Deep‐level characterization of emissive interface states in Alq3‐based OLEDs

We have succesfully investigated emissive interface states in fabricated indium‐tin‐oxide (ITO)/N,N′‐di‐1‐naphthyl‐N,N′‐diphenyl‐1,1′‐biphenyl‐4,4′diamine (α‐NPD)/tris(8‐hydroxyquinoline) aluminum (Alq₃)/LiF/Al organic light‐emitting diodes (OLEDs) by a modified deep‐level optical spectroscopy (DLOS) technique. In the vicinity of the α‐NPD/Alq₃ emissive interface, a discrete trap level was found to be located at ～1.77 eV below the conduction band of Alq₃, in addition to band‐to‐band transitions of carriers from α‐NPD to Alq₃. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Transport and recombination in organic light-emitting diodes studied by electrically detected magnetic resonance

We have used electrically detected magnetic resonance (EDMR) to study a series of multilayer organic devices based on aluminum (III) 8-hydroxyquinoline (Alq₃). These devices were designed to identify the microscopic origin of different spin-dependent processes, i.e. hopping and exciton formation. The EDMR signal in organic light-emitting diodes (OLEDs) based on Alq₃ is only observed when the device is electroluminescent and is assigned to spin-dependent exciton formation. It can be decomposed in at least two Gaussians: one with peak-to-peak line ( ΔH_PP) of 1.6 mT and another with ΔH_PP of 2.0 to 3.4 mT, depending on bias and temperature. The g-factors of the two components are barely distinguishable and close to 2.003. The broad line is attributed to the resonance in Alq₃ anions, while the other line is attributed to cationic states. These attributions are supported by line shape and its electrical-field dependence of unipolar Alq₃-based diodes, where hopping process related to dication and dianion formation is observed. In these unipolar devices, it is shown that the signal coming from spin-dependent hopping occurs close to organic semiconductor/metal interfaces. The sign of the magnetic-resonance-induced conductivity change is dominated by charge injection rather than charge mobility. Our results indicate that the probability of singlet exciton formation in our OLEDs is smaller than 25%.     

The effect of alkaline metal chlorides on the properties of organic light-emitting diodes

The multilayer organic light-emitting diodes (OLEDs) have been fabricated with a thin alkaline metal chloride layer inserted inside an electron transport layer (ETL), tris (8-hydroxyquinoline) aluminum (Alq₃). The alkaline metal chloride layer was inserted inside 60 nm Alq₃ at d=0, 10, 20 and 30 nm positions (d is the distance of the interlayer away from the Al cathode). The devices, with alkaline metal chlorides inserted at the Alq₃/Al interface, showed electron injection and electroluminescence (EL) intensity improvements. When the alkaline metal chlorides were inserted inside the Alq₃ layer at 10, 20 or 30 nm position apart from the Al cathode, both EL intensity and efficiency were enhanced for the devices with a thin potassium chloride (KCl) or rubidium chloride (RbCl) layer. On the contrary, the improvements were not observed for the OLEDs with a thin sodium chloride (NaCl) layer. A proposed insulator buffer layer model is employed to explain these characteristics of the devices.     

Enhanced brightness of organic light-emitting diodes based on Mg:Ag cathode using alkali metal chlorides as an electron injection layer

Different thicknesses of cesium chloride (CsCl) and various alkali metal chlorides were inserted into organic light-emitting diodes (OLEDs) as electron injection layers (EILs). The basic structure of OLED is indium tin oxide (ITO)/N,N′-diphenyl-N,N′-bis(1-napthyl-phenyl)-1.1′-biphenyl-4.4′-diamine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq₃)/Mg:Ag/Ag. The electroluminescent (EL) performance curves show that both the brightness and efficiency of the OLEDs can be obviously enhanced by using a thin alkali metal chloride layer as an EIL. The electron injection barrier height between the Alq₃ layer and Mg:Ag cathode is reduced by inserting a thin alkali metal chloride as an EIL, which results in enhanced electron injection and electron current. Therefore, a better balance of hole and electron currents at the emissive interface is achieved and consequently the brightness and efficiency of OLEDs are improved.     

