高性能白光有机发光二极管的湿法制备及其相关材料研究

硕士学位论文论文题目：高性能白光有机发光二极管的湿法制备及其相关材料研究SolutionProcessedHigh-performanceWhiteOrganicLightEmittingDiodesandRelatedMaterials摘要WOLED由于具有轻薄、可实现柔性、节能环保、易于大面积制备和生理友好等优势被誉为下一代照明技术，目前已有相关商业化的照明产品面世。本论文针对湿法加工WOLED研究当前存在的部分难题，提出了我们的解决思路，以推动OLED照明的产业化应用。基于PVK基聚合物互补色WOLED研究中普遍存在的发光光谱不稳定现象，我们构筑了本体系所独有的器件结构：ITO/PEDOT:PSS(35nm)/(PVK:OXD-7:FIrpic(7:3:1)):wt%Ir(bt)2(acac)(55nm)/TPBI(35nm)/Ca:Ag，并对客体的掺杂比例进行优化探索，成功制得具有优良光谱稳定性的白光器件，同时器件最大亮度达50000cd/m2，最大电流效率为25.5cd/A，且CRI达到了72，属于同类器件中的最高水平。针对溶液加工型WOLED难以获得“双高”效果的问题，采用了光物理性能优良的三苯胺衍生物作主体材料，并将之与高性能新型客体材料及常规磷光客体搭配使用，制备了一系列互补色、三基色和四基色WOLED。性能最好的四基色器件总能量效率达33.6lm/W，同时具有高达83的CRI和适中的CCT，为该类问题的应对提供了新的解决思路。暖白光对抗黑变激素具有较低的抑制作用，是一种生理友好的理想照明光源。我们针对湿法加工暖白光OLED当前存在的色品质不高且光谱不稳定的情况，利用自主合成的咔唑衍生物小分子作为主体，对制备出高性能的湿法加工暖白光器件进行了有益尝试。我们制备的四基色暖白光器件在100-10000cd/m2的亮度范围内保持了2500K以下的低色温和稳定的白光发射，CRI高达83，CIE色坐标也落在了标准暖白光点附近，同时最大流明效率达到了18.0cd/A，与传统白炽灯的水平相当。关键词:白光，溶液加工，磷光，有机发光二极管，低色温，三苯胺，咔唑

AbstractWhiteorganiclight-emittingdiodes(WOLED)featuringlightinweight,flexible,energy-saving,easeoflarge-areafabrication,andbio-friendlydiffusivewarmlight,havebeengenerallyrecognizedasthemostpromisingcandidatefornextgenerationlightingtechnique,andevencommerciallightingpanelmodelshaveemerged.Inthisthesis,weputforwardsomemethodstosolvetheissuesfacedwithsolutionprocessedWOLED,inordertopromotetheindustrializationofOLEDlighting.Fortheinstableelectroluminescencespectrumofthetwo-componentWOLEDusingPVKasthehost,wefabricatedanuniquedevicestructureasfollows:ITO/PEDOT:PSS(35nm)/(PVK:OXD-7:FIrpic(7:3:1)):wt%Ir(bt)2(acac)(55nm)/TPBI(35nm)/Ca:Ag,andthenweoptimizedthedopingcontentofIr(bt)2(acac).Ourdeviceshowsstableemissionundertheappliedvoltagesrangingfrom5-11V,maximumbrightnessofaround50000cd/m2,highefficiencywiththemaximumcurrentefficiencyof25.5cd/A.What’smore,italsoperformshighCRIvalueof72,makesitthebestvalueseverreportedbefore.AstothebalancedconsiderationproblemsbetweencolorqualityandELefficiency,weusedanoveltriphenylaminederivativenamedDTPAFBasoursmallmolecularhost,whichpessessexcellentphotophysicalproperties.Furthercombiningthenewlydevelopedphosphorescentmaterialswiththecommonmaterials,wegotaseriesofbinaryBOcomplementarycolorWOLED,RGBthree-componentWOLED,RGBOfourprimarycolorWOLED.TheRGBOdevice,whichexihibitsthebestperformance,possessatotalpowerefficiencyreaches33.6lm/W,aswellasahighCRIof83,mediateCCT,warmandsofttohumaneye.Thiskindofworkwillprovideagoodguideforfurthermaterial-choosingandWOLEDsfabrication.Warmlightingsourcesarepreferredforphysiologically-friendlyilluminationduetotheirlowsuppressionofmelatoninsecretion.AsthereisstillamumberofchallengestothecolorqualityandthestabilityoftheELspectrumforsolutionprocessedwarmWOLED,Wetriedtofabricatelow-CCTdevicesusinganovelcarbazolederivativeashost.FinallywefoundthatourfourprimarycolordeviceshowsaCCTlessthan2500Kandexactlystableelectroluminescencespectruminabrightnessofabout100-10000cd/m2,withahighCRIof83.Moreover,thesedevicesexhibitapeakcurrentefficiencyof18.0cd/A,whichiscomparablewithincandescentbulbs.Keywords:whiteemission,solutionprocess,phosphorescence,OLED,lowcolortemperature,triphenylamine,carbazole

