Effect of Ca and buffer layers on the performance of organic light-emitting diodes based on tris-(8-hydroxyquinoline) aluminum

The effects of buffer layers, including LiF, LiCl, NaF, NaCl, NaI, KI, RbF, RbCl, CsF, CsCl, MgF₂, CaF₂, BaF₂, and BaCl₂ on electron injection and device performance in organic light-emitting diodes based on tris-(8-hydroxyquinoline) aluminum, were investigated systematically. The insertion of the buffer layers at the organic/cathode interface not only reduced the operating voltage, but also enhanced the luminance and efficiency, which is attributed to the improvement of electron injection efficiency. It was found that the efficiency of the electron injection was closely related to the inherent properties of the buffer layer, such as its melting point (MP) and dielectric constant (ε), as well as with the buffer layer's interface with the metallic electrode through the effective work function (WF). Low MP, low ε and low WF values result in an effective improvement in the injection of the electrons, and thus to the device performance. The electroluminescent performance was further improved by the introduction of calcium between the buffer layer and the aluminum electrode.     

Study on energy relation between blue and red emissive layer of organic light-emitting diodes by inserting spacer layer

In this paper, energy relation between blue emissive layer (blue-EML) and red emissive layer (red-EML) in organic light-emitting diodes based on blue-emitting and red-emitting phosphorescent dopants, bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl) iridium III (Firpic) and bis(2-(2′-benzo[4,5-α]thienyl)pyridinato-N,C3′)iridium(acetylacetonate) (Btp₂Ir(acac)), was studied. Two phosphorescent dopants, Firpic and Btp₂Ir(acac), were co-doped in the single emissive layer, and the results exhibit complete energy transfer from Firpic to Btp₂Ir(acac). Then, Firpic and Btp₂Ir(acac) were doped into blue-EML and red-EML, separately. By inserting 4,4′-bis(N-carbazolyl)biphenyl (CBP) spacer between blue- and red-EML, energy relation between blue- and red-EML was researched. The results of this work reveal that, CBP spacer may strengthen energy transfer between blue- and red-EML. The reason is that CBP triplets at blue-/red-EML interface can transfer their energies to both CBP molecules of red-EML and Firpic molecules of blue-EML in spacer-without devices, while CBP triplets in the spacer can transfer their energies only to CBP molecules of red-EML. Therefore, energy flow from blue- to red-EML is strengthened because of the avoidance of energy transfer from CBP triplets in the spacer to Firpic molecules of blue-EML, leading to the relative enhancement of red emission in CBP-spacer devices.     

Surface conditioning of indium-tin oxide anodes for organic light-emitting diodes

Oxygen-plasma treatment of indium-tin oxide (ITO) anodes is now widely used as one of the most effective ways to improve the device performance of organic light-emitting diodes (LEDs). However, the role of oxygen-plasma treatment has not been clearly understood. We have performed detailed studies of the surface and bulk of the ITO thin films exposed to oxygen-plasma. We employed a multitude of experimental techniques, including X-ray and ultraviolet photoelectron spectroscopies, atomic force microscopy, dynamic contact angle measurement, four-point probe and Hall measurements to investigate the changes induced by the plasma. We have also analyzed the device characteristics of polymer LEDs fabricated with these anodes. We found significant modifications of the physico-chemical, morphological, transport and optical properties of the oxygen-plasma treated ITO. Although oxygen-plasma does not show any measurable etching effect, it induces considerable changes leading to an increase in work function, electron carrier concentration and conductivity. It also increases the surface energy and polarity. We relate these modifications to enhancement of the device performance, such as electroluminescence efficiency and lifetime, through their effects on hole injection, and interface structure and stability. Finally, we show that even in the presence of a hole-transport layer such as a poly(styrene sulphonate)-doped poly(3,4-ethylene dioxythiophene) (PEDOT:PSS) inserted between the anode and the emissive polymer layer, oxygen-plasma treatment of the ITO anodes is still beneficial for the devices.     

Influence of heat treatment on indium-tin-oxide anodes and copper phthalocyanine hole injection layers in organic light-emitting diodes

Modifications of indium-tin-oxide (ITO) and copper phthalocyanine (CuPc) layers by heat treatment aimed at lowering driving voltage in organic light-emitting diodes (OLEDs) are examined. Significant changes were observed in the surface morphology and carrier injection properties of ITO and CuPc layers after annealing at T = 250 °C for 0-60 min in a glove box. In the case of ITO annealing, although the ITO work function gradually decreased and the surface of the ITO layer became smoother than that of an unannealed ITO layer, we observed an appreciable decrease in the driving voltage with an increase in annealing time. In the case of CuPc annealing, on the other hand, we observed deterioration of the OLED's characteristics. All devices demonstrated an increase in driving voltage due to the pronounced crystallization of the CuPc layer.     

