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基于溶液加工小分子材料发光层的有机-无机复合发光器件

范昌君 王瑞雪 刘振 雷勇 李国庆 熊祖洪 杨晓晖

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基于溶液加工小分子材料发光层的有机-无机复合发光器件

范昌君, 王瑞雪, 刘振, 雷勇, 李国庆, 熊祖洪, 杨晓晖

Phosphorescent hybrid organic-inorganic light emitting devices with solution-processed small molecule emissive layers

Fan Chang-Jun, Wang Rui-Xue, Liu Zhen, Lei Yong, Li Guo-Qing, Xiong Zu-Hong, Yang Xiao-Hui
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  • 报道了基于溶液加工有机小分子材料发光层、聚乙烯亚胺电子注入层的有机-无机复合发光器件. 优化了空穴传输层和磷光染料的掺杂浓度, 得到最佳发光效率的器件. 蓝光、黄光和红光器件的最大外量子效率为17.3%, 10.7% 和7.3%. 在发光亮度为1000 cd/m2 时, 蓝光、黄光和红光器件的外量子效率分别为17.0%, 10.6% 和5.8%, 器件效率下降较小. 原因在于同时采用空穴传输型和电子传输型的小分子材料作为共同主体材料, 器件具有较宽的载流子复合区域, 降低了三线激发态-三线激发态湮灭和三线激发态-极化子相互作用对器件发光效率的影响. 白光器件在亮度为1000 cd/m2时, 发光效率和功率效率为31 cd/A和 14.8 lm/W. 器件的色度为(0.32, 0.42), 色度比较稳定, 随电流的变化微小. 器件的效率较以往报道的有机-无机复合发光器件有显著的提高, 主要归因于在聚乙烯亚胺上能够制备特性良好的小分子材料薄膜, 以及小分子主体材料拥有较高的三线态能量和平衡的载流子传输特性, 能够获得高效的磷光发射.
    We report efficient phosphorescent hybrid organic-inorganic light emitting devices using poly(ethylenimine) as electron-injection layer and interfacial modifier for metal oxides and solution-processed small molecule emissive layers. As a first step, the hole transport layers with various HOMO levels and the hole mobility values including TAPC, TCTA and mCP are evaluated. The results indicate that devices using a TAPC layer show the best luminance and power efficiencies. Subsequently, the optimum phosphor concentration is determined to be ca. 5%. Enlarged efficiency roll-off with increasing current density is observed in devices using the phosphor concentration above the optimum value. We also investigate the morphologies of films having different phosphor concentrations on the top of bare or PEIE-covered glass substrates, which is closely related to device performance. All the films have the RMS values of ca. 1 nm, indicating high-quality solution processed small molecule films. The blue, yellow and red devices show the maximum external quantum efficiencies of 17.3%, 10.7% and 7.3%, respectively. These efficiencies are 17.0%, 10.6% and 5.8% at 1000 cd·m-2, only showing a small roll-off, which can be attributed to alleviated triplet-triplet and triplet-polaron interactions in a broad carrier recombination zone due to using the mixed hole-transport and electron-transport materials as the co-hosts. In addition, these devices exhibit the respective Commission International Eclairage (CIE) coordinates of (0.16, 0.36), (0.50, 0.49) and (0.66, 0.32), which almost traverse the whole visible light region. Furthermore, the hybrid two-colored white devices show a luminance efficiency of 31 cd·A-1, power efficiency of 14.8 lm·W-1 at 1000 cd·m-2 and the operating current-insensitive CIE coordinates of (0.32, 0.42). The efficiencies represent the significant improvement over the previously reported values, which can be attributed to high-quality small molecule films on PEIE, and in particular to the unique properties of small molecule host materials such as balanced carrier transport and high triplet energy. Further efforts including selection of high-mobility electron transport host material and phosphors with high luminescence quantum yield are made to increase the efficiency and reliability of hybrid organic-inorganic light emitting device.
    • 基金项目: 国家自然科学基金(批准号: 61177030, 11374242, 11474232)、教育部新世纪优秀人才支持计划(批准号: NCET-11-0705)和西南大学博士基金(批准号: SWU111057)资助的课题.
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 61177030, 11374242, 11474232), the Program for New Century Excellent Talents in University of Ministry of Education of China (Grant No. NCET-11-0705), and the Fund for the Doctoral Program of Southwest University, China (Grant No. SWU111057).
    [1]

