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。     

Spectral Characteristics of White Organic Light-emitting Diodes Based on Novel Phosphorescent Sensitizer

采用新型贵金属铱的配合物bis(1,2-dipheny1-1H-benzoimida-zole)iridium (acetylacetonate)作为磷光敏化剂,与荧光染料4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-en-yl)-4H-pyran共同掺杂到聚合物主体材料poly(N-vinylcarbazole)中,以N,N'-diphenyl-N,N'-bis(1-naphthyl) (1,1'-biphenyl)-4,4'-diami-ne作为蓝光发光层,制备了白色有机电致发光器件. 通过对掺杂体系的紫外-可见吸收光谱、光致发光光谱以及电致发光光谱的表征,分析了该磷光敏化体系的能量转移机制. 结果表明,在该聚合物磷光荧光双掺杂体系中,由于磷光与荧光材料之间的不完全的F?rster能量传递过程,导致电致发光光谱中同时存在磷光材料三线态到基态与荧光材料单线态到基态的辐射衰减发光. 该掺杂体系成功实现了白光发射,随着偏置电压的升高,器件的CIE色坐标有微小的红移,但都非常接近等能白光点,器件表现出了很好的色纯度.     

基于量子点和MEH-PPV的白光发光二极管的研究

利用无机纳米材料与有机聚合物材料相结合的方法制备白光发光二极管器件, 研究了蓝光量子点QDs(B)掺杂聚[2-甲氧基-5-(2-乙基己氧基-1, 4-苯撑乙烯撑](MEH-PPV) 复合体系的发光特性及量子点QDs(B) 掺杂浓度(质量分数)不同对器件发光特性的影响. 制备了ITO/PEDOT:PSS/MEH-PPV:QDs(B)/LiF/Al 结构的电致发光器件, 测试了器件的电致发光光谱和电学、光学特性. 当QDs掺杂浓度为40%, 驱动电压为8 V时器件能得到较为理想的白光发射. 同时, 对比研究了非掺杂体系的发光特性, 制备了结构为ITO/PEDOT:PSS/MEH-PPV/QDs(B)/LiF/Al的器件, 掺杂体系相较于非掺杂体系, 器件的最大亮度增大, 启亮电压降低, 并分析了掺杂体系器件性能改善的原因.     

一种基于PFO掺杂的理想白光有机电致发光器件

研究了以芴类蓝光材料PFO为主体,通过掺杂MEH-PPV得到单层的白光有机电致发光器件,并从掺杂浓度对器件的光谱特性和色坐标稳定性的影响方面对其发光性能进行了分析研究。在MEH-PPV以2.5Wt%掺杂时,器件开启电压为3V,发光色坐标可达到标准白光等能点(0.33,0.33),器件发光色坐标在5～20V很宽的范围内随电压变化幅度很小,基本稳定在白光区。     

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/聚合物白光电致发光器件

将聚合物材料作为空穴传输材料,以有机小分子蓝光染料1,1,4,4－四苯基丁二烯,绿光染料8－羟基喹啉铝和黄光染料5,6,11,12－四苯基四苯并作为产生白光所需要的三种色源,制备了有机／聚合物白光电致发光器件。这种器件的设计使聚合物的热电稳定性好的优点与有机小分子材料荧光效率高的优点相结合,拓宽了材料的选择范围,更有利于选择能带匹配的材料体系。器件的开启电压为2.5V左右,发光效率在9V时达到最大1.24lm／W,该电压下的亮度达到1600cd/m^2,器件的最大亮度超过20000cd/m^2（18V）,器件最佳色度为（0.319,0.332),这在目前国际上有报道的有机／聚合物白光发光器件中居领先水平。     

紫外转化的PPV薄膜电致发光性质的研究

PPV是一种常用的高荧光效率的黄绿色的电致发光共轭聚合物,因为PPV不易溶解于有机溶剂,所以在有机电致发光(OLEDs)中PPV薄膜的制备通常是PPV的预聚体旋涂成膜,然后在高温、真空条件下转化成PPV薄膜。这种高温转化制膜的方法无法对其进行掺杂,限制了PPV在OLED中的应用。文章利用紫外光照射,PPV预聚体薄膜在室温和真空条件下转化成PPV薄膜,它与热处理得到的PPV薄膜的光致发光(PL)和拉曼(Raman)光谱一致;利用这种方法制备了非掺杂和红色荧光染料掺杂的有机电致发光器件,实现了以PPV为主体和能量给体的不同染料的掺杂发光,并获得绿色和橙色的电致发光。电致发光器件的发光效率和发光强度还有待进一步提高。     

