Aggregation-enhanced emission and efficient electroluminescence of conjugated polymers containing tetraphenylethene units

Tetraphenylethene (TPE) is a popular luminogen characterized by aggregation-induced emission and has been widely used to construct solid-state emissive materials. In this work, two thermally stable polymers (P1 and P2) consisting of TPE conjugated to the 2,7-positions of fluorene and carbazole, respectively, are synthesized and characterized. Both polymers are weakly fluorescent in solutions but show greatly enhanced emission as the aggregate formation, presenting an aggregation-enhanced emission feature. Two kinds of polymer light-emitting diodes are fabricated utilizing P1 and P2 as emitters (EML) (device I: ITO/PEDOT:PSS (45 nm)/PVK:EML (1:1 wt%, 55 nm)/TPBI (38 nm)/Ca:Ag; device II: ITO/PEDOT:PSS (45 nm)/ PVK:OXD-7:EML (3:1:3 wt%, 55 nm)/TPBI (38 nm)/Ca:Ag). The device II of P2 shows the best performances, affording a maximum luminance of 6500 cd/m 2 and a high peak efficiency of 2.11 cd/A.     

Synthesis and electroluminescent properties of naphthalimide derivatives

Naphthalimide derivatives, N-ethyl-4-acetylamino-l ,8-naphthalimide (EAAN) and polymer with N-propyl-4-acetylamino-l,8-naphthalimide (PAAN) side-chain (P-PAAN) were successfully synthesized. Electroluminescent devices of ITO/PVK(120nm)/EAAN(50nm)/Al(150nm) (Ⅰ) and ITO/PVK P-PAAN( 10:1) (50nm)/Al(150nm) (Ⅱ) constructed with EAAN and P-PAAN as the emitting layer were investigated, whereas the single-layer devices of ITO/EAAN or P-PAAN(50nm)/Al(l50nm) (Ⅲ) were not observed to have any e-mission light. The emission results revealed that the exciton recombination formed by positive and negative charge carriers injected from electrodes of devices Ⅰ and Ⅱ was much more balanced than that of devices Ⅲ, which implied that naphthalimide derivatives are a new type of electron-transporting materials with high performance. The electron-transporting properties of naphthalimide derivatives were also elucidated by investigation of the electroluminescent behaviors from both devices of ITO/PPV (80nm)/Al and ITO/P     

Bright red electroluminescent devices based on a soluble lanthanide complex Eu(DBM)_3(phen)

Electroluminescent devices with PVK film doped with Eu(DBM)3(phen) and PBD were fabricated. The device structure of glass substrate/indium-tin-oxide/PPV/PVK:Eu(DBM)3-(phen):PBD/Alq3/Al was employed. The emissive layer was formed by spin-casting method. A sharply red electroluminescence with a maximum luminance of 114.4 cd/m2 was achieved at 42 V.     

Photoluminescence and Electroluminescence Properties of 2, 5-Bis[2,2′-bis （5-phenyl ）- 1, 3,4-oxadiazole] Thiophene （T-OXD） and T-OXD／Poly（9-vinylcarbazole） Blends

The photoluminescence(PL) and the electroluminescence(EL) properties of a novel organic compound, 2,5-bis (2,2‘-bis(5-phenyl)-1, 3,4-oxadiazole (T-OXD), were studied in chloroform and in a solid thin film. The PL and the EL properties of T-OXD/poly(9-vinylcarbazole)(PVK) blends were also studied, which contained various contents of T-OXD. The PL maximum emission peaks of T-OXD/PVK blends show gradual bathochromtic-shift with the increase of the T-OXD content. The EL spectra of T-OXD/PVK devices are similar to their PL spectra, and all the EL maximum emission peaks show bathochromtic-shift compared with the corresponding PL spectra, which is ascribed to the formation of electroplex. The turn-on voltages for ITO/T-OXD; PVK/AI devices decreased from 13.5 V of the device cotaining 0. 1% T-OXD(mass fraction) to 5 V of the device containing 5% T-OXD, which suggests that T-OXD improves the energy level match between T-OXD and PVK and enhances the emission efficiency. The experimental results indicate that T-OXD can be used as a good electron transporting material.     

