含载流子基团的红色磷光铱配合物的电致发光特性

将含载流子基团的铱配合物Ir-1或Ir-2掺杂到聚芴(PFO)和2-(4-二苯基)-5-(4-叔丁苯基)-1,3,4-噁二唑(PBD)中作为发光层,采用旋涂法制备电致发光器件。通过改变发光层中铱配合物的掺杂浓度,研究了不同掺杂比例对器件性能的影响。结果表明,当铱配合物的掺杂质量分数为2%时,器件的电致发光性能最好。和含苯基的Ir-1比较发现,以含空穴传输基团三苯胺的Ir-2为客体材料的器件性能更好,能够更有效地避免T-T猝灭,器件的最大流明效率为2.78 cd·A-1,最大亮度为5 718 cd·m-2。     

三元铱配合物磷光体系的白光有机电致发光器件光谱特性研究

将黄光磷光材料bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2’]iridium (acetylacetonate) [(t-bt)₂Ir(acac)]超薄层作为黄光发光层,两个蓝光磷光染料iridium(Ⅲ) bis(4’,6’-difluorophenylpyridinato)tetrakis(1-pyrazolyl)borate (FIr6)和bis[(4,6-difluorophenyl)-pyridinato-N,C2’](picolinate) iridium (Ⅲ) (FIrpic)掺杂层作为蓝光发光层,制备了三元发光层的白光有机电致发光器件。该器件具有三元磷光染料分子协同发光特性,并且利用合适厚度的隔层,将三线态激子束缚在各自激子复合区域内,获得了稳定电致发光光谱,CIE色坐标为(0.29±0.01, 0.34±0.01),处于理想的白光区域。通过器件电学特性的测试,验证了磷光染料在三元发光层器件中电致发光作用的机理,同时结果表明,三元发光层器件由于稳定的激子复合区域而有效减弱了器件效率滚降现象。     

新型红色磷光铱配合物的合成与电致发光性能

设计并合成了含羟基配体8-苯并噻唑基2-萘酚(HNBT),并以其为辅助配体、2-苯基吡啶(ppy)为第一配体合成了红色磷光铱配合物Ir(ppy)₂(NBT)。采用真空蒸镀的方法,以Ir(ppy)₂(NBT)为发光中心制备了红色有机电致磷光器件,详细研究了配合物Ir(ppy)₂(NBT)的热稳定性、光物理与电致发光性能。值得注意的是,配合物Ir(ppy)₂(NBT)的发射谱图近似于高斯形状,只有一个位于614 nm的发射主峰,没有肩峰出现,且半峰宽仅为65 nm;此外,基于配合物Ir(ppy)₂(NBT)的最佳器件的最大亮度和效率分别是6 400 cd/m²和4.53 cd/A。     

磷光吡嗪铱(Ⅲ)配合物的合成及发光性质

合成了4种吡嗪铱配合物,用质谱和1H NMR对配合物结构进行了表征,通过紫外-可见吸收光谱和光致发光光谱对其光物理性质进行了研究。结果表明:4种铱配合物都出现了金属-配体电荷转移(MLCT)吸收峰。铱配合物1[(DFMPPZ)_2Ir(pic)]、2[(DFMPPZ)_2Ir Cl(PPh_3)]、3[(DFMPPZ)_2Ir(CN)(PPh_3)]和4[(DPPF)_2Ir(acac)]的发射波长分别为528,536,535,561 nm,都是潜在的黄、绿色磷光材料。以铱配合物4为客体材料,制备了结构为ITO/Mo O_3(1 nm)/CBP(35 nm)/CBP∶Ir(15 nm)/TPBi(50 nm)/Li F(1nm)/Al(100 nm)的一系列不同掺杂浓度的器件,器件的发射波长为567 nm,最大亮度达到32 110 cd·m-2,最大电流效率为32.4 cd·A-1,最大功率效率为28.2 lm·W-1。     