Electroluminescence enhancement in ultraviolet organic light‐emitting diode with graded hole‐injection and ‐transporting structure

Electroluminescent intensity and external quantum efficiency (EQE) in ultraviolet organic light‐emitting diodes (UV OLEDs) have been remarkably enhanced by using a graded hole‐injection and ‐transporting (HIT) structure of MoO₃/N,N ′‐bis(naphthalen‐1‐yl)‐N,N ′‐bis(phenyl)‐benzidine/MoO₃/4,4′‐bis(carbazol‐9‐yl)biphenyl (CBP). The graded‐HIT based UV OLED shows superior short‐wavelength emis‐ sion with spectral peak of ～410 nm, maximum electroluminescent intensity of 2.2 mW/cm² at 215 mA/cm² and an EQE of 0.72% at 5.5 mA/cm². Impedance spectroscopy is employed to clarify the enhanced hole‐injection and ‐transporting capacity of the graded‐HIT structure. Our results provide a simple and effective approach for constructing efficient UV OLEDs. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Color-tunable organic light-emitting devices using a thin N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine layer at heterojunction interface

Novel types of multilayer color-tunable organic light-emitting devices (OLEDs) with the structure of indium tin oxide (ITO)/N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB)/aluminum (III)bis(2-methyl-8-quinolinato)4-phenylphenolato (BAlq)/tris-(8-hydroxyquinolate)-aluminum (Alq₃)/Mg:Ag were fabricated. By inserting a thin layer with different thickness of a second NPB layer at the heterojunction interface of BAlq/Alq₃, the emission zone of devices shifted greatly and optoelectronic characteristics underwent large variation. Although BAlq was reported as a very good hole-blocking and blue-light-emission material, results of measurements in this paper suggested that a certain thickness of NPB layer between BAlq and Alq₃ plays an important role to modify device characteristics, which can act as recombination-controlling layer in the multilayer devices. It also provides a simple way to fabricate color-tunable OLEDs by just changing the thickness of this “recombination-controlling” layer rather than doping by co-evaporation.     

Development of organic light‐emitting diodes for electro‐optical integrated devices

Organic light‐emitting diodes (OLEDs) are discussed for electro‐optical integrated devices that are used for optical signal transmission. Organic optical devices including polymeric optical fibers are used for optical communication applications to realize polymeric electro‐optical integrated devices. The OLEDs were fabricated by vacuum process, i.e. the organic molecular beam deposition (OMBD) technique or a solution process on a polymeric or a glass substrate, for comparison. Optical signals faster than 100 MHz have been created by applying pulsed voltage directly to the OLED utilizing rubrene doped in 8‐hydoxyquinolinum aluminum (Alq₃), as an emissive layer. OLEDs fabricated by solution process utilizing rubrene doped in carrier‐transporting materials have also discussed. OLEDs utilizing polymeric materials by solution process are also fabricated and discussed. Moving‐picture signals are transmitted utilizing both vacuum‐ and solution‐processed OLEDs, respectively.     

Exciplex or electroplex emissions from the interface between aromatic diamine and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline?

Organic light-emitting diodes (OLEDs) have been fabricated which consist of N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine) (TPD), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), and tris(8-hydroxyquinoline) aluminum (Alq₃). Four emission peaks located at about 401 nm, 425 nm, 452 nm and 480 nm have been obtained in the electroluminescence (EL) spectra of these devices. The former two emissions originate from the exciton emission of TPD molecular. The last two emissions could be attributed to local (LOC) exiplex emission and charge transfer (CT) exiplex emission at the interface between TPD and BCP layers, respectively.     

Investigation of an efficient YbF3/Al cathode for tris-(8-hydroxyquinoline)aluminum-based small molecular organic light-emitting diodes

Efficient tris-(8-hydroxyquinoline)aluminum (Alq₃)-based organic light-emitting diodes (OLEDs) using YbF₃ as the electron injection layer have been investigated. With an YbF₃ (3.0 nm)/Al cathode, the device with Alq₃ as the emitting layer achieved a better performance than the control device with a LiF (0.5 nm)/Al cathode. The release of the low-work-function metal Yb is responsible for the performance enhancement. From the analysis by atomic force spectroscopy and X-ray photoemission spectroscopy, it is observed that the Alq₃-cathode interface could be well covered by YbF₃ at an optimum thickness of 3.0 nm, which helps to prevent the contact between Alq₃ and Al, and to reduce the destruction of Alq₃ by Al.     

Highly efficient yellow organic light-emitting diodes based on a hole-dominant host layer co-doped with yellow emitting and electron transporting guests

We fabricated high efficiency yellow-color organic light-emitting diodes (OLEDs) by co-doping 2,8-di(t-butyl)-5,11-di[4-(t-butyl)phenyl]-6,12-diphenylnaphthacene (TBRb) and tris(8-hydroxyquinolinato)aluminum (Alq₃) guests in a N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) host. Co-doping of electron-transporting Alq₃ with yellow dopant TBRb in hole-dominant NPB layers resulted in substantial luminance-yield improvement compared to TBRb-only counterparts without color contamination from Alq₃ green emission. The luminance yield of 11.4 cd/A, corresponding to the co-doping of 8% TBRb and 2% Alq₃, is larger than previously reported luminance-yield values of conventional TBRb-based yellow OLEDs. Another advantage of the TBRb-Alq₃ co-doped OLEDs is an insignificant roll-off of efficiency at high current-density and/or brightness levels.     

