251 resultados para tta
Resumo:
本论文以提高有机/聚合物电致发光材料的发光效率为目的,通过改善发光材料分子的载流子传输平衡、增大分子体积为手段来减小荧光淬灭,设计并合成了一系列新型结构的络合物和聚合物。发现了一种合成五配位8-轻基喳琳铝络合物和双核铝8-轻基喳琳络合物的新方法,在分子中引入了电子和空穴传输基团改善了分子的载流子传输平衡,设计并合成了新型大体积的分子,提高了材料的发光效率,并系统地研究了分子结构与发光波长和发光效率的关系。主要工作如下:1发现了一种合成五配位8-经基喳琳铝络合物和双核铝8-经基喳琳络合物的新方法,克服了没有2一甲基的空间位阻作用很难形成五配位8-轻基喳琳铝络合物的困难。2合成了五配位2-甲基-8-轻基喳琳铝络合物并引入了具有不同空穴传输能力的第二配体。结果表明,与A 1 q;,相比,2-甲基-8-经基喳琳的引入导致了五配位络合物发光的蓝移,同时具有空穴传输能力的三苯胺基团的引入使电致发光器件的效率降低。3设计并合成了五配位8-轻基喳琳铝络合物,同时与Alq做了对比研究。研究发现,这一系列五配位络合物发射绿色荧光,五配位8-轻基喳琳铝络合物的发光波长主要由第一配体决定。4以五配位2-甲基-8-轻基喳琳铝和五配位8-轻基喳琳铝络合物为发光层制备了双层器件。结果表明,五配位8-经基喳琳铝络合物的电致发光波长主要由第一配体决定,第二配体只起到微弱的调节作用;第一配体对器件的发光效率起决定性的作用,第二配体的结构对络合物器件发光效率的影响在同一系列络合物中表现得非常明显。5从增加分子体积能够减小分子之间聚集,增强荧光效率这一观点出发,合成了具有双核铝的8一TTA-基喳琳络合物Me-DAlqz和PPv-DAlq3,用Me-DAlq,作发光层制备了双层器件,并与Alq_3i和AIMq_3作了对比研究。结果表明,DA 1 q,双层器件中的发光效率比Alq_3器件的性能稍高一些,证明了大体积分子能够增加荧光效率的观点。6合成了含有空穴传输性能的三苯胺基团的嗯二吟配体,并用其合 成了金属络合物。这些络合物发射蓝色的荧光,与不带三苯胺的德二哇金属络合物在溶液中发基本相同波长的荧光。但在薄膜和单层电致发光器件中,络合物的荧光发生了不同程度的红移。含三苯胺络合物的单层器件发光效率高于不含三苯胺络合物的单层器件的效率,证实了三苯胺的引入改进了载流子的传输平衡。7合成了系列嗯二哇基团两侧带有蔡环的金属络合物并以这些络合物为发光层制备了双层有机电致发光器件。结果表明,蔡环的引入导致了嗯二哇金属络合物在薄膜状态和电致发光器件中的发光波长比在溶液中的发光波长有了很大的红移。8设计并合成了既具有空穴传输性能又具有电子传输性能的蓝色发光聚合物。用电化学方法证明了它们具有两极性质,表明嗯二哇的引入增加了聚合物的电子传输能力。
Resumo:
本文用循环伏安法对十三种稀土双酞菁(LnPc_2H)在邻二氯代苯中进行了研究,发现徐文献曾报道过的二个氧化还原反应之外,还具有另外的二个氧化还原反应,测定了全部氧化还原反应的半波电位(E_(1/2))。由循环伏安曲线上的电化学参数及文献曾报道的电子转移数测定结果来判断,四个氧化还原反应均为可逆(准可逆)的单电子转移过程。各种稀土双酞菁的四个反应半波电位变化规律是:随稀土离子的原子序数增大,其中二个氧化反应,E_(1/2)往负电位方向移动分别约为110和170 mV,而对二个还原反应,轻稀土双酞菁和重稀土双酞菁的E_(1/2)各为一定值,由此可认为轻、重稀双酞菁之间存在一定的差别。此外还测定了十三种稀土双酞菁在CH_2Cl_2和DMF中氧化还原反应的半波电位,结果表明,溶剂的供体数DN (Donor Number)的增大,溶剂化作用的加强,对于各种稀土双酞菁,使得二个氧化反应的半波电位往正电位方向移动分别约为60和150 mV,而对于二个还原反应的半波电位无显著的影响。