具有减少自猝灭效果的铱配合物掺杂型红色聚合物磷光器件

将双(2-(2'-苯并 噻吩基)-5-三氟甲基吡啶)乙酰丙酮合铱配合物 及电子传输材料PBD掺杂到基质材料PVK中,利用旋涂的方法制备聚合物磷光器件。铱配合物的掺杂质量分数分别为8%、10%、15%及18%,当掺杂质量分数为15%时获得了最大外量子效率4.5%,而同样结构的经典的红光材料(btp)₂Ir(acac)的掺杂质量分数为4%时最大外量子效率为3.3%。可以看出,含三氟甲基的新铱配合物制备的聚合物器件具有明显的减少浓度猝灭效果,这可能由于三氟甲基基团改变了分子堆积状态,减少了分子间相互作用的结果。该聚合物器件最大发射峰位648 nm,色坐标为(0.71,0.29), 没有PVK的蓝光发射峰。     

磷光铱配合物的纯度对其电致发光性能的影响

采用不同的真空热梯度升华条件,获得了不同纯度的乙酰丙酮酸二(2-苯基吡啶)铱Ir(ppy)₂(acac)。以不同纯度Ir(ppy)₂(acac)为客体材料,制备了结构为ITO:MoO₃/CBP/CBP:Ir(ppy)₂(acac)/TPBi/LiF:Al的有机发光二极管(OLEDs),其中CBP和TPBi分别是4,4'-二(9-咔唑)联苯和1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯。评价了不同纯度磷光铱配合物制备的器件的电致发光性能,探索了磷光铱配合物纯度对器件性能的影响。结果表明:Ir(ppy)₂(acac)升华后可以提高器件的稳定性,纯度高的材料可以在较低的掺杂浓度下获得较高的发光效率。     

新型蓝色磷光嘧啶铱(Ⅲ)配合物的合成及发光性质

设计并合成了以2-(2,4-二氟苯基)嘧啶(DFPPM)为主配体的两种新型二嗪铱配合物 (Ph:苯基)和,用核磁共振(NMR)和质谱等方法对其进行了表征,并用紫外-可见吸收光谱和光致发光光谱对其光学性质进行了研究。光致发光光谱结果显示:配合物 的发射峰波长为472 nm和489 nm;而配合物 的发射峰波长为447 nm和472 nm,1931CIE色度坐标为(0.14,0.15),是一种深蓝色磷光材料。以 为客体材料、PVK为主体材料制备了电致发光器件,研究了其电致发光光谱。结果表明,电致发光光谱与光致发光光谱相比有较大程度的红移。     

一种新型铱(Ⅲ)配合物及其有机电致发光器件

报道了一种新的基于2,5-二（4’-乙基苯基）吡啶配体的铱（Ⅲ）配合物,并用于有机电致发光器件,得到λmax=548nm的绿光发射,其最大发光效率为23cd／A,最大亮度为10800cd／m^2。与基于其他绿光铱（Ⅲ）配合物的器件相比,该器件的电流饱和特性也得到进一步改善。     

有机金属配合物电致发光材料的研究进展

有机电致发光材料是平板显示领域最有发展前景的材料之一。其中有机配合物应用最早,一般为五元环或六元环结构,性质比较稳定,熔点高,固体荧光效率高,应用十分广泛。将从配体和金属原子发光方面对其近年来在有机EL器件中的应用研究做一综述。     