Kinetics process of Tb(Ⅲ)/Tb couple at liquid Zn electrode and thermodynamic properties of Tb-Zn alloys formation

Electrochemical properties of rare-earth elements in the LiCl-KCl eutectic are important for the pyrometallurgical recycling process of spent nuclear fuels. In this work, the electrochemical properties of Tb(Ⅲ)/Tb(0) couple were studied by the cyclic voltammetry(CV) at a liquid Zn pool electrode. The results showed that this electrochemical reaction is quasi-reversible with mixed reversible diffusion control and the charge transfer control. The diffusion coefficient of Tb(Ⅲ) was determined to be in the order of ~10.5 cm2 s.1. Moreover, kinetic parameters, such as the standard rate constants(ks) and charge transfer coefficient(α) for the electroreduction of Tb(Ⅲ) to Tb(0) at the liquid Zn electrode, were calculated by the Nicholson method at 873 K. Additionally, it was found that Tb-Zn intermetallic compounds were easily to be formed in the measurements. Hence, the reduction process of Tb(Ⅲ)/Tb(0) couple on the Zn-coated Mo electrode was also studied to obtain more information of the Tb-Zn intermetallic compounds. Electrochemical signals stemming from various intermetallic compounds associated with TbZn12, Tb2Zn17, Tb13Zn58, Tb3Zn11, TbZn3, TbZn2 and TbZn, were observed. The thermodynamic data were thereafter estimated by applying the emf method at 823–923 K. The standard formation Gibbs energies and the standard equilibrium constant of each Tb-Zn intermetallic compounds were also calculated. Finally, enthalpies and entropies of formation and the apparent standard potentials of various Tb-Zn intermetallic compounds were also obtained.     

Preparation and characterization of Ag~+ ion-exchanged zeolite-Matrimid~5218 mixed matrix membrane for CO_2/CH_4 separation

In this work, the zeolite-Y was ion-exchanged by introducing silver cations into the framework of microsized nano-porous sodium zeolite-Y using a liquid-phase ion exchanged method. The Ag+ion-exchanged zeolite, was then embedded into the Matrimid~5218 matrix to form novel mixed matrix membranes(MMMs). The particles and MMMs were characterized by ultraviolet-visible diffuse reflectance spectroscopy(UV–vis DRS), N_2 adsorption–desorption isotherm, X-ray diffraction(XRD), Fourier transform infrared(FTIR) and scanning electron microscopy(SEM). Furthermore, the effects of filler content(0–20wt%) on pure and mixed gas experiments, feed pressure(2–20 bar) and operating temperature(35–75 oC)on CO_2/CH_4 transport properties of Matrimid/Ag Y MMMs were considered. Characterization results confirmed an appropriate ion-exchange treatment of the zeolites. The SEM results confirmed the superior interfacial adhesion between polymer and zeolites, particularly in the case of Matrimid/Ag Y membranes.This is due to the proper silverous zeolite/Matrimid functional groups' interactions. The gas permeation results showed that the CO_2 permeability increased about 123%, from 8.34 Barrer for pure Matrimid to18.62 Barrer for Matrimid/Ag Y(15 wt%). The CO_2/CH_4 selectivity was improved about 66%, from 36.3 for Matrimid to 60.1 for Matrimid/Ag Y(15 wt%). The privileged gas separation performance of Matrimid/Ag Y(15 wt%) was the result of a combined effect of facilitated transport mechanism of Ag+ions as well as the intrinsic surface diffusion mechanism of Y-type zeolite. In order to survey the possibility of using the developed MMMs in industry, the CO_2-induced plasticization effect and mixed gas experiment were accomplished. It was deduced that the fabricated MMMs could maintain the superior performance in actual operating conditions.     

CARRIER PHOTOGENERATION IN POLY（N-VINYL-CARBAZOLE）-BASED PHOTOCONDUCTIVE THIN-FILM DEVICES

In this paper, photoexcitation processes in the bilayer devices based on inorganic materials and poly（N-vinylcarbazole） （PVK） were investigated. In order to clarify the roles of inorganic materials in photoconductive properties of bilayer devices, TiO2 and ZnS were chosen to combine with PVK. A model for generation of photocurrent （Iph） in single layer device of PVK was obtained. It is deduced that the recombination rate constant （Pcomb） and the ionization rate constant （y） ofexcitons should be considered as the most important factors for Iph. For inorganic materials （TiO2 or ZnS）/PVK bilayer devices, in reverse bias of-4 V, the photocurrent of 115 mA/cm^2 in the TiO2/PVK device was observed, but the photocurrent in the ZnS/PVK device was only 10 mA/cma under the illumination light of 340 nm and the light intensity of 14.2 mW/cm^2. The weaker photocurrent is attributed to the absorption of ZnS within UV region and the energy offset at the interface between PVK and ZnS, which impedes the transport of charge carriers.     