目录第一章绪论 11.1OLED技术的发展历程 21.2OLED的基本结构及工作原理 41.3OLED的器件制备工艺 61.4本论文的主要工作 9第二章WOLED概述 112.1WOLED的研究进展 112.2WOLED的产业化情况 122.2.1WOLED在国际上的产业化情况 122.2.2我国WOLED的产业化情况 152.2.3WOLED的市场前景预测 162.3WOLED的实现方法 182.4WOLED的性能指标 192.5本章小结 21第三章光谱稳定的基于聚合物主体的全磷光WOLED研究 223.1引言 223.2实验部分 233.2.1材料 233.2.2器件的制备与测试 243.3结果与讨论 263.3.1发光层物质的光物理性质与能量传递机理研究 263.3.2聚合物基全磷光WOLED的色品质及光谱稳定性 273.3.3聚合物基全磷光WOLED的J-V-L特性与器件效率 293.4本章小结 30第四章基于三苯胺衍生物小分子主体材料的可湿法加工全磷光WOLED研究 324.1引言 324.2实验部分 334.3结果与讨论 344.3.1材料的光物理性质研究 344.3.2主体-客体掺杂系统研究 364.3.3有机薄膜的形貌研究 374.3.4基于三苯胺衍生物小分子主体的可湿法加工互补色全磷光WOLED 384.3.5基于三苯胺衍生物小分子主体的可湿法加工三基色全磷光WOLED 404.3.6基于三苯胺衍生物小分子主体的可湿法加工四基色全磷光WOLED 424.4本章小结 45第五章基于咔唑衍生物小分子主体材料的可湿法加工暖白光器件研究 475.1引言 475.2实验部分 485.3结果与讨论 495.3.1发光层物质的光物理性质与能量传递机理研究 495.3.2有机薄膜的形貌研究 505.3.3基于咔唑衍生物小分子主体的WOLED的色品质及光谱稳定性 515.3.4基于咔唑衍生物小分子主体的WOLED的J-V-L特性与器件效率 535.4本章小结 54第六章总结与展望 55参考文献 57附录1攻读硕士学位期间撰写的论文 61附录2攻读硕士学位期间申请的专利 62附录3攻读硕士学位期间参加的科研项目 63致谢 64绪论有机发光二极管（OrganicLight-EmittingDiode，OLED）自发明以来，一直是世人关注的焦点。如今经过二十多年突飞猛进的发展，OLED已经向人类展示出在未来显示、照明、液晶显示器背光源等领域将对未来社会产生重要影响的巨大潜力。在显示领域，人类自进入互联网时代以来，信息传递方式已由早期的固定显示、可变显示、电子显示演变成为如今的交互显示，而未来显示的发展仍将继续秉承“以人为本”的导向。目前平板显示技术已成功实现了轻薄和便携，下一步人类追求的必定是柔性显示，OLED技术将会承担起这个重要角色。从技术的角度来说，OLED具有轻薄、省电、对比度高、自发光、可视角宽、响应频率高、驱动电压低、可实现大尺寸和柔性显示等特性，有望带来显示领域市场的又一轮变革ADDINEN.CITE<EndNote><Cite><Author>黄春辉</Author><Year>2005</Year><RecNum>12</RecNum><DisplayText><styleface="superscript">[1]</style></DisplayText><record><rec-number>12</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">12</key></foreign-keys><ref-typename="Book">6</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">黄春辉</style></author><author><styleface="normal"font="default"charset="134"size="100%">李富友</style></author><author><styleface="normal"font="default"charset="134"size="100%">黄维</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">有机电致发光材料与器件导论</style></title></titles><section>446</section><dates><year>2005</year></dates><publisher><styleface="normal"font="default"charset="134"size="100%">复旦大学出版社</style></publisher><urls></urls></record></Cite></EndNote>[\o"黄春辉,2005#12"1]。产品方面，从1997年第一台OLED显示屏问世起，市场上OLED的新应用的种类和数量逐年都在递增ADDINEN.CITE<EndNote><Cite><RecNum>14</RecNum><DisplayText><styleface="superscript">[2]</style></DisplayText><record><rec-number>14</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">14</key></foreign-keys><ref-typename="WebPage">12</ref-type><contributors></contributors><titles></titles><dates></dates><urls><related-urls><url>/oled-news/200810/172.shtml</url></related-urls></urls></record></Cite></EndNote>[\o",#14"2]，尤其近几年，OLED更是高端新品迭出，颇为让人振奋。尤其是三星公司，作为OLED显示领域的带头大哥，在OLED真正走向市场的过程中起到了最重要的推动作用。