铱金属配合物磷光材料掺杂聚合物体系的电致发光特性

通过对一种新型贵金属铱的配合物磷光材料(pbi)₂Ir(acac)与咔唑共聚物进行物理掺杂, 制备了结构为indium-tin oxide(ITO)/poly(N-vinylcarbazole)(PVK): (pbi)₂Ir(acac)(x)/2,9-dimethyl-4,7-diphenyl-1,10-phenan throline(BCP)(20nm)/8-Hydroxyquinoline aluminum(Alq₃)(10nm)/Mg:Ag的聚合物电致磷光器件,研究了磷光聚合物掺杂体系在低掺杂浓度时(0.1%和0.5%(质量百分数,全文同))的光致发光(PL)和电致发光(EL)特性. 结果表明, 该掺杂体系的PL光谱和EL光谱中均同时存在主体材料PVK与磷光客体(pbi)₂Ir(acac)的发光光谱, 但主客体的发射强度不同,推测该掺杂体系在电致发光条件下, 同时存在主体材料到客体的不完全的能量传递和载流子直接俘获过程. 磷光掺杂浓度为0.1%的器件在19V电压下实现了白光发射, 色坐标为(0.32, 0.38), 掺杂浓度为0.5%的器件在20.6V电压下的最大发光亮度为11827 cd·m^-2, 而在13.4V电压下的最大流明效率为4.13 cd·A^-1. 关键词： 有机电致发光器件 铱配合物磷光 聚合物掺杂     

High performance polymer light-emitting diodes doped with a novel phosphorescent iridium complex

High performance polymer light-emitting diodes (PLEDs) based on a phosphor of noble metal complex bis(1,2-dipheny1-1H-benzoimidazole) iridium (acetylacetonate) [(pbi)₂Ir(acac)] doped in poly(N-vinylcarbazole) (PVK) host with various concentration were demonstrated. The photoluminescence (PL) and electroluminescence (EL) spectra of the PLEDs exhibited an emission intensity decrease of PVK and a gradually enhanced feature of (pbi)₂Ir(acac) with increased doping concentration. The device with a 5 wt% (pbi)₂Ir(acac) doped PVK system showed a high power efficiency of 3.84 lm/W and a luminance of 26,006 cd/m². The results indicated that both energy transfer and charge trapping have a significant influence on the performance of PLEDs. The devices have a broadened EL spectrum of full-width at half-maximum (FWHM) more than 100 nm, which can be realized for WOLEDs.     

Electroluminescence of organic light-emitting diodes consisting of an undoped (pbi)2Ir(acac) phosphorescent layer

The electroluminescence (EL) characteristics of phosphorescent organic light-emitting diodes (OLEDs) with an undoped bis(1,2-dipheny1-1H-benzoimidazole) iridium (acetylacetonate) [(pbi)₂Ir(acac)] emissive layer (EML) of various film thicknesses were studied. The results showed that the intensity of green light emission decreased rapidly with the increasing thickness of (pbi)₂Ir(acac), which was relevant to the triplet excimer emission. It suggested that the concentration quenching of monomer emission in the undoped (pbi)₂Ir(acac) film was mainly due to the formation of triplet excimer and partly due to the triplet-triplet annihilation (TTA) and triplet-polaron annihilation (TPA). A green OLED with a maximum luminance of 26,531 cd/m², a current efficiency of 36.2 cd/A, and a power efficiency of 32.4 lm/W was obtained, when the triplet excimer emission was eliminated. Moreover, the white OLED with low efficiency roll-off was realized due to the broadened recombination zone and reduced quenching effects in the EML when no electron blocking layer was employed.     

Spectral studies of thin films based on poly(N-vinylcarzole) and red dopant

Organic light-emitting diodes were fabricated with a structure of indium-tin-oxide (ITO)/poly(N-vinylcarzole)(PVK):4-(dicyanom-ethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB)/8-tris-hydroxyquinoline aluminum (Alq₃)/lithium fluoride (LiF)/Al. The energy transfer from PVK to Alq₃ then to DCJTB and the charge trapping processes were investigated by employing the photoluminescence (PL) and electroluminescence (EL) spectra. With increasing thickness of the Alq₃ layer, the PL and EL emission from PVK were decreased gradually, which indicated that the effective energy transfer occurred from PVK to Alq₃ and then from Alq₃ to DCJTB. At the same time, we found that the exciton recombination zone could be adjusted by controlling the Alq₃ layer thickness and the applied voltages. The effects of different DCJTB concentrations on the optical and electrical characteristics of the devices were investigated, and an obvious red-shift was observed with the DCJTB dopant concentrations increasing in the PL and EL spectra.     

