高性能白光有機發(fā)光二極管的濕法制備及其相關(guān)材料研究

碩士學位論文論文題目：高性能白光有機發(fā)光二極管的濕法制備及其相關(guān)材料研究SolutionProcessedHigh-performanceWhiteOrganicLightEmittingDiodesandRelatedMaterials摘要WOLED由于具有輕薄、可實現(xiàn)柔性、節(jié)能環(huán)保、易于大面積制備和生理友好等優(yōu)勢被譽為下一代照明技術(shù)，目前已有相關(guān)商業(yè)化的照明產(chǎn)品面世。本論文針對濕法加工WOLED研究當前存在的部分難題，提出了我們的解決思路，以推動OLED照明的產(chǎn)業(yè)化應(yīng)用。基于PVK基聚合物互補色WOLED研究中普遍存在的發(fā)光光譜不穩(wěn)定現(xiàn)象，我們構(gòu)筑了本體系所獨有的器件結(jié)構(gòu)：ITO/PEDOT:PSS(35nm)/(PVK:OXD-7:FIrpic(7:3:1)):wt%Ir(bt)2(acac)(55nm)/TPBI(35nm)/Ca:Ag，并對客體的摻雜比例進行優(yōu)化探索，成功制得具有優(yōu)良光譜穩(wěn)定性的白光器件，同時器件最大亮度達50000cd/m2，最大電流效率為25.5cd/A，且CRI達到了72，屬于同類器件中的最高水平。針對溶液加工型WOLED難以獲得“雙高”效果的問題，采用了光物理性能優(yōu)良的三苯胺衍生物作主體材料，并將之與高性能新型客體材料及常規(guī)磷光客體搭配使用，制備了一系列互補色、三基色和四基色WOLED。性能最好的四基色器件總能量效率達33.6lm/W，同時具有高達83的CRI和適中的CCT，為該類問題的應(yīng)對提供了新的解決思路。暖白光對抗黑變激素具有較低的抑制作用，是一種生理友好的理想照明光源。我們針對濕法加工暖白光OLED當前存在的色品質(zhì)不高且光譜不穩(wěn)定的情況，利用自主合成的咔唑衍生物小分子作為主體，對制備出高性能的濕法加工暖白光器件進行了有益嘗試。我們制備的四基色暖白光器件在100-10000cd/m2的亮度范圍內(nèi)保持了2500K以下的低色溫和穩(wěn)定的白光發(fā)射，CRI高達83，CIE色坐標也落在了標準暖白光點附近，同時最大流明效率達到了18.0cd/A，與傳統(tǒng)白熾燈的水平相當。關(guān)鍵詞:白光，溶液加工，磷光，有機發(fā)光二極管，低色溫，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

目錄第一章緒論 11.1OLED技術(shù)的發(fā)展歷程 21.2OLED的基本結(jié)構(gòu)及工作原理 41.3OLED的器件制備工藝 61.4本論文的主要工作 9第二章WOLED概述 112.1WOLED的研究進展 112.2WOLED的產(chǎn)業(yè)化情況 122.2.1WOLED在國際上的產(chǎn)業(yè)化情況 122.2.2我國WOLED的產(chǎn)業(yè)化情況 152.2.3WOLED的市場前景預(yù)測 162.3WOLED的實現(xiàn)方法 182.4WOLED的性能指標 192.5本章小結(jié) 21第三章光譜穩(wěn)定的基于聚合物主體的全磷光WOLED研究 223.1引言 223.2實驗部分 233.2.1材料 233.2.2器件的制備與測試 243.3結(jié)果與討論 263.3.1發(fā)光層物質(zhì)的光物理性質(zhì)與能量傳遞機理研究 263.3.2聚合物基全磷光WOLED的色品質(zhì)及光譜穩(wěn)定性 273.3.3聚合物基全磷光WOLED的J-V-L特性與器件效率 293.4本章小結(jié) 30第四章基于三苯胺衍生物小分子主體材料的可濕法加工全磷光WOLED研究 324.1引言 324.2實驗部分 334.3結(jié)果與討論 344.3.1材料的光物理性質(zhì)研究 344.3.2主體-客體摻雜系統(tǒng)研究 364.3.3有機薄膜的形貌研究 374.3.4基于三苯胺衍生物小分子主體的可濕法加工互補色全磷光WOLED 384.3.5基于三苯胺衍生物小分子主體的可濕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體的可濕法加工四基色全磷光WOLED 424.4本章小結(jié) 45第五章基于咔唑衍生物小分子主體材料的可濕法加工暖白光器件研究 475.1引言 475.2實驗部分 485.3結(jié)果與討論 495.3.1發(fā)光層物質(zhì)的光物理性質(zhì)與能量傳遞機理研究 495.3.2有機薄膜的形貌研究 505.3.3基于咔唑衍生物小分子主體的WOLED的色品質(zhì)及光譜穩(wěn)定性 515.3.4基于咔唑衍生物小分子主體的WOLED的J-V-L特性與器件效率 535.4本章小結(jié) 54第六章總結(jié)與展望 55參考文獻 57附錄1攻讀碩士學位期間撰寫的論文 61附錄2攻讀碩士學位期間申請的專利 62附錄3攻讀碩士學位期間參加的科研項目 63致謝 64緒論有機發(fā)光二極管（OrganicLight-EmittingDiode，OLED）自發(fā)明以來，一直是世人關(guān)注的焦點。如今經(jīng)過二十多年突飛猛進的發(fā)展，OLED已經(jīng)向人類展示出在未來顯示、照明、液晶顯示器背光源等領(lǐng)域?qū)ξ磥砩鐣a(chǎn)生重要影響的巨大潛力。在顯示領(lǐng)域，人類自進入互聯(lián)網(wǎng)時代以來，信息傳遞方式已由早期的固定顯示、可變顯示、電子顯示演變成為如今的交互顯示，而未來顯示的發(fā)展仍將繼續(xù)秉承“以人為本”的導(dǎo)向。目前平板顯示技術(shù)已成功實現(xiàn)了輕薄和便攜，下一步人類追求的必定是柔性顯示，OLED技術(shù)將會承擔起這個重要角色。