目前世界上90%以上的OLED手机都是三星的产品，且三星一直都在自己的众多款旗舰机上搭载AMOLED显示屏ADDINEN.CITE<EndNote><Cite><Author>A</Author><Year>6</Year><RecNum>4</RecNum><DisplayText><styleface="superscript">[3]</style></DisplayText><record><rec-number>4</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">4</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>A</author></authors></contributors><titles></titles><dates><year>6</year></dates><urls></urls></record></Cite></EndNote>[\o"A,6#4"3]。除此之外，LG逐年不断刷新其OLED电视记录，至今已实现多款显示效果极佳的曲面OLED电视ADDINEN.CITE<EndNote><Cite><Author>A</Author><Year>1</Year><RecNum>16</RecNum><DisplayText><styleface="superscript">[4]</style></DisplayText><record><rec-number>16</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">16</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>A</author></authors></contributors><titles></titles><dates><year>1</year></dates><urls></urls></record></Cite></EndNote>[\o"A,1#16"4]。华为和苹果公司也分别在今年3月份刚刚结束的2015MWC以及苹果发布会上展示了各自搭载OLED显示屏的智能手表ADDINEN.CITE<EndNote><Cite><Author>A</Author><Year>2</Year><RecNum>17</RecNum><DisplayText><styleface="superscript">[5]</style></DisplayText><record><rec-number>17</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">17</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>A</author></authors></contributors><titles></titles><dates><year>2</year></dates><urls></urls></record></Cite></EndNote>[\o"A,2#17"5]，尤其是苹果，作为世界消费电子界的“风向标”，本次初步试水OLED应用，无疑将牵动整个行业的神经，势必重新定义整个智能穿戴领域，为OLED的发展带来前所未有的机遇。在照明应用方面，轻薄、可挠、接近太阳光的白光有机发光二极管（WOLED），被视为下世代的照明新星。OLED是面光源，比较柔和，人眼直视不会眩晕，适用于室内照明。有机材料丰富的发光特性使制备的OLED很容易进行颜色调节，实现高的显色性，此外OLED光源还有可弯曲特性且无高热问题，易与建筑材料直接结合，让设计师在设计时拥有更多的弹性。目前为止，国内外已出现多款用于百货、咖啡厅等情境的创意OLED灯具ADDINEN.CITE<EndNote><Cite><Author>A</Author><Year>3</Year><RecNum>19</RecNum><DisplayText><styleface="superscript">[6]</style></DisplayText><record><rec-number>19</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">19</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>A</author></authors></contributors><titles></titles><dates><year>3</year></dates><urls></urls></record></Cite></EndNote>[\o"A,3#19"6]，WOLED照明的市场正在逐步扩大。OLED在作为TFT-LCD技术背光源的应用方面也显现出独特的优势。由于通常用作背光源的LED灯为点光源，故在生产中需加入光扩散膜工艺，而白光OLED为面光源，光扩散膜工序就可省去，工艺成本下降可观。有报道指出，早在2011年，三星、LG已开建用OLED作背光源的TFT-LCD新生产线ADDINEN.CITE<EndNote><Cite><Author>申智源</Author><Year>2011</Year><RecNum>20</RecNum><DisplayText><styleface="superscript">[7]</style></DisplayText><record><rec-number>20</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">20</key></foreign-keys><ref-typename="Book">6</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">申智源</style></author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">TFT-LCD</style><styleface="normal"font="default"charset="134"size="100%">技术——结构、原理及制造技术</style></title></titles><pages>400</pages><dates><year>2011</year></dates><publisher><styleface="normal"font="default"charset="134"size="100%">电子工业出版社</style></publisher><urls></urls></record></Cite></EndNote>[\o"申智源,2011#20"7]。本章将首先对OLED器件的发展历史与现状做一简单的总结回顾，然后介绍了OLED器件的基本结构及工作原理，接下来进一步阐述了OLED的制备工艺，最后简要概括了本论文的主要工作。