Dielectric properties depending on frequency in organic light-emitting diodes

Dielectric properties of organic light-emitting diodes were investigated using ITO/Alq₃/Al device. In spite of various advantages in organic light-emitting diodes, a fundamental study on physical properties is not yet sufficient. Dielectric properties are used for studying fundamental physical properties of materials through a frequency-dependent response. We have investigated magnitude and phase of impedance, electrical conductivity, and the dielectric loss depending on a bias-voltage variation using ITO/Alq₃(60 nm)/Al device. The device shows a frequency-dependent response such that a major contribution is resistive below time constant and capacitive above time constant. Also, the device shows a voltage-dependent electrical conductivity in low-frequency region. A bulk resistance rapidly decreases as the frequency increases above 1 MHz. The dielectric loss shows that there appears an interfacial polarization in low-frequency region, and an orientational polarization in high-frequency region.     

Efficient top-emitting organic light-emitting diodes with Sm/Ag bilayer cathode

A bilayer is used as a semitransparent cathode for top-emitting organic light emitting devices (top-emitting OLEDs). The bilayer cathode consists of samarium (Sm) and silver (Ag). Top-emitting OLEDs with the bilayer cathode showed enhanced current injection and high electroluminescence efficiency as compared with a Sm cathode. The maximum current efficiency of the top-emitting OLEDs with a Sm/Ag cathode is 9.9 cd/A, much greater than 4.9 cd/A obtained from the top-emitting OLEDs with a Sm cathode. The improved performance can be attributed to the balance between optical transparency and electrical conductivity of the Sm/Ag cathode.     

Optical and electroluminescent properties of samarium complex-based organic light-emitting diodes

The optical and electroluminescent (EL) properties of newly synthesized tris(hexafluoroacethylacetonato)(phenanthroline)samarium(III)mono-methanol [Sm(hfa)₃(phen)₂MeOH]-based organic light-emitting diodes (OLEDs) were investigated. The as-prepared photoluminescence (PL) spectrum of Sm(hfa)₃(phen)₂MeOH-doped PMMA film exhibits the peaks at the wavelength around 564, 598, 645 and 710 nm which correspond to the ⁴G_5/2 → ⁷H5_/2, ⁴G_7/2 → ⁷H_7/2, ⁴G_5/2 → ⁷H_9/2 and ⁴G_5/2 → ⁷H_11/2 transitions of the Sm³⁺ ion, respectively. The best organic light-emitting device performance is obtained for a device using 8 wt.% Sm(hfa)₃(phen)₂MeOH and 40 wt.% 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4,-oxadiazole doped in poly(N-vinylcarbazole) as a emitting layer. The optimal device exhibits maximum luminance of 135 candela (cd)/m² at the current density of 0.16 A/cm², with current efficiency of 0.1 cd/A at the current density of 0.08 A/cm². The EL spectrum from optimal device has the Commission Internationale De L'Eclairage (CIE) coordinate of (0.60, 0.36).     

High quantum efficiency in simple blue phosphorescent organic light-emitting diodes without any electron injection layer

High efficiency simple blue phosphorescent organic light-emitting diodes (PHOLEDs) without any electron injection layer were developed using a spirobifluorene-based phosphine oxide (SPPO13) as a host material in the emitting layer. A high quantum efficiency of 20.3% was obtained from the SPPO13 device, with a common device structure and quantum efficiency of 19% achieved in the simple blue device without any LiF electron injection layer. Efficient electron injection from the Al cathode to the SPPO13, without any electron injection layer, was responsible for the high quantum efficiency in the blue PHOLEDs.     

Characteristics of AlGaN-based deep ultraviolet light-emitting diodes with a hole strengthened-injection layer

The optical and electrical properties of AlGaN-based deep ultraviolet light-emitting diodes (DUV LEDs) with the novel Mg-doping hole strengthened-injection layer (HSIL) are studied numerically and compared with conventional DUV LEDs. In this paper, two kinds of inserted layer of DUV LEDs have been investigated theoretically by the advanced physical model of semiconductor device (APSYS) software. The internal quantum efficiency, light output power, energy band diagrams, distributions of carrier concentration, radiative recombination rate and spontaneous emission intensity of three structures are calculated. The simulation results reveal that the carrier concentration and radiative recombination rates in the multiple quantum wells of DUV LEDs with HSIL are enhanced significantly. Moreover, the HSIL between EBL and p-doped region is able to reduce effective barrier height for holes in valence band, which is beneficial for hole injection from the p-doped region. As a result, the devices with HSIL, which is capable of alleviating the efficiency droop as the injection current increases, show excellent optical performance.     

