Cadmium-free quantum dots based violet light-emitting diodes: High-efficiency and brightness via optimization of organic hole transport layers

Bright and efficient violet quantum dot (QD) based light-emitting diodes (QD-LEDs) with heavy-metal-free ZnSe/ZnS have been demonstrated by choosing different hole transport layers, including poly(4-butyl-phenyl-diphenyl-amine) (poly-TPD), poly[9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB), and poly-N-vinylcarbazole (PVK). Violet QD-LEDs with maximum luminance of about 930 cd/m², the maximum current efficiency of 0.18 cd/A, and the peak EQE of 1.02% when poly-TPD was used as HTL. Higher brightness and low turn-on voltage (3.8 V) violet QD-LEDs could be fabricated when TFB was used as hole transport material. Although the maximum luminance could reach up to 2691 cd/m², the devices exhibited only low current efficiency (∼0.51 cd/A) and EQE (∼2.88%). If PVK is used as hole transport material, highly efficient violet QD-LEDs can be fabricated with lower maximum luminance and higher turn-on voltages compared with counterpart using TFB. Therefore, TFB and PVK mixture in a certain proportion has been used as HTL, turn-on voltage, brightness, and efficiency all have been improved greatly. The QD-LEDs is fabricated with 7.39% of EQE and 2856 cd/m² of maximum brightness with narrow FWHM less than 21 nm. These results represent significant improvements in the performance of heavy-metal-free violet QD-LEDs in terms of efficiency, brightness, and color purity.     

Simplified phosphorescent organic light-emitting diodes with a WO3-doped wide bandgap organic charge transport layer

The effects of p-type doping of wide bandgap ambipolar 4,4′-N,N′-dicarbazolebiphenyl (CBP) with WO₃ were investigated through detailed electrical device characterization. It was found that, to achieve effective doping for improved hole injection and transport, the doping level should be greater than 20 mol% and the doped layer should be at least 10 nm thick. A large downward shift of the Fermi level in WO₃-doped CBP causes band bending and depletion at the doped/undoped CBP interface, resulting in an additional energy barrier which hampers hole transport. Simplified green phosphorescent organic light-emitting diodes (PhOLEDs) with CBP as the hole transport and host material were fabricated. With a WO₃-doped hole transport layer, the PhOLEDs attained brightness of 11,163 cd/m² at 20 mA/cm², and exhibited an improved reliability under constant-current stressing as compared to undoped PhOLEDs.     

Synthesis and electroluminescent properties of highly efficient anthracene derivatives with bulky side groups

Three new asymmetric light emitting organic compounds were synthesized with diphenylamine or triphenylamine side groups; 10-(3,5-diphenylphenyl)-N,N-diphenylanthracen-9-amine (MADa), 4-(10-(3,5-diphenylphenyl)anthracen-9-yl)-N,N-diphenylaniline (MATa), and 4-(10-(3′,5′-diphenylbiphenyl-4-yl)anthracen-9-yl)-N,N-diphenylaniline (TATa). MATa and TATa had a PL_max at 463 nm in the blue region, and MADa had a PL_max at 498 nm. MADa and MATa had T_g values greater than 120 °C, and TATa had a T_g of 139 °C. EL devices containing the synthesized compounds were fabricated in the configuration: ITO/4,4′,4′′-tris(N-(2-naphthyl)-N-phenyl-amino)-triphenylamine (2-TNATA) (60 nm)/N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine (NPB) (15 nm)/MADa or MATa or TATa or 9,10-di(2′-naphthyl)anthracene (MADN) (30 nm)/8-hydroxyquinoline aluminum (Alq₃) (30 nm)/LiF (1 nm)/Al (200 nm). The efficiency and color coordinate values (respectively) were 10.3 cd/A and (0.199, 0.152; bluish-green) for the MADa device, 4.67 cd/A and (0.151, 0.177) for the MATa device, and 6.07 cd/A and (0.149, 0.177) for the TATa device. The TATa device had a high external quantum efficiency (EQE) of 6.19%, and its luminance and power efficiencies and life-time were more than twice those of the MADN device.     

