Effects of surface treatment of ITO anode layer patterned with shadow mask technology on characteristics of organic light-emitting diodes

We investigated the effects of various surface treatments of indium tin oxide (ITO) on the electrical and optical characteristics of organic light-emitting diodes (OLEDs). A 150-nm-thick ITO anode layer was patterned directly with a shadow mask during the sputtering process without the use of a conventional photolithography patterning method. The sputtered ITO layer was subjected to thermal and oxygen plasma treatments to reduce the sheet resistance and improve surface roughness. The thermal treatment was performed for 1 h at temperatures of 250 and 380 °C, which were chosen so that the glass substrates would not deform from thermal damage. The measured sheet resistance decreased from 30.86 Ω/sq for the as-sputtered samples to 8.76 Ω/sq for the samples thermally treated at 380 °C for 1 h followed by oxygen plasma treatment. The root-mean-square surface roughness measured by atomic force microscopy considerably decreased to 3.88 nm with oxygen plasma treatment. The thermal treatment considerably decreased the sheet resistance of the ITO anode layer patterned with the shadow mask. The spike-like structures that are often formed and observed in shadow mask-patterned ITO anode layers were almost all removed by the oxygen plasma treatment. Therefore, a smooth surface for shadow mask-patterned ITO layers with low sheet resistance can be obtained by combining thermal and oxygen plasma treatments. A smooth surface and low sheet resistance improves the electrical and optical characteristics of OLEDs. The surface-treated ITO layer was used to fabricate and characterize green phosphorescent OLED devices. The typical characteristics of OLED devices based on surface-treated shadow mask-patterned ITO layers were compared with those fabricated on untreated and photolithography-patterned ITO layers to investigate the surface treatment effects. The OLED devices fabricated by thermal treatment at 380 °C for 1 h followed by oxygen plasma treatment for 180 s showed the highest luminance and current density. Furthermore, the leakage current that might be induced by the rough ITO surface was dramatically reduced to 0.112 mA/cm². Our study showed that the shadow mask-patterned ITO anode layer treated by heat and plasma and having a low sheet resistance and surface roughness yielded excellent electrical and optical properties for OLEDs compared to those based on an untreated ITO layer. The fabricated OLED devices using the surface-treated shadow mask-patterned ITO layer exhibited comparable characteristics to those obtained from a conventional photolithography-patterned ITO anode.     

Improved property in organic light-emitting diode utilizing two Al/Alq3 layers

We reported on the fabrication of organic light-emitting devices (OLEDs) utilizing the two Al/Alq₃ layers and two electrodes. This novel green device with structure of Al(110 nm)/tris(8-hydroxyquinoline) aluminum (Alq₃)(65 nm)/Al(110 nm)/Alq₃(50 nm)/N,N′-dipheny1-N, N′-bis-(3-methy1phyeny1)-1, 1′-bipheny1-4, 4′-diamine (TPD)(60 nm)/ITO(60 nm)/Glass. TPD were used as holes transporting layer (HTL), and Alq₃ was used as electron transporting layer (ETL), at the same time, Alq₃ was also used as emitting layer (EL), Al and ITO were used as cathode and anode, respectively. The results showed that the device containing the two Al/Alq₃ layers and two electrodes had a higher brightness and electroluminescent efficiency than the device without this layer. At current density of 14 mA/cm², the brightness of the device with the two Al/Alq₃ layers reach 3693 cd/m², which is higher than the 2537 cd/m² of the Al/Alq₃/TPD:Alq₃/ITO/Glass device and the 1504.0 cd/m² of the Al/Alq₃/TPD/ITO/Glass. Turn-on voltage of the device with two Al/Alq₃ layers was 7 V, which is lower than the others.     

Bright green organic light-emitting devices having a composite electron transport layer

A bright green organic light-emitting device employing a co-deposited Al-Alq₃ layer has been fabricated. The device structure is glass/indium tin oxide (ITO)/ N, N′-diphenyl-N, N′- (3-methylphenyl)-1, 1′-biphenyl-4, 4′-diamine (TPD)/tris(8-quinolinolato) aluminum (Alq₃)/ Al-Alq₃/Al. In this device, Al-Alq₃ is used as electron transport layer (ETL). The device shows an operation voltage of 6.1 V at 20 mA/cm². At optimal condition, the brightness of a device at 20 mA/cm² is 2195 cd/m² achieved a luminance efficiency of 5.64lm/W. The result proves that the composite Al-Alq₃ layer is suitable for the ETL of organic light-emitting devices (OLEDs).     

