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     

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。     

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。     

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。     

级联敏化三元旋涂型磷光器件电致发光性能

金属配合物磷光分子在高浓度下易产生发光猝灭,通常采用主客体两元掺杂结构来提高电致发光效率。热激活延迟荧光(TADF)材料通过三线态激子的反向系间窜越理论上可达到100%的内量子效率。为探究不同主体材料在三元敏化磷光体系中的作用,本文基于TADF聚合物作为敏化剂、黄橙光磷光配合物作为发光材料,分别研究了以传统荧光材料和蓝色TADF主体构建的三元敏化的旋涂型有机电致发光器件性能。研究表明,在客体浓度分别为1%、5%、50%时,基于TADF主体的器件电致发光性能均优于相同浓度下以传统荧光主体构建的器件性能。其中当磷光配合物PO-01-TB掺杂浓度为1%时,以天蓝光TADF材料为主体制备的器件最大外量子效率为12.2%,相较于以传统荧光为主体的器件外量子效率(10.7%)提高了14%。这源于本身具有双极传输特性的TADF主体通过反向系间窜越通道增强了对敏化剂和客体的级联能量传递作用,减少了三线态激子的浓度猝灭和湮灭过程,提高了大电流注入下的激子利用率。     

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.     

一种基于二-[2',6'-二氟-2,3'-联吡啶-N,C4'][3-乙酰基-1,7,7-三甲基-双环[2.2.1]-2-庚酮-O,O]铱(Ⅲ)的非掺杂蓝色磷光发光器件

以2',6'-二氟-2,3'-联吡啶(Hdfpypy)为主配体,空间位阻的3-乙酰基樟脑(Hacam)为辅助配体,合成了二-[2',6'-二氟-2,3'-联吡啶-N,C4'][3-乙酰基-1,7,7-三甲基-双环[2.2.1]2-庚酮-O,O]铱(Ⅲ)((dfpypy)2Ir(acam))。在四氢呋喃(THF)溶液中,配合物光致发光(PL)光谱最大发射峰值为466 nm,在487nm左右有一个不明显的肩峰,半峰宽为55 nm。配合物在脱气THF溶液中的PL量子效率为0.51。以(dfpypy)2Ir(acam)为发光层,制备了器件结构为ITO/HATCN(1 nm)/TAPC(40 nm)/(dfpypy)2Ir(acam)(10 nm)/BmpypB(40 nm)/LiF(1 nm)/Al(90 nm)的蓝色非掺杂磷光发光器件。电致发光(EL)光谱的最大发射峰值为474 nm。器件的启动电压为3.5 V。在电流密度为20 mA·cm-2时,CIE色坐标值为(0.17,0.29)。在驱动电压为11 V时,器件最大亮度为2 170 cd·m-2。在驱动电压为4.2 V时,最大功率效率为5.25 lm·W-1,最大亮度效率为6.45 cd·A-1。     

含铱配合物的聚对苯类电磷光聚合物

通过Suzuki聚合法合成了以聚对苯为主链的含铱配合物的电磷光共轭聚合物。部分苯环单元被β-二酮结尾的烷氧基链取代,进而与2-苯基吡啶配位形成悬垂的铱配合物侧链。宽带隙的聚对苯主链使主体与客体的能级匹配,从而有利于能量的转移。铱配合物通过长β-二酮结尾的烷氧基链悬挂在聚对苯的侧链上提高了聚合物的溶解性,有利于器件的制作。另外,由于连在氧原子上的β-二酮具有较大的旋转自由度,增大了β-二酮的反应活性有利于配位反应的进行。聚合物的EL光谱只显示客体铱配合物的发射,主体的发射已被完全猝灭。这表明聚合物主体和铱配合物客体之间发生了有效的能量转移。PPPIrPPy2聚合物发光器件的EL光谱发光波长为525nm,最大外量子效率为2.6%。     

一种基于三氟甲基取代的2-苯并[b]噻吩基吡啶配体的红色电致磷光材料及器件

研究了一种新型红色磷光材料及其在有机电致磷光器件(OLEDs)中应用.在经典红色磷光材料btp₂Ir(acac)的配体2-苯并噻吩吡啶的吡啶环的5位引入吸电子基团CF₃,将辅助配体换为2-吡啶甲酸,成功研制出了双(2-(2′-苯并[b]噻吩基)吡啶)吡啶甲酸合铱配合物[(btfmp)₂Ir(pic)].这种结构可以改变了原配合物的电子云分布,三氟甲基的引入将导致原分子的LUMO能下降,减小了HOMO与LUMO的能隙,引起发光峰位的红移,但2-吡啶甲酸又可引起发光蓝移,最终得到了最大峰位为637nm的饱和红光新的铱(Ⅲ)配合物,为通过简单配体修饰设计和制备新的有机磷光材料提供了一种简洁途径.     