從技術(shù)的角度來說，OLED具有輕薄、省電、對比度高、自發(fā)光、可視角寬、響應(yīng)頻率高、驅(qū)動電壓低、可實現(xiàn)大尺寸和柔性顯示等特性，有望帶來顯示領(lǐng)域市場的又一輪變革ADDINEN.CITE<EndNote><Cite><Author>黃春輝</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%">黃春輝</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%">黃維</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">有機電致發(fā)光材料與器件導(dǎo)論</style></title></titles><section>446</section><dates><year>2005</year></dates><publisher><styleface="normal"font="default"charset="134"size="100%">復(fù)旦大學出版社</style></publisher><urls></urls></record></Cite></EndNote>[\o"黃春輝,2005#12"1]。產(chǎn)品方面，從1997年第一臺OLED顯示屏問世起，市場上OLED的新應(yīng)用的種類和數(shù)量逐年都在遞增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]，尤其近幾年，OLED更是高端新品迭出，頗為讓人振奮。尤其是三星公司，作為OLED顯示領(lǐng)域的帶頭大哥，在OLED真正走向市場的過程中起到了最重要的推動作用。目前世界上90%以上的OLED手機都是三星的產(chǎn)品，且三星一直都在自己的眾多款旗艦機上搭載AMOLED顯示屏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逐年不斷刷新其OLED電視記錄，至今已實現(xiàn)多款顯示效果極佳的曲面OLED電視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]。華為和蘋果公司也分別在今年3月份剛剛結(jié)束的2015MWC以及蘋果發(fā)布會上展示了各自搭載OLED顯示屏的智能手表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]，尤其是蘋果，作為世界消費電子界的“風向標”，本次初步試水OLED應(yīng)用，無疑將牽動整個行業(yè)的神經(jīng)，勢必重新定義整個智能穿戴領(lǐng)域，為OLED的發(fā)展帶來前所未有的機遇。在照明應(yīng)用方面，輕薄、可撓、接近太陽光的白光有機發(fā)光二極管（WOLED），被視為下世代的照明新星。OLED是面光源，比較柔和，人眼直視不會眩暈，適用于室內(nèi)照明。有機材料豐富的發(fā)光特性使制備的OLED很容易進行顏色調(diào)節(jié)，實現(xiàn)高的顯色性，此外OLED光源還有可彎曲特性且無高熱問題，易與建筑材料直接結(jié)合，讓設(shè)計師在設(shè)計時擁有更多的彈性。目前為止，國內(nèi)外已出現(xiàn)多款用于百貨、咖啡廳等情境的創(chuàng)意OLED燈具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照明的市場正在逐步擴大。OLED在作為TFT-LCD技術(shù)背光源的應(yīng)用方面也顯現(xiàn)出獨特的優(yōu)勢。由于通常用作背光源的LED燈為點光源，故在生產(chǎn)中需加入光擴散膜工藝，而白光OLED為面光源，光擴散膜工序就可省去，工藝成本下降可觀。有報道指出，早在2011年，三星、LG已開建用OLED作背光源的TFT-LCD新生產(chǎn)線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%">技術(shù)——結(jié)構(gòu)、原理及制造技術(shù)</style></title></titles><pages>400</pages><dates><year>2011</year></dates><publisher><styleface="normal"font="default"charset="134"size="100%">電子工業(yè)出版社</style></publisher><urls></urls></record></Cite></EndNote>[\o"申智源,2011#20"7]。本章將首先對OLED器件的發(fā)展歷史與現(xiàn)狀做一簡單的總結(jié)回顧，然后介紹了OLED器件的基本結(jié)構(gòu)及工作原理，接下來進一步闡述了OLED的制備工藝，最后簡要概括了本論文的主要工作。OLED技術(shù)的發(fā)展歷程人類對有機物的電致發(fā)光的認識最早是在上世紀三十年代，當時科學家將有機熒光材料填充于聚合物中，發(fā)現(xiàn)了最早的有機電致發(fā)光現(xiàn)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]。此后的幾十年內(nèi)，陸續(xù)也有一些在有機材料兩端施加電壓產(chǎn)生發(fā)光的現(xiàn)象的報道，但由于初期的器件所施加電壓都比較大，人類尚不能看到該類現(xiàn)象具體的應(yīng)用價值，因而一直未引起人們的太多重視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，美國柯達公司的鄧青云研究員及其助手在美國著名的學術(shù)期刊《應(yīng)用物理快報》上發(fā)表了他們的最新成果，文中指出他們采用了新穎的三明治型的器件結(jié)構(gòu)，首次獲得了具有突破性的高亮度和高效率有機電致發(fā)光器件，并且器件的操作電壓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]。