New carbazole-based copolymers as amorphous hole-transporting materials for multilayer light-emitting diodes

New carbazole-based copolymers, which contain various concentrations of 9-alkyl-3, 6-carbazole fragments in the main chain connected via alkylene spacers, have been synthesized by Ni(0)-catalyzed Yamamoto-type aryl-aryl coupling reactions. Full characterization of the copolymer structure by NMR spectroscopy and elemental analysis is presented. These compounds represent amorphous materials of high thermal stability with glass transition temperatures of 151-162 degrees C and thermal decomposition starting at temperatures > 390 degrees C. UV-Vis absorption and photoluminescence emission of the copolymers confirmed that the effectively conjugated segment in the 3,6-linked carbazole-type copolymers is limited to dyads (dimeric units). However, copolymers with varying concentrations of the oligocarbazole chromophores demonstrate different charge injection and transport properties in multilayer light-emitting diodes with the copolymers as the hole transport and Alq(3) as the electroluminescent/electron transport layer. The device based on a copolymer composed of oligocarbazole blocks with an average length of around four carbazoles exhibited the best overall performance with a turn-on voltage of 3.5 V, a maximal photometric efficiency of 4.1 cd center dot A(-1) and maximum brightness of about 4 200 cd center dot m(-2).

Improved performances of organic light-emitting diodes with metal oxide as anode buffer

We demonstrate extremely stable and highly efficient organic light-emitting diodes (OLEDs) based on molybdenum oxide (MoO3) as a buffer layer on indium tin oxide (ITO). The significant features of MoO3 as a buffer layer are that the OLEDs show low operational voltage, high electroluminescence (EL) efficiency and good stability in a wide range of MoO3 thickness. A green OLED with structure of ITO/MoO3/N,N-'-di(naphthalene-1-yl)-N,N-'-diphenyl-benzidene (NPB)/NPB: tris(8-hydroxyquinoline) aluminum (Alq(3)):10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzopyropyrano(6,7-8-i,j)quinolizin-11-one (C545T)/Alq(3)/LiF/Al shows a long lifetime of over 50 000 h at 100 cd/m(2) initial luminance, and the power efficiency reaches 15 lm/W. The turn-on voltage is 2.4 V, and the operational voltage at 1000 cd/m(2) luminance is only 6.9 V. The significant enhancement of the EL performance is attributed to the improvement of hole injection and interface stability at anode.

Improved efficiency by doping blue iridium (III) complex in europium complex-based light-emitting diodes

We demonstrated high-efficiency red organic light-emitting diodes (OLEDs) employing a europium complex, Eu (III) tris( thenoyltrifluoroacetone) 3,4,7,8-tetramethyl-1,10-phenanthroline (Eu(TTA)(3)(Tmphen)), as an emitter and a blue electrophosphorescent complex, Iridium ( III) bis[4,6-di-fluorophenyl-pyridinato-N,C-2] picolinate (FIrpic), as an assistant dopant codoped into 4,4-N, N-dicarbazole-biphenyl (CBP) host as an emissive layer. A pure red electroluminescence (EL) only from Eu3+ ions at 612 nm with a full width at half maximum of 3 nm was observed and the EL efficiency was significantly enhanced. The maximum EL efficiency reached 7.9 cd A(-1) at 0.01 mA cm(-2) current density, which is enhanced by 2.8 times compared with electrophosphorescence-undoped devices. The large improvements are attributed to energy transfer assistance effects of FIrpic, indicating a promising method for obtaining efficient red OLEDs based on rare-earth complexes.

Ligand effect on the performance of organic light-emitting diodes based on europium complexes

A series of europium complexes were synthesized and their electroluminescent (EL) characteristics were studied. It was found by comparison that the different substituted groups, such as methyl, chlorine, and nitryl, on ligand 1,10-phenanthroline affect significantly the EL performance of devices based on these complexes. The more methyl-substituted groups on ligand 1,10-phenanthroline led to higher device efficiency. A chlorine-substituted group showed the approximate EL performance as two methyl-substituted groups, whereas a nitryl substituent reduced significantly the EL luminous efficiency. However, beta-diketonate ligand TTA and DBM exhibited similar EL performance. The improved EL luminous efficiency by proper substituted groups on the 1, 10-phenanthroline was attributed to the reduction of the energy loss caused by light hydrogen atom vibration, as well as concentration quenching caused by intermolecular interaction, and the match of energy level between the ligand and Eu3+.