掺杂DCJTB聚合物电化学池（LEC）的发光性质

通过在聚合物电化学池(LEC)发光器件的发光材料MEH-PPV中掺杂红光染料DCJTB,对LEC器件的发光性质进行研究。基于器件结构为ITO/MEH-PPV PEO LiCF3SO3/Al的薄膜LEC器件,其电致发光峰在570nm左右,通过在MEH-PPV与PEO的混合膜中掺杂不同比例的红光染料DCJTB,随着掺杂比例的增加,器件的发光峰由570nm向红光波段移动,通过控制DCJTB的掺杂比例制备了发光峰在570~650nm连续变化的LEC电致发光器件。对其分析认为从LEC主体发光聚合物MEH-PPV到染料DCJTB间发生了良好的能量传递。     

有机电致发光器件中新型芴类小分子材料的光谱特性

针对新型芴类小分子材料6,6′-(9H-fluoren-9,9-diyl)bis(2,3-bis (9,9-dihexyl-9H-fluoren-2-yl) quinoxaline) (BFLBBFLYQ)和空穴传输材料N,N′-biphenyl-N,N′-bis-(3-methylphenyl)-1, 1′-biphenyl-4,4′-diamine(TPD)及二者混合体系的荧光光谱和吸收光谱进行了测试表征,制备了结构为indium-tin oxide (ITO)/BFLBBFLYQ∶TPD/Alq/Mg∶Ag的双层有机电致发光器件。研究发现,BFLBBFLYQ∶TPD混合薄膜存在一个不同于单独分子薄膜的低能量发射光谱,发光峰在530 nm处,与tris(8-hydroxyquinolinato)aluminum(Alq)薄膜的荧光光谱相同,亦与结构为BFLBBFLYQ∶TPD/Alq双层器件的电致发光光谱相同。鉴于荧光染料4-(dicyanomethylene)-2-tert-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl) -4H-pyran(DCJTB)的吸收光谱与Alq的荧光光谱有很好的重叠,利用Forster能量传递理论,将DCJTB红色染料引入双层器件,通过调节掺杂位置,考察器件的发光光谱情况,进而对BFLBBFLYQ∶TPD/Alq双层器件的载流子复合区域进行了研究。结果表明,双层器件的载流子复合区域位于BFLBBFLYQ∶TPD/Alq界面附近的Alq层内。     

Enhanced amplified spontaneous emission by assistant Förster energy transfer in DCJTB-C545T-Alq3 coguest-host system

Amplified spontaneous emission (ASE) characteristics of a red fluorescent dye 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) were significantly improved by assistant Förster energy transfer. The coguest-host system was composed of an electron transport organic molecule tris(8-hydroxyquinoline) aluminum (Alq₃) as host and a green fluorescent dye (10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one) (C545T) as assistant dopant codoped with the guest red dye DCJTB as emitter in a matrix of polystyrene (PS). It was found that the threshold and loss were greatly reduced to 0.007 mJ?pulse^-1 and 7 cm^-1, and the gain was significantly enhanced to 52 cm^-1 by doping of C545T. The improvement of ASE performance in Alq₃:C545T:DCJTB film was attributed to the energy assistant effect of C545T, leading more exciton energy to transfer to DCJTB.     

利用级联式能量传递的有机电致发光器件

为了提高掺杂型有机电致发光器件(OLED)中主体发光材料与客体荧光染料间能量传递的效率,2-对联苯-8-羟基喹啉锌(Zn ₂)作为NPB : DCJTB掺杂体系的能量助传递剂,制备了结构如:ITO/NPB/NPB : DCJTB/Zn ₂/BCP/Al的有机电致发光器件。助传递剂Zn ₂的加入,能够两次利用Frster能量转移,实现NPB向DCJTB级联式的能量传递过程,提高低浓度时掺杂染料DCJTB红光发射的纯度;此外,还探讨了三者间能量传递的有效距离,即当助传递剂与掺杂体系的距离在小于10 nm的范围内,其参与能量传递的效率随着距离的增加而逐渐下降。     

掺杂PVK薄膜中两种组分相互作用的光谱及形貌研究

将两种荧光材料Alq₃和DCJTB 同时掺杂到聚合物PVK中,通过混合薄膜的光学及电学性质研究了能量传递过程及电荷陷阱作用。同时用AFM分析了不同掺杂浓度下混合薄膜的相分离现象。发现随着DCJTB染料比例的增加,两种染料在PVK中的分散越来越均匀,说明在双掺杂体系中存在Alq₃和DCJTB 的某种作用,这种作用打散了混合物中Alq₃的聚集,但随着掺杂浓度的进一步增加,DCJTB形成了自己独立的电荷传输通道,从而降低了电致发光器件的启亮电压。     