Efficient nondoped organic light-emitting diodes with Cu complex emitter

In Cu^I complex based organic light emitting diodes (OLEDs) a host matrix is traditionally thought to be required to achieve high efficiency. Herein, it is found that the device ITO/MoO₃ (1 nm)/4,4′-N,N′-dicarbazole-biphenyl (CBP, 35 nm)/[Cu(μ-I)dppb]₂ (dppb = 1,2-bis[diphenylphosphino]benzene, 20 nm)/1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi, 65 nm)/LiF (1 nm)/Al (100 nm) with a vacuum thermal evaporated nondoped Cu^I complex emissive layer (EML) showed external quantum efficiency and current efficiency of 8.0% and 24.3 cd/A at a brightness of 100 cd/m², respectively, which are comparable to the maximum efficiencies reported in an optimized doped OLED with the same emitter, higher efficiency than the OLED with a [Cu(μ-I)dppb]₂:CBP EML, and much higher efficiencies than the nondoped OLED with a bis(2-phenylpyridine)(acetylacetonate)iridium [Ir(ppy)₂(acac)] EML. A series of reference films and single carrier devices were fabricated and studied to understand the difference between Cu^I and Ir^III complex based nondoped OLEDs.     

Exciton formation and light emission near the organic–organic interface in small-molecule based double-layer OLEDs

We investigate the efficiency and emission color of small-molecule based double-layer organic light-emitting diodes (OLEDs) based on 4,4′-bis[1-naphthyl (phenyl) amino]-1,1′-biphenyl (α-NPD) and aluminum (III) bis (2-methyl-8-quinolinato)4-phenylphenolato (BAlq) by studying the charge transport and photophysics near the organic–organic interface between the emitting layers. For that purpose, the light-emission profile is reconstructed from full angle, wavelength and polarization dependent electroluminescence spectra. By increasing the thickness of the BAlq layer from 100 to 300 nm, at a fixed 160 nm α-NPD layer thickness, the emission color is found to vary from deep blue to green, yellow-green, white and back to blue. We demonstrate that this is due to a gradual emission profile shift, in combination with a wavelength and layer thickness dependent light outcoupling efficiency. The emission profile shift, from an approximately 20 nm-wide zone on the α-NPD-side of the interface to a very narrow zone on the BAlq-side of the interface, gives rise to a changing balance between the contributions from BAlq excitons, α-NPD excitons and charge-transfer excitons. It also contributes to a pronounced layer thickness dependence of the external quantum efficiency. The shift of the emission profile is explained by a charge transport and recombination model.     

Transparent Al/WO3/Au film as anode for high efficiency organic light-emitting diodes

A transparent Al/WO₃/Au anode is introduced to fabricate high efficiency organic light-emitting devices (OLEDs). By optimizing the thicknesses of each layers of the Al/WO₃/Au structure, the transmittance of Al(7 nm)/WO₃(3 nm)/Au(13 nm) has reached over 55%. Concerning the performance of OLEDs using the optimized anode, the electroluminescence (EL) current efficiency and brightness are enhanced and the EL spectrum is greatly narrowed as compared to the OLEDs using indium-tin-oxide (ITO) as the anode. The results indicate that the metal/metal oxide/metal transparent electrode is a good structure for the anode of high performance OLEDs. In addition, Al/WO₃/Au can function as a composite transparent electrode for top-emitting OLEDs.     

Chemical degradation processes of highly stable red phosphorescent organic light emitting diodes

We investigate the chemical degradation processes of highly stable red organic light emitting diodes (OLEDs) based on the triplet emitter tris(1-phenylisoquinoline)iridium(III) by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF-MS). The analysis of LDI-TOF spectra, collected on OLEDs driven at different current densities, shows a direct correlation between the lifetime of the devices and the formation of the three different reaction products: a BPhen dimer, an adduct of BPhen dimer with cesium, and the complex [BAlq₂ + Al(Me-q)₂]⁺ as well. Additionally it was possible to identify another degradation product, whose chemical structure is related to the α-NPD molecule as well to the fluorine of the used p-dopant. This product is only observable in devices aged at very high current densities.     