OLED技术的发展历程人类对有机物的电致发光的认识最早是在上世纪三十年代，当时科学家将有机荧光材料填充于聚合物中，发现了最早的有机电致发光现象ADDINEN.CITE<EndNote><Cite><Author>Destriau</Author><Year>1936</Year><RecNum>116</RecNum><DisplayText><styleface="superscript">[8]</style></DisplayText><record><rec-number>116</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">116</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Destriau,G</author></authors></contributors><titles><title>Scintillationsofzincsulfideswithalpha-rays</title><secondary-title>J.ChimiePhysique</secondary-title></titles><periodical><full-title>J.ChimiePhysique</full-title></periodical><pages>587</pages><volume>33</volume><dates><year>1936</year></dates><urls></urls></record></Cite></EndNote>[\o"Destriau,1936#116"8]。此后的几十年内，陆续也有一些在有机材料两端施加电压产生发光的现象的报道，但由于初期的器件所施加电压都比较大，人类尚不能看到该类现象具体的应用价值，因而一直未引起人们的太多重视ADDINEN.CITE<EndNote><Cite><Author>Pope</Author><Year>1963</Year><RecNum>23</RecNum><DisplayText><styleface="superscript">[9,10]</style></DisplayText><record><rec-number>23</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">23</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Pope,M.</author><author>Kallmann,H.P.</author><author>Magnante,P.</author></authors></contributors><titles><title>ElectroluminescenceinOrganicCrystals</title><secondary-title>TheJournalofChemicalPhysics</secondary-title></titles><periodical><full-title>TheJournalofChemicalPhysics</full-title></periodical><pages>2042-2043</pages><volume>38</volume><number>8</number><dates><year>1963</year></dates><urls><related-urls><url>/content/aip/journal/jcp/38/8/10.1063/1.1733929</url></related-urls></urls><electronic-resource-num>doi:/10.1063/1.1733929</electronic-resource-num></record></Cite><Cite><Author>Bernanose</Author><Year>1953</Year><RecNum>117</RecNum><record><rec-number>117</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">117</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bernanose,A</author><author>Comte,M</author><author>Vouaux,P</author></authors></contributors><titles><title>Anewmethodofemissionoflightbycertainorganiccompounds</title><secondary-title>J.Chim.Phys</secondary-title></titles><periodical><full-title>J.Chim.Phys</full-title></periodical><pages>64-68</pages><volume>50</volume><dates><year>1953</year></dates><urls></urls></record></Cite></EndNote>[\o"Pope,1963#23"9,\o"Bernanose,1953#117"10]。直至八十年代末，美国柯达公司的邓青云研究员及其助手在美国著名的学术期刊《应用物理快报》上发表了他们的最新成果，文中指出他们采用了新颖的三明治型的器件结构，首次获得了具有突破性的高亮度和高效率有机电致发光器件，并且器件的操作电压也降到了非常低的水平ADDINEN.CITE<EndNote><Cite><Author>Tang</Author><Year>1987</Year><RecNum>24</RecNum><DisplayText><styleface="superscript">[11]</style></DisplayText><record><rec-number>24</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">24</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Tang,C.W.</author><author>VanSlyke,S.A.</author></authors></contributors><titles><title>Organicelectroluminescentdiodes</title><secondary-title>AppliedPhysicsLetters</secondary-title></titles><periodical><full-title>AppliedPhysicsLetters</full-title></periodical><pages>913-915</pages><volume>51</volume><number>12</number><dates><year>1987</year></dates><urls><related-urls><url>/content/aip/journal/apl/51/12/10.1063/1.98799</url></related-urls></urls><electronic-resource-num>doi:/10.1063/1.98799</electronic-resource-num></record></Cite></EndNote>[\o"Tang,1987#24"11]。