19（d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "= 4.5 Hz，1H），7.77~7.64（m，2H），7.50（d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=8.6 Hz，1H），7.44~7.24（m，7H），4.00（t，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=6.7 Hz，2H）， 2.06~1.87（m，4H），1.79~1.64（m，2H），1.34~0.96（m，14H），0.81（t，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=7.1 Hz，3H），0.73~0.52（m，4H）。Anal. calcd for C" }, { "name": "sub", "data": [ { "name": "text", "data": "33" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "41" } ] }, { "name": "text", "data": "NO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": ": C, 79.32; H, 8.27;N, 2.80;O,9.61；found:C,79.40；H,8.29；N, 2.83; O, 9.48。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2.3　配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA‐BTz‐Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic‐FL）的合成" } ], "level": "3", "id": "s2b3" } }, { "name": "p", "data": [ { "name": "text", "data": "在100 mL单口瓶中，依次加入配体CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq（340 mg，0.51 mmol）、水合三氯化铱（61 mg，0.21 mmol）、15 mL乙二醇单乙醚、5 mL 蒸馏水，在氮气保护下100 ℃反应36 h。停止反应，冷却至室温，加入15 mL蒸馏水，二氯甲烷萃取，饱和食盐水洗涤，有机层无水MgSO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "干燥。过滤后，减压蒸馏除去溶剂，真空干燥，得黑红色氯桥连固体（400 mg），直接用于下一步反应。将氯桥连固体加入50 mL单口瓶中，再依次加入化合物FL-pic（260 mg，0.52 mmol）、无水Na" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "CO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（82 mg，0.78 mmol）、15 mL乙二醇单乙醚，在氮气保护下110 ℃反应36 h。停止反应，冷却至室温，加入15 mL蒸馏水，二氯甲烷萃取，饱和食盐水洗涤，有机层无水MgSO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "干燥。过滤后，减压蒸馏除去溶剂，粗产品用二氯甲烷∶乙酸乙酯=2∶1（" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "text", "data": "）为洗脱剂，柱层析分离，得红色固体148 mg，产率29%。" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR（400 MHz，DMSO-" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "），" }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "（10" }, { "name": "sup", "data": [ { "name": "text", "data": "-6" } ] }, { "name": "text", "data": "）: 9.69（d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=8.8 Hz，1H），9.48（d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "= 8.8 Hz，1H），8.57（d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=6.4 Hz，1H），8.07（d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "= 8.0 Hz，2H），7.88（d，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=6.4 Hz，1H），7.76~7.63（m，8H），7.58（d， " }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=6.8 Hz，1H），7.38（t，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=6.0 Hz，3H），7.26~7.17（m， 9H），7.00~6.91（m，16H），6.50（t，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=9.0 Hz，4H），6.40（s，1H），6.17（s，1H），4.62（t，" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=6.0 Hz，4H）， 3.94~3.92（m，2H），3.75（s，12H），2.00~1.90（m，8H）， 4.50~1.47（m，2H），1.27~0.92（m，34H），0.76~0.69（m， 9H），0.49~0.42（m，4H）。" }, { "name": "sup", "data": [ { "name": "text", "data": "13" } ] }, { "name": "text", "data": "C NMR（101 MHz，CDCl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "）， " }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "（10" }, { "name": "sup", "data": [ { "name": "text", "data": "-6" } ] }, { "name": "text", "data": "）:171.22，170.37，169.25，160.58， 159.03，158.58，156.02，155.83，150.59，148.59，148.17，145.05，144.93，144.84，141.53，141.08， 140.79， 140.54，140.26，137.36，137.16，130.86，130.25，129.34，129.22，129.01，128.47，127.92， 127.06，126.85，126.73，126.49，125.59，122.88， 122.65， 120.20，119.84，119.64，114.65，114.57，69.89，56.18，55.89，55.54，54.99，40.34，31.80，30.10，29.78，29.24，29.14，28.73，26.72，26.64，25.49，23.74，22.66，14.12。 MALDI-TOF MS（" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "） for C" }, { "name": "sub", "data": [ { "name": "text", "data": "119" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "124" } ] }, { "name": "text", "data": "IrN" }, { "name": "sub", "data": [ { "name": "text", "data": "11" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": ", Calcd: 2 012.542; found, 2 011.978 [M]" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "。" } ] } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　结果与讨论" } ], "level": "1", "id": "s3" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　铱（Ⅲ）配合物的热稳定性和光物理性能" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "是配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）在氮气流下测试的热失重（TGA）曲线。由测试结果可知，配合物分子表现出良好的热稳定性，其热分解温度为342 ℃，与之前报道的没有辅助配体功能化的配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Irpic相比（热失重温度为244 ℃）" }, { "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": "有约100 ℃的提高，这表明在辅助配体中引入芴基团有助于提高配合物的热稳定性能，使其更适于有机光电材料的制备。