Synthesis,Crystal Structures and Photo- and Electro-Luminescence of Copper(I) Complexes Containing Electron-Transporting Diaryl-1,3,4-Oxadiazole

Two mononuclear Cu(I) complexes based on 2-(2-pyridyl)benzimidazolyl derivative ligand containing electron-transporting 1,3,4-oxadiazole group (L), [Cu(L)(PPh₃)₂](BF₄) and [Cu(L)(DPEphos)](BF₄), where L?=?1-(4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)benzyl)-2-(pyridin-2-yl)benzimidazole and DPEphos?=?bis[2-(diphenylphosphino)phenyl]ether, have been successfully synthesized and characterized. The X-ray crystal structure analyses of the ligand L and the complex [Cu(L)(PPh₃)₂](BF₄) were described. The photophysical properties of the complexes were examined by using UV–vis, photoluminescence spectroscopic analysis. The doped light-emitting devices using the Cu(I) complexes as dopants were fabricated. With no electron transporting layers employed in the devices, yellow electroluminescence from Cu(I) complexes were observed. The devices based on the complex [Cu(L)(DPEphos)](BF₄) possess better performance as compared with the devices fabricated by the complex [Cu(L)(PPh₃)₂](BF₄). The devices with the structure of ITO/MoO₃ (2 nm)/NPB (40 nm)/CBP:[Cu(L)(DPEphos)](BF₄) (8 wt%, 30 nm)/BCP (30 nm)/LiF (1 nm)/Al (150 nm) exhibit a maximum efficiency of 3.04 cd/A and a maximum brightness of 4,758 cd/m².     

Photoluminescence and electroluminescence of a novel green-yellow emitting material-5,6-Bis-[4-(naphthalene-1-yl-phenyl-amino)-phenyl]-pyrazine-2,3-dicarbonitrile

A new compound with intramolecular charge transfer (ICT) property—5,6-Bis-[4-(naphthalene-1-yl-phenyl-amino)-phenyl]-pyrazine-2,3-dicarbonitrile(BNPPDC) was synthesized. The new compound was strongly fluorescent in non-polar and moderately polar solvents, as well as in thin solid film. The absorption and emission maxima shifted to longer wavelength with increasing solvent polarity. The fluorescence quantum yield also increased with increasing solvent polarity from non-polar to moderately polar solvents, then decreased with further increase of solvent polarity. This indicates both “positive” and “negative” solvatokinetic effects co-existed. Using this material as hole-transporting emitter and host emitter, we fabricated two electroluminescent (EL) devices with structures of A (ITO/BNPPDC (45 nm)/1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) (45 nm)/Mg:Ag (200 nm) and B (ITO/N,N′-diphenyl-N,N′-bis-(3-methylphenyl) (1,1′-diphenyl)4,4′-diamine (TPD) (50 nm)/BNPPDC (20 nm)/1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) (45 nm)/Mg:Ag (200 nm). The devices showed green-yellow EL emission with good efficiency and high brightness. For example, the device A exhibited a high brightness of 17400 cd/m² at a driving voltage of 11 V and a very low turn-on voltage (2.9 V), as well as a maximum luminous efficiency 3.61 cd/A. The device B showed a similar performance with a high brightness of 12650 cd/m² at a driving voltage of 13 V and a maximum luminous efficiency 3.62 cd/A. In addition, the EL devices using BNPPDC as a host and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as a dopant (configuration: ITO/TPD (60 nm)/BNPPDC:DCJTB (2%) (30 nm)/TPBI (35 nm)/Mg:Ag (200 nm)) showed a good performance with a brightness of 150 cd/m² at 4.5 V, a maximum brightness of 12600 cd/m² at 11.5 V, and a maximum luminous efficiency of 3.30 cd/A.     

Highly efficient organic ultraviolet photodetectors based on excellent Cu (I) complexes

We demonstrate high response organic ultraviolet photodetectors using 4,4′,4″-tris[3-methyl-pheny(phenyl)amino]tri-phenylamine (m-MTDATA) and two novel Cu(I) complexes, [Cu(DPEphos)(PyPhen)]BF4 (CuDP)(DPEphos = Bis [2-(diphenylphosphino)phenyl]ether, PyPhen = pyrazino[2,3-f][1,10]phenanthroline) and [Cu(DPEbenz)(PyPhen)]BF₄ (CuBP) (DPEbenz = 1,2-bis(diphenylphosphino)benzene) to act as the electron donor and acceptor, respectively. Strong photoluminescence quenching of m-MTDATA by Cu(I) complexes is observed manifesting the efficient photoinduced charge transfer that occurs between m-MTDATA and Cu(I) complexes. The optimized photodetector based on CuBP exhibits a maximum response of 276 mA/W at ?12 V under an illumination of 365 nm UV light irradiation with an intensity of 1.75 mW/cm². The high response is attributed to feasible energy level match, efficient electron transfer from m-MTDATA to CuBP and skillful device design. More detailed working mechanism of harvesting high performance is also discussed.     