高亮度下具有较高效率的绿色和蓝绿色有机电致发光器件的制备和性能研究(英文)

以铱配合物Ir(tfmppy)2(tpip)(1,tfmppy=4-三氟甲基苯基吡啶,tpip=四苯基膦酰胺)和Ir(dfp-py)2(tpip)(2,dfppy=4,6-二氟苯基吡啶)为发光中心分别制备了绿色和蓝绿色有机电致发光器件ITO/TAPC(1,1-bis[4-[N,N-di(p-tolyl)amino]phenyl]cyclohexane,60 nm)/Ir(Ⅲ)complex(x%,质量分数)∶Sim-CP(3,5-bis(9-carbazolyl)tetraphenylsilane,40 nm)/TPBi(2,2’,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole,60 nm)/LiF(1 nm)/Al(100 nm)。配合物Ir(tfmppy)2(tpip)掺杂质量分数为6%时,以其为发光中心的绿色器件在5 930 cd/m2亮度下的最大电流效率为47.10 cd/A,CIE色坐标为(0.28,0.65),在16.4V驱动电压下的最大发光亮度为38 674 cd/m2。配合物Ir(dfppy)2(tpip)掺杂质量分数为10%时,以其为发光中心的蓝绿色器件在3 175 cd/m2亮度下的最大电流效率为14.80 cd/A,色坐标为(0.15,0.50),在11.8 V驱动电压下的最大发光亮度为25 985 cd/m2。     

Optimization of polymeric host composition for polymer-based electrophosphorescent devices

We have demonstrated an optimized polymeric host material comprising a blend of poly(9-vinylcarbazole) (PVK) and a fluorescent polymer for a highly efficient electrophosphorescence system. Although the chemical compatibility between the blue-emitting-fluorescent polymer and iridium complex, tris[2-phenylpyridine]iridium(III) (Ir-(ppy)₃), is very poor, efficient energy transfers from the blended host to the Ir complex was observed when a small amount of blue-emitting-fluorescent polymer was added to the PVK matrix. The device showed a maximum external quantum efficiency at 5 wt% blue-emitting-fluorescent polymer and 8 wt% Ir complex doping concentrations.     

Highly efficient polymer phosphorescent light-emitting devices based on a new polyfluorene derivative as host

Several highly efficient iridium-complex polymer light-emitting devices (PLEDs) are fabricated,with a newly synthesized blue conjugated polymer,poly[(9,9-bis(4-(2-ethylhexyloxy)phenyl)-fluorene)-co-(3,7-dibenziothiene-S,S-dioxide15)] (PPF-3,7SO15),chosen as host.High luminous efficiencies of 7.4 cd·A 1 and 27.4 cd·A 1 are achieved in red and green PLEDs,respectively,by optimizing the doping concentrations of red phosphorescent dye iridium bis(1-phenylisoquinoline) (acetylacetonate) (Ir(piq)) and green phosphorescent dye iridium tris(2-(4-tolyl)pyridinato-N,C 2) (Ir(mppy) 3).Furthermore,highly efficient white PLEDs (WPLEDs) with the Commission Internationale de l’Eclairage (CIE) coordinates of (0.35,0.38) are successfully produced by carefully controlling the doping concentration of the irid-ium complex.The obtained WPLEDs show maximal efficiencies of 14.4 cd·A 1 and 10.1 lm·W 1,which are comparable to those of incandescent bulbs.Moreover,the electroluminescent spectrum of the white device with an initial luminance of about 1000 cd·m 2 is stable,subject to constant applied current stress,indicating that good device stability can be obtained in this system.     

Hybrid light-emitting devices based on phosphorescent platinum(II) complex sensitized CdSe/ZnS quantum dots

We report on hybrid light-emitting devices based on the emission of phosphorescent sensitized colloidal CdSe/ZnS quantum dots (QDs). Emission lifetime measurements demonstrated that the energy transfer (ET) from square-planar platinum(II) complex [4-CF3-(NC^N^)PtC≡CC6H-4'-F] (NC^HN^=1, 5-bis(2'-pyridyl)benzene) (Pt-2) to QDs is more efficient than that from octahedral iridium(III) complex bis[(4,6-difluorophenyl)pyridinato-N, C2]-(picolinato)iridium (FIrpic). This different ET efficiency might be attributed to the different spatial structures between Pt-2 and FIrpic. Pure red emission with CIE coordinates of (0.66, 0.33) and maximum external quantum efficiency of 2.08% and white emission with power efficiency of 3.15 lm/W were realized at different concentrations of Pt-2 and QDs, respectively.     

Addition reaction and characterization of chlorotris(triphenylphosphine)iridium(I) on silicon(1 1 1) surfaces

Studies were performed to determine the chemical addition of a metal complex molecule, chlorotris(triphenylphosphine)iridium(I), on hydrogen passivated Si(1 1 1) surfaces to form a self-assembled monolayer (SAM). The iridium complex was synthesized prior to chemical addition, for which modified reaction conditions were chosen. Following addition, the silicon surfaces were characterized with X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). The XPS results revealed that the surfaces consisted of the expected elemental percentages and that the iridium has a slightly higher success rate at attaching to oxide-free surfaces. XPS data also strongly indicate that the iridium complex remained intact upon chemisorption and did not decompose during the addition reaction. CV data show a difference between iridium treated surfaces and control samples. Hydrogen passivated wafers with iridium complex were much more conductive than those which were terminated with just an oxide or with an oxide and iridium complex. Furthermore, no free iridium reagent was detected as an additional feature in the current profile, indicating there was no physisorbed layer.     