Enhanced performance in organic light-emitting diodes by sputtering TiO2 ultra-thin film as the hole buffer layer

Organic light-emitting diodes were prepared using titanium oxide (TiO₂) ultra-thin film by RF magnetron sputtering as the hole buffer layer. The device configuration is ITO/TiO₂/N-N′-diphenyl-N-N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine/tris(8-quinolinolato)-aluminum/LiF/Al. The maximum luminous efficiency for the 1.2 nm TiO₂ device is increased by approximately 46% (6.0 cd/A), in comparison with that of the control device (4.1 cd/A). The atomic force microscopy shows that with the insertion of TiO₂ buffer layer, the roughness of ITO surface decreases, which is favorable to improve the device luminance and increase the device lifetime. The mechanism behind the enhanced performance is that the TiO₂ layer enhances most of the holes injected from the anode and improves the balance of the hole and electron injections.     

Micropatterning of emitting layers by microcontact printing and application to organic light-emitting diodes

The microcontact printing (μCP) technique, which is a simple and low damage fabrication technique for thin films, was successfully applied to fabricate patterned emitting layers such as polyfluorene (PF). We fabricated micropatterns by transferring dried and uniform thin films, and observed strong electroluminescence (EL) from the fabricated organic light-emitting diodes (OLEDs) with the patterned emitting layers. The performance of the fabricated device was superior to that of a conventionally fabricated device. This demonstrates the well-controlled interfaces achieved by μCP. Furthermore, we succeeded in fabricating OLEDs with multiple emitting layers. These results show that this technique is promising for application to cost-effective, high luminance and multicolored OLED displays.     

Modeling and numerical study of electrical characteristics of polymer light-emitting diodes containing an insulating buffer layer

In order to improve the electrical characteristic of polymer light-emitting diodes, a simple model for the device characteristic with an insulating buffer layer at cathode is proposed. This model is based on Fowleer-Nordhein tunneling mechanism and Poission's equation. An additional tunneling factor which characterises the tunneling effect of buffer layer is introduced. The simulated current-voltage characteristic indicates how an insulating buffer layer with suitable thickness decreases the barrier height at the cathode and therefore increases the electron injection. The model is validated by experimental results of devices with BaO as the buffer material and poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylenevinylene] as the emission material. An optimum thickness of the buffer layer is also obtained from the model, which provides a guide to device design.     

Enhanced performance of organic light-emitting diodes by inserting wide-energy-gap interlayer between hole-transport layer and light-emitting layer

We demonstrated that driving voltages, external quantum efficiencies, and power conversion efficiencies of organic light-emitting diodes (OLEDs) are improved by inserting a wide-energy-gap interlayer of (4,4′-N,N′-dicarbazole)biphenyl (CBP) between a hole-transport layer of N,N-di(naphthalen-1-yl)-N,N′-diphenyl-benzidine (α-NPD) and a light-emitting layer of tris(8-hydroxyquinoline)aluminum. By optimization of CBP thicknesses, the device with a 3-nm-thick CBP layer had the lowest driving voltage and the highest power conversion efficiency among the OLEDs. We attributed these improvements to enhancement of a carrier recombination efficiency and suppression of exciton–polaron annihilation. Moreover, we found that the degradation of the OLEDs is caused by decomposition of CBP molecules and excited-state α-NPD molecules.     

Top emission organic light-emitting devices with CsCl capping layer

We have developed top emission organic light-emitting devices using a CsCl capping layer on top of semitransparent Ca/Ag cathode. By using a CsCl capping layer, the transmittance of top electrode can be improved by 93%. While the electrical conduction characteristic of device is not influenced by the capping layer, the current efficiency increases with increasing the transmittance of Ca/Ag/CsCl cathode. For example, as the transmittance of top electrode increases from 55 to 91% by varying CsCl thickness, the current efficiency of green fluorescent top-emitting device increases from 8 to 18 cd/A.     