New hole blocking material for green-emitting phosphorescent organic electroluminescent devices

The new amorphous molecular material, 2,5-bis(4-triphenylsilanyl-phenyl)-[1,3,4]oxadiazole, that functions as good hole blocker as well as electron transporting layer in the phosphorescent devices. The obtained material forms homogeneous and stable amorphous film. The new synthesized showed the reversible cathodic reduction for hole blocking material and the low reduction potential for electron transporting material in organic electroluminescent (EL) devices. The fabricated devices exhibited high performance with high current efficiency and power efficiency of 45 cd/A and 17.7 lm/W in 10 mA/cm², which is superior to the result of the device using BAlq (current efficiency: 31.5 cd/A and power efficiency: 13.5 lm/W in 10 mA/cm²) as well-known hole blocker. The ITO/DNTPD/α-NPD/6% Ir(ppy)₃ doped CBP/2,5-bis(4-triphenylsilanyl-phenyl)-[1,3,4]oxadiazole as both hole blocking and electron transporting layer/Al device showed efficiency of 45 cd/A and maximum brightness of 3000 cd/m² in 10 mA/cm².     

All-solution-processed blue small molecular organic light-emitting diodes with multilayer device structure

All-solution-processed multilayer blue small molecular organic light-emitting diodes are fabricated by blade coating method. Fluorescent blue host,1-(7-(9,9′-bianthracen-10-yl)- 9,9-dioctyl-9H-fluoren-2-yl)pyrene, and blue dopant, 4,4′-(1E,1′E)-2,2′-(naphthalene-2,6-diyl)bis(ethene-2,1-diyl)bis(N,N-bis(4-hexylphenyl)aniline), are used to achieve good solubility and pinhole-free thin film by solution process. The multilayer device structure with hole/electron transport layer is achieved by blade coating method without the dissolution problem between layers. The efficiency of the all-solution-processed device is 4.8 cd/A at 1200 cd/m², close to that by thermal deposition in high vacuum chamber. The device performance is optimized with the annealing temperature of TPBi layer at 50 °C.     

Fine tuning hole injection for high-performance polyfluorene-based blue emitting device by adjusting work function of anode via deposition of CFx layer with proper ionization potential on indium tin oxide

By introducing CF_x thin film as hole injection layer on top of indium tin oxide (ITO) anode via plasma polymerization of CHF₃, the device with poly(9,9-dioctylfluorene) (PFO) as emitting layer, ITO/CF_x(35 W)/PFO/CsF/Ca/Al, is prepared. At the optimal C/F atom ratio using the radio frequency power 35 W, the device performance is optimal having the maximum current efficiency 3.1 cd/A and maximum brightness 8400 cd/m². This is attributed to a better balance between hole and electron fluxes, resulting from a decrease in hole injection barrier as manifested by ultraviolet photoelectron spectroscopy and scanning surface potential microscopy.     

High-efficiency hybrid organic–inorganic light-emitting devices

We report efficient red, orange, green and blue organic–inorganic light emitting devices using light emitting polymers and polyethylenimine ethoxylated (PEIE) interlayer with the respective luminance efficiency of 1.3, 2.7, 10 and 4.1 cd A⁻¹, which is comparable to that of the analogous conventional devices using a low work-function metal cathode. This is enabled by the enhanced electron injection due to the effective reduction of the ZnO work-function by PEIE, as well as hole/exciton-blocking function of PEIE layer. Due to the benign compatibility between PEIE and the neighboring organic layer, the novel phosphorescent organic–inorganic devices using solution-processed small molecule emissive layer show the maximum luminance efficiency of 87.6 cd A⁻¹ and external quantum efficiency of 20.9% at 1000 cd m⁻².     

High-performance inverted top-emitting green electrophosphorescent organic light-emitting diodes with a modified top Ag anode

Green electrophosphorescent inverted top-emitting organic light-emitting diodes with a Ag/1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile (HAT-CN) anode are demonstrated. A high current efficacy of 124.7 cd/A is achieved at a luminance of 100 cd/m² when an optical outcoupling layer of N,N′-di-[(1-naphthyl)-N,N′-diphenyl]-1,1′-biphenyl-4,4′-diamine (α-NPD) is deposited on the anode. The devices have a low turn-on voltage of 3.0 V and exhibit low current efficacy roll-off through luminance values up to 10,000 cd/m². The angle dependent spectra show deviation from Lambertian emission and color change with viewing angle. Hole-dominated devices with Ag/HAT-CN electrodes show current densities up to three orders of magnitude higher than devices without HAT-CN.     

