Tuning the energy level and photophysical and electroluminescent properties of heavy metal complexes by controlling the ligation of the metal with the carbon of the carbazole unit

Four novel Ir-III and Pt-II complexes with cyclometalated ligands bearing a carbazole framework are prepared and characterized by elemental analysis, NMR spectroscopy, and mass spectrometry. Single-crystal X-ray diffraction studies of complexes 1, 3, and 4 reveal that the 3- or 2-position C atom of the carbazole unit coordinates to the metal center. The difference in the ligation position results in significant shifts in the emission spectra with the changes in wavelength being 84 nm for the Ir complexes and 63 nm for the Pt complexes. The electrochemical behavior and photophysical properties of the complexes are investigated, and correlate well with the results of density functional theory (DFT) calculations. Electroluminescent devices with a configuration of ITO/NPB/CBP:dopant/BCP/AlQ(3)/LiF/Al can attain very high efficiencies.

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.

Synthesis, structure and luminescence properties of zinc (II) complexes with terpyridine derivatives as ligands

Five zinc (II) complexes (1-5) with 4 '-phenyl-2,2 ':6 ',2 ''-terpyridine (ptpy) derivatives as ligands have been synthesized and fully characterized. The para-position of phenyl in ptpy is substituted by the group (R), i.e. tert-butyl (t-Bu), hexyloxy (OHex), carbazole-9-yl (Cz), naphthalen-1-yl-phenyl-amine-N-yl (NPA) and diphenyl amine-N-yl (DPA), with different electron-donating ability. With increasing donor ability of the R, the emission color of the complexes in film was modulated from violet (392 nm) to reddish orange (604 nm). The photoexcited luminescence exhibits significant solvatochromism because the emission of the complexes involves the intra-ligand charge transfer (ILCT) excited state. The electrochemical investigations show that the complexes with stronger electro-donating substituent have lower oxidation potential and then higher HOMO level. The electroluminescence (EL) properties of these zinc (II) complexes were studied with the device structure of ITO/PEDOT/Zn (II) complex: PBD:PMMA/BCP/AlQ/ LiF/Al. Complexes 3, 4 and 5 exhibit EL wavelength at 552, 600 and 609 nm with maximum current efficiency of 5.28, 2.83 and 2.00 cd/A, respectively.

Highly efficient green-emitting phosphorescent iridium dendrimers based on carbazole dendrons

Green-emitting iridium dendrimers with rigid hole-transporting carbazole dendrons are designed, synthesized, and investigated. With second-generation dendrons, the photoluminescence quantum yield of the dendrimers is up to 87% in solution and 45% in a film. High-quality films of the dendrimers are fabricated by spin-coating, producing highly efficient. non-doped electrophosphorescent organic light-ernitting diodes (OLEDs). With a device structure of indium tin oxide/poly(3,4-ethylenedioxythiopheiie):poly(styrene sulfonic acid)/neat dendrimer/1,3,5-tris(2-N-phenylbenzimidazolyl)benzene/LiF/Al, a maximum external quantum efficiency (EQE) of 10.3% and a maximum luminous efficiency of 34.7 cd A(-1) are realized. By doping the dendrimers into a carbazole-based host, the maximum EQE can be further increased to 16.6%. The integration of rigid hole-transporting dendrons and phosphorescent complexes provides a new route to design highly efficient solution-processable dendrimers for OLED applications.

Memory devices based on lanthanide (SM3+, EU3+, Gd3+) complexes

Memory effects in single-layer organic light-emitting devices based on Sm3+, Gd3+, and Eu3+ rare earth complexes were realized. The device structure was indium-tin-oxide (ITO)/3,4-poly(ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT)/Poly(N-vinyl carbazole) (PVK): rare earth complex/LiF/Ca/Ag. It was found experimentally that all the devices exhibited two distinctive bistable conductivity states in current-voltage characteristics by applying negative starting voltage, and more than 10(6) write-read-erase-reread cycles were achieved without degradation. Our results indicate that the rare earth organic complexes are promising materials for high-density, low-cost memory application besides the potential application as organic light-emitting materials in display devices.

Investigation of charge-carrier injection characteristics in NPB/Alq3 heterojunction devices

The effect of copper phthalocyanine (CuPc) and LiF interfacial layers on the charge-carrier injection in NN'-di(naphthalene-l-yl)N,N'-diphenyl-benzidine (NPB)/tris(8-hydroxyquinoline) aluminium (Alq(3)) organic heterojunction devices have been studied through the analysis of current-voltage characteristics. The investigation clearly demonstrated that the hole injection into NPB from anode is Fowler-Nordheim (FN) tunneling and the electron injection into Alq3 from cathode is Richardson-Schottky (RS) thermionic emission. The barrier heights obtained from the FN and RS models proved that the band alignments for charge-carrier injection are greatly improved by the CuPc and LiF interfacial layers, which should fully clarify the role of the interfacial layer on the improvement of device performance.