Synthesis and properties of solution-processible oligomers for the use of organic light-emitting diodes (OLEDs)

Two oligomers with X-shaped repeating units bearing anthracene and fluorene units were synthesized in a facile procedure, and exhibited high photoluminescence efficiencies, thermal stabilities and good solubility. Their ease of processing enabled spin coating with an electron-transporting bitriazine layer to afford organic light-emitting diodes which displayed a light blue emission with the maximum luminance of 3650 cd/m² and the current efficiency of 0.69 cd/A at an operation voltage of 10 V.     

Organic light-emitting devices with a mixed layer acting as a hole transport and as an emitting/electron transport layer

The electrical and the optical properties of organic light-emitting devices (OLEDs) with a mixed layer acting as a hole transport layer and as an emitting layer/electron transport layer were investigated. The OLEDs with a mixed layer showed the highest efficiency, and the emitting color of the OLEDs was pure yellow. The enhancement of the luminous efficiency in the OLEDs with a mixed layer was attributed to a decrease in hole mobility.     

Efficient red electrophosphorescent organic light-emitting diodes based on the new sensitized heteroleptic tris-cyclometalated Ir(III) complexes

Organic light-emitting device (OLED) was fabricated using the novel red phosphorescent heteroleptic tris-cyclometalated iridium complex, bis(2-phenylpyridine)iridium(III)[2(5′-methylphenyl)-4-diphenylquinoline] [Ir(ppy)₂(dpq-5CH₃)], based on 2-phenylpyridine (ppy) and 2(5′-methylphenyl)-4-diphenylquinoline (dpq-5CH₃) ligand. Generally, the ppy ligand in heteroleptic iridium complexes plays an important role as “sensitizer” in the efficient energy transfer from the host (CBP; 4,4,N,N′-dicarbazolebiphenyl) to the luminescent ligand (dpq-5CH₃). We demonstrated that high efficiency through the “sensitizer” can be obtained, when the T₁ of the emitting ligand is close to T₁ of the sensitizing ligand. The device containing Ir(ppy)₂(dpq-5CH₃) produced red light emission of 614 nm with maximum luminescence efficiency and power efficiency of 8.29 cd/A (at 0.09 mA/cm²) and 5.79 lm/W (at 0.09 mA/cm²), respectively.     

Efficient blue-green organic light-emitting diodes based on heteroleptic tris-cyclometalated iridium(III) complexes

The blue-green organic light-emitting diodes based on heteroleptic tris-cyclometalated iridium(III) complexes containing the F₂-ppy (2,4-difluorophenylpyridine) and ppy (2-phenylpyridine) ligands were fabricated. Ir(ppy)₃ has been known to have a high phosphorescence efficiency in electroluminescence owing to its strong metal-to-ligand-charge transfer (MLCT) excited state, whereas the luminous efficiency of Ir(F₂-ppy)₃ was found to be low due to weak MLCT. Herein, we report two heteroleptic phosphorescent blue-green emitters, Ir(ppy)₂(F₂-ppy) and Ir(ppy)(F₂-ppy)₂, that exhibit emission peaks at 502 nm and 495 nm, respectively. The maximum luminous efficiencies of the devices with Ir(ppy)₂(F₂-ppy) and Ir(ppy)(F₂-ppy)₂ were 8.93 cd/A and 13.80 cd/A, respectively. The quantum efficiency of the device containing Ir(ppy)(F₂-ppy)₂ was 3.63% at J = 10 mA/cm².     

Electron injection mechanisms of green organic light-emitting devices fabricated utilizing a double electron injection layer consisting of cesium carbonate and fullerene

Electron injection mechanisms of the luminance efficiency of green organic light-emitting devices (OLEDs) fabricated utilizing a cesium carbonate (Cs₂CO₃)/fullerene (C₆₀) heterostructure acting as an electron injection layer (EIL) were investigated. Current density-voltage and luminance-voltage measurements showed that the current densities and the luminances of the OLEDs with a Cs₂CO₃ or Cs₂CO₃/C₆₀ EIL were higher than that of the OLEDs with a Liq EIL. The luminance efficiency of the OLEDs with a Cs₂CO₃ EIL was almost three times higher than that of the OLEDs with a Liq EIL. Because the electron injection efficiency of the Cs₂CO₃ layer in OLEDs was different from that of the C₆₀ layer, the luminance efficiency of the OLEDs with a double EIL consisting of a Cs₂CO₃ layer and a C₆₀ layer was smaller than that of the OLEDs with a Cs₂CO₃ EIL. The electron injection mechanisms of OLEDs with a Cs₂CO₃ and C₆₀ double EIL are described on the basis of the experimental results.