Preparation and characterization of In and Cu co-doped ZnS photocatalysts for hydrogen production under visible light irradiation

In this work, a new photocatalyts In(0.1),Cu(x)-Zn S(x = 0.01, 0.03, 0.05) is successfully synthesized using simple hydrothermal method. The physical and chemical properties of the In and Cu co-doped Zn S photocatalyst were characterized by X-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), diffuse reflectance UV-visible spectroscopy(DR UV-visible) and photoluminescence spectroscopy(PL). The photocatalytic activity of the as-prepared In and Cu co-doped Zn S for hydrogen production from water with Na_2SO_3 and Na_2S as sacrificial agent under visible light irradiation(λ≥ 425 nm) was investigated. The presence of co-dopants facilitated the separation of electron-hole as well as increases the visible light absorption. The absorption edge of the co-doped Zn S photocatalyst shifted to longer wavelength as the amount of Cu increases. This indicates that the absorption properties depended on the amount of Cu doped. The photocatalytic activity of single doped In(0.1)-Zn S was significantly enhanced by co-doping with Cu under visible light irradiation. The highest photocatalytic activity was observed on In(0.1),Cu(0.03)-Zn S with the hydrogen production rate of 131.32 μmol/h under visible light irradiation.This is almost 8 times higher than single doped In(0.1)-Zn S.     

High-efficiency saturated red emission from binuclear cyclo-metalated platinum complex containing 5-(4-octyloxyphenyl)-1,3,4-oxadiazole-2-thiol ancillary ligand in PLED

A novel red-emitting binuclear platinum complex (dfppy)2Pt2(C8OXT)2 was synthesized and characterized,in which dfppy represents 2-(4’,6’-difluorophenyl)pyridinato unit and C8OXT is abbreviated for 5-(4-octyloxyphenyl)-1,3,4-oxadiazole-2-thiol as a bridging ancillary ligand.Its photophysical,electrochemical and electroluminescent characteristics were primarily studied.The made single-emissive-layer (SEL) polymer light-emitting devices using (dfppy)2Pt2(C8OXT)2 as emitter exhibited a saturated red emission peaked at 620nm.The best device performances were obtained in the device at 8wt% dopant concentration,with a maximum external quantum efficiency of 8.4%,a current efficiency of 4.2cd/A and brightness of 3228cd/m2.This work provides an effective approach to obtain high-efficiency red emission through construction of new binuclear platinum complex and its doped SEL devices.     

A purely organic D-π-A-π-D emitter with thermally activated delayed fluorescence and room temperature phosphorescence for near-white OLED

A purely organic D-π-A-π-D type emitter showing thermally activated delayed fluorescence(TADF) and room temperature phosphorescence(RTP) was designed and synthesized by utilizing the benzophenone as an acceptor and the N-phenyl-2-napthylamine as a donor moiety.It exhibits considerable TADF character in doped PMMA film and room temperature phosphorescence with a long lifetime of 74 ms at466 nm in solid state.The devices with the configuration of ITO/Mo_2 O_3(4 nm)/mCP(30 nm)/mCP:x wt%NP2 BP/TmTyPB(60 nm)/LiF(1.5 nm)/AI(100 nm) were prepared by vacuum evaporation to explore their electroluminescent performance.Intere stingly,the non-doped device has obtained near-white emission with a fluorescence emission peak at 475 nm and a phosphore scence emission peak at 563 nm having the CIE coordinate of(0.23,0.32) and the maximum external quantum efficiency of 1.09%.     

一种含载流子传输基的铱配合物:合成及深黄色电致磷光器件

合成了一种含有载流子传输基新的铱配合物(BPPBI)2Ir(ECTFBD)[HBPPBI:1-苯基-2-(4-联苯基)苯并咪唑,HECTFBD:1-(9-乙基-3-咔唑基)-4,4,4-三氟-1,3-丁二酮],其结构和组成经核磁共振氢谱和元素分析所证实。研究了这种铱配合物二氯甲烷溶液的光物理和电化学性质。制作了基于这种铱配合物的电致磷光器件。器件结构是ITO/MoO3(10 nm)/NPB(80 nm)/CBP:x%(BPPBI)2Ir(ECTFBD)(20 nm)/TPBi(45 nm)/LiF/Al[x%:质量百分比为4%和7%的掺杂浓度;NPB:N4,N4′-二(1-萘基)-N4,N4′-二苯基-4,4′-联苯二胺,CBP:4,4′-二(9-咔唑基)联苯,TPBi:1,3,5-三(2-(1-苯基)苯并咪唑基)苯]。这些器件显示出深黄色的发射。对于7%掺杂浓度器件,最大的电流效率和最大发光亮度分别是5.2 cd.A-1和8 690 cd.m-2。     