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    [3]

    Zhang K, Zhong C M, Liu S J, Liang A H, Dong S, Huang F 2014 J. Mater. Chem. C 2 3270

    [4]

    Brine H, Juan F, Bolink H J 2013 Org. Electron. 14 164

    [5]

    Bolink H J, Coronado E, Repetto D, Sessolo M, Barea E M, Bisquert J, Garcia-Belmonte G, Prochazka J, Kavan L 2008 Adv. Funct. Mater. 18 145

    [6]

    Chen J S, Shi C S, Fu Q, Zhao F C, Hu Y, Feng Y L, Ma D G 2012 J. Mater. Chem. 22 5164

    [7]

    Morii K, Ishida M, Takashima T 2006 Appl. Phys. Lett. 89 183510

    [8]

    Lu L P, Kabra D, Friend R H 2012 Adv. Funct. Mater. 22 4165

    [9]

    Bolink H J, Coronado E, Orozco J, Sessolo M 2009 Adv. Mater. 21 79

    [10]

    Bolink H J, Brine H, Coronado E 2010 Adv. Mater. 22 2198

    [11]

    Lu L P, Kabra D, Johnson K, Friend R H 2012 Adv. Funct. Mater. 22 144

    [12]

    Bolink H J, Brine H, Coronado E 2010 ACS Appl. Mater. Interfaces 2 2694

    [13]

    Bolink H J, Coronado E, Sessolo M 2009 Chem. Mater. 21 439

    [14]

    Yook K S, Lee J Y 2014 Adv. Mater. 26 4218

    [15]

    Zhou Y, Fuentes-Hernandez C, Shim J, Meyer J, Giordano A J, Li H, Winget P, Papadopoulos T, Cheun H, Kim J, Fenoll M, Dindar A, Haske W, Najafabadi E, Khan T M, Sojoudi H, Barlow S, Graham S, Brédas J L, Marder S R, Kahn A, Kippelen B 2012 Science 336 327

    [16]

    Yang X H, Wang R X, Fan C J, Li G Q, Xiong Z H, Jabbour G E 2014 Org. Electron. 15 2387

    [17]

    Kim Y H, Han T H, Cho H, Min S Y, Lee C L, Lee T W 2014 Adv. Funct. Mater. 24 3808

    [18]

    Liu J, Shi X D, Wu X K 2014 Org. Electron. 15 2492

    [19]

    Fu Q, Chen J S, Shi C S, Ma D G 2012 ACS Appl. Mater. Interfaces 4 6579

    [20]

    Sun Y M, Seo J H, Takacs C J, Seifter J, Heeger A J 2011 Adv. Mater. 23 1679

    [21]

    Tsuboi T, Liu S W, Wu M F, Chen C T 2009 Org. Electron. 10 1372

    [22]

    Chang Y T, Chang J K, Lee Y T, Wang P S, Wu J L, Hsu C C, Wu I W, Tseng W H, Pi T W, Chen C T, Wu C I 2013 ACS Appl. Mater. Interfaces. 5 10614

    [23]

    Lu M T, Bruyn P D, Nicolai H T, Wetzelaer G J A H, Blom P W M 2012 Org. Electron 13 1693

    [24]

    Lamansky S, Djurovich P, Murphy D 2001 J. Am. Chem. Soc. 123 4304

    [25]

    Walikewitz B H, Kabra D, Gélinas S, Friend R H 2012 Phys. Rev. B 85 045209

    [26]

    Baldo M A, Adachi C, Forrest S R 2001 Phys. Rev. B 62 10967

    [27]

    Reineke S, Walzer K, Leo K 2007 Phys. Rev. B 75 125328

    [28]

    Duan L, Hou L D, Lee T W, Qiao J A, Zhang D Q, Dong G F, Wang L D, Qiu Y 2010 J. Mater. Chem. 20 6392

  • [1]

    Sessolo M, Bolink H J 2011 Adv. Mater. 23 1829

    [2]