Efficient white organic light-emitting devices using 4,7-diphenyl-1,10-phenanthroline as block layer

A white light-emitting device has been fabricated with a structure of ITO/m-MTDATA (45 nm)/NPB (10 nm)/DPVBi (8 nm)/DPVBi:DCJTB 0.5% (15 nm)/BPhen (x nm)/Alq₃ [(55−x) nm]/LiF (1 nm)/Al, with x=0, 4, and 7. BPhen was used as the hole-blocking layer. This results in a mixture of lights from DPVBi molecules (blue-light) and DCJTB (yellow-light) molecules, producing white light emission. The chromaticity can be readily adjusted by only varying the thickness of the BPhen layer. The CIE coordinates of the device are largely insensitive to the driving voltages. When the thickness of BPhen is 7 nm, the device exhibits peak efficiency of 6.87 cd/A (3.59 lm/W) at the applied voltage of 6 V, the maximum external quantum efficiency η_ext=2.07% corresponding to 6.18 cd/A, and the maximum brightness is 18494 cd/m² at 15 V.     

Synthesis and electroluminescent properties of a carbozole-functionalized europium(III) complex

A novel europium(III) complex, tris(dibenzoylmethanate){1-[9-hexyl-9H-carbazole]-2-(2-pyridyl)-benzimidazole}europium(III) [Eu(DBM)₃(CAR-PyBM)] functionalized by a carbozole fragment, was synthesized and used as emitting material in organic electroluminescent (EL) devices. Compared with the device based on an unfunctional Eu(III) complex, [Eu(DBM)₃HPyBM] (HPyBM=2-(2-pyridyl)benzimidazole), the EL performances of the device using [Eu(DBM)₃(CAR-PyBM)] as an emitter was significantly enhanced due to the improvement of hole-transporting ability. The maximum efficiency and luminance of red emission achieved from the device with the configuration of ITO/N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′diamine (TPD, 50 nm)/ [Eu(DBM)₃(CAR-PyBM)] (30 nm)/1,3,5-tirs-(N-phenylbenzimidazol-2-yl)benzene (TPBI, 20 nm)/LiF (1.5 nm)/Al were 4.2 cd/A and 200 cd/m², respectively.     

Highly efficient greenish blue-emitting organic diodes based on pyrene derivatives

We report the synthesis of pyrene derivatives as the light emissive layer for highly efficient organic electroluminescence (EL) diodes. Multilayer devices were fabricated with pyrene derivatives (ITO/NPB (50 nm)/blue material (30 nm)/BCP (10 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al). By using 1,1′-dipyrene (DP) and 1,4-dipyrenyl benzene (DPB), the devices produced the blue EL emissions with 1931 Commission International de L’Eclairage coordinates of (x=0.21, y=0.35) and (x=0.19, y=0.25), respectively. The device with DPB shows a maximum brightness of 42,445 cd/m² at 400 mA/cm² and the luminance efficiency of 8.57 cd/A and 5.18 lm/W at 20 mA/cm².     

Synthesis and luminescent properties of two Schiff-base boron complexes

Schiff bases N,N′-o-phenylenebis (salicylideneimine) (H₂L¹), N,N′-p-phenylenebis (salicylideneimine) (H₂L²) and their corresponding boron complexes (BF₂)₂L¹, (BF₂)₂L² were synthesized, respectively. The two boron complexes have been characterized by ¹H NMR, mass spectrometry and elemental analysis, while the luminescent properties of them were investigated with UV-VIS spectroscopy and photoluminescence spectroscopy. Then the three-layer devices [ITO/NPB (60 nm)/(BF₂)₂L¹ (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device I) and [ITO/NPB (60 nm)/(BF₂)₂L² (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device II) were fabricated by vacuum deposition. These two devices both exhibited blue green emission at 500 nm, but showed different luminances and efficiencies.     