荧光染料和磷光染料激子形成截面的比较

为了比较单线态激子与三线态激子形成截面的大小,作者将荧光染料4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) 和磷光材料factris-(2-phenylpyridine) iridium [Ir(ppy)₃]共掺杂在N-vinylcarbazole (PVK)中作为发光层,制作了多层有机电致发光器件。通过对其光致发光及电致发光特性的研究,计算出Ir(ppy)₃激子的形成截面比DCJTB激子的形成截面大得多。     

基于CBP:BCzVB:Btp2Ir(acac)体系的白色有机电致发光器件色度飘移研究

以苯乙烯类化合物BCzVB为蓝色荧光染料,以铱配合物Btp_2Ir(acac)为红色磷光染料,共掺杂到CBP基质中作为发光层,制备了白色有机电致发光器件,研究了该体系发光色度漂移的原因。器件在掺杂CBP:6?zVB: 0．2%Btp_2Ir(acac),在．驱动电流从4～200 mA/cm~2变化范围内,发光色坐标从(0．340,0．273)飘移到(0．308, 0．273),色坐标轻微蓝移。对器件发光光谱和亮度-电流密度曲线等分析表明:器件色度的轻微蓝移是由于CBP基质向Btp_2Ir(acac)掺杂剂完全的能量传递、荧光染料BCzVB向磷光染料Btp_2Ir(acac)不完全的能量传递等内在物理过程和磷光染料Btp_2Ir(acac)自身发光饱和等特性共同决定的。     

Efficient red organic light-emitting diode sensitized by a phosphorescent Ir compound

The efficiencies of red organic light-emitting diode (OLED) using tris-(8-hydroxy-quinoline)aluminum (Alq₃) as host and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as dopant were greatly increased by adding a small amount (0.3 wt%) of Ir compound, iridium(III) bis(3-(2-benzothiazolyl)-7-(diethylamino)-2H-1-benzopyran-2-onato-N′,C⁴) (acetyl acetonate) (Ir(C6)₂(acac)), as a sensitizer. The device has a sandwiched structure of indium tin oxide (ITO)/4,4′,4″-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine (T-NATA) (40 nm)/N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′ diamine (NPB) (40 nm)/Alq₃:DCJTB (0.7 wt%):Ir(C6)₂(acac) (0.3 wt%) (40 nm)/Alq₃ (40 nm)/LiF (1 nm)/Al (120 nm). It can be seen that the current efficiencies of this device remained almost (13.8±1) cd/A from 0.1 to 20,000 cd/m² and the Commission International d’Eclairage (CIE) coordinates at (0.60, 0.37) in the range of wide brightness. The significant improvement was attributed to the sensitization effect of the doped Ir(C6)₂(acac), thus the energy of singlet and triplet excitons is simultaneously transferred to the DCJTB.     

PBD的掺杂对PVK:Ir(ppy)3体系发光特性的影响

从三线态激子的发光机理入手,研究了PBD作为电子传输材料对PVK:Ir(ppy)3体系的影响。实验中制备了单层器件ITO/PVK:Ir(ppy)3/PBD/Al,ITO/PVK:Ir(ppy)3:PBD/Al和双层器件,ITO/PVK:Ir(ppy)3:PBD/BCP/Al,其中PVK:Ir(ppy)3的掺杂浓度比例不变,通过改变PBD的掺杂浓度,其变化范围是PBD与PVK的质量比从0:100到20:100,制得了一系列器件,研究了它们的光致发光(PL)光谱和电致发光(EL)光谱。发现PBD这种电子传输材料的加入对器件的亮度有很大提高,当PBD与PVK质量比为10%时,器件亮度最大。     

一种基于环金属铱配合物的高效绿色聚合物电致发光器件

以2-苯基吡啶为主配体,3-乙酰基樟脑为辅助配体合成了一种新型的具有大空间位阻的环金属铱配合物Ir[(PPy)2(acam)],对它的化学结构和光物理性质进行了表征.以环金属铱配合物Ir[(PPy)2(acac)]的发光效率(0.34)为参照物,配合物在2-甲基四氢呋喃溶液中的光致发光效率为0.54,表明在配合物中引入...     