带烷氧基的苯基蒎烯吡啶铱配合物在聚合物电致发光器件中的应用研究

采用旋涂法将一组带烷氧基的苯基蒎烯吡啶铱(Ⅲ)配合物(Ir(RO-pppy)₃)磷光材料掺杂到PVK中,制作出了聚合物电致发光器件:ITO/PE-DOT:PSS(40 nm)/PVK_0.7:PBD_0.3:(x%.)Ir-complex(80 nm)/CsF(1.5 nm)/Mg:Ag(200 nm).实验结果表明,带有长烷氧基链配体的铱(Ⅲ)配合物能表现出更好的器件行为,当掺杂浓度为3.2%时,器件的最高发光效率达19.9 cd/A(7.8 lm/W,9.1V),CIE为(0.20,0.56);器件最大亮度为15700 cd/m²(8.4V).通过对这组铱(Ⅲ)配合物的光物理行为及电化学性能的研究,考察了主体材料与配合物之间的能级配置以及能量转移的机理.     

Polycyclic aromatic hydrocarbon-bridged coumarin derivatives for organic light-emitting devices

Three biscoumarin dyes bridged by polycyclic aromatic bridges (anthracen, pyrene and dibenzo[g,p]chrysene) were prepared as the emissive materials for the application of organic light-emitting devices. The relationship between their structures, photophysical properties, electrochemical properties and performances of organic light-emitting devices are described. The multilayered doped devices with a configuration of ITO/NPB (20 nm)/TBADN: biscoumarin compound (x wt%, 30 nm)/TPBi (30 nm)/Liq (2 nm)/Al (100 nm) have been successfully fabricated by vacuum-deposition method. All the devices showed green emission with high electroluminescent efficiencies. Especially, the device based on the compound containing pyrene as a bridge group at 7% doping concentration showed the best performance with a maximum brightness of 10552 cd/m², maximum luminous efficiency of 5.39 cd/A and maximum external quantum efficiency (EQE) of 2.35%.     

Synthesis,structures, and electroluminescence properties of a 1D zinc(II) coordination polymer containing both dicyanamide and pyrazinamide ligands

A 1D coordination polymer, {[Zn(μ_1,5-dca)₂(PZA)₂](PZA)₂}_n (1), has been synthesized and characterized by single-crystal X-ray crystallography. The coordination modes of the dicyanamide (dca) and the pyrazinamide (PZA) were inferred by IR spectroscopy. The complex was applied to organic electroluminescent (EL) devices as the emitting materials. The electroluminescent device of ITO/NPB (40 nm)/Zn polymer: CBP (30 nm) (30 nm)/BCP (15 nm)/Alq (30 nm)/LiF (1 nm)/Al (100 nm) was fabricated. The EL device emits cyan light originating from this complex with high brightness and efficiencies. For 1, a maximum luminance of 34.9 cd/A was achieved at 9 V.     

Efficient electroluminescence from new lanthanide (Eu3+, Sm3+) complexes

The syntheses, structures, and electroluminescent properties are described for two new lanthanide complexes Ln(HFNH)3phen [HFNH = 4,4,5,5,6,6,6-heptafluoro-1-(2-naphthyl)hexane-1,3-dione; phen = 1,10-phenanthroline; Ln = Eu3+ (1), Sm3+ (2)]. Both complexes exhibit bright photoluminescence at room temperature (RT) due to the characteristic emission of Eu3+ and Sm3+ ion. Several devices using the two complexes as emitters were fabricated. The performances of these devices are among the best reported for devices using europium complex and samarium complex as emitters. The device based on 1 with the structure ITO/TPD (50 nm)/1:CBP (10%, 40 nm)/BCP (20 nm)/AlQ (30 nm)/LiF (1 nm)/Al (200 nm) exhibits the maximum brightness of 957 cd/m2, current efficiency of 4.14 cd/A, and power efficiency of 2.28 lm/W with a pure red Eu3+ ion emission. Especially, at the high brightness of 200 cd/m2, the device of 1 still has a high current efficiency of 2.15 cd/A. The device of 2 with a three-layer structure of ITO/TPD (50 nm)/2 (50 nm)/BCP (20 nm)/LiF (1 nm)/Al (200 nm) gives the maximum brightness of 42 cd/m2, current efficiency of 0.18 cd/A. By the comparison of the electroluminescent properties of devices based on Eu(TTA3phen (TTA = 2-thenoyltrifluoroacteonate) and 1, we conclude that the polyfluoration on the alkyl group of the ligand and the introduction of the long conjugate naphthyl group into the ligand improve the efficiency of 1-doped devices, especially at high current densities.     