Efficient fluorescent white organic light-emitting diodes using co-host/emitter dual-role possessed di(triphenyl-amine)-1,4-divinyl-naphthalene

Efficient fluorescent white organic light-emitting diodes with low carrier-injection barriers were fabricated with device structure of indium tin oxide/N,N′-bis-(1-naphthy)-N,N′-diphenyl-1,1′-biphenyl-4-4′-diamine/white emission layer/1,3,5-tris(N-phenyl-benzimidazol-2-yl)benzene/lithium fluoride/aluminium. By blending in the blue host of 1-butyl-9,10-naphthalene-anthracene in the emissive layer an efficient electro-luminescent greenish-blue co-host of di(triphenyl-amine)-1,4-divinyl-naphthalene, with the doping of a trace amount of red dye of 4-(dicyano-methylene)-2-methyl-6-(julolidin-4-yl-vinyl)-4H-pyran, bright and colour-stable white emission with high power-efficiency of 14.6 lm/W at 100 cd/m² or current efficiency of 19.2 cd/A at 300 cd/m² or 18.7 cd/A at 10,000 cd/m² was obtained. The resulted synergistic increase in brightness and efficiency may be attributed to the presence of cascading new routes with comparatively lower electron injection barrier.     

All-small-molecule efficient white organic light-emitting diodes by multi-layer blade coating

Blue and white small-molecule organic light-emitting diodes are fabricated by multi-layer blade coating on hot plate at 80 °C with hot wind. Uniform multi-layer structures are made without dissolution due to rapid drying. Only small molecules originally developed for vacuum deposition are used. For hole transport layer of, 4′,4″-tris(carbazol-9-yl)triphenylamine (TCTA), electron transport layer of 2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TBPI), emissive layer host of, 6-bis(3-(9H-carbazol-9-yl)phenyl)pyridine (26DCzPPy), triplet emitters of bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III) (FIrpic), and cathode of LiF/Al, the peak current efficiency for blue emission is 25.1 cd/A (10.8% and 9.3 lm/W). Orange emitter iridium(III)bis (4-(4-t-butylphenyl) thieno[3,2-c]pyridinato-N,C2′)acetylacetonate (PO-01-TB) is added to obtain white emission with CIE coordinate of (0.39, 0.46) [1]. The current efficiency is 34.2 cd/A (11.6% and 12 lm/W) at maximum, 32.4 cd/A at 1000 cd/m², and 31 cd/A at 10,000 cd/m².     

Improved performance of polymer light-emitting devices based on blend of MEH–PPV and vinyl copolymer with 1,3,4-oxadiazole chromophores

We have developed a simple method to overcome the intrinsic defect of well-known poly[2-methoxy-5-(2′-ethylhexoxy)–p-phenylenevinylene] (MEH–PPV), i.e. rampant inter-chain interaction and imbalanced hole and electron fluxes, by blending with copolymer of polystyrene containing pendant aromatic 1,3,4-oxadiazole (PSOXD12). The addition of PSOXD12 reduces the inter-chain interaction and balances charge carrier transport simultaneously. Photoluminescence (PL), PL excitation and electroluminescence (EL) spectra of the blends reveal that the inter-chain interactions, such as aggregation and excimer/exciplex, are reduced markedly due to the presence of PSOXD12. Enhanced EL device performance has been achieved (16,261 cd/m², 4.79 cd/A) as a result of both reduced inter-chain interaction and balanced charge transport.     

Interface electronic structures of organic light-emitting diodes with WO3 interlayer: A study by photoelectron spectroscopy

The energy level alignment and chemical reaction at the interface between the hole injection and transport layers in an organic light-emitting diode (OLED) structure has been studied using in-situ X-ray and ultraviolet photoelectron spectroscopy. The hole injection barrier measured by the positions of the highest occupied molecular orbital (HOMO) for N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB)/indium tin oxide (ITO) was estimated 1.32 eV, while that with a thin WO₃ layer inserted between the NPB and ITO was significantly lowered to 0.46 eV. This barrier height reduction is followed by a large work function change which is likely due to the formation of new interface dipole. Upon annealing the WO₃ interlayer at 350 °C, the reduction of hole injection barrier height largely disappears. This is attributed to a chemical modification occurring in the WO₃ such as oxygen vacancy formation.     