Highly efficient red electroluminescence induced by efficient electron injection and exciton confinement

HigWy efficient DCJTB-doped device was realized by enhanced electron injection and exciton confinement. A fluorine end-capped linear phenylene/oxadiazole oligomer 2,5-bis(4-fluorobiphenyl-4'-yl)-1,3,4-oxadiazole (1) and a trifluoromethyl end-capped oligomer 2,5-bis(4-trifluoromethylbiphenyl-4'-yl)-1,3,4-oxadiazole (2) were designed and incorporated as an electron transporting/hole blocking material in the device structure ITO/NPB (60 mn)/DCJTB:Alq(3) (0.5%, 10 nm)/1 or 2 (20 nm)/Alq(3) (30 mn)/LiF (1 nm)/Al (100 nm). The devices showed highly efficient red luminescence. In particular, the device based on 1 achieved pure red luminescence at 620 run originating from DCJTB, with a narrow FWHI of 65 nm, maximal brightness of 13,300 cd/m(2) at voltage of 20.8 V and current density of ca. 355 mA/cm(2). High current and power efficiencies (> 3.6 cd/A. 1.01m/W) were retained within a wide range of current densities. Our results show efficient and stable DCJTB-doped red electroluminescence could be anticipated for practical applications by taking advantage of the present approaches. The control experiments using BCP were also studied.

High efficiency red organic light-emitting diodes based on microcavity structure

We demonstrate high efficiency red organic light-emitting diodes (OLEDs) based on a planar microcavity comprised of a dielectric mirror and a metal Mirror. The microcavity devices emitted red light at a peak wavelength of 610 nm with a full width at half maximum (FWHM) of 25 nm in the forward direction, and an enhancement of about 1.3 factor in electroluminescent (EL) efficiency has been experimentally achieved with respect to the conventional noncavity devices. For microcavity devices with the structure of distributed Bragg reflectors (DBR)/indium-tin-oxide(ITO)/V2O5/N,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine(NPB)/4-(dicy-anome-thylene)-2-t-butyl-6(1,1,7,7-tetrame-thyljulolidyl-9-enyl)-4H-pyran(DCJTB):tris(8-hydroxyquinoline) aluminium (Alq(3))/Alq(3)/LiF/Al, the maximum brightness arrived at 37000 cd/m(2) at a current density of 460.0 mA/cm(2), and the current efficiency and power efficiency reach 13.7 cd/A at a current density of 0.23 mA/cm(2) and 13.3 lm/W respectively.

Improved performance and stability by an Al/Ni bilayer cathode in organic light-emitting diodes

Al/Ni bilayer cathode was used to improve the electroluminescent (EL) efficiency and stability in N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1' biphenyl 4,4'-dimaine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq(3))-based organic light-emitting diodes. The device with LiF/Al/Ni cathode achieved a maximum power efficiency of 2.8 lm/W at current density of 1.2 mA/cm(2), which is 1.4 times the efficiency of device with the state-of-the-art LiF/Al cathode. Importantly, the device stability was significantly enhanced due to the utilization of LiF/Al/Ni cathode. The lifetime at 30% decay in luminance for LiF/Al/Ni cathode was extrapolated to 400 It at an initial luminance of 100 cd/m(2), which is 10 times better than the LiF/Al cathode.

NaCl/Ca/Al as an efficient cathode in organic light-emitting devices

An efficient cathode NaCl/Ca/Al used to improve the performance of organic light-emitting devices (OLEDs) was reported. Standard NM-bis(1-naphthyl)-NAP-diphenyl-1,1' biphenyl 4,4'-dimaine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq(3)) devices with NaCl/Ca/Al cathode showed dramatically enhanced electroluminescent (EL) efficiency. A power efficiency of 4.6 lm/W was obtained for OLEDs with 2 nm of NaCl and 10 nm of Ca, which is much higher than 2.0 lm/W, 3.1 lm/W, 2.1 lm/ W and 3.6 lm/W in devices using, respectively, the LiF (1 nm)/Al, LiF (1 nm)/Ca (10 nm)/Al, Ca (10 nm)/Al and NaCl (2 nm)/ Al cathodes. The investigation of the electron injection in electron-only devices indicates that the utilization of the NaCl/Ca/Al cathode substantially enhances the electron injection current, which in case of OLEDs leads to the improvement of the brightness and efficiency.