该成果一经公布，立刻引起了科学界的轰动，自此OLED技术开始受到了世界的瞩目和研究，而邓博士本人也获得了“OLED之父”的美誉，并于去年一度传言成为2014年度“诺贝尔化学奖”候选人而受到媒体热捧ADDINEN.CITE<EndNote><Cite><Author>A</Author><Year>7</Year><RecNum>25</RecNum><DisplayText><styleface="superscript">[12]</style></DisplayText><record><rec-number>25</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">25</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>A</author></authors></contributors><titles></titles><dates><year>7</year></dates><urls></urls></record></Cite></EndNote>[\o"A,7#25"12]。从彼时起，人们对OLED的研究热情前所未有的高涨起来，关于OLED的研究进展层出不穷地涌现，不断地促使OLED一步步走向产业化。接下来，仅就OLED技术发展至今的整个历程当中一些重要的发展节点作以梳理和回顾。1988年，Adachi等人首次在OLED器件结构中引入空穴传输、电子传输等更多有机功能层，极大提高了器件性能的同时，也更加丰富了材料种类ADDINEN.CITE<EndNote><Cite><Author>C</Author><Year>1988</Year><RecNum>26</RecNum><DisplayText><styleface="superscript">[13]</style></DisplayText><record><rec-number>26</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">26</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>AdachiC</author><author>TokitoS</author><author>TsutsuiT</author><author>AC</author></authors></contributors><titles><title>Electroluminescenceinorganicfilmswiththree-layerstructure</title><secondary-title>JapaneseJournalofAppliedPhysic</secondary-title></titles><periodical><full-title>JapaneseJournalofAppliedPhysic</full-title></periodical><pages>L269-L271</pages><volume>27</volume><number>2</number><dates><year>1988</year></dates><urls></urls></record></Cite></EndNote>[\o"C,1988#26"13]。1990年，剑桥大学卡文迪许实验室的friend教授课题组将共轭聚合物PPV作为发光材料，首次实现了聚合物电致发光，开创了有机发光二极管的新的研究领域PLEDADDINEN.CITE<EndNote><Cite><Author>Burroughes</Author><Year>1990</Year><RecNum>27</RecNum><DisplayText><styleface="superscript">[14]</style></DisplayText><record><rec-number>27</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">27</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Burroughes,JH</author><author>Bradley,DDC</author><author>Brown,AR</author><author>Marks,RN</author><author>Mackay,K</author><author>Friend,RH</author><author>Burns,PL</author><author>Holmes,AB</author></authors></contributors><titles><title>Light-emittingdiodesbasedonconjugatedpolymers</title><secondary-title>nature</secondary-title></titles><periodical><full-title>nature</full-title></periodical><pages>539-541</pages><volume>347</volume><number>6293</number><dates><year>1990</year></dates><isbn>0028-0836</isbn><urls></urls></record></Cite></EndNote>[\o"Burroughes,1990#27"14]。