Improved efficiency of organic light-emitting diodes based on a europium complex by fluorescent dye

Improved efficiency of organic light-emitting diodes (OLEDs) based on europium complexes have been realized by using a fluorescent dye 4-(dicyanomethylene)-2-t-butyl-6 (1,1,7,7-tetramethyljulolidyl-9-enyl))-4H-pyran (DCJTB) doping. The luminous efficiency of the devices with a fluorescent dye in the emissive layer was found to improve two times of that in devices without fluorescent dye. The devices showed pure red light, which is the characteristic emission of trivalent europium ion with a full-width at half-maximum of 3 nm. The maximum brightness and luminous efficiency reached 1200 cd/m(2) at 23 V and 7.3 cd/A (2.0 Im/w), respectively, at a current density of 0.35 mA/cm(2).

Effect of doped dye on the charge-carrier transport and electroluminescent performance in molecularly doped polymer light-emitting diodes

The effects of the concentration of 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzopyropyrano(6, 78-i,j)quinolizin-11-one (C545T) as dopant in polyfluorene (PFO) on the charge-carrier transport and electroluminescence (EL) performance were investigated by steady-state and transient EL measurements. A fully green emission from C545T was observed and the EL performance depends strongly on the C545T concentration. The mobility in the C545T-doped PFO film was determined by transient EL. The dopant concentration dependence of the current-voltage relationship indicated clearly the carrier trapping by the C545T molecules. The mobility in C545T:PFO changed significantly with the C545T concentration, and showed a nontrivial dependence on the doping level. The behavior may be understood in terms of the formation of an additional energy disorder due to potential fluctuation caused by the Coulomb interaction of the randomly distributed doping molecules.

Improved color purity and efficiency in polyfluorene-based light-emitting diodes

Polyfluorene (PF) is a class of typical blue electroluminescent (EL) material, but it exhibits undesired feature in the green spectral region under operation condition. We investigated the spectral properties of different device structures of poly(9,9-dioctylfluorene) (PFO)-based light-emitting diodes, and found that the interaction between cathode and PFO is the main origination of green emission in EL devices. The general method of inserting a buffer layer between the PFO and cathode can decrease the low energy band emission to purify the color and improve the EL performance of devices.

Near infrared light-emitting diodes based on composites of near infrared dye, CdSe/CdS quantum dots and polymer

Near infrared (NIR) light emitting diodes employing composites of an IR fluorescent dye, CdSe/CdScore/shell semiconductor quantum dots and poly( N-vinylcarbazole) (PVK) have been demonstrated. The device, with a configuration of indium-tin-oxide (ITO)//PEDOT:PSS//PVK:NIR Dye:CdSe/CdS//Al, had a turn-on voltage of 7 V, emitted the NIR light with a maximum at 890 nm and the irradiance intensity of 96 mu W. The electroluminescence efficiency of 0.02% was achieved at a current density of 13 mA cm(-2).

Effects of doped dye on the charge carrier injection, transport, and electroluminescent performance in polymeric light-emitting diodes

The effects of doped fluorescent dye 4-(dicyanomethylene)-2-i-propyl-6-(1, 1, 7, 7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTI) on the charge carrier injection, transport and electroluminescence (EL) performance in polyfluorene (PFO)-based polymer light-emitting diodes (PLEDs) were investigated by steady-state current-voltage (I-V) characteristics and transient EL measurements. A red EL from DCJTI was observed and the EL performance depended strongly on the DCJTI concentration. The analysis of the steady-state I-V characteristics at different DCJTI concentrations found that three regions was shown in the I-V characteristics, and each region was controlled by different processes depending on the applied electric field. The effect of the dopant concentration on the potential-barrier height of the interface is estimated using the Fowler-Nordheim model. The dopant concentration dependence of the current-voltage relationship indicated clearly the carrier trapping by the DCJTI molecules. The mobility in DCJTI: PFO changed significantly with the DCJTI concentration, and showed a nontrivial dependence on the doping level. The behavior may be understood in terms of the formation of an additional energy disorder due to potential fluctuation caused by the Coulomb interaction of the randomly distributed doping molecules.

Efficient red organic light-emitting diodes based on a dinuclear europium complex

Pure red organic light-emitting diodes based on a dinuclear europium complex with a structure of (TTA)(3)Eu(PYO)(2)Eu(TTA)3 (TTA = thenoyltrifluoroacetonate, PYO = pyridine N-oxide) were presented. The devices showed pure red emission at a peak wavelength of 612 nm with a full width at half maximum of 3 nm, which is a characteristic emission from Eu3+ ion based on D-5(0) -> F-7(2) transition. The maximum brightness and electroluminescent (EL) efficiency reached 340 cd/m(2) at a driving voltage of 19 V and 2.4 cd/A (0.78 lm/W) at a current density of 0.14 mA/cm(2), respectively.