Reduced ambient reflection of organic light-emitting diodes by utilizing multilayer low-reflection cathodes

Ambient reflection of organic light-emitting diodes (OLEDs) is reduced by utilizing a multilayer low-reflection cathode. The low-reflection cathode structure consists of a semitransparent cathode layer, a transparent spacing layer and a high reflective layer. Metals with different optical properties, including silver (Ag) and samarium (Sm), are used as the semitransparent cathode layer, tris(8-quinolinolato) aluminium (Alq(3)) and aluminium (Al) are used as the spacing layer and high reflective layer, respectively. The incident ambient light could be reduced by the cathode structure via destructive optical interference. It is found that the Ag/Alq(3)/Al cathode shows a strong wavelength-dependent reflection. However, the Sm/Alq(3)/Al cathode demonstrates a low reflection in the whole visible range, and the resulting OLED shows a reduced luminous reflectance of 2.7% as compared to 81% for a control device with LiF/Al cathode. A further reduction to 0.9% is realized by replacing a multilayer of Alq(3)/Sm/Alq(3) for the single layer of Alq(3).

White organic electroluminescence based on a new boron complex

A bright blue boron complex BPh2(pybm) containing 2-(2-pyridyl)benzimidazole ligand was designed and synthesized by using N, N-bidentate ligand instead of N, O-bidentate one such as 8-quinolinol. For three-layer LED devices with the configuration of ITO/NPB/BPh2(pybm)/Alq(3)/LiF/Al, the white light emission covering the whole visible region from 400 to 750 nm with the maximum brightness of 110 cd/m(2) and the luminous efficiency of 0.8 cd/A was observed.

Synthesis, characterization, photoluminescent and electroluminescent properties of new conjugated 2,2 '-(arylenedivinylene)bis-8-substituted quinolines

A series of new PPV oligomers containing 8-substituted quinoline, 2,2'-(arylenedivinylene) bis-8-quinoline derivatives, were designed and synthesized via a Knoevenagel condensation reaction of quinaldine, 8-hydroxy-or 8-methoxy-quinaldine with aromatic dialdehydes. These PPV oligomers were characterized by H-1 and C-13-NMR, X-ray diffraction, elemental analysis, UV-visible and fluorescence spectroscopies. The X-ray diffraction investigation showed that there are intermolecular pi...pi interactions in the solid state in 1 and 3. The optical and photoluminescent properties study demonstrated that the emission color of the resulting materials varies from blue to yellow and is dependent on the substituents (pi-donor and pi-acceptor groups) on both sides of the conjugated molecules and the aromatic core in the middle of the conjugated backbones. The electroluminescent devices using compounds 1-4 as the emitters and electron-transporting layers were fabricated with the structure ITO/NPB/emitter/LiF/Al. The best device performance with the maximum brightness of 5530 cd m(-2) and the luminous efficiency of 2.4 cd A(-1) is achieved by using compound 4, with intramolecular charge transfer character, as the emitter; these values represent a more than 5-fold improvement in brightness and efficiency compared to compound 3 without methoxy groups on the phenyl rings.

Efficient red organic light-emitting devices based on a europium complex

An efficient organic light-emitting device using a trivalent europium (Eu) complex Eu(Tmphen)(TTA)(3) (TTA=thenoyltrifluoroacetone, Tmphen=3,4,7,8-tetramethyl-1,10-phenanthroline) as the dopant emitter was fabricated. The devices were a multilayer structure of indium tin oxide/N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl-4,4-diamine (40 nm)/ Eu complex:4,4-N,N-dicarbazole-biphenyl (1%, 30 nm)/2,9-dimethyl,4,7-diphenyl-1,10phenanthroline (20 nm)/AlQ (30 nm)/LiF (1 nm)/Al (100 nm). A pure red light with a peak of 612 nm and a half bandwidth of 3 nm, which is the characteristic emission of trivalent europium ion, was observed. The devices show the maximum luminance up to 800 cd/m(2), an external quantum efficiency of 4.3%, current efficiency of 4.7 cd/A, and power efficiency of 1.6 lm/W. At the brightness of 100 cd/m(2), the quantum efficiency reaches 2.2% (2.3 cd/A).

A hydroxyphenyloxadiazole lithium complex as a highly efficient blue emitter and interface material in organic light-emitting diodes

We synthesized a hydroxyphenyloxadiazole lithium complex (LiOXD) as a blue light-emitting and electron injection/transport material to be used in double-layer organic electroluminescent devices. Devices with the concise configuration of ITO/TPD/LiOXD/Al showed bright blue EL emission centered at 468 nm with a maximum luminance of 2900 cd m(-2). A current efficiency of 3.9 cd A(-1) and power efficiency of 1.1 lm W-1 were obtained. LiOXD was also examined as an interface material. The efficiency of an ITO/NPB/Alq(3)/Al device increased considerably when LiOXD was inserted between Alq(3) and aluminium. The improvement of the device characteristics with LiOXD approached that observed with the dielectric LiF salt.