6-N,N-diphenylaminobenzofuran-derived pyran containing fluorescent dyes: a new class of high-brightness red-light-emitting dopants for OLED

Dye-doped organic light-emitting diode of ITO/alpha-NPB (70 nm)/Bebq(2)-1 (7 nm)/BCP (5 nm)/Bebq(2) (33 nm)/LiF (1 nm)/Al (150 nm) shows red electroluminescence with the efficiency of 2.9 cd/A at 100 cd/m(2) and maximum brightness of 62000 cd/m(2). The physical organic aspects of the current-induced fluorescent quenching effect are discussed. [structure: see text]     

3-[2-(8-羟基喹啉基)-乙烯基]-N-芳基咔唑及其金属配合物的合成和光电性能研究

设计合成了3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲苯基咔唑(8)和3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲氧苯基咔唑(9)及其金属锌配合物(10和11), 用UV-Vis, FTIR, ESI-MS, FAB-MS, ¹H NMR和元素分析确认了化合物的结构. 热重分析实验结果表明, 金属锌配合物(10和11)有很好的热稳定性, 这对真空蒸镀制电致发光器件是有益的. 金属锌配合物组装成有机单层发光器件的结构为ITO/Organ layer(50 nm)/Al(100 nm), 其荧光发射峰分别位于592和583 nm, 为稳定的黄色光. 这两个发光器件的最大亮度分别为489和402 cd/m², 最大电流效率分别为0.41和1.81 cd/A. 电致发光研究表明, 通过化学修饰8-羟基喹啉的2-位取代基可以改变这两个金属锌配合物的电致发光性能.     

Electroplex emission from a blend of poly(N-vinylcarbazole) and 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline

The PL and EL spectra of poly(N-vinylcarbazole) (PVK) : 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline (BCP) (1:1 w/w) film were found completely different. The PL spectrum is a single peak at 415 nm that originates from excitons emission from PVK, and the tail of the spectrum is suggested to be excimer emission from BCP molecules. However, a new emission at 595 nm was found in the EL spectra of devices ITO/PEDOT:PSS(50 nm)/PVK:BCP(1:1)(100 nm)/Al. After aggregate, exciplex and product of electrochemical reaction were ruled out, the new emission was proposed to be electroplex emission that occurred between PVK and BCP molecules. Under high voltage, only electroplex emission can be observed in the EL spectra.     

Novel Iridium Complex with Carbazol-2-yl-β-diketone Derivative: Low-energy Excitation and Red Electrophosphorescent Devices

A novel iridium-complex, (BPPBI)₂Ir(2-TFDBC)[BPPBI=2-(biphenyl-4-yl)-1-phenyl-1H-benzo[d]imi- dazole, 2-TFDBC=1-(9-ethyl-9H-carbazol-2-yl)-4,4,4-trifluorobutane-1,3-dione], was synthesized, and its structure and component were confirmed by ¹H NMR and element analysis, respectively. UV-Vis absorption and photoluminescent(PL) spectra of (BPPBI)₂Ir(2-TFDBC) in dichloromethane were investigated. The Ir-complex exhibited a long wavelength excitation of 470 nm, i.e., low-energy excitation. So, it is a promising candidate for phosphorescent probe and PL material. (BPPBI)₂Ir(2-TFDBC)-based electroluminescent devices, ITO/MoO₃(10 nm)/NPB(80 nm)/ CBP:x(BPPBI)₂Ir(2-TFDBC)(20 nm)/TPBi(45 nm)/LiF/Al, were fabricated, where x(%) was of 4% or 8% doping concentration(mass fraction); ITO=indium tin oxides; NBP=N,N'-bis-(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)- 4,4'-diamine, CBP=4,4'-bis(N-carbazolyl)-1,1'-biphenyl, TPBi=1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene. The devices showed a red emission of 620 nm. The maximum current efficiency and brightness were 1.7 cd/A and 4063 cd/m² for a device of 8%(mass fraction) doping level, respectively. The moderate luminous efficiency was due to the inadequate energy transfer from the host material to the guest material.