Highly efficient all phosphorescent white organic light-emitting diodes for solid state lighting applications

We report highly efficient all phosphorescent white organic light-emitting diodes (OLEDs) with an exciton-confinement structure. By stacking two emissive layers (EMLs) with different charge transporting properties, effective charges as well as exciton confinements were achieved. Accordingly, efficient blue OLEDs with a peak external quantum efficiency (EQE) over 22% and power efficacy (PE) over 50 lm/W were developed by using iridium(III) bis(4,6-(difluorophenyl) pyridinato-N,C2′)picolinate (FIrpic) as an electro-phosphorescent dopant. When the optimized orange and red EMLs were sandwiched between the stacked two blue EMLs, white OLEDs with an EQE and PE of 24.3% and 45.9 lm/W at a luminance of 1000 cd/m² were obtained without the use of any out-coupling techniques. In addition, these white OLEDs exhibit a color rendering index (CRI) value of 84 with high efficacy.     

Low-energy electron diffraction,Auger electron spectroscopy,and thermal desorption studies of chemisorbed CO and O2 on the (111) and stepped [6(111) × (100)] iridium surfaces

The adsorption of CO, O₂, and H₂O was studied on both the (111) and [6(111) × (100)] crystal faces of iridium. The techniques used were LEED, AES, and thermal desorption. Marked differences were found in surface structures and heats of adsorption on these crystal faces. Oxygen is adsorbed in a single bonding state on the (111) face. On the stepped iridium surface an additional bonding state with a higher heat of adsorption was detected which can be attributed to oxygen adsorbed at steps. On both (111) and stepped iridium crystal faces the adsorption of oxygen at room temperature produced a (2 × 1) surface structure. Two surface structures were found for CO adsorbed on Ir(111); a (√3 × √3)R30° at an exposure of 1.5–2.5 L and a (2√3 × 2√3)R30° at higher coverage. No indication for ordering of adsorbed CO was found on the Ir(S)-[6(111) × (100)] surface. No significant differences in thermal desorption spectra of CO were found on these two faces. H₂O is not adsorbed at 300 K on either iridium crystal face. The reaction of CO with O₂ was studied on Ir(111) and the results are discussed. The influence of steps on the adsorption behaviour of CO and O₂ on iridium and the correlation with the results found previously on the same platinum crystal faces are discussed.     

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。     

Efficient blue-green and white organic light-emitting diodes with a small-molecule host and cationic iridium complexes as dopants

Using cationic iridium complexes as dopants and a small molecule, 9,9-bis[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]fluorene, as the host, efficient organic light-emitting diodes (OLEDs) have been fabricated from a solution process. The blue-green OLEDs achieve a peak current efficiency of 19.8 cd?A^?1 and a maximum brightness of 17700 cd?m^?2. White OLEDs have been fabricated with a peak current efficiency of 16.8 cd?A^?1 and Commission Internationale de l’Éclairage coordinates around (0.37, 0.44). It is suggested that cationic iridium complexes, in addition to their use in light-emitting electrochemical cells, are promising phosphorescent dopants for solution-processed small-molecule OLEDs.     

Etude par spectroscopie de photoelectrons des interactions metal—support dans des catalyseurs a l'iridium depose sur des oxydes metalliques

Several iridium supported catalyst were studied by means of x-ray photoelectron spectroscopy. These catalysts contain 5 wt. % iridium impregnated from aqueous solution of hexachloroiridic acid on δ-alumina, silica, zinc oxide, titanium oxide and Ketjen silica alumina and are used in catalytic oxidation of olefins.Photoelectron spectra of oxides, impregnated oxides and hydrogen reduced catalysts have been recorded. Chemical shifts observed on impregnated oxides indicate that alumina and titanium oxide make possible the reduction of some of the hexachloroiridates ions into an iridium(III) chloro complex. This reaction is not detected with zinc oxide and silica.For the reduced catalysts, the iridium 4f doublet is shifted to higher binding energies with respect to that of unsupported iridium and the iridium lines have an anomalous breadth. We have postulated that an electronic interaction occurs between the support acting as an electron acceptor and the metal acting as an electron donor. The chemical shifts depend on the nature of the support, increasing ZnO < SiO₂ < TiO₂ < Al₂O₃, and may be correlated with the Fermi level in the metallic oxide. With silica-alumina and progressively de-aluminated silica-alumina, a simultaneous variation of the iridium chemical shift and catalytic activity is observed.     

基于1,3,5-tri(9H-carbazol-9-yl)benzene 主体材料的高效蓝色电致磷光器件

以1,3,5-tri(9H-ctarbazol-9-yl)benzene(TCzP)为主体材料,制备了FIrpic掺杂的高效有机电致蓝光双发光层器件,最大亮度为11957 cd/m2;最大电流效率为18.8 cd/A;色坐标为(0.17,0.37);光谱峰值位于472nm,在496 nm处有一肩峰;即使在1 000cd...