关于稀土单酞菁的电致变色性质的研究尚无文献报道。本文用循环伏安法分别对LnPcAc_2H、LnPcOH LnPcCl等三种类型的稀土单酞菁进行了研究,发现它们均具有二个氧化还原反应。获得了各氧化还原反应的半波电位值,并用循环伏安法,以二茂铁为标准物质,测定了LuPcAc_2H、LuPcCl LuPcOH等三种镥单酞菁的氧化还原反应电子转移数(n)。根据上述结果,指出各稀土单酞菁发生的二个氧化还原反应均为可逆(准可逆)的单电子转移过程。而且电子转移发生在酞菁环上,参与配位的阴离子Ac~-, OH~- Cl~-及稀土离子均无明显的影响。此外,研究了四种溶剂对LuPcCl的氧化还原反应半波电位的影响,发现随溶剂供体数增大、与配合物的作用增强,对氧化反应的半波电位有较大影响,而对还原反应的影响较小。用光谱电化学方法研究了镥单酞菁和镥双酞菁在DMF中的电致变色现象,发现随电解电压的变化,二者能发生紫色(对双酞菁)、兰色、绿色、黄色、棕红色等一系列颜色的连续变化。实验结果表明,两者的还原产物在空气中不稳定。而由镥单酞菁LuPcCl的电氧化产物的可见光谱随放置时间的监测结果指出,该氧化产物在空气中能稳定10分钟左右,60分钟之后,完全变为电解前的颜色和光谱。本文对十三种稀土双酞菁的可见光谱进行测定,得到了这些配合物在三种溶剂(CH_2Cl_2、邻二氯代萃、DMF)中的可见光谱吸收峰的波长λ_(Max),并由结果讨论了稀土离子和溶剂对λ_(Max)的影响。稀土单酞菁的顺磁共振研究尚无文献报道。本文对几种稀土单酞菁和纯酞菁H_2Pc进生顺磁共振研究,发现它们具有与自由电子近乎相等的g值(2.003)和共振磁场(3360 ± 5高斯)。因纯酞菁也具有顺磁信号,故本文认为稀土单酞菁的顺磁信号主要是由酞菁大环所引起的。此外,还采用电解与顺磁联合测试法研究了镥单酞(LuPcAc_2H LuPcCl)在DMF中的顺磁信号,发现随电解电压的增大,LuPcCl的顺磁信号强度增大,而LuPcAc_2H的顺磁信号强度减小。我们认为,顺磁信号的强度变化与稀土单酞菁的氧化还原反应有关。综合上述的一些结果,并根据已有的文献报道,我们认为稀土双酞菁和单酞菁电氧化或电还原产物的颜色。本文还对文献曾报道的含β一二酮的稀土单酞菁合成方法进行了改进,并用改进后的方法合成了文献尚未报道的ErPc(HNPA)和ErPc(TTA)_2H (NPA为4-硝基邻苯二甲酸,TTA为噻吩甲酰三氟丙酮)以及文献中曾用基它方法合成过的ErPc(dbm)_2H (dbm为二苯甲酰基甲烷)。经元素分析、质谱、红外光谱、核磁共振、顺磁共振、热分析及循环伏安法的表征,认为符合其组成,并初步提出了这些化合物的可能结构。
Resumo:
稀土离子的敏化发光早在1942年就被Weissiman发现了,后来,人们对这一现象作了大量的研究工作,并且,开始用于稀土离子的测试。高灵敏度和好的选择性一直是分析工作者追求的真正目的。为此,很长时间以来,人们从化学体系上入手,不断地在配体种类;配体条件;溶剂作用;第二配体影响;胶束;表面活性剂等方面入手,来寻找可获得高的灵敏度和好的选择性的测试体系,并取得了一定的成绩,但还远远满足不了分析工作者的要求。近年来,随着仪器设备的不断改进,人们想到,能否通过新的仪器的出现来改善分析测试的灵敏度和选择性。时间分辨光谱法就是在这种条件下产生的,并且,初步的实验就得到了令人十分满意的结果。时间分辨光谱法顾名思义是以时间做为分辨量的一种方法,是一种多维萤光技术,它采用脉冲激光做为光源和门控检测系统相结合,因此,不但获得了高子常规法的灵敏度,而且还解决了光谱峰有干扰的发光组分的测定,提高了选择性。