    Huang J Z, Li S S, Feng X P 2010 Acta Phys. Sin. 59 5480 (in Chinese) [黄金昭, 李世帅, 冯秀鹏 2010 物理学报 59 5480]

    [3]

    Zhang K, Zhong C M, Liu S J, Liang A H, Dong S, Huang F 2014 J. Mater. Chem. C 2 3270

    [4]

    Brine H, Juan F, Bolink H J 2013 Org. Electron. 14 164

    [5]

    Bolink H J, Coronado E, Repetto D, Sessolo M, Barea E M, Bisquert J, Garcia-Belmonte G, Prochazka J, Kavan L 2008 Adv. Funct. Mater. 18 145

    [6]

    Chen J S, Shi C S, Fu Q, Zhao F C, Hu Y, Feng Y L, Ma D G 2012 J. Mater. Chem. 22 5164

    [7]

    Morii K, Ishida M, Takashima T 2006 Appl. Phys. Lett. 89 183510

    [8]

    Lu L P, Kabra D, Friend R H 2012 Adv. Funct. Mater. 22 4165

    [9]

    Bolink H J, Coronado E, Orozco J, Sessolo M 2009 Adv. Mater. 21 79

    [10]

    Bolink H J, Brine H, Coronado E 2010 Adv. Mater. 22 2198

    [11]

    Lu L P, Kabra D, Johnson K, Friend R H 2012 Adv. Funct. Mater. 22 144

    [12]

    Bolink H J, Brine H, Coronado E 2010 ACS Appl. Mater. Interfaces 2 2694

    [13]

    Bolink H J, Coronado E, Sessolo M 2009 Chem. Mater. 21 439

    [14]

    Yook K S, Lee J Y 2014 Adv. Mater. 26 4218

    [15]

    Zhou Y, Fuentes-Hernandez C, Shim J, Meyer J, Giordano A J, Li H, Winget P, Papadopoulos T, Cheun H, Kim J, Fenoll M, Dindar A, Haske W, Najafabadi E, Khan T M, Sojoudi H, Barlow S, Graham S, Brédas J L, Marder S R, Kahn A, Kippelen B 2012 Science 336 327

    [16]

    Yang X H, Wang R X, Fan C J, Li G Q, Xiong Z H, Jabbour G E 2014 Org. Electron. 15 2387

    [17]

    Kim Y H, Han T H, Cho H, Min S Y, Lee C L, Lee T W 2014 Adv. Funct. Mater. 24 3808

    [18]

    Liu J, Shi X D, Wu X K 2014 Org. Electron. 15 2492

    [19]

    Fu Q, Chen J S, Shi C S, Ma D G 2012 ACS Appl. Mater. Interfaces 4 6579

    [20]

    Sun Y M, Seo J H, Takacs C J, Seifter J, Heeger A J 2011 Adv. Mater. 23 1679

    [21]

    Tsuboi T, Liu S W, Wu M F, Chen C T 2009 Org. Electron. 10 1372

    [22]

    Chang Y T, Chang J K, Lee Y T, Wang P S, Wu J L, Hsu C C, Wu I W, Tseng W H, Pi T W, Chen C T, Wu C I 2013 ACS Appl. Mater. Interfaces. 5 10614

    [23]

    Lu M T, Bruyn P D, Nicolai H T, Wetzelaer G J A H, Blom P W M 2012 Org. Electron 13 1693

    [24]

    Lamansky S, Djurovich P, Murphy D 2001 J. Am. Chem. Soc. 123 4304

    [25]

    Walikewitz B H, Kabra D, Gélinas S, Friend R H 2012 Phys. Rev. B 85 045209

    [26]

    Baldo M A, Adachi C, Forrest S R 2001 Phys. Rev. B 62 10967

    [27]

    Reineke S, Walzer K, Leo K 2007 Phys. Rev. B 75 125328

    [28]

    Duan L, Hou L D, Lee T W, Qiao J A, Zhang D Q, Dong G F, Wang L D, Qiu Y 2010 J. Mater. Chem. 20 6392

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出版历程
  • 收稿日期:  2015-02-10
  • 修回日期:  2015-04-06
  • 刊出日期:  2015-08-05

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