High light electroluminescence of novel Cu(I) complexes

Three novel Cu(I) complexes, [CuDPEphos(NN)]BF₄, where NN=1-(4-5′-phenyl-1,3,4-oxadiazolylbenzyl)-2-pyridinylbenzoimidazole (OXD-Pybm; L1) (1), 1-(4-carbazolylbutyl)-2-pyridinylbenzimidazole (Carl-Pybm; L2) (2), and 1-H-2-pyridinylbenzimidazole (HPybm; L3) (3), were synthesized. The photoluminescent (PL) properties of 1-3 and the electroluminescent (EL) properties of complexes 1 and 2 were systematically studied. The maximum brightness of 2-based devices was 8669 cd/m², which should be the best among the reported Cu(I) complexes-based devices.     

Exchange bias and negative magnetoresistance in [Co/Bi/Co]/IrMn thin films]

The artificial control of grain-boundary resistance and its contribution to magnetic and magneto-transport properties in [Co(3 nm)/Bi(2.5 nm)/Co(3 nm)]Ir₂₀Mn₈₀(12 nm) thin films that exhibit exchange bias is studied. Transverse magnetoresistance (MR) loops exhibit a negative MR in thin films grown by magnetron sputtering on Si/SiN_x(100 nm) substrates. This negative MR effect is of the giant-MR (GMR) type, although its magnitude is less than 1%. A considerable exchange bias (EB) effect is observed only at lower temperatures, where both, GMR and isothermal magnetization loops exhibit a shift of −600 Oe at 5 K.     

Improved O2 sensing performance by modifying P–P ligand in [Cu(N–N)(P–P)] complex

In this paper, a diamine ligand of 2-(5-phenyl-[1,3,4]oxadiazol-2-yl)-pyridine (OP) and its corresponding Cu(I) complex of [Cu(OP)(POP)]BF₄ with bis(2-(diphenylphosphanyl)phenyl) ether (POP) as the phosphorous ligand are synthesized. Full characterization on [Cu(OP)(POP)]BF₄, including NMR, elemental analysis and single crystal analysis, confirms its molecular identity. Upon photon excitation, the emission of [Cu(OP)(POP)]BF₄ owns a long excited state lifetime of 42.92 μs and shows a maximum at 570 nm, under pure N₂ atmosphere. Theoretical calculation on [Cu(OP)(POP)]BF₄ single crystal suggests that the excited state has a triplet metal-to-ligand-charge-transfer character. By embedding [Cu(OP)(POP)]BF₄ into a optical silica supporting matrix of MCM-41, the emission signal is found to be sensitive towards various oxygen concentrations, with a maximum sensitivity of 7.31 (sensitivity=luminescence intensity in O₂ medium/luminescence intensity in N₂ medium). This improved sensitivity value compared with literature values is attributed to the introduction of POP ligand, which can suppress the intermolecular aggravation between [Cu(OP)(POP)]BF₄ molecules and favor the oxygen attack on [Cu(OP)(POP)]BF₄ excited state. Due to the same reason, a short response time is also observed with stable quenching signal.     

Synthesis and electroluminescence properties of benzothiazole derivatives

Benzothiazole-based blue fluorescent materials N-(4-(benzo[d]thiazol-2-yl)phenyl)-N-phenylbenzenamine (BPPA) and N-(4-(benzo[d]thiazol-2-yl)phenyl)-N-phenylnaphthalen-1-amine (BPNA) were synthesized for use in organic light-emitting diodes (OLEDs). Electroluminescent device with a configuration of ITO/NPB/BPPA/BCP/Alq₃/LiF/Al showed a maximum brightness of 3760 cd/m² at 14.4 V with the CIE coordinates of (0.16, 0.16). A current efficiency of 3.01 cd/A and an external quantum efficiency of 2.37% at 20 mA/cm² were obtained from this device. Molecules derived from BPPA and BPNA with incorporated dicyanomethylidene, which is a functional group for most red fluorescent molecules, were designed, synthesized and characterized to study the red fluorescence properties of the benzothiazole derivatives.     

Effect of interfacial diffusion on microstructure and properties of FePt/B4C multifunctional multilayer composite films

FePt/B₄C multilayer composite films were prepared by magnetron sputtering and subsequent annealing in vacuum. By changing Fe layer thickness of [Fe/Pt]₆/B₄C films, optimal magnetic property (8.8 kOe and remanence squareness is about 1.0) is got in [Fe(5.25 nm)/Pt(3.75 nm)]₆/B₄C sample whose composition is Fe rich and near stoichiometric ratio. The characterizations of microstructure demonstrate that the diffusion of B and C atoms into FePt layer depends strongly on B₄C interlayer thickness. When B₄C interlayer thickness of [Fe(2.625 nm)/Pt(3.75 nm)/Fe(2.625 nm)/B₄C]₆ films is bigger than 3 nm, stable value of grain size (6-6.5 nm), coercivity (6-7 kOe) and hardness (16-20 GPa) is observed. Finally, the multifunctional single FePt/B₄C composite film may find its way to substitute traditional three-layer structure commonly used in present data storage technology.     