Efficient organic light-emitting diodes with zinc acetate as an effective electron injection layer

We report on the fabrication of organic light-emitting diodes (OLEDs) using a zinc acetate ((CH₃COO)₂Zn) layer as the cathode buffer layer. The results show that the device containing a (CH₃COO)₂Zn interlayer shows improved luminance and efficiency due to the Zn–N bond formation resulting in the occurrence of Alq₃ anion and also due to the band bending at the Alq₃/Al interface, which is beneficial to electron injection by lowering electron injection barrier. And the devices with structured cathodes (CH₃COO)₂Zn/LiF/Al and LiF/(CH₃COO)₂Zn/Al have a higher luminance and efficiency than the LiF/Al cathode-based device.     

The enhanced electron injection by fluorinated tris-(8-hydroxy-quinolinato) aluminum derivatives in high efficient Si-anode OLEDs

Fabrication of organic light-emitting diodes (OLEDs) and lasers on silicon substrates is a feasible route to integrate microelectronic chips with optical devices for telecommunications. However, the efficiency of Si-anode based OLEDs is restricted by the imbalance of hole-electron injection because a p-type Si anode owns better hole injection ability than ITO. We have used fluorinated tris-(8-hydroxy-quinolinato) aluminum (FAlq₃) derivatives to prepare Si-anode based OLEDs. We observed that, when tris-(5-fuloro-8-hydroxyquinolinato) aluminum (5FAlq₃) is used as the electron-transporting material instead of Alq₃, the cathode electron injection is enhanced due to its lower lowest unoccupied molecular orbital (LUMO) compared to the Alq₃. The device can keep the relative carrier balance even when a Si anode capable of stronger hole injection was used. Further optimization of the device structure by introducing 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) as a hole blocking layer showed significant increase in the device power efficiency from 0.029 to 0.462 lm/W. This indicates that use of fluorinated Alq₃ derivatives is an effective way to improve the performance of Si-anode based OLEDs.     

Probing electric field distribution in organic double-layer diode by electric field induced optical second harmonic generation

Analyzing spectroscopic optical properties of an organic double-layer diode comprised of α-NPD and Alq₃ layers, we studied the selectively probing of electric field distribution in one of the two layers by using the microscopic electric field induced optical second harmonic generation (EFISHG) measurement. Spectroscopic SHGs from Indium–Zinc-Oxide/N,N-Di(naphthalene-1-yl)-N,N′-diphenyl-benzidine/tris(8-quinolinolato) aluminium/Al (IZO/α-NPD/Alq₃/Al) diodes were measured. Results showed that the SHG peaks were generated at 940 and 1050 nm from the α-NPD and Alq₃ layers, respectively, due to the EFISHG process, and the electric field in each layer can be selectively probed. The contribution of the accumulated charge at the double-layer α-NPD and Alq₃ interface was also identified by the d.c. voltage dependence on the EFISHG intensity.     

On the origin of exciton formation in dye doped Alq3 OLEDs

Electrically Detected Magnetic Resonance (EDMR) was used to investigate the influence of dye doping on spin-dependent exciton formation in aluminum (III) 8-hydroxyquinoline (Alq₃) based Organic Light Emitting Diodes (OLEDs) with different device structures. 4-(dicyanomethylene)-2-methyl-6-{2-[(4-diphenylamino)-phenyl]ethyl}-4H-pyran (DCM-TPA) and 5,6,11,12-tetraphenylnaphthacene (Rubrene) were used as dopants. Results at room temperature show significant differences on the EDMR spectra (g-factor and linewidth) of doped and undoped devices. Signals from DCM-TPA and Rubrene dye doped OLEDs showed strong temperature dependence, with signal intensity increasing by 2 orders of magnitude below 200 K for DCM-TPA dye doped OLEDs and increasing by ～1 order of magnitude below 225 K for the Rubrene dye doped device, while undoped devices shows almost no temperature dependence. By adding a “spacer” layer of undoped Alq₃ at the recombination zone, changes in bias voltage were used to shift the recombination from doped to undoped region and correlate that with changes in the EDMR spectrum. Our results are indicating that charge trapping on the dopant followed by recombination is the main mechanism of light emission in the investigated devices.     