Y.Cao（曹镛）和艾伦黑格等人又于1992年利用溶液加工法将MEH-PPV制备于柔性塑料衬底上制得了首个可弯曲的PLED显示器，将OLED技术最具魅力的一面展示给了公众ADDINEN.CITE<EndNote><Cite><Author>Cao</Author><Year>1992</Year><RecNum>28</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>28</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">28</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Cao,Yong</author><author>Treacy,GeorgeM</author><author>Smith,Paul</author><author>Heeger,AlanJ</author></authors></contributors><titles><title>Solution‐castfilmsofpolyaniline:Optical‐qualitytransparentelectrodes</title><secondary-title>Appliedphysicsletters</secondary-title></titles><periodical><full-title>AppliedPhysicsLetters</full-title></periodical><pages>2711-2713</pages><volume>60</volume><number>22</number><dates><year>1992</year></dates><isbn>0003-6951</isbn><urls></urls></record></Cite></EndNote>[\o"Cao,1992#28"15]。1994年，日本Kido课题组制备了发白光的WOLED，为OLED在固态照明领域的研究和应用开辟了先河ADDINEN.CITE<EndNote><Cite><Author>Kido</Author><Year>1994</Year><RecNum>29</RecNum><DisplayText><styleface="superscript">[16]</style></DisplayText><record><rec-number>29</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">29</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kido,Junji</author><author>Hongawa,K</author><author>Okuyama,K</author><author>Nagai,K</author></authors></contributors><titles><title>Whitelight‐emittingorganicelectroluminescentdevicesusingthepoly(N‐vinylcarbazole)emitterlayerdopedwiththreefluorescentdyes</title><secondary-title>AppliedPhysicsLetters</secondary-title></titles><periodical><full-title>AppliedPhysicsLetters</full-title></periodical><pages>815-817</pages><volume>64</volume><number>7</number><dates><year>1994</year></dates><isbn>0003-6951</isbn><urls></urls></record></Cite></EndNote>[\o"Kido,1994#29"16]。次年，加州大学裴启兵和黑格等人在科学杂志上报道他们研制的一种新型器件——有机发光电化学池（OLEC），再次为聚合物发光开辟了新领域ADDINEN.CITE<EndNote><Cite><Author>Pei</Author><Year>1995</Year><RecNum>30</RecNum><DisplayText><styleface="superscript">[17]</style></DisplayText><record><rec-number>30</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">30</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Pei,Qibing</author><author>Yu,Gang</author><author>Zhang,Chi</author><author>Yang,Yang</author><author>Heeger,AlanJ</author></authors></contributors><titles><title>Polymerlight-emittingelectrochemicalcells</title><secondary-title>Science</secondary-title></titles><periodical><full-title>Science</full-title></periodical><pages>1086-1088</pages><volume>269</volume><number>5227</number><dates><year>1995</year></dates><isbn>0036-8075</isbn><urls></urls></record></Cite></EndNote>[\o"Pei,1995#30"17]。到1998年，吉林大学马於光课题组将有机金属配合物掺杂于主体材料，首次实现了基于三线态发光的磷光OLEDADDINEN.CITE<EndNote><Cite><Author>Ma</Author><Year>1998</Year><RecNum>31</RecNum><DisplayText><styleface="superscript">[18]</style></DisplayText><record><rec-number>31</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">31</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ma,Yuguang</author><author>Zhang,Houyu</author><author>Shen,Jiacong</author><author>Che,Chiming</author></authors></contributors><titles><title>Electroluminescencefromtripletmetal—ligandcharge-transferexcitedstateoftransitionmetalcomplexes</title><secondary-title>SyntheticMet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0935-9648(Linking)</