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的TGA曲线" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "TGA curve of （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865543&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865552&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865549&type=", "width": "63.91564941", "height": "44.79364014", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "在室温下，配体CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq和配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）在二氯甲烷溶液（10" }, { "name": "sup", "data": [ { "name": "text", "data": "-5" } ] }, { "name": "text", "data": " mol/L）中的紫外-可见（UV-Vis）吸收和光致发光（PL）光谱如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "所示，配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）在固体膜中的UV-Vis吸收和PL光谱也如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "所示，数据见" }, { "name": "xref", "data": { "text": "表1", "type": "table", "rid": "T1", "data": [ { "name": "text", "data": "表1" } ] } }, { "name": "text", "data": "。由图可知，在溶液中，配体CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq吸收光谱在280~550 nm范围内有两个明显的吸收峰，分别位于295 nm 和393 nm左右，这分别归属于分子的π-π" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "电荷跃迁和分子内电子转移跃迁（ICT）吸收。配合物的吸收光谱位于280～600 nm范围，与配体的吸收光谱相比，在300 nm左右的强吸收归属于主配体和辅助配体内自旋允许的" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "LC π-π" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "电荷跃迁，400~500 nm的吸收峰归属于强的D-A作用导致ICT吸收，500~550 nm的弱吸收峰归属于自旋允许的金属到配体的电荷转移（" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "MLCT）和配体到配体的电荷转移跃迁（" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "LLCT）以及自旋禁阻的 " }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "MLCT 和 " }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "ILCT 的混合态吸收。在固体薄膜状态下，最大吸收峰的位置有约15 nm的红移，这是因为分子间的π-π堆积导致的。由光致发光光谱可知，在480 nm的激发波长下，配合物在二氯甲烷溶液中的最大发射峰位于717 nm的近红外区域，在固体薄膜中的最大发射峰约有5 nm的红移,位于722 nm。与CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq（激发波长为390 nm，最大发射波长为575 nm）发射光谱相比，配合物的最大发射峰有约140 nm的红移，这主要归因于MLCT跃迁发射。与前期报道的没有辅助配体功能化的母体配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Irpic相比" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "（最大发射峰位于718 nm），光致发光位置没有明显变化，这表明，通过烷氧基链引入芴基团至铱（Ⅲ）配合物辅助配体中对配合物光致发光峰位置影响不大。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "配体CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq和（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）在二氯甲烷溶液（10" }, { "name": "sup", "data": [ { "name": "text", "data": "-5" } ] }, { "name": "text", "data": " mol/L）以及（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）在固体薄膜中的紫外-可见吸收和光致发光光谱" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "UV-Vis absorption and photoluminescence spectra at room temperature of CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq ligand and （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL） in dichloromethane solution（10" }, { "name": "sup", "data": [ { "name": "text", "data": "-5" } ] }, { "name": "text", "data": " mol/L）， and （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL） in solid film." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865555&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865561&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865557&type=", "width": "69.53088379", "height": "44.79364014", "fontsize": "" } ] } }, { "name": "table", "data": { "id": "T1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "表1" } ], "title": [ { "name": "text", "data": "配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的光物理、电化学和热稳定性数据" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Tab.1" } ], "title": [ { "name": "text", "data": "Photophysical， electrochemical and thermal parameters properties of （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）" } ] } ], "note": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "sup", "data": [ { "name": "text", "data": "a" } ] }, { "name": "text", "data": "Measured in degassed CH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Cl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（10" }, { "name": "sup", "data": [ { "name": "text", "data": "-5" } ] }, { "name": "text", "data": " mol/L）. 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[ { "name": "text", "data": "f" } ] }, { "name": "text", "data": "/eV" } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "p", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "/" } ] }, { "name": "p", "data": [ { "name": "sup", "data": [ { "name": "text", "data": "o" } ] }, { "name": "text", "data": "C" } ] } ] } ] ], "body": [ [ { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "304， 365， 467， 545 305， 370， 490， 560" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "717， 790 722， 791" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "0.37" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "0.46" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "1.24" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "2.69" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "-5.09/-3.03" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "2.06" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "342" } ] } ] ], "foot": [] } ], "graphics": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865567&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865564&type=", "width": "162.79998779", "height": "17.64233017", "fontsize": "" } } }, { "name": "p", "data": [ { "name": "text", "data": "为了更好地了解配合物的光物理性能，采用参比法测试和计算了其光致发光量子效率（Photoluminescence quantum yield，PLQY），参比样品为Ru（byp）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（PF" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "Ф" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "r" } ] }, { "name": "text", "data": "=6.2%）。测试和计算结果表明，配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的PLQY为0.46%，比母体配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Irpic（" }, { "name": "italic", "data": [ { "name": "text", "data": "Ф" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "r" } ] }, { "name": "text", "data": "=0.30%）有所提高" }, { "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": "，这表明辅助配体中芴衍生物的引入可以提高（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的发光量子效率，与预计结果相符。我们还测试了配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）在脱气二氯甲烷溶液中的发光衰减特性，如图S1所示（见本文补充文件），其发光寿命（" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "text", "data": "）可以单指数拟合，拟合的" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "text", "data": "为0.37 μs，如此短的激发态寿命有利于缓解发光器件在高电流密度下的效率滚降。通过公式：" } ] }, { "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=35865574&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865569&type=", "width": "12.78466606", "height": "3.80999994", "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=35865579&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865575&type=", "width": "22.77533340", "height": "4.57200003", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF2" } }, { "name": "p", "data": [ { "name": "text", "data": "计算得到配合物的辐射和非辐射跃迁速率（" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "r" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "k" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "sub", "data": [ { "name": "text", "data": "r" } ] }, { "name": "text", "data": "），与母体配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Irpic相比" }, { "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": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "r" } ] }, { "name": "text", "data": "=0.62×10" }, { "name": "sup", "data": [ { "name": "text", "data": "4 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，" }, { "name": "italic", "data": [ { "name": "text", "data": "k" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "sub", "data": [ { "name": "text", "data": "r" } ] }, { "name": "text", "data": "=2.07×10" }, { "name": "sup", "data": [ { "name": "text", "data": "6 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "），（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）具有较高的" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "r" } ] }, { "name": "text", "data": "，这表明芴衍生物的引入可以提高材料的辐射跃迁速率，具体数据见" }, { "name": "xref", "data": { "text": "表1", "type": "table", "rid": "T1", "data": [ { "name": "text", "data": "表1" } ] } }, { "name": "text", "data": "。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　铱（Ⅲ）配合物的电化学性能" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "text", "data": "配合物的前线分子轨道能级，尤其是最高占据轨道和最低未占轨道能级对器件结构的设计具有十分重要的意义。因此，通过循环伏安法（CV）测试了配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的氧化和还原电位，研究了其电化学性能，如图S2所示（见本文补充文件），数据见" }, { "name": "xref", "data": { "text": "表1", "type": "table", "rid": "T1", "data": [ { "name": "text", "data": "表1" } ] } }, { "name": "text", "data": "。由图可知，配合物分别在0.53 V和-1.53 V处出现明显的氧化和还原峰。根据公式" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "HOMO/LUMO" } ] }, { "name": "text", "data": "=-（" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "[onset ox/red " } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "vs" } ] } ] }, { "name": "sub", "data": [ { "name": "text", "data": " Fc+/Fc]" } ] }, { "name": "text", "data": "-4.80） eV可以计算出配合物的HOMO和LUMO能级分别为-5.09 eV和-3.03 eV。依据经验公式 " }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "LUMO " } ] }, { "name": "text", "data": "-" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "HOMO" } ] }, { "name": "text", "data": "，计算出相应的能隙为2.06 eV。配合物具有较低的LUMO能级，这有助于器件中电子的捕获，平衡电 子‐空穴的复合，提高器件的效率。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.3　铱（Ⅲ）配合物的电致发光性能" } ], "level": "2", "id": "s3c" } }, { "name": "p", "data": [ { "name": "text", "data": "为了研究配合物的电致发光性能，以（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）为发光掺杂剂制备了电致发光器件，具体结构为：ITO/PEDOT∶PSS （40 nm）/m-MTDATA∶" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "% iridium（Ⅲ） complex（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": " =3, 6, 9, 12）（40 nm）/TmPyPB（30 nm）/Liq（1 nm）/Al（100 nm）（器件Ⅰ），其HOMO/LUMO能级图和器件相关材料分子式如" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "所示。