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 N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′ biphenyl 4,4′-dimaine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq₃) 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.     

Magneto-transport properties of [Co/Bi]n wire structures

The present study examines the artificial control of grain-boundary resistance and its contribution to the magneto-transport properties of [Co(1 nm)/Bi(2.5 nm)]_n (n=10 or 20) line structures on the Si(0 0 1)/SiN_x substrate. Conventional patterning and deposition processes are applied for the fabrication of a device that consists of five-line structures with a line width of 2 μm. A ΔR/R=80% ratio was observed in the five-line structure of [Co(1 nm)/Bi(2.5 nm)]₁₀ multilayers at 10 K. Our measurements indicate that grain-boundary effects can be associated with the large ΔR/R ratio of transverse magnetoresistance.     

High thermal stability and low thermal conductivity in Ga30Sb70/Sb80Te20 nanocomposite multilayer films

The reliability characteristics and thermal conductivity of Ga₃₀Sb₇₀/Sb₈₀Te₂₀ nanocomposite multilayer films were investigated by isothermal resistance and transient thermoreflectance (TTR) measurements, respectively. The crystallization temperature and activation energy for the crystallization can be modulated by varying the layer thickness of Ga₃₀Sb₇₀. A data retention time of ten years of the amorphous state [Ga₃₀Sb₇₀ (3 nm)/Sb₈₀Te₂₀ (5 nm)]₁₃, [Ga₃₀Sb₇₀ (5 nm)/Sb₈₀Te₂₀ (5 nm)]₁₀, and [Ga₃₀Sb₇₀ (10 nm)/Sb₈₀Te₂₀ (5 nm)]₇ was estimated when ambient temperature is 137, 163, and 178 °C, respectively. Ga₃₀Sb₇₀/Sb₈₀Te₂₀ nanocomposite multilayer films were found to have lower thermal conductivity in both the amorphous and crystalline state compared to Ge₂Sb₂Te₅ film, which will promise lower programming power in the phase-change random access memory.     

White organic light-emitting diodes based on benzothiazole derivative

This paper describes the white organic light-emitting diodes (WOLEDs) made from a benzothiazole derivative, N-(4-(benzo[d]thiazol-2-yl)phenyl)-N-phenylnaphthalen-1-amine (BPNA). The bright yellowish-white emission was obtained from a non-doped triple-layer device: ITO/NPB (40 nm)/BPNA (50 nm)/Alq₃ (40 nm)/LiF/Al. The Commission Internationale de L’Eclairage (CIE) coordinates of the device were (0.24, 0.36) at 10 V. The maximum brightness of the device was 9225 cd/m² at 14.4 V. A current efficiency of 3.08 cd/A, a power efficiency of 1.21 lm/W and an external quantum efficiency of 1.18% at a driving current density of 20 mA/cm² were achieved. WOLED with a DCJTB-doped structure of ITO/TcTa/BPNA/BPNA: DCJTB (0.5%)/BPNA/BCP/Alq₃/LiF/Al was fabricated in comparison with the non-doped device. The device emitted bright white light with the CIE coordinates of (0.33, 0.29) at 10 V and a maximum luminance of 7723 cd/m² at 14.8 V.     

High efficiency small molecule white organic light-emitting devices with a multilayer structure

In this paper, a new white organic light-emitting device (WOLED) with multilayer structure has been fabricated. The structure of devices is ITO/N, N-bis-(1-naphthyl)-N, N^′-diphenyl-1, 1′-biphenyl-4, 4′-diamine (NPB) (40 nm)/NPB: QAD (1%): DCJTB (1%) (10 nm) /DPVBi (10 nm) /2, 9-dimethyl, 4, 7-diphenyl, 1, 10-phenanthroline (BCP) (d nm)/tris-(8-hydroxyquinoline) aluminium (Alq₃)(50-d nm)/LiF (1 nm)/Al (200 nm). In our devices, a red dye 4-(dicyanomethylene)-2-t-butyl-6 (1, 1, 7, 7-tetramethyl julolidyl-9-enyl)-4H-pyran (DCJTB) and a green dye quinacridone (QAD) were co-doped into NPB. The device with 8 nm BCP shows maximum luminance of 12 852 cd/m² at 20 V. The current efficiency and power efficiency reach 9.37 cd/A at 9 V and 3.60 lm/W at 8 V, respectively. The thickness of the blocking layer permit the tuning of the device spectrum to achieve a balanced white emission with Commission International de’Eclairage (CIE) chromaticity coordinates of (0.33,0.33). The CIE coordinates of device change from (0.3278, 0.3043) at 5 V to (0.3251, 0.2967) at 20 V that are well in the white region, which is largely insensitive to the applied bias.     