The electroluminescent investigation of double layer Eu-complex organic electronic luminescence diodes

Double layer organic electronic luminescence diodes (OLEDs) based on europium(dibenzoylmethanato)₃monophenanthroline [Eu(DBM)₃bath], ITO/N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine (TPD)/Eu(DBM)₃bath/LiF/Al have been fabricated. With increasing the thickness of hole transporting layer, the maximum EL efficiency was increased, and the EL efficiency of 10 cd/A was achieved when the thickness of TPD layer was 80 nm; however, at high current density, the EL efficiency of all devices was decreased drastically. Besides, the evolution of EL emission spectra with increasing operating voltage was found, the mechanisms of the symmetry around the ion improved and the annihilation of excited state of Eu(DBM)₃bath were discussed in explaining this phenomenon.     

有机/聚合物异质结电致发光器件的光电性能

器件结构是影响有机发光器件(OLED)性能的重要因素之一.采用8-hydroxyquinoline-aluminum(AlQ)作为发光层(EML)和电子传输层(ETL),polyvinylcarbazole (PVK)作为空穴传输层(HTL),制备了具有有机小分子/聚合物异质结结构的OLED器件,通过其电压-电流-发光亮度(V-J-B)特性测试,研究了HTL的引入及其膜厚对器件性能的影响.实验结果表明,HTL的引入有效地改善了OLED的光电性能,同时HTL膜厚对器件性能具有显著影响,当HTL膜厚为20 nm时,所制备的OLED器件具有最小的驱动电压和启亮电压、最大的发光亮度和发光效率.

Abstract：

The device construction plays an important role in improving the optoelectronic performance of organic electroluminescence devices (OLEDs). Heterojunction OLEDs with a configuration of glass/ITO/PVK/AlQ/Mg/Al were fabricated by using 8-hydroxyquinoline-aluminum (AlQ) as the emission layer (EML) and electron transport layer (ETL) and polyvinylcarbazole (PVK) as the hole transport layer (HTL). The effect of the HTL thickness on the performance of OLEDs was investigated with respect to the driving voltage, turn-on voltage, electroluminescence brightness and efficiency of the devices. Experimental results demonstrate that the optical and electrical properies of OLEDs are closely related to the HTL thickness. The device fabricated with the HTL thickness of 20 nm possesses the best photoelectric properties such as the minimum driving voltage and turn-on voltage, and the maximum electroluminescence brightness and efficiency.     

Single walled carbon nanotube anodes based high performance organic light-emitting diodes with enhanced contrast ratio

Commercially-available single walled carbon nanotubes (SWCNTs) were used to fabricate SWCNT sheets for anodes of organic light-emitting diodes (OLEDs) by spray-coating process without any use of surfactant or acid treatment. A layer of DMSO doped PEDOT:PSS was spray-coated on the SWCNT sheets to not only lessen the surface roughness to an acceptable level, but also improve the conductivity by more than three orders of magnitude. For our SWCNT-based OLEDs of tris-(8-hydroxquinoline) aluminum (Alq₃) emission layers, a maximum luminance 4224 cd/m² and current efficiency 3.12 cd/A were achieved, which is close to the efficiency of ITO-based OLEDs. We further found out that our OLEDs based on the PEDOT:PSS covered SWCNT anodes tripled the contrast ratio of the conventional indium tin oxide (ITO) based OLEDs.     