器件Ⅰ中，Liq为电子注入材料，TmPyPB因具有良好的电子迁移率和较低的HOMO能级用来作为电子传输/空穴阻挡层，m-MTDATA为主体材料。电致发光光谱如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "所示，详细数据见" }, { "name": "xref", "data": { "text": "表2", "type": "table", "rid": "T2", "data": [ { "name": "text", "data": "表2" } ] } }, { "name": "text", "data": "。在电致发光光谱中，位于710 nm处的近红外发射峰归属于配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的本征发射。除此之外，图中还显示了一个位于480 nm左右的发射峰，这归属于主体材料m-MTDATA的发射。在" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（a）中，配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的HOMO/ LUMO能级基本上嵌入在主体材料m-MTDATA的HOMO/LUMO能级内，但是它们的HOMO能级几乎相同，这可能是导致电致发光光谱图中主体-客体能量传递不完全的原因。" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "和" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "为器件Ⅰ的外量子效率-电流密度（EQE" }, { "name": "italic", "data": [ { "name": "text", "data": "‐J" } ] }, { "name": "text", "data": "）和电流密度-电压-辐照度（" }, { "name": "italic", "data": [ { "name": "text", "data": "J‐V‐R" } ] }, { "name": "text", "data": "）曲线，详细数据见" }, { "name": "xref", "data": { "text": "表2", "type": "table", "rid": "T2", "data": [ { "name": "text", "data": "表2" } ] } }, { "name": "text", "data": "。由图中可知，在掺杂浓度为9%，电流密度（" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "）为0.4 mA/cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-2" } ] }, { "name": "text", "data": "时获得了0.61%的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "，最大辐照度（" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "）为18 383 mW/（Sr·m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）。然而，由于主体和客体之间的HOMO能级相差很小，不利于能量的传输，因此器件的EQE在高电流密度下有明显的效率滚降现象。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "（a）器件中各材料的HOMO和LUMO能级图；（b）器件中使用材料的分子结构。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "（a）Energy level diagram of HOMO and LUMO levels. （b）Molecular structures of materials used in this study." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865583&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865586&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865585&type=", "width": "114.02581787", "height": "100.50445557", "fontsize": "" } ] } }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "铱（Ⅲ）配合物在器件Ⅰ中不同掺杂浓度的归一化EL光谱" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "Normalized EL spectra of the iridium（Ⅲ） complex-doped OLEDs at different concentrations in Device Ⅰ" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865590&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865595&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865593&type=", "width": "63.97711182", "height": "44.79364014", "fontsize": "" } ] } }, { "name": "table", "data": { "id": "T2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "表2" } ], "title": [ { "name": "text", "data": "铱（Ⅲ）配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA‐BTz‐Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（pic‐FL）在不同器件结构和掺杂浓度下的器件电致发光性能" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Tab.2" } ], "title": [ { "name": "text", "data": "The EL performance of OLEDs with iridium（Ⅲ） complexes （CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（pic-FL） at different devices and doping concentrations" } ] } ], "note": [], "table": [ { "head": [ [ { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "text", "data": "Device" } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "text", "data": "Ratio/%" } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "p", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL，max" } ] }, { "name": "text", "data": "/" } ] }, { "name": "p", "data": [ { "name": "text", "data": "nm" } ] } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { 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"italic", "data": [ { "name": "text", "data": "‐J" } ] }, { "name": "text", "data": " characteristics of the iridium（Ⅲ） complex-doped OLEDs at different doping concentrations in Device Ⅰ" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865603&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865608&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865606&type=", "width": "64.34014893", "height": "46.24377441", "fontsize": "" } ] } }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "铱（Ⅲ）配合物在器件Ⅰ中不同掺杂浓度下的电流密度-电压-辐照度（" }, { "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": "R" } ] }, { "name": "text", "data": "）曲线。