为了有效地应用时间分辨光谱法即获得更高的灵敏度和更好的选择性,时间分辨光支要求:①待测定的物质必须有较强的发光,这是提高灵敏度的前提:②待测定的物质的寿命必须合适(如测单组分时是通过延迟消除噪声,则被测组分的寿命至少要比噪音信号长;若是二组分的分辨光谱法测定,就要求二组分间寿命差要尽可能大),这样才可能效分辨;③适合彼此间有光谱干扰的多组分中单一组分的测定,这是时间分辨光谱法优于常远见二维光法的最为突出的一点。Eu-TTA_3和SmTTA_3是较合适时间分辨测定体系。Eu_TTA_3和S_m-TTA_3 二元络合物不但有较强的萤光,而且寿命差较大,EuTTA_39寿命400微秒)。SmTTA_3(寿命21微秒),并且Eu和Sm间有光谱干扰,因此在混合体系下,时间分辨光谱法测定Eu和Sm才充分显示了伏越性。为此,为了研究稀土元素的时间分辨光谱测定,本论文分三部分完成。第一部分:几种稀土离子萤光络合物体系的选择通过对Eu~(3+)、Tb~(3+)、Dy~(3+)络合体系最强发光的条件实验,期望找到一系列既有较强的发光,元素间又存在着光谱干扰。而常规法又难以测试的络合物体系。为此,在现有条件下,做了TTA、DBM、Phen、AAE、Sal五种配体Eu~(3+)、Sm~(3+)、Tb~(3+)、Py~(3+)四种稀土离子所有可能的络合物组成的发光条件试验,主要为配体浓度和PH值的影响。确定了不同络合物的最佳组成条件。并且考虑到苯的毒性和萃取的繁琐性。选用乙醇做为溶剂。最后得到TTA、DBM是Eu、Sm较好的络合剂,而且它们与Phen的三元络合物也具有强的发光。Sml:是Tb和Dy的较好络合剂,并且它们与Phen形成三元络合物也具有较强的萤光,AAE、Phen是选择性最差的络合剂,它们与Tb、Eu、Sm、Dy都能形成有一定发光强度的络合剂Eu和Sm以及Tb和Dy之间是无论配体息样变化都有光谱干扰的两对元素。第二部分;发光络合物的萤光寿命的测试:除了要求从化学体系入手,得到具有较强的发光络合物之外,时间分辨光谱法还要求;待分辩的物质间有较大的寿命差异。寿命τ是进行时间分辨光谱法的理论基础。为此,在本室和11室自己安装的仪器上做了已讨论的最佳条件下合成的络合物萤光寿命的测试,并给出了许多络合物的寿命数据。同时还讨论了配体种类,稀土离子浓度,对寿命大小的影响,得出不同的稀土离子络合物寿命差异很大,即使是相同的稀土离子,配体不同,寿命也是不同的,一般而言,Eu,Tb寿命较长,达几百微秒,Dy、Sm寿命较短,一般仅为几微秒或几十微秒,并总有寿命Tb > Eu > Sm > Dy。为了讨论稀土离子浓度对寿命的影响。选Eu. Sm-TTA和Tb. Dy-Sal-乙醇溶液为例,进行了浓度影响实验,得到浓度粹灭的同时,不仅萤光强度减弱,而且寿命缩短,最后总结出: Eu. Sm-TTA(Phen)二元(或三元)络合物和Tb. Dy-Sal(Phen)二元(或三元)络合物彼此间寿命差最大。第三部分:时间分辨光谱法研究在前二部分准备工作完成后,基本上就确定了可供时间分辩的最佳体系,即Eu. Sm-TTA二元络合物(或它与Phen形成的三元络合物)和Tb、Dy-Sal二元络合物(或与Phen形成的三元络合物)-乙醇体系。关于Eu.Sm-TTA体系的时间分辨光谱法测定,已有过研究并得到了十分满意的结果,因此,本论文选不曾有过报导的Tb、Dy-Sal 乙醇体系为时间分辨光谱法研究的对象。首先在本室和11室自建的时间分辨光谱仪上进行了仪器测量参数的选择,然后,对Tb、Dy-sal的时间分辨光谱法给以原理性的讨论,得到在延迟大于30微秒后,可消除Dy对Tb测定的干扰的结果,之后,又作了当延迟大于100微秒的条件下的时间分辩光谱法在Dy存在下测定Rb[Sal]_3的检测限的探索,并与MPF-4型萤光分光光度计的测试结果做了比较,得到了可高于常规法三个数量级的灵敏度的初步结果。本论文建立了寿命测量和激光时间分辨的实验装置,并且完成了原理性实验,在选择体系测定寿命和利用时间分辨排除稀土离子干扰方面得到了较好的初步结果,积累了大量数据完成了本论文目的要求。