LiF层对ITD/Alq~3/LiF∶Al器件性能的影响

分别制备了4种有机电致发光器件(OLEDs):ITO/Alq3/Al;ITO/Alq3/LiF(1.0nm):Al;ITO/Alq3/LiF(1.5nm)∶Al;ITO/Alq3/LiF∶(2.0nm)Al。研究了LiF的引入对金属电极与发光层界面的影响以及各种不同的界面态对器件发光性能的影响。研究结果表明:适当的LiF厚度的引入不仅可以改善器件的界面特性,而且可以提高器件的发光亮度及发光效率。     

无氧溅射方法制备OLED的ITO透明电极

采用氧化铟锡(ITO)合金材料作为靶材,通过射频磁控溅射制备ITO膜.将获得的ITO膜应用于结构为ITO/m-MTDATA(30 nm)/NPB(20 nm)/Alq3(50 nm)LiF(0.8 nm)/Al(100 nm)的有机电致发光器件(OLED),得到了最大亮度为11560 cd/m2(电压为25V)、最大效率为2.52 cd/A(电压为14 V)的结果.为了获得双面发光,制作了结构为ITO/m-MTDATA(30 nm)/NPB(20 nm)/Alq3(50 nm)LiF(0.8 nm)/Al(20 nm)/ITO(50 nm)的器件,其阳极出光的最大亮度为14460 cd/m2(电压为18V)、最大效率为2.16 cd/A(电压为12V),阴极出光的最大亮度为1 263 cd/m2(电压为19 V)、最大效率为0.26 cd/A(电压为16V).     

Stacked inverted top-emitting green electrophosphorescent organic light-emitting diodes on glass and flexible glass substrates

Stacked inverted top-emitting green electrophosphorescent organic light-emitting diodes (OLEDs) are demonstrated on glass and flexible glass substrates. A single-unit OLED is shown to have a current efficacy of 46.8 cd/A at a luminance of 1215 cd/m². When two of these OLEDs are stacked, the double-unit OLED exhibits a current efficacy more than twice that of the single-unit OLED, with a current efficacy of 97.8 cd/A at a luminance of 1119 cd/m². With the addition of an optical outcoupling layer of N,N′-Di-[(1-naphthyl)-N,N′-diphenyl]-1,1′-biphenyl)-4,4′-diamine (α-NPD) on top of the semitransparent gold anode, the double-unit stacked OLED achieves a maximum current efficacy of 205 cd/A at a luminance of 103 cd/m², maintaining a high current efficacy of 200 cd/A at a luminance of 1011 cd/m². These stacked inverted OLED combine the advantages of inverted OLEDs with the benefits of having a stacked architecture.     

Designing a solution-processable electron transport layer for transparent organic light-emitting diode

In this work, the extensively used opaque metal cathodes of the conventionally structured OLEDs were replaced with the widely used transparent electrode indium tin oxide (ITO) for solution-processed transparent organic light-emitting diode (T-OLED). A new solution-processable electron transport layer (ETL), aside from facilitating the efficient injection of electrons into the T-OLED, protected the organic emission layer (EML) of the T-OLED against the plasma damage during top ITO cathode sputter deposition. The newly designed solution-processed ETL was the composite of the zinc oxide nanoparticles (ZnO-NPs), and cesium carbonate-doped ethoxylated polyethyleneimine (d-PEIE) with the semi-hydrophilic poly (methyl methacrylate) (PMMA) interlayer coated on the EML insured the good wettability and contact of the hydrophilic ETL with the hydrophobic EML. The solution-processed T-OLED emitted the total maximum luminance of about 2417 cd/m² (bottom side emission at 1455 cd/m² and top emission at 962 cd/m²), total maximum current efficiency at 3.12 cd/A (bottom and top emissions at about 1.78 and 1.34 cd/A, respectively), and total maximum power efficiency at 1.64 l m/W (bottom and top emissions at about 0.95 and 0.69 l m/W, respectively) while having a very high optical transmittance of around 85% at 550 nm light wavelength.     

用ZnS薄膜作为空穴缓冲层的高效率有机发光二极管

用磁控溅射方法制备的ZnS薄膜作为有机发光器件(OLEDs)的空穴缓冲层,使典型结构的 OLEDs(ITO/TPD/Alq/LiF/Al) 的发光性能得到改善.ZnS 缓冲层厚度对器件性能影响的实验结果表明,当ZnS缓冲层厚度为 5 nm 时,器件的亮度增加了2倍多;当ZnS缓冲层厚度为5、10 nm时,器件的发光电流效率增加40%.研究结果表明 ZnS 薄膜是一种好的缓冲层材料,它能够提高器件的发光效率,改善器件的稳定性.     