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     

基于双极传输母体的高效有机磷光发光器件

将红、绿、蓝3种不同颜色的染料分别掺杂到相同的母体材料2,7-二（二苯基磷酰）-9-（4-二苯基胺）苯基-9-苯基芴（POAPF）中,制得了可发3种颜色光的高效率有机电致发光器件。进一步将两种互为补偿色的发光材料以合适的掺杂浓度掺到POAPF中,制得了高效率白光器件。该白光器件采用了单发光层结构,器件电致发光光谱稳定性好,随驱动电压变化较小。4种不同颜色的发光器件的最大功率效率分别为16.50,43.72,29.78,32.83 lm/W。     

三波段白光有机电致发光器件及其色稳定性的控制

制备并研究了基于3种小分子荧光材料的白光有机电致发光器件。发光层采用红色发光材料DCJTB掺杂绿光材料Alq3构成混合发光层,与OXD-7构成的蓝色发光层形成异质结的结构,并以NPB为空穴注入层。通过改变结构参数详细研究了发射光谱及其色坐标的电场依赖性。通过分析载流子注入/传输特性,控制激子的复合区域等措施得到了色坐标稳定性好、光谱丰富的高性能白光电致发光器件。经过优化的器件结构可以覆盖更大的可见光区域,当电压从9 V增加到13 V时,色坐标仅从CIE(x,y)=(0.364,0.314)偏移到CIE(x,y)=(0.332,0.291),具有较好的色稳定性。     

Efficient Solution-Processed Blue Electrophosphorescent Devices Based on a Novel Small-Molecule Host

Efficient blue small molecular phosphorescent fight-emitting diodes with a blue phosphorescent dye bis（3,5- difluoro-2-（2-pyridyl）-phenyl-（2-carboxypride） iridium （Ⅲ） （Flrpic） doped into a novel small-molecule host 9,9- bis[4-（3,6-di-tert-butylcarbazol-9-yl）phenyl] fluorene （TBCPF） as the light-emitting layer have been fabricated by spin-coating. The host TBCPF can form homogeneous amorphous films by spin-coating and has triplet energy higher than that of the blue phosphorescent dye Flrpic. All the devices with different Flrpic concentration in the emitting layer give emission from Flrpic indicating complete energy transfer from TBCPF to Flrpic. The device shows the best performance with a peak brightness of 8050 cd/m^2 at 10.2 V and the maximum current efficiency up to 3.52 cd/A, when the Flrpic doped concentration is as high as 16%.     

高效率有机蓝光和白光电致发光器件

以蓝光材料FIrpic同时掺杂空穴传输层TCTA和电子传输层TPBI,制备了具有双发光层的高效率蓝光器件(D-BOLED),D-BOLED最大发光效率达23.4 cd/A,比单发光层蓝光器件(S-BOLED)提高了约36.8%.这是因为双发光层结构能够更有效地利用扩散到激子复合界面两边载流子传输层的三线态激子.结合基于...     

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.     

High-efficiency organic light-emitting diodes based on ultrathin blue phosphorescent modification layer

Yellow organic light-emitting devices(YOLEDs) with a novel structure of ITO/MoO_3(5 nm)/NPB(40 nm)/TCTA(15 nm)/CBP:(tbt)_2Ir(acac)(x%)(25 nm)/FIrpic(y nm)/TPBi(35 nm)/Mg:Ag are fabricated. The ultrathin blue phosphorescent bis[(4,6-difluorophenyl)-pyridi-nato-N,C2■](picolinate) iridium(Ⅲ)(FIrpic) layer is regarded as a highperformance modification layer. By adjusting the thickness of FIrpic and the concentration of (tbt)_2Ir(acac), a YOLED achieves a high luminance of 41618 cd/m~2, power efficiency of 49.7 lm/W, current efficiency of 67.3 cd/A, external quantum efficiency(EQE) of 18%, and a low efficiency roll-off at high luminance. The results show that phosphorescent material of FIrpic plays a significant role in improving YOLED performance. The ultrathin FIrpic modification layer blocks excitons in EML. In the meantime, the high triplet energy of FIrpic(2.75 eV) alleviates the exciton energy transport from EML to FIrpic.     