該成果一經(jīng)公布，立刻引起了科學界的轟動，自此OLED技術(shù)開始受到了世界的矚目和研究，而鄧博士本人也獲得了“OLED之父”的美譽，并于去年一度傳言成為2014年度“諾貝爾化學獎”候選人而受到媒體熱捧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]。從彼時起，人們對OLED的研究熱情前所未有的高漲起來，關(guān)于OLED的研究進展層出不窮地涌現(xiàn)，不斷地促使OLED一步步走向產(chǎn)業(yè)化。接下來，僅就OLED技術(shù)發(fā)展至今的整個歷程當中一些重要的發(fā)展節(jié)點作以梳理和回顧。1988年，Adachi等人首次在OLED器件結(jié)構(gòu)中引入空穴傳輸、電子傳輸?shù)雀嘤袡C功能層，極大提高了器件性能的同時，也更加豐富了材料種類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，劍橋大學卡文迪許實驗室的friend教授課題組將共軛聚合物PPV作為發(fā)光材料，首次實現(xiàn)了聚合物電致發(fā)光，開創(chuàng)了有機發(fā)光二極管的新的研究領(lǐng)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（曹鏞）和艾倫黑格等人又于1992年利用溶液加工法將MEH-PPV制備于柔性塑料襯底上制得了首個可彎曲的PLED顯示器，將OLED技術(shù)最具魅力的一面展示給了公眾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課題組制備了發(fā)白光的WOLED，為OLED在固態(tài)照明領(lǐng)域的研究和應(yīng)用開辟了先河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，加州大學裴啟兵和黑格等人在科學雜志上報道他們研制的一種新型器件——有機發(fā)光電化學池（OLEC），再次為聚合物發(fā)光開辟了新領(lǐng)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，吉林大學馬於光課題組將有機金屬配合物摻雜于主體材料，首次實現(xiàn)了基于三線態(tài)發(fā)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>SyntheticMetals</secondary-title></titles><periodical><full-title>SyntheticMetals</full-title></periodical><pages>245-248</pages><volume>94</volume><number>3</number><dates><year>1998</year></dates><isbn>0379-6779</isbn><urls></urls></record></Cite></EndNote>[\o"Ma,1998#31"18]。同年，F(xiàn)orrest研究小組制備出效率極大提升的磷光發(fā)光器件，相關(guān)成果發(fā)表在nature雜志上，自此，有機磷光電致發(fā)光開始引起人們的巨大關(guān)注ADDINEN.CITE<EndNote><Cite><Author>Baldo</Author><Year>1998</Year><RecNum>32</RecNum><DisplayText><styleface="superscript">[19]</style></DisplayText><record><rec-number>32</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">32</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Baldo,MA</author><author>O'brien,DF</author><author>You,Y</author><author>Shoustikov,A</author><author>Sibley,S</author><author>Thompson,ME</author><author>Forrest,SR</author></authors></contributors><titles><title>Highlyefficientphosphorescentemissionfromorganicelectroluminescentdevices</title><secondary-title>Nature</secondary-title></titles><periodical><full-title>nature</full-title></periodical><pages>151-154</pages><volume>395</volume><number>6698</number><dates><year>1998</year></dates><isbn>0028-0836</isbn><urls></urls></record></Cite></EndNote>[\o"Baldo,1998#32"19]。