Bismuth Trifluoride as a low-temperature-evaporable insulating dopant for efficient and stable organic light-emitting diodes

Bismuth Trifluoride (BiF₃), with a high thermal stability and a low deposition temperature, has been studied as a novel dopant for the conventional hole transporting material of N,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB). The efficiency and lifetime of organic light-emitting diodes (OLEDs) have been remarkably improved by using BiF₃ doped NPB. For an optimized green device, a current efficiency of 21.6 cd/A is reached, 40% higher than the control device without BiF₃. And the lifetime is increased from 115 h to 222 h at room temperature. The enhanced efficiency and lifetime are attributed to the improved balance of holes and electrons in the emissive layer. Most importantly, the thermal stability at an elevated temperature of the OLEDs with BiF₃ doped NPB is largely improved, showing an order of magnitude longer lifetime than the control device at 80 °C.     

Silver grid transparent conducting electrodes for organic light emitting diodes

Polymer organic light emitting diodes (OLEDs) were fabricated using thin silver hexagonal grids replacing indium tin oxide (ITO) as the transparent conducting electrodes (TCE). Previous literature has assumed that thick metal grids (several hundred nanometres thick) with a lower sheet resistance (<10 Ω/□) and a similar light transmission (>80%) compared to thinner grids would lead to OLEDs with better performance than when thinner metal grid lines are used. This assumption is critically examined using OLEDs on various metal grids with different thicknesses and studying their performances. The experimental results show that a 20 nm thick silver grid TCE resulted in more efficient OLEDs with higher luminance (10 cd/A and 1460 cd/m² at 6.5 V) than a 111 nm thick silver grid TCE (5 cd/A and 159 cd/m² at 6.5 V). Furthermore, the 20 nm thick silver grid OLED has a higher luminous efficiency than the ITO OLED (6 cd/A and 1540 cd/m² at 6.5 V) at low voltages. The data shows that thinner metal grid TCEs (about 20 nm) make the most efficient OLEDs, contrary to previous expectations.     

超微OLED的制备及其光电特性的研究

为了实现高亮度有机电致发光器件(OLED)及其尺寸的微型化,采用接触式光刻技术,通过真空热蒸镀制备了具有不同掩膜版结构的OLED。器件的结构为玻璃衬底/ITO/LiF/空穴传输层(HTL,NPD)/发光层(EML,0.5-0.6vol%Rubrene:Alq3)/电子传输层(ETL,Alq3)/阴极,其中LiF作为绝缘层。分别制得发光面积为45μm×2mm的微细器件和直径为44μm的微小器件。实验研究了其光电特性,结果表明,4.5μm×2.0mm微细器件的最大电流密度为7A/cm2,为44μm微小器件的最大电流密度为40A/cm2。     

Optoelectrical characteristics of organic light-emitting devices fabricated with different cathodes

Organic light-emitting devices (OLEDs) with various cathode structures were prepared on indium tin oxide (ITO) substrates by vacuum sublimation technique, and the effects of the device cathodes on the electroluminescence (EL) characteristics of OLEDs were studied in terms of the luminance, efficiency, driving voltage and threshold voltage. The results demonstrate that the optical and electrical performance of OLEDs depend on the properties of the devices' cathodes and the characteristics of the cathode–organic interface and the organic–organic interface. The optoelectrical performance of a device with composite cathodes is better than that of the devices with metal alloy and pure metal cathodes. The improvement in the device performance can be attributed to a more efficient electron injection at the cathode–organic interface, a better balanced hole and electron recombination in the light-emitting layer and fewer accumulated charges near the organic–organic interface.     

基于四取代铜酞菁的有机近红外电致磷光器件

制备了结构为ITO/NPB/TPBI:(4-tert)CuPc/BCP/Alq3/Al的近红外(NIR)有机电致发光器件(OLED),器件在室温下的发射峰位于1110nm附近,来源于(4-tert)CuPc分子的磷光发射,器件的最佳掺杂浓度为14wt%。制备了结构为ITO/NPB/TPBI:(4-tert)CuPc/DCJTB/BCP/Alq3/Al的器件,结果表明,DCJTB层的加入没有改变器件的NIR电致发光(EL)峰位置,而器件的NIR发光强度与没有DCJTB层的器件相比,提高了50%左右,这是由于DCJTB向(4-tert)CuPc进行了有效的能量传输。