Non-doped red to yellow organic light-emitting diodes with an ultrathin 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) layer

In this letter, bright non-doped red to yellow organic light-emitting diodes (OLEDs) with ultrathin 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) layer as the emitting layer were fabricated. It was investigated that the effect of the ultrathin DCJTB layer on the electroluminescent (EL) performance of OLEDs. The DCJTB layer was incorporated at different positions in the conventional tris(8-quinolinolato)-aluminum (AlQ)-based devices (ITO/NPB/AlQ/LiF/Al). The emission of DCJTB was dominative in the EL spectra of the devices, in which the position of 0.3 nm DCJTB layer was less than 10 nm from the NPB/AlQ interface. The EL peak emission of DCJTB shifted to blue side as DCJTB position moved gradually from AlQ to NPB layer. The highest brightness of the device with 0.3 nm DCJTB layer inserted into NPB reached 16,200 cd/m² at 15 V, with the CIE coordinates of (0.522, 0.439).     

Nondoped phosphorescent organic quantum well light-emitting device based on iridium complex: Synthesis, characterization, photophysical property, and electroluminescence performance

In this paper, we report a phosphorescent Ir(III) emitter of Ir(acac)(F-BT)₂, where acac=acetylacetonate and F-BT=2-(2-fluorophenyl)benzo[d]thiazole, including its crystal structure, electronic nature, photophysical characteristics, thermal, and electrochemical properties. Data suggest that Ir(acac)(F-BT)₂ is a promising emitter with high quantum yield of 0.61 and good thermal stability, along with its proper energy levels for charge carrier transportation. Multiple quantum well (MQW) structured OLEDs using Ir(acac)(F-BT)₂ as emitter are also fabricated, and their electroluminescence (EL) are investigated in detail. The optimal EL device with 4,4′-N,N′-dicarbazole-biphenyl as potential well layer shows a maximum luminance of 85,500 cd/cm² and a peak current efficiency of 31.5 cd/A, and the efficiency roll-off is efficiently reduced.     

Ir(PPY)3掺杂PVK的电致发光机理

近几年来发展起来的电致磷光(electrophosphorescence)是有机发光二极管(OLED)研究的新生长点。对电致磷光发光机理的研究随即得到了人们普遍的关注。比较了不同正向偏压条件下Ir(PPY)₃掺杂聚乙烯基咔唑(PVK)的光致发光(PL)和电致发光(EL)光谱。研究结果显示在电场和注入电流的共同作用下,PL光谱中基质PVK发光的相对强度并没有发生显著的变化。电场或注入载流子不会影响PVK向Ir(PPY)₃的能量传递。磷光掺杂聚合物EL主要是由于载流子在掺杂磷光分子上的直接复合,而不是由基质向磷光掺杂分子的能量传递。     

发光层厚度变化的高效红色有机电致磷光器件

以铱配合物红色磷光体为掺杂剂，制备了基于TPBi材料的红色电致磷光器件,其结构为ITO/CuPc/NPB/TPBi:Btp₂Ir(acac)/ TPBi/Alq/LiF/Al.取得了在x=0.62，y=0.35的色度下，效率最高达2.43cd/A；电流密度为20mA/cm²时，亮度431cd/m²；电流密度为400mA/cm²时，亮度4798 cd/m²的结果.讨论了不同的发光层厚度影响器件色度和 关键词： 三线态 红光掺杂剂 有机电致磷光 T-T湮没     

Ir（PPY）3对Rubrene荧光材料的敏化性研究

最近几年,磷光器件是有机电致发光研究领域和产业化的一大热点。在实验中作者发现PVK∶PBD∶Rubrene共掺体系的发光中存在较强的PVK发光,能量传递不充分。由于一些具有重金属离子的有机物,存在强的自旋-轨道耦合作用,引入到共掺体系可以充分利用单线态和三线态的发光,从而获得高于一般有机材料器件所达到的内量子效率。为获得单色性较好的Rubrene发光,作者将磷光敏化剂Ir(ppy)3引入到PVK∶PBD∶Rubrene共掺溶液中,得到了纯正Rubrene发光,Forester能量传递也更加充分。当进一步提高Rubrene掺杂浓度以后,单色性Rubrene发光更加明显,并讨论了Ir(ppy)3所起的作用和器件的发光机理。磷光材料与有机小分子材料共掺的方法,可以有效提高器件的发光亮度及效率。     

以CBP为主体的高色纯度红色磷光有机电致发光器件

以铱配合物红色磷光体Ir(piq)2(acac)为掺杂剂,制备了基于CBP材料的一系列红色电致磷光器件(PLED),其结构为ITO/CuPC(1nm)/Ir(piq)2(acac):CBP(25nm)/BCP(10nm)/Alq3(35nm)/LiF(1nm)/Al(100nm),对4种不同的掺杂剂浓度进行了比较,研究了它们的电致发光特性。得出了Ir(piq)2(acac)的最佳掺杂比为8%,此时器件的色坐标都非常接近标准红色,且色纯度超过了98%以上;在16V时,色坐标为(x=0.67,y=0.32),色纯度为99.74%,基本满足了全色显示对红色发光的要求。