isbn><accession-num>24807691</accession-num><urls><related-urls><url>/pubmed/24807691</url></related-urls></urls><electronic-resource-num>10.1002/adma.201306266</electronic-resource-num></record></Cite><Cite><Author>X</Author><Year>1</Year><RecNum>119</RecNum><record><rec-number>119</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">119</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>X</author></authors></contributors><titles></titles><dates><year>1</year></dates><urls></urls></record></Cite></EndNote>[\o"Yook,2014#118"21,\o"X,1#119"22]。但可喜的是，新世纪以来，OLED技术还是取得过一些较重要的突破性进展的。例如2012年时，日本九州大学Adachi课题组在nature上报道了一种热致延迟荧光（TADF）现象，首次实现了荧光材料的IQE达到100%，突破了长期以来的只有高IQE器件只有磷光金属配合物的限制，引起了世界范围内的关注，相信不久的将来必将会展现出对OLED产业的重大作用ADDINEN.CITE<EndNote><Cite><Author>Uoyama</Author><Year>2012</Year><RecNum>36</RecNum><DisplayText><styleface="superscript">[23]</style></DisplayText><record><rec-number>36</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">36</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Uoyama,Hiroki</author><author>Goushi,Kenichi</author><author>Shizu,Katsuyuki</author><author>Nomura,Hiroko</author><author>Adachi,Chihaya</author></authors></contributors><titles><title>Highlyefficientorganiclight-emittingdiodesfromdelayedfluorescence</title><secondary-title>Nature</secondary-title></titles><periodical><full-title>nature</full-title></periodical><pages>234-238</pages><volume>492</volume><number>7428</number><dates><year>2012</year></dates><isbn>0028-0836</isbn><urls></urls></record></Cite></EndNote>[\o"Uoyama,2012#36"23]；2015年初，南京邮电大学黄维院士课题组在世界上首次设计制备出了长余辉的有机磷光材料——纯有机的“夜明珠”，这对OLED材料发光行为的研究以及激发态的调控具有革命性的意义，相关成果发表于NatureMaterials上ADDINEN.CITE<EndNote><Cite><Author>An</Author><Year>2015</Year><RecNum>37</RecNum><DisplayText><styleface="superscript">[24]</style></DisplayText><record><rec-number>37</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">37</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>An,Zhongfu</author><author>Zheng,Chao</author><author>Tao,Ye</author><author>Chen,Runfeng</author><author>Shi,Huifang</author><author>Chen,Ting</author><author>Wang,Zhixiang</author><author>Li,Huanhuan</author><author>Deng,Renren</author><author>Liu,Xiaogang</author><author>Huang,Wei</author></authors></contributors><titles><title>Stabilizingtripletexcitedstatesforultralongorganicphosphorescence</title><secondary-title>NatMater</secondary-title></titles><periodical><full-title>NatMater</full-title></periodical><volume>advanceonlinepublication</volume><dates><year>2015</year><pub-dates><date>04/06/online</date></pub-dates></dates><publisher>NaturePublishingGroup</publisher><isbn>1476-4660</isbn><work-type>Letter</work-type><urls><related-urls><url>/10.1038/nmat4259</url></related-urls></urls><electronic-resource-num>10.1038/nmat4259 /nmat/journal/vaop/ncurrent/abs/nmat4259.html#supplementary-information</electronic-resource-num></record></Cite></EndNote>[\o"An,2015#37"24]。图1.1 黄维课题组于2015年4月份报道出的有机磷光材料