深陷阱对有机磷光双掺杂体系电致发光器件效率衰退的影响

研究利用溶液法制备的有机磷光双重掺杂体系电致发光器件的光致发光特性与电致发光特性,并研究了在这种体系中深能级陷阱导致的器件效率衰退现象。首先利用紫外光谱仪和光致瞬态寿命测试系统对基于旋涂法制备的以宽带隙材料4,4’-bis(N-carbazolyl)-1,1’-biphenyl（CBP）为主体,绿色磷光材料tris(2-phenylpyridine) iridium(Ⅲ)（Ir(ppy)₃）和红色磷光材料tris(1-phenylisoquinolinato-C2,N)iridium(Ⅲ)（Ir(piq)₃）为客体材料的薄膜进行了光致发射光谱测试和薄膜在Ir(ppy)₃发光峰516 nm处的光致发光寿命测试,实验发现在Ir(ppy)₃掺杂比例保持定值时,随着深能级掺杂材料Ir(piq)₃的引入,其光致发光光谱中Ir(ppy)₃的相对发光强度减弱且发光寿命变短,当Ir(piq)₃掺杂浓度继续提高时,薄膜光致发光光谱基本保持不变且Ir(ppy)₃的发光寿命基本不变。实验说明在低浓度掺杂下两者的三线态能级之间存在着能量传递,但当掺杂浓度达到高浓度时,能量传递主要来自于主客体之间的传递,两者作为独立的发光中心发光。然后利用溶液法制备了发光层分别为CBP∶Ir(ppy)₃,CBP∶Ir(ppy)₃∶Ir(piq)₃和CBP∶Ir(ppy)₃∶PTB7的三组器件,器件结构为ITO/PEDOT∶PSS/Poly-TPD/EML/TPBi（15 nm）/Alq₃（25 nm）/LiF（0.6 nm）/Al（80 nm）。在Ir(ppy)₃和Ir(piq)₃共掺杂器件和Ir(ppy)₃单掺杂器件的对比实验中发现,加入一定比例的深能级材料后,器件的电致发光光谱发生改变,Ir(piq)₃的相对发光强度增强,器件发光效率下降且效率滚降现象明显。通过对器件进行J-V测试,发现在Ir(ppy)₃单掺杂器件中陷阱填充电流随着掺杂材料浓度的提高而提高,但在加入等浓度深能级材料Ir(piq)₃后,陷阱填充电流基本保持一致。瞬态电致发光测试表明,随着Ir(ppy)₃掺杂比例的提高,器件内由于陷阱载流子释放而产生的瞬时发光强度降低,这是由于Ir(ppy)₃具有一定的传导电荷作用,会减少器件中的陷阱载流子,这进一步说明了具有较深能级的Ir(piq)₃是限制载流子的主要能级陷阱。同时发现随反向偏压的增大,瞬态发光强度增大且发光衰减加速,这是因为位于深能级陷阱的载流子在高电压下被释放,重新复合发光,说明深能级陷阱的确限制住了大量载流子,而由于主体三线态激子具有较长的寿命,激子间相互作用产生的单线态激子在高反压下解离,从而引起三线态激子-极化子相互作用的加剧,导致发光衰减加速。在窄带隙聚合物材料PTB7与Ir(ppy)₃共掺杂器件实验中发现,随着PTB7掺杂浓度提高,陷阱浓度变大且器件效率降低,具有较深能级的PTB7成为了限制载流子的深能级陷阱。因此说明在双掺杂有机磷光电致发光器件中,深能级材料会成为限制载流子的能级陷阱,引起载流子大量堆积,从而导致三线态激子与极化子相互作用加剧,使器件的发光效率衰退。     

Electroluminescence quenching mechanism in Rubrene doped host-guest system

In this paper, the electroluminescence quenching mechanism in a 5,6,11,12-tetraphenylnaphthacene (Rubrene) doped host--guest system is studied by utilizing a specially designed organic light-emitting diode with an emission layer consisting of a few periodic host/guest structures. Tris-(8-hydroxyquinoline) aluminium (Alq₃) and Rubrene are used as the host and the guest, respectively. The thickness variation of the guest layer in each period enables the study of the effect of molecule aggregation, and the thickness variation of the host layer suggests a long range quenching mechanism of dipole--dipole interaction. The long range quenching mechanism is a F?rster process, and the F?rster radius of Rubrene is between 3 and 10~nm.     

掺杂离子型配合物的高效聚合物白光发光二极管

研究了掺杂离子型铱配合物的单发光层聚合物白光器件.根据二元互补色获得白光的原理,所采用离子型橙光材料为六氟磷酸合[二(2-(萘基-1-基)吡啶)(1-乙基-2-(9-(2-乙基己基)-9H-咔唑-3-基)-1H-咪唑并[4,5-f][1,10]菲啰啉)铱(Ⅲ)]([(npy)₂Ir(c-phen)]PF₆),天蓝光材料为二(2-(4,6-二氟苯基)吡啶-N,C(2))吡啶甲酰合铱(Firpic).器件结构为氧化铟锡/苯磺酸掺杂聚乙烯基二氧噻吩(40 nm)/发光 关键词： 聚合物发光二极管 白光 二元互补色 离子型铱配合物     

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.     