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "Current density-voltage-irradiance（" }, { "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": "R" } ] }, { "name": "text", "data": "） curves of iridium（Ⅲ） complex at different doping concentrations in Device Ⅰ" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865611&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865617&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865613&type=", "width": "73.22064209", "height": "45.57360840", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "为了进一步优化器件性能，我们又制备了器件结构为ITO/PEDOT∶PSS（35 nm）/poly-TPD（30 nm）/PVK∶OXD-7（70∶30）∶" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%iridium（Ⅲ） complex（" }, { "name": "italic", "data": [ { "name": "text", "data": "x " } ] }, { "name": "text", "data": "=4, 6, 8）（60 nm）/TmPyPB（50 nm）/Liq（1 nm）/Al（100 nm）的器件Ⅱ，其器件相关物质分子式和HOMO/LUMO能级如" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "所示。器件Ⅱ中增加了30 nm的poly-TPD空穴传输层，并选用PVK和OXD-7作为主体材料，电致发光光谱如" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "所示，测试条件与器件Ⅰ相同，详细数据见" }, { "name": "xref", "data": { "text": "表2", "type": "table", "rid": "T2", "data": [ { "name": "text", "data": "表2" } ] } }, { "name": "text", "data": "。由" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "可以明显地看出，器件Ⅱ的电致发光光谱最大发光峰与器件Ⅰ相似，唯一不同的是主体材料的发射峰消失了。由" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "器件Ⅱ的器件能级图可以看出，配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）的HOMO和LUMO能级完全嵌入了主体材料PVK和OXD-7的HOMO和LUMO能级，这就使得主体到客体材料的能量传递非常完全，电致发光光谱中主体材料发射峰完全消失。" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "和" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "为器件Ⅱ的EQE-" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "和" }, { "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": "R" } ] }, { "name": "text", "data": "曲线，详细数据见" }, { "name": "xref", "data": { "text": "表2", "type": "table", "rid": "T2", "data": [ { "name": "text", "data": "表2" } ] } }, { "name": "text", "data": "。由图中可知，在掺杂浓度为4%时获得了0.92%的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "为7 630 mW/（Sr·m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）。由于poly-TPD空穴传输层的引入和PVK∶OXD-7（70∶30）主体材料的更换，器件在高电流密度下的效率滚降受到了抑制，使得器件效率有明显提升，较我们之前报道的没有辅助配体功能化的母体配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Irpic" }, { "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": "（EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "= 0.41%@723 nm）有了进一步的提升。这表明高荧光量子效率芴基团的引入可以改善材料的光电性能，提高器件效率。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "铱（Ⅲ）配合物在器件Ⅱ中不同掺杂浓度的归一化EL光谱" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "Normalized EL spectra of the iridium（Ⅲ） complex-doped OLEDs at different concentrations in Device Ⅱ" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865621&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865629&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865625&type=", "width": "63.97711182", "height": "44.79364014", "fontsize": "" } ] } }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "铱（Ⅲ）配合物在器件Ⅱ中不同掺杂浓度的EQE-" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "特性" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.9" } ], "title": [ { "name": "text", "data": "EQE-" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": " characteristics of the iridium（Ⅲ） complex-doped OLEDs at different doping concentrations in Device Ⅱ" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865632&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865638&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865635&type=", "width": "62.80914307", "height": "44.59024048", "fontsize": "" } ] } }, { "name": "fig", "data": { "id": "F10", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图10" } ], "title": [ { "name": "text", "data": "铱（Ⅲ）配合物在器件Ⅱ中不同掺杂浓度下的" }, { "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": "R" } ] }, { "name": "text", "data": "曲线" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.10" } ], "title": [ { "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": "R" } ] }, { "name": "text", "data": " curves of iridium（Ⅲ） complex at different doping concentrations in Device Ⅱ" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865641&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865645&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865643&type=", "width": "73.33065796", "height": "45.85314941", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　结　　论" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "本文设计并合成了一种新型辅助配体功能化铱（Ⅲ）配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL），在辅助配体中引入柔性烷基链和高荧光量子效率的刚性芴基团有助于提高其光物理和电致发光性能。在OLEDs中，采用（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ir（pic-FL）作为发光掺杂剂，器件在722 nm处获得了0.92%的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "，这是没有辅助配体功能化的母体配合物（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "OTPA-BTz-Iq）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Irpic的2.24倍。" } ] }, { 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