Pure blue emission from undoped organic light emitting diode based on anthracene derivative

This paper presents organic light emitting diodes (OLEDs) which were fabricated by using undoped 9,10-di(2-naphthyl)anthracene (ADN) as the emitting layer, N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-amine (TPD) as the hole transporting layer, and one of tris-(8-hydroxy-quinolinato) aluminum (Alq₃), 4,7-diphenyl-1,10-phenanthroline (Bphen) and 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD) as the electron transporting layer. By optimization for the thickness of device, efficient pure blue organic light emitting diodes were obtained, which is attributed to the synergy of both the hole transporting layer and the electron transporting layer.     

Modification of anode surface in organic light-emitting diodes by chalcogenes

Influence of thin chalcogen X (S, Se, Te) interlayer between anode (indium-tin oxide, ITO) and a layer of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) used as a hole-transport layer (HTL) on the operating characteristics of organic light-emitting diodes (OLEDs) of composition ITO/X/TPD/Alq₃/Yb (Alq₃ - aluminum 8-quinolinolate) has been investigated. It was found that the sulphur layer decreases operating voltage and enhances operating stability of a device while the selenium or tellurium interlayers impair these characteristics.     

Improvement of performance of tetraphenylporphyrin-based red organic light emitting diodes using WO3 and C60 buffer layers

One of the porphyrin derivatives, meso-tetraphenylporphyrin (TPP), has been synthesized and examined as an emitter material (EM) for efficient fluorescent red organic light-emitting diodes (OLEDs). By inserting a tungsten oxide (WO₃) layer into the interface of anode (ITO) and hole transport layer N,N′-Di-[(1-napthyl)-N,N′-diphenyl]-(1,1′-biphenyl)-4,4′-diamine (NPB) and by using fullerene (C₆₀) in contact with a LiF/Al cathode, the performance of devices was markedly improved. The current density–voltage–luminance (J–V–L) characterizations of the samples show that red OLEDs with both WO₃ and C₆₀ as buffer layers have a lower driving voltage and higher luminance compared with the devices without buffer layers. The red OLED with the configuration ITO/WO₃ (3 nm)/NPB (50 nm)/TPP (60 nm)/BPhen (30 nm)/C₆₀ (5 nm)/LiF (0.8 nm)/Al (100 nm) achieved the high luminance of 6359 cd/m² at the low driving voltage of 8 V. At a current density of 20 mA/cm², a pure red emission with CIE coordinates of (0.65; 0.35) is observed for this device. Moreover, a power efficiency of 2.07 lm/W and a current efficiency of 5.17 cd/A at 20 mA/cm² were obtained for the fabricated devices. The study of the energy level diagram of the devices revealed that the improvement in performance of the devices with buffer layers could be attributed to lowering of carrier-injecting barrier and more balanced charge injection and transport properties.     

Color tunable high efficiency microcavity organic light-emitting diodes

Color tunable microcavity organic light-emitting diodes (OLEDs) with structure of distributed Bragg reflectors (DBR)/indium-tin-oxide (ITO)/N,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB)/tris(8-hydroxyquinoline) aluminum (Alq₃)/LiF/Al were fabricated. Orange red and green light emissions with full width at half maximum (FWHM) of less than 20 nm were obtained through simply changing the thickness of NPB layer. Furthermore, due to the effective modification of the spontaneous emission within microcavity, the brightness and electroluminescent (EL) efficiency of the microcavity OLEDs were significantly enhanced. The maximum brightness and current efficiency, respectively, reached 31000 cd/m² at a current density of 480.0 mA/cm² and 8.3 cd/A at a current density of 110.0 mA/cm² for green devices, and 9700 cd/m² at a current density of 180.0 mA/cm² and 6.6 cd/A at a current density of 36.4 mA/cm² for red devices, which are over 1.5 times higher than those of noncavity OLEDs.      

The influence of exciton behavior on luminescent characteristics of organic light-emitting diodes

We used N,N′-bis-(1-naphthyl)-N,N′-1-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB), 4,4′-N,N′-dicarbazole-biphenyl (CBP) and tris(8-hydroxyquinoline) aluminum (Alq₃) to fabricate tri-layer electroluminescent (EL) device (device structure: ITO/NPB/CBP/Alq₃/Al). In photoluminescence (PL) spectra of this device, the emission from NPB shifted to shorter wavelength accompanying with the decrease of its emission intensity and moreover the emission intensity of Alq₃ increased relatively with the increase of reverse bias voltage. The blue-shifted emission and the decrease in emission intensity of NPB were attributed to the polarization and dissociation of NPB excitons under reverse bias voltage. The increase of emission intensity of Alq₃ benefited from the recombination of electrons (produced by the dissociation of NPB exciton) and holes (injected from the 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 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.