Effect of PEDOT–PSS resistivity and work function on PLED performance

The effect of a commonly used hole injection layer, poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT–PSS), on polymer light-emitting diode (PLED) performance has been investigated. A series of four different types of commercial PEDOT–PSS, with varying resistivity and work function were examined in devices with the structure Indium Tin Oxide (ITO)/PEDOT–PSS/High Molecular Weight Poly(n-vinylcarbazole) (PVKH): 30% N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD)/Low molecular Weight Poly(n-vinylcarbazole) (PVKL): 40% 2-(4-Biphenyl)-5-(4-tert-butylphenyl)-1,2,4-oxadiazole (PBD): 8% Ir(ppy)₃. It was found that the PEDOT–PSS with the highest work function and resistivity produced the devices with the highest efficiencies; this is due to the improved hole injection effect, the decrease in electron leakage current and the prevention of pixel crosstalk. A maximum device current efficiency of 33.4 cd A⁻¹ has been achieved for the most resistive PEDOT; this corresponded to an external quantum efficiency (E.Q.E.) of 11%. Increasing the work function of the PEDOT used resulted in a 60% increase in E.Q.E. and device efficiency for PEDOTs in the same resistivity range. Drift–diffusion simulations, carried out using SEmiconducting Thin Film Optics Simulation software (SETFOS) 3.2, produced J–V curves in good agreement with the experimentally observed results; this allowed us to extract qualitative values for the effective device mobility along with the PEDOT work function and resistivity.     

High performance top-emitting organic light-emitting diodes with copper iodide-doped hole injection layer

Efficient top-emitting organic light-emitting diodes were fabricated using copper iodide (CuI) doped 1,4-bis[N-(1-naphthyl)-N′-phenylamino]-4,4′-diamine (NPB) as a hole injection layer and Ir(ppy)₃ doped CBP as the emitting layer. CuI doped NPB layer functions as an efficient p-doped hole injection layer and significantly improves hole injection from a silver bottom electrode. The top-emitting device shows high current efficiency of 69 cd/A with Lambertian emission pattern. The enhanced hole injection is originated from the formation of the charge transfer complex between CuI and NPB.     

Highly efficient green phosphorescent organic light emitting diodes with simple structure

A series of simple structures is investigated for realization of the highly efficient green phosphorescent organic light emitting diodes with relatively low voltage operation. All the devices were fabricated with mixed host system by using 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC) and 1,3,5-tri(p-pyrid-3-yl-phenyl)benzene (TpPyPB) which were known to be hole and electron type host materials due to their great hole and electron mobilities [μ_h(TAPC): 1 × 10^?2 cm²/V s and μ_e(TpPyPB): 7.9 × 10^?3 cm²/V s] [1]. The optimized device with thin TAPC (5–10 nm) as an anode buffer layer showed relatively high current and power efficiency with low roll-off characteristic up to 10,000 cd/m². The performances of the devices; with buffer layer were compared to those of simple devices with single layer and three layers. Very interestingly, the double layer device with TAPC buffer layer showed better current and power efficiency behavior compared to that of three layer device with both hole and electron buffer layers (TAPC, TpPyPB, respectively).     

Efficient electron transport in 4,4′-bis[N-(1-napthyl)-N-phenyl-amino] biphenyl and the applications in white organic light emitting devices

The electron transport capability of 4,4′-bis[N-(1-napthyl)-N-phenyl-amino] biphenyl (α-NPD) was investigated by fundamental physical measurements named as current–voltage (I–V) electrical property evaluation and displacement current measurement (DCM). In electron-dominated devices, the I–V characteristics of α-NPD were similar as that of (8-hydroxyquinolino) aluminum (Alq₃) owing to their same order of electron mobilities. The interface of Al/LiF and α-NPD was proven to be an Ohmic contact through the evaluation of I–V characteristics at low bias regime (<3 V). And an electron injection barrier, 0.21 eV, at Al/LiF/α-NPD was obtained by extrapolating the temperature dependent I–V curves. The electron transport behavior in α-NPD film was further confirmed by DCM evaluations. Furthermore, an efficient white organic light emission device was successfully fabricated by using α-NPD as hole transport layer and electron transport layer, respectively.     

Investigation of voltage reduction in nanostructure-embedded organic light-emitting diodes

We investigated the reduction of the operating voltage in organic light-emitting diodes containing WO₃ nanoislands. The thickness of the organic layer and the periodicity of the nanoislands were varied in order to quantitatively analyze the electrical changes. The thickness of the N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine (NPB) layer was varied from 150 nm to 600 nm, and various periodic nanoislands of 300 nm, 330 nm, and 370 nm were fabricated. Two geometric factors, which are the effective length and effective area, influence the operating voltage. The effective length is determined by the relative thickness of the nanoislands compared with the organic thickness, and the reduction of the operating voltage is linearly proportional to the relative thickness. The effective area is a nonlinear function of periodicity, and the voltage is reduced as the periodicity decreases.     