Efficient white organic light-emitting diodes based on an orange iridium phosphorescent complex

Stable and efficient white light emission is obtained by mixing blue fluorescence and orange phosphorescence. The introduction of double exciton blocking layers brings about well confinement of both charge-carriers and excitons in the emission layer. By systematically adjusting blue fluorescent and orange phosphorescent emission layers thickness, carriers in emission zone are balanced, and electrically generated excitons can be efficiently utilized. One white device with power efficiency of 14.4 lm/W at 100 cd/m² has excellently stable spectra. The improvement of performance is attributed to efficient utilization of the excitons and more balance of charge-carriers in emission layer.     

掺杂型有机电致发光二极管的研究进展

有机电致发光具有结构简单、成本低、平面光源、节省能源等优点,其中掺杂型电致发光二极管因可以同时利用单重态和三重态的激子来发光和理论上能使器件内量子效率达到100%而倍受关注。从掺杂型电致发光二极管发光机理、主体材料、掺杂剂材料、白光器件几个方面阐述了该领域的研究进展。     

Stable efficiency roll-off in red phosphorescent organic light-emitting diodes using a spirofluorene-benzofluorene based carbazole type host material

Red phosphorescent organic light-emitting diodes (PHOLEDs) with stable efficiency roll-off were developed using a spirofluorene-benzofluorene based carbazole type host material. 9-(Spiro[benzo[c]fluorene-7,9′-fluorene]-2′-yl)-9H-carbazole with a spiro[benzofluorene-7,9′-fluorene] and a carbazole unit was synthesized and it was used as the host material for the red PHOLED. The quantum efficiency of the red PHOLED was optimized at a doping concentration of 1% and the efficiency decrease at 10,000 cd/m² from the maximum efficiency was less than 10%.     

芴-咔唑新型共聚物/PVK掺杂体系的电致发光特性研究

研究了新型的芴-咔唑共聚物(PFC)与聚乙烯咔唑(PVK)掺杂体系的光致发光和电致发光特性.制备了结构分别为indium-tin-oxide(ITO)/PVK:PFC/bathocuproine(BCP)/tris-(8-hydroxylquinoline)-aluminum (Alq₃) /Mg:Ag，ITO/PFC/BCP/Alq₃/Mg∶Ag和ITO/PVK/BCP/Alq₃/Mg∶Ag的三种有机电致发光器件.对器件的光电特性进行了测试.结果表明，掺杂体系中的PVK有效地抑制了固态膜中PFC激基缔合物的形成.掺杂器件在不同的外加电场作用下发生发光层位置的移动，通过调节外加电场，可以获得从绿光到蓝光的可见光发射.当外加电压大于7V时，掺杂器件的蓝色发光亮度达到1650cd/m²，推测其中可能存在从PVK到PFC的能量传递过程.     

DFT/TDDFT investigation on the photophysical properties of a series of phosphorescent cyclometalated complexes based on the benchmark complex FIrpic

The photophysical properties of four Ir(III) complexes have been investigated by means of the density functional theory/time-dependent density functional theory (DFT/TDDFT). The effect of the electron-withdrawing and electron-donating substituents on charge injection, transport, absorption and phosphorescent properties has been studied. The theoretical calculation shows that the lowest-lying singlet absorptions for complexes 1–4 are located at 387, 385, 418 and 386 nm, respectively. For 1–4, the phosphorescence at 465, 485, 494 and 478 nm is mainly attributed to the LUMO → HOMO and LUMO → HOMO-1 transition configurations characteristics. In addition, ionisation potential (IP), electron affinities (EAs) and reorganisation energy have been investigated to evaluate the charge transfer and balance properties between hole and electron. The balance of the reorganisation energies for complex 3 is better than others. The difference between hole transport and electron transport for complex 3 is the smallest among these complexes, which is beneficial to achieve the hole and electron transfer balance in emitting layer.     

Control of device performances of phosphorescent white organic light-emitting diodes by managing charge transport properties of host materials

Interlayer-free phosphorescent white organic light-emitting diodes (PHWOLEDs) with a mixed-host emitting structure in red emitting layer were developed and device performances were investigated according to the host composition in the red emitting layer. Device performances could be effectively managed by a simple change of host materials in the red emitting layer. A high quantum efficiency was obtained in PHWOLEDs with electron transport-type host in the red emitting layer and red emission was strong in PHWOLEDs with mixed-host in the red emitting layer. In addition, stable color performances were obtained in electron transport-type host rich devices.