仍是1998年，Hebner等人發(fā)明了制備OLED的新方法——噴墨打印法，進一步推動了OLED產(chǎn)品走向市場ADDINEN.CITE<EndNote><Cite><Author>Hebner</Author><Year>1998</Year><RecNum>33</RecNum><DisplayText><styleface="superscript">[20]</style></DisplayText><record><rec-number>33</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">33</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hebner,TR</author><author>Wu,CC</author><author>Marcy,D</author><author>Lu,MH</author><author>Sturm,JC</author></authors></contributors><titles><title>Ink-jetprintingofdopedpolymersfororganiclightemittingdevices</title><secondary-title>AppliedPhysicsLetters</secondary-title></titles><periodical><full-title>AppliedPhysicsLetters</full-title></periodical><pages>519-521</pages><volume>72</volume><number>5</number><dates><year>1998</year></dates><isbn>0003-6951</isbn><urls></urls></record></Cite></EndNote>[\o"Hebner,1998#33"20]。到了20世紀末，OLED經(jīng)過過去的十年之內(nèi)獲得了突飛猛進的飛躍式發(fā)展，已逐步羽翼豐滿，積聚了真空蒸鍍工藝、濕法加工、高效率技術(shù)、白光技術(shù)、聚合物發(fā)光等走向市場應(yīng)用的技術(shù)儲備，逐步破除產(chǎn)業(yè)化道路上的一個又一個障礙。經(jīng)過初期的飛速突破和技術(shù)積淀，在此后的時期OLED技術(shù)上的發(fā)展趨于平緩，要想取得OLED領(lǐng)域的突破性進展也變得越來越有難度，OLED在產(chǎn)業(yè)化規(guī)模不斷擴大的同時，也遇到了自身發(fā)展的一些瓶頸問題，比如藍光器件的效率仍比較低，溶液加工法的效率跟蒸鍍法比較仍然存在較大差距，OLED產(chǎn)品制造成本仍然比較高等ADDINEN.CITE<EndNote><Cite><Author>Yook</Author><Year>2014</Year><RecNum>118</RecNum><DisplayText><styleface="superscript">[21,22]</style></DisplayText><record><rec-number>118</rec-number><foreign-keys><keyapp="EN"db-id="xdtz5w5e4fd9r4e2006xwevld50zrv5rpvv2">118</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Yook,K.S.</author><author>Lee,J.Y.</author></authors></contributors><auth-address>DepartmentofPolymerScienceandEngineering,DankookUniversity,126,Jukjeon-dong,Suji-gu,Yongin,Gyeonggi,448-701,Korea.</auth-address><titles><title>Smallmoleculehostmaterialsforsolutionprocessedphosphorescentorganiclight-emittingdiodes</title><secondary-title>AdvMater</secondary-title><alt-title>Advancedmaterials</alt-title></titles><alt-periodical><full-title>AdvancedMaterials</full-title></alt-periodical><pages>4218-33</pages><volume>26</volume><number>25</number><dates><year>2014</year><pub-dates><date>Jul2</date></pub-dates></dates><isbn>1521-4095(Electronic) 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，新世紀以來，OLED技術(shù)還是取得過一些較重要的突破性進展的。例如2012年時，日本九州大學Adachi課題組在nature上報道了一種熱致延遲熒光（TADF）現(xiàn)象，首次實現(xiàn)了熒光材料的IQE達到100%，突破了長期以來的只有高IQE器件只有磷光金屬配合物的限制，引起了世界范圍內(nèi)的關(guān)注，相信不久的將來必將會展現(xiàn)出對OLED產(chǎn)業(yè)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，南京郵電大學黃維院士課題組在世界上首次設(shè)計制備出了長余輝的有機磷光材料——純有機的“夜明珠”，這對OLED材料發(fā)光行為的研究以及激發(fā)態(tài)的調(diào)控具有革命性的意義，相關(guān)成果發(fā)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]。圖1.1 黃維課題組于2015年4月份報道出的有機磷光材料