Efficient red organic light-emitting diode sensitized by a phosphorescent Ir compound

The efficiencies of red organic light-emitting diode (OLED) using tris-(8-hydroxy-quinoline)aluminum (Alq₃) as host and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as dopant were greatly increased by adding a small amount (0.3 wt%) of Ir compound, iridium(III) bis(3-(2-benzothiazolyl)-7-(diethylamino)-2H-1-benzopyran-2-onato-N′,C⁴) (acetyl acetonate) (Ir(C6)₂(acac)), as a sensitizer. The device has a sandwiched structure of indium tin oxide (ITO)/4,4′,4″-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine (T-NATA) (40 nm)/N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′ diamine (NPB) (40 nm)/Alq₃:DCJTB (0.7 wt%):Ir(C6)₂(acac) (0.3 wt%) (40 nm)/Alq₃ (40 nm)/LiF (1 nm)/Al (120 nm). It can be seen that the current efficiencies of this device remained almost (13.8±1) cd/A from 0.1 to 20,000 cd/m² and the Commission International d’Eclairage (CIE) coordinates at (0.60, 0.37) in the range of wide brightness. The significant improvement was attributed to the sensitization effect of the doped Ir(C6)₂(acac), thus the energy of singlet and triplet excitons is simultaneously transferred to the DCJTB.     

White organic light emitting diodes based on DCM dye sandwiched in 2-methyl-8-hydroxyquinolinolatolithium

Stable white electroluminescence (EL) has been achieved from organic LED, in which an ultrathin 4-(dicyanomethylene)-2-methyl-6-(p-dimethyl-aminostyryl)-4H-pyran (DCM) dye layer has been inserted in between two 2-methyl-8-hydroxyquinolinolatolithium [LiMeq] emitter layer and by optimizing the position of the DCM dye layer from the α-NPD/LiMeq interface. Electroluminescence spectra, current-voltage-luminescence (I-V-L) characteristics of the devices have been studied by changing the position of the dye layer. As the distance of DCM layer from α-NPD/LiMeq interface is increased, the intensity of host emission enhances rapidly. Introduction of thin layer of DCM in emissive layer increases the turn on voltage. The best Commission International de L’ Eclairage (CIE) coordinates i.e. (0.32, 0.33) were obtained with device structure ITO/α-NPD(30 nm) /LiMeq(10 nm)/DCM(1 nm)/LiMeq(25 nm)/BCP(6 nm)/Alq₃(28 nm)/LiF(1 nm)/Al(100 nm). The EL spectrum covers the whole visible spectra range 400-700 nm. The color rendering index (CRI) for our best white light (Device 4) is 47.4. The device shows very good color stability in terms of CIE coordinates with voltages. The maximum luminescence 1240 cd/m⁻² has been achieved at 19 V.     

A terbium (III) complex with triphenylamine-functionalized ligand for organic electroluminescent device

A novel ligand, 4-diphenylamino-benzoic acid (HDPAB), and the corresponding Tb (III) complex, Tb (DPAB)₃ which can be dissolved easily in organic solvents were synthesized and characterized. Organic electroluminescent (EL) device with a structure of indium tin oxide (ITO)/poly(N-vinylcarbazole) (PVK): Tb (DPAB)₃ (50 wt%, 80 nm)/1,3,5-tris-(N-phenylbenzimidazol-2-yl)benzene (TPBI) (30 nm)/tri(8-hydroxyquinoline)aluminum (AlQ) (20 nm)/LiF (1 nm)/Al (150 nm) in which Tb (DPAB)₃ acted as an emitter were fabricated. The maximum luminance of 230 cd m⁻² at 20 V and the maximum efficiency of 0.62 cd A⁻¹ were obtained due to the introduction of hole-transporting group, representing the best result to date among Tb (III) carboxylate complexes based EL devices. These results indicate that modifications of rare earth complexes are a promising way to improve the properties of EL devices.