Synthesis and characterization of fluorene-based copolymers as electron-transporting materials for PLEDs

Owing to their low cost, easy processing, and the possibility of flexible fabrication, polymer light-emitting diodes (PLEDs) are emerging as an important class of materials. Despite promising characteristics, the relatively easy ionization of the well-known low-work-function cathodes such as Ca and Ba prevents the full usage of these materials. Herein, we report the syntheses of three alcohol-soluble conjugated polymers with different conjugation lengths and electron affinities as electron injection and transport materials for PLEDs: poly[9,9-bis(2-dihexylaminoethoxy)fluorene-co-tetrafluorobenzene] (PFOH-1), poly[9,9-bis(2-dihexylaminoethoxy)fluorene-co-thiophene] (PFOH-2), and poly[9,9-bis(2-dihexylaminoethoxy)fluorene-co-benzo-thiadiazole] (PFOH-3). For comparison, devices using Al, Ca, and Al cathodes were also fabricated. The device based on the Al cathode showed lower performance with a luminescence efficiency of 0.93 cd/A and a luminance of 248 cd/m²; that based on the low-work-function metal Ca as the cathode showed a near-threefold increase in luminescence efficiency at 2.51 cd/A and brightness at 856 cd/m² owing to greatly enhanced electron injection from the cathode; and the device employing the PFOH-3/Al cathode exhibited a luminescence efficiency of 2.35 cd/A and a brightness of 667 cd/m² at a current density of 35 mA/cm², which is comparable with the performance of the device with the Ca cathode.     

White emission polymer light-emitting devices with efficient electron injection from alcohol/water-soluble polymer/Al bilayer cathode

We demonstrate highly efficient white emission polymer light-emitting diodes (WPLEDs) from multilayer structure formed by solution processed technique, in which alcohol/water-soluble polymer, poly [(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) was incorporated as electron-injection layer and Al as cathode. It was found that the device performance was very sensitive to the solvents from solution of which the PFN electron-injection layer was cast. Devices with electron-injection layer cast from methanol solution show degraded performance while the best device performance was obtained when mixed solvent of water and methanol with ratio of 1:3 was used. We attribute the variation in device performance to washing out the electron transport material in the emissive layer due to rinse effect. As a result of alleviative loss of electron transport material in the emissive layer, the optimized device with a peak luminous efficiency of 18.5 cd A^?1 for forward-viewing was achieved, which is comparable to that of the device with same emissive layer but with low work-function metal Ba cathode (16.6 cd A^?1). White emission color with Commission International de I’Eclairage coordinates of (0.321, 0.345) at current 10 mA cm^?2 was observed.     

Optoelectronic characteristics of MEH-PPV polymer LEDs with thin,doped composition-graded a-SiC:H carrier injection layers

The optoelectronic characteristics of poly(2-methoxy-5-(2′ethyl-hexoxy)-1,4-phenylene-vinylene) (MEH-PPV) polymer LEDs (PLEDs) have been improved by employing thin doped composition-graded (CG) hydrogenated amorphous silicon–carbide (a-SiC:H) films as carrier injection layers and O₂-plasma treatment on indium–tin-oxide (ITO) transparent electrode, as compared with previously reported ones having doped constant-optical-gap a-SiC:H carrier injection layers. For PLEDs with an n-type a-SiC:H electron injection layer (EIL) only, the electroluminescence (EL) threshold voltage and brightness were improved from 7.3 V, 3162 cd/m² to 6.3 V, 5829 cd/m² (at a current density J = 0.6 A/cm²), respectively, by using the CG technique. The enhancement of EL performance of the CG technique was due to the increased electron injection efficiency resulting from a smoother barrier and reduced recombination of charge carriers at the EIL and MEH-PPV interface. Also, surface modification of the ITO transparent electrode by O₂-plasma treatment was used to further improve the EL threshold voltage and brightness of this PLED to 5.1 V, 6250 cd/m² (at J = 0.6 A/cm²). Furthermore, by employing the CG n[p]-a-SiC:H film as EIL [hole injection layer (HIL)] and O₂-plasma treatment on the ITO electrode, the brightness of PLEDs could be enhanced to 9350 cd/m² (at a J = 0.3 A/cm²), as compared with the 6450 cd/m² obtained from a previously reported PLED with a constant-optical-gap n-a-SiCGe:H EIL and p-a-Si:H HIL.