Tunability of resonant wavelength by Fabry-Perot microcavity in organic light-emitting diodes

Distributed Bragg reflectors (DBR) with different reflection wavelengths were designed, and were used to fabricate microcavity organic light-emitting diodes (OLEDs) based on tris(8-hydroxyquinoline)-aluminum (Alq(3)) as the emitter and N, N'-di(naphthalene-1-yl)-N, N'-diphenyl-benzidine (NPB) as the hole-transporting layer. The microcavity was composed of DBR dielectric mirror and metal electrode aluminum (Al) mirror. Some effects of vertical optical Fabry-Perot microcavity on spontaneous emission in OLEDs were investigated. Spectral narrowing, enhancement of emitting intensity and anglular dependence of emission were observed due to the microcavity effect. It was found experimentally that the utilization of DBR is a better method to adjust the emissive mode in the resonant cavity in OLEDs well. Thus the realization of different color light emission becomes possible by the combination of carefully designed microcavity and electroluminescent organic semiconductors in a single LED.

High-efficiency blue light-emitting diodes based on a polyphenylphenyl compound with strong electron-accepting groups

The synthesis and characterization of two new polyphenylphenyl compounds is reported. One compound (CPP) acts as a blue light-emitting material, but contains strong electron-accepting groups that form exciplexes with electron-donating arylamines that are widely used as hole-transporting materials. Inserting a layer of the other compound into the organic light-emitting diodes (see figure) suppresses the formation of exciplexes, and gives high-efficiency blue-light emission from the CPP layer.

Novel heteroleptic Cu-I complexes with tunable emission color for efficient phosphorescent light-emitting diodes

A series of orange-red to red phosphorescent heteroleptic Cu-I complexes (the first ligand: 2,2 '-biquinoline (bq), 4,4 '-diphenyl2,2 '-biquinoline (dpbq) or 3,3 '-methylen-4,4 '-diphenyl-2,2 '-biquinoline (mdpbq); the second ligand: triphenylphosphine or bis[2-(diphenylphosphino)phenyl]ether (DPEphos)) have been synthesized and fully characterized. With highly rigid bulky biquinoline-type ligands, complexes [Cu(mdpbq)(PPh3)(2)](BF4) and [Cu(mdpbq)(DPEphos)](BF4) emit efficiently in 20 wt % PMMA films with photoluminescence quantum yield of 0.56 and 0.43 and emission maximum of 606 nm and 617 nm, respectively. By doping these complexes in poly(vinyl carbazole) (PVK) or N-(4-(carbazol-9-yl)phenyl)-3,6-bis(carbazol-9-yl) carbazole (TCCz), phosphorescent organic light-emitting diodes (OLEDs) were fabricated with various device structures. The complex [Cu(mdpbq)(DPEphos)](BF4) exhibits the best device performance. With the device structure of ITO/PEDOT/ TCCz:[Cu(mdpbq)(DPEphos)](BF4) (15 wt %)/TPBI/LiF/Al (III), a current efficiency up to 6.4 cd A(-1) with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.61, 0.39) has been realized. To our best knowledge, this is the first report of efficient mononuclear Cu complexes with red emission.

Negative differential resistance and memory effect in diodes based on 1,4-dibenzyl C60 and zinc phthalocyanine doped polystyrene hybrid material

Negative differential resistance (NDR) and memory effect were observed in diodes based on 1,4-dibenzyl C60 (DBC) and zinc phthalocyanine doped polystyrene hybrid material. Certain negative starting sweeping voltages led to a reproducible NDR, making the hybrid material a promising candidate in memory devices. It was found that the introduction of DBC enhanced the ON/OFF current ratio and significantly improved the memory stability. The ON/OFF current ratio was up to 2 orders of magnitude. The write-read-erase-reread cycles were more than 10(6), and the retention time reached 10 000 s without current degradation.

Effect of dye concentration on the charge carrier transport in molecularly doped organic light-emitting diodes

The effect of the concentration of 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7, 7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as dopant in tris(8-quinolinolato) aluminum (Alq(3)) on the charge carrier transport in Alq(3):DCJTB was investigated by measuring the steady current-voltage characteristics and the transient electroluminescence. The dopant concentration dependence of the current-voltage relationship clearly indicates the carrier trapping by the DCJTB molecule. The DCJTB concentration significantly affects the electron mobility in Alq(3):DCJTB. The mobility has a nontrivial dependence on the doping level. For relatively low doping levels, less than 1%, the electron mobility of Alq(3):DCJTB decreases with the doping level. An increasing mobility is then observed if the dopant concentration is further increased, followed by a decrease for doping levels larger than similar to2%. The change of the electron mobility with the DCJTB concentration in Alq(3) is attributed to the additional energetic disorder due to potential fluctuations caused by the dipole-dipole interaction of random distribution dopant at the relatively low doping concentration, and to the phase separation at the high doping concentration.