Resumo:
稀土元素的荧光光度分析是一类重要的分析方法,是元素荧光分析的一个重要方面。而在稀土元素总量中测定某一个单独的稀土元素,且是一种必然的要求。目前人们也在知方百计地寻找各种方法以提高荧光法的灵敏度、选择性及稳定性基于此本文做了如下三个方面的工作:一、7-碘-8-羟基喹啉-5-磺酸=溶化十六烷三甲铵荧光光度法测定痕量谱。。荥光法测定镨的报道十分罕见,8-羟基喹啉及共衍生物是带用的荧光试剂之一。它们已被广泛应用于铝、鎵、铟、锌、镉、锆、镧、钇等元素的荧光测定中,应用表面活性剂的胶束荧光体系带具有增铬、增数、增稳,提高选择性,改善实验条件的特点。在此基础上并建立了一些高灵敏度、高选择性的荧光分析方法。但用8-羟基喹啉衍生物测定镨的荧光法研究还未见报道。本文研究了镥-7-碘-8-羟茎喹啉-5-磺酸-表面活性剂的三元荧光体系,试验并确定了配合物形成的条件,不同表面活性剂对此体系的增敏作用表明:溴化十六烷茎二甲铵(CTMAB)的增敏效果最好,测定镥的最低浓度可达8.8ng/ml,试验了其它共存离子的影响,通过萃取色谱分离后,本方法可较好的用于测定天然混合稀坤的镥。二、偏最小二乘法(PLS)荧光光度法同时测定锌、铽、镨。通过直接激发便稀土离子产生荧光进行荧光分析的方法称直接荧光法(或无试剂荧光法)用这种方法对锌、铽、镨分别测定已有报道,但在用直接荧光法同时测定锌、铽、镨时彼此互相干扰,为解决这个问题,本文将PLS法应用荧光光度法直接同时测定铈、铽、镨、各取了三个水平9个标准样,在355-560nm之间选择27个发射波长点测量荧光强度。并引入不相容因子来检验结果的可靠性,此法用于龙南稀土样品中铈、铽、镨的同时测定,获得了满意的结果。三、Eu~(3+)-2-喀吩甲酰三氟丙酮-N_(263)-Triton X-100体系荧光分光光度测定痕量的铕本文首次提出了Eu~(3+)-TTA-N——(263)-Triton X-100体系的荧光光度法测定铕,试验了该荧光体系的检测下限可述,0.9ng/ml,并可允许存在一定量的其它共存稀土元素,较好地应用直接测定包头混合稀土氧化物中的痕量铕。
Resumo:
In this study, we investigated the electroluminescence (EL) mechanisms and processes of hole block material in the multilayer devices with Eu(TTA)(3)phen (TTA = thenoyltrifluoroacetone, phen = 1,10-phenanthroline) doped CBP (4,4'-N,N'-dicarbazolebiphenyl) as the light-emitting layer (EML). First, the hole block ability of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was experimentally confirmed by comparing the EL spectra. With increasing hole injection, BCP emission emerges and increases gradually due to the increasing hole penetration from EML into the hole block layer (HBL).