新型有机电致磷光白光器件的研究

制备了结构为ITO/NPB/TCTA/FIrpic∶TCTA/Ir(MDQ)2(acac)∶TmPyPB/FIrpic∶TmPyPB/TmPyPB/LiF/Al的有机电致磷光发光器件。通过在双蓝光发光层之间插入较薄的红光层Ir(MDQ)2(acac)∶TmPyPB调节载流子、激子在各发光层中的分布,并结合TCTA和TmPyPB对发光层内载流子和激子的有效阻挡作用,混合实现白光发射。研究了红光层在不同厚度、不同掺杂浓度下对器件发光性能的影响。结果表明,红光发光层厚度为2nm、质量浓度为5%时,结合蓝光发光层和红光发光层,实现了色坐标为(0.333,0.333)、最大发光效率为11.50cd/A的白光发射。     

Pure blue and white light electroluminescence in a multilayer organic light-emitting diode using a new blue emitter

We characterized the 6,12-bis{[N-（3,4-dimethylphenyl）-N-（2,4,5-trimethylphenyl）]amino} chrysene （BmPAC）, which has been proven to be a blue fluorescent emission with high EL efficiency. The blue fluorescent device exhibits good performance with an external quantum efficiency of 5.8% and current efficiency of 8.9 cd/A, respectively. Using BmPAC, we also demonstrate a hybrid phosphorescence/fluorescence white organic light-emitting device （WOLED） with high efficiency of 36.3 cd/A. In order to improve the relative intensity of blue light, we plus a blue light-emitting layer （BEML） in front of the orange light emitting layer （YEML） to take advantage of the excess singlet excitons. With the new emitting layer of BEML/YEML/BEML, we demonstrate the fluorescence/phosphorescence/fluorescence WOLED exhibits good performance with a current efficiency of 47 cd/A and an enhanced relative intensity of blue light.     

Abrupt change of luminescence spectrum in single-layer phosphorescent polymer light emitting diode

PVK-based single-layer phosphorescent polymer OLEDs (organic light emitting diodes) with different rubrene concentrations were fabricated and examined for the Förster energy transfer from phosphorescent FIrpic dye to rubrene. We found out that at a certain rubrene concentration the energy transfer occurs abruptly and the transfer shows an abnormal evolution of electroluminescence (EL) spectrum due to the coincidence of peak wavelengths of bis[(4,6-difluorophenyl)-pyridinato-N,C^2′](picolinate) iridium(III) (FIrpic) emission and 5,6,11,12-tetraphenylnaphthacene (rubrene) absorption. With the calculation of Förster radius and average distance between FIrpic molecules, we have related the calculated ratio between the number of FIrpic molecules within to that out of Förster radius with the degree of Förster energy transfer from EL spectra measured in the experiment. Experimental results were found to fit well with the predicted results especially at low rubrene concentrations.     

高效率共轭聚合物主体绿光磷光发光二极管

因电致发光效率高和器件制备工艺简单,聚合物为主体的绿色磷光电致发光成为一个研究热点.共轭聚合物的三线态能级一般低于绿色磷光材料的三线态能级,易对磷光的发光引起猝灭导致低的发光效率,所以较少被用作绿色磷光材料的主体.通过增加聚乙烯基咔唑（PVK）作为空穴传输层,获得了高发光效率的共轭聚合物聚芴（PFO）作主体绿色磷光发射,甚至高于相同条件下以PVK为主体的绿色磷光发射.究其原因,PVK的电子阻挡作用使发光中心靠近PVK与PFO的界面,界面处PVK因为其高的三线态能级增强了绿色磷光的发光.当三-（2-苯基吡啶）-Ir（Ir（ppy）₃）掺杂浓度为2％时得到了最高的亮度效率24.8 cd/A,此时的电流密度为4.65 mA/cm²,功率效率为11 lm/W,最高亮度达到35054 cd/m²,色坐标是（0.39,0.56）. 关键词： 共轭聚合物 磷光 绿光发光     

Intramolecular energy transfer by singlet and triplet excitons in macromolecules

Absorption, luminescence and photo-oxidation of polyvinylcarbazole (PVCa) and polyvinylbenzocarbazole (PVBCa) in weak solutions have been studied. It is found that fluorescence and phosphorescence spectra, observed at 293, 77 and 4.2 K, depend on the molecular mass M of the polymer and on the experimental conditions. Due to efficient intramolecular energy transfer the fluorescence spectrum includes the emission of excimers, emission of end groups and that of internal structural defects of a macrochain. The relative role of each emission markedly depends on M. Phosphorescence is largely determined by the annihilation effects between triplet excitations, these effects being pronounced in long macrochains. The data show the excitonic nature of the singlet and triplet excitation energy transfer in the polymers studied. The migration of one-dimensional singlet and triplet excitons strongly influences the luminescent properties of PVCa and PVBCa macromolecules, as well as their photochemical reactions. The range of singlet excitons in PVCa and PVBCa macromolecules is determined both at room temperature and at low temperatures.