Near-infrared luminescence from sol-gel materials doped with holmium(III) and thulium(III) complexes
Resumo:
A series of ternary Ln(tta)(3)L complexes (Ln = Ho, Tm; Htta = 2-thenoyltrifluoroacetone; L = 1,10-phenanthroline, 2,2'-bipyridine, or triphenyl phosphate oxide) and their corresponding sol-gel hybrid materials formed via the in situ synthesis process (designated as Ln-T-L gel) were reported. The complexes and the gels were studied in detail, which suggest the complexes have been successfully synthesized in the corresponding gels.
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Efficient white organic light-emitting diodes (WOLEDs) using europium complex as the red unit are presented. The WOLEDs were fabricated by using the structure of indium tin oxide (ITO)/N, N'-di(naphthalene-1-yl)-N, N'-diphenyl-benzidine (NPB)/4,4-N, N-dicarbazolebiphenyl (CBP) : bis(2,4-diphenylquinolyl-N, C-2) iridium (acetylacetonate) ((PPQ)(2)Ir(acac)) : Eu (III) tris(thenoyltrifluoroacetone) 3,4,7,8-tetramethyl-1,10-phenanthroline (Eu(TTA)(3)(Tmphen))/NPB/2-methyl-9,10-di(2-naphthyl)anthracene (MADN) : p-bis (p-N, N-di-phenyl-aminostyryl)benzene (DSA-Ph)/9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)/tris(8-hydroxyquinoline) aluminium (Alq3)/LiF/Al.
Resumo:
In this study, we investigated the dependence of electroluminescence (EL) efficiency on carrier distribution in the light-emitting layer (EML) of the device based on Eu(TTA)(3)phen (TTA = thenoyltrifluoroacetone, phen = 1, 10-phenanthroline) doped 4,4'-N,N'-dicarbazole- biphenyl (CBP) system. We found that EL efficiency increases monotonously with increasing hole injection even when holes are the majority carriers. This phenomenon was attributed to the accumulation of holes in EML, which improves the balance of holes and electrons on Eu(TTA)(3)phen molecules, thus enhancing the EL efficiency.
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In this paper, a quantum chemistry method was used to investigate the effect of different sizes of substituted phenanthrolines on absorption, energy transfer, and the electroluminescent performance of a series of Eu(TTA)(3)L (L = [1,10] phenanthroline (Phen), Pyrazino[2,3-f][1,10]phenanthroline (PyPhen), 2-methylprrazino[2,3-f][1,10] phenanthroline(MPP), dipyrido[3,2-a:2',3'-c]phenazine(DPPz), 11-methyldipyrido[3,2-a:2',3'c]phenazine(MDPz), 11.12-dimethyldipyrido[3,2-a:2',3'-c]phenazine(DDPz), and benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (BDPz)) complexes. Absorption spectra calculations show that different sizes of secondary ligands have different effects on transition characters, intensities, and absorption peak positions.
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Ternary europium complex Eu(tta)(3)phen was covalently bonded with the general mesoporous. material SBA-15 and SBA-15-type of periodic mesoporous organosilica (PMO) material via impregnation of Eu(tta)(3)center dot 2H(2)O into phen-S15 and phen-PMO, respectively, through a ligand exchange reaction. The parent materials of phen-S15 and phen-PMO were synthesized by co-condensation of tetraethylorthosilicate (TEOS) or 1,2-bis(triethoxysilyl)ethane (BTESE) and the functionalized chelate ligand 5-(N,N-bis(3-triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as template, which were confirmed by SEM, XRD, FTIR, Si-29 CP-MAS NMR, and N-2 adsorption measurements.
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Two beta-diketones 4,4,4-trifluoro-1-2-thenoyl-1,3-butanedione (Htta) and 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione (Htfnb), which contain trifluoroalkyl chain, were selected as the main sensitizer for synthesizing Tm(L)(3)phen (L = tta, tfnb) complexes. The two near-infrared (NIR) luminescent thulium complexes have been covalently bonded to the ordered mesoporous material MCM-41 via a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) [The resultant mesoporous materials are denoted as Tm(L)(3)phen-MCM-41 (L = tta, tfnb)]. The Tm(L)(3)phen-MCM-41 (L = tta, tfnb) mesoporous materials were characterized by small-angle Xray diffraction (XRD) and N-2 adsorption/desorption, and they show characteristic mesoporous structure of MCM-41.
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In this work, the detailed conversion process of the dominant electroluminescence (EL) mechanism in a device with Eu(TTA)(3)phen (TTA=thenoyltrifluoroacetone, phen=1,10-phenanthroline) doped CBP (4,4(')-N,N-'-dicarbazole-biphenyl) film as the emitting layer was investigated by analyzing the evolution of carrier distribution on dye and host molecules with increasing voltage. Firstly, it was confirmed that only electrons can be trapped in Eu(TTA)(3)phen doped CBP. As a result, holes and electrons would be situated on CBP and Eu(TTA)(3)phen molecules, respectively, and thus creates an unbalanced carrier distribution on both dye and host molecules. With the help of EL and photoluminescence spectra, the distribution of holes and electrons on both Eu(TTA)(3)phen and CBP molecules was demonstrated to change gradually with increasing voltage. Therefore, the dominant EL mechanism in this device changes gradually from carrier trapping at relatively low voltage to Forster energy transfer at relatively high voltage.
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We have fabricated and measured a series of electroluminescent devices with the structure of ITO/TPD/Eu(TTA)(3)phen (x):CBP/BCP/ ALQ/LiF/Al, where x is the weight percentage of Eu(TTA)3phen (from 0% to 6%). At very low current density, carrier trapping is the dominant luminescent mechanism and the 4% doped device shows the highest electroluminescence (EL) efficiency among all these devices. With increasing current density, Forster energy transfer participates in EL process. At the current density of 10.0 and 80.0mA/ cm(2), 2% and 3% doped devices show the highest EL efficiency, respectively. From analysis of the EL spectra and the EL efficiency-current density characteristics, we found that the EL efficiency is manipulated by Forster energy transfer efficiency at high current density. So we suggest that the dominant luminescent mechanism changes gradually from carrier trapping to Forster energy transfer with increasing current density. Moreover, the conversion of dominant EL mechanism was suspected to be partly responsible for the EL efficiency roll-off because of the lower EL quantum efficiency of Forster energy transfer compared with carrier trapping.
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Organic-inorganic hybrids containing luminescent lanthanide complex Eu(tta)(3)Phen (tta = thenoyltrifluoroaceton, phen = 1,10-phenanthroline) and silver nanoparticles have been prepared via mixing rare earth complex and nanoparticles with the precursors of di-ureasil using a sol-gel process. The obtained hybrid materials with transparent and elastomeric features were characterized by transmission electron microscope, solid-state Si-29 magic-angle spinning NMR spectra, diffuse reflectance, UV-visible absorption and photoluminescence spectroscopies. The effect of the silver nanoparticles on the luminescence properties was investigated. The experimental results showed that the luminescence intensity of the Eu(tta)(3)phen complex could be enhanced by less than ca. 9.5 nM of silver nanoparticles with the average diameter of 4 nm, and reached its maximum at the concentration of ca. 3.6 nM. Further increasing the concentration of the silver nanoparticles (> 9.5 nM) made the luminescence quenched. The enchancement and quench mechnism was discussed.
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We demonstrated high-efficiency red organic light-emitting diodes (OLEDs) employing a europium complex, Eu (III) tris( thenoyltrifluoroacetone) 3,4,7,8-tetramethyl-1,10-phenanthroline (Eu(TTA)(3)(Tmphen)), as an emitter and a blue electrophosphorescent complex, Iridium ( III) bis[4,6-di-fluorophenyl-pyridinato-N,C-2] picolinate (FIrpic), as an assistant dopant codoped into 4,4-N, N-dicarbazole-biphenyl (CBP) host as an emissive layer. A pure red electroluminescence (EL) only from Eu3+ ions at 612 nm with a full width at half maximum of 3 nm was observed and the EL efficiency was significantly enhanced. The maximum EL efficiency reached 7.9 cd A(-1) at 0.01 mA cm(-2) current density, which is enhanced by 2.8 times compared with electrophosphorescence-undoped devices. The large improvements are attributed to energy transfer assistance effects of FIrpic, indicating a promising method for obtaining efficient red OLEDs based on rare-earth complexes.