The road to high efficiency organic light emitting devices

Advances leading to very high efficiency organic light emitting devices for use in flat panel displays and solid state illumination are described. The topics addressed in the Special Issue on High Efficiency Organic Light Emitting Devices are introduced.     

柔性有机电致发光器件的研究进展

柔性OLED技术尚未成熟,要实现产业化,其稳定性和显示效率仍有待进一步改善.本文从FOLED衬底材料的选取和处理、阳极材料的选取和设计、柔性器件的包封等方面,介绍了FOLED几项关键技术研究进展,并对其研究与应用前景进行了展望.     

Enhanced efficiency and brightness in organic light- emitting devices with MoO3 as hole-injection layer

The organic light-emitting devices (OLEDs) using 4,4’,4’’-tris{N-(3-methylphenyl)-N-phenylamin}triphenylamine (m-MTDATA) and MoO3 or 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-tetrachloride (TAPC) and MoO3 as the hole-injection layer (HIL) were fabricated. MoO3 can be expected to be a good injection layer material and thus enhance the emission performance of OLED. The highest occupied molecular (HOMO) of MoO3 is between those of m-MTDATA or TAPC and N,N’-bis-(1-naphthyl)-N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB), which reduces the hole-injection barrier and improves the luminance of the OLEDs. The current efficiency is improved compared with that of the device without the MoO3 layer. The highest luminous efficiency of the device with 2-nm-thick MoO3 as HIL is achieved as 5.27 cd/A at 10 V, which is nearly 1.2 times larger than that of the device without it. Moreover, the highest current efficiency and power efficiency of the device with the structure indium-tin oxide (ITO)/TAPC (40 nm)/MoO3 (2 nm)/TcTa:Ir(ppy)3 (10%, 10 nm)/ tris-(8-hydroxyquinoline) aluminium (Alq) (60 nm)/LiF (1 nm)/Al are achieved as 37.15 cd/A and 41.23 lm/W at 3.2 V and 2.8 V, respectively.     

Investigation of TDAPBs as hole‐transporting materials for organic light‐emitting devices (OLEDs)

The performance of organic light‐emitting devices (OLEDs) is strongly influenced by the electronic properties of the employed materials. In order to determine the effect of these materials' parameters, several different hole‐transporting 1,3,5‐tris(4‐diphenylaminophenyl)benzenes (TDAPBs) were synthesised. These TDAPBs contained different substituents, different numbers of substituents and different positions of theses substituents. For the evaluation of the electronic properties, cyclic voltammetry was employed in order to determine the HOMO values, and time‐of‐flight (TOF) measurements to obtain the hole mobilities. OLEDs were prepared consisting of the TDAPBs blended in a polymer matrix, and of Alq₃ as electron‐conducting and light‐emitting layer. These devices were investigated regarding their current density/voltage characteristics, efficiencies, onset voltages for electroluminescence, and lifetimes. For hole‐transporting blend systems an exponential relationship between the current density and the HOMO levels of the TDAPBs was found. However, even though the HOMO values cover a range from −5.09 to −5.35 eV, no effects on the performance of the OLEDs were detected for electroluminescent two‐layer systems. In this case the initial voltage seems to be a determining parameter for the behaviour of the devices during operation. Copyright © 1999 John Wiley & Sons, Ltd.     

High electron mobility triazine for lower driving voltage and higher efficiency organic light emitting devices

The triazine compound 4,4′-bis-[2-(4,6-diphenyl-1,3,5-triazinyl)]-1,1′-biphenyl (BTB) was developed for use as an electron transport material in organic light emitting devices (OLEDs). The material demonstrates an electron mobility of ∼7.2 × 10⁻⁴ cm² V⁻¹ s⁻¹ at a field of 8.00 × 10⁵ V cm⁻¹, which is 10-fold greater than that of the widely used material tris(8-hydroxyquinoline) aluminum (AlQ₃). OLEDs with a BTB electron transport layer showed a ∼1.7–2.5 V lower driving voltage and a significantly increased efficiency, compared to those with AlQ₃. These results suggest that BTB has a strong potential for use as an OLED electron transport layer material.     

Tunable chromaticity stability in solution-processed organic light emitting devices

Efficient solution-processed color-stable and color-tunable white organic light emitting diodes (OLEDs) have been realized by judicious selection of the host materials for the emission layers. The color-tunable OLED demonstrates the unique characteristic of modulating the electroluminescence by using the applied voltage of the device and displays color temperatures ranging from 1600 K to 4600 K around the daylight locus, with a peak external quantum efficiency of 13.6% and a peak current efficiency of 22.5 cd A⁻¹. On the other hand, the chromaticity-stable device shows a negligible color change, from 300 to 2000 nits. The manipulation of chromaticity is attributed to the energy transfer dynamics of the hosts and dopants under different electric fields.     

High efficiency warm white phosphorescent organic light emitting devices based on blue light emission from a bipolar mixed-host

In this study, we demonstrate a high-efficiency and low turn-on voltage warm white phosphorescent organic light emitting devices (PH-WOLEDs) based on a blue mixed-host emission layer (EML) and an orange ultrathin layer. The device has a simple structure and would simplify the fabrication process and reduce fabrication costs. The concept is based on the design a high-efficiency blue mixed-host EML, using an electron-transport material, 4,6-Bis(3,5-di(pyridin-4-yl) phenyl)-2-(3-(pyridin-3-yl) phenyl) pyrimidine (B4PYMPM) to enhance the carrier balance ability of the hole-transport material 1,3-Bis(carbazol-9-yl) benzene (MCP) which operates as the mixed-host and when the MCP: B4PYMPM ratio in the mixed-film was 4:1 got better effects. Based on the blue EML, we realized WOLEDs, characterized by a peak power efficiency of 71.3 lm/W at 3.1 V and a low turn-on voltage of 2.65 V. The mixed-host blue EML exhibited a much higher performance compared to the MCP host. Stable warm white light emission with Commission International de L'Eclairage (CIE) coordinates from (0.37, 0.45) to (0.38, 0.47) for a luminance value ranging from 1000 to 10,000 cd/m² was obtained.     

White organic light emitting devices with a color conversion layer

A white organic light emitting device (WOLED) combining the blue organic light emitting device with a red color conversion layer (CCL) is reported, which includes a fluorescent material N-(4-((E)-2-(6-((E)-4-(diphenylamino) styryl)naphtha len-2-yl)vinyl) phenyl)-N-phenylbenzenamine (N-BDAVBi) doped into 4,4′-N,N′-dicarbazole-biphenyl (CBP) as the blue light emitting layer, and the poly (2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylene vinylene (MEH-PPV) as a red CCL. By optimizing the concentration of MEH-PPV in the CCL, a good white light emission is obtained, which shows that the stable CIE coordinates of (0.33, 0.34) will have a slight change when the driving voltage is increased from 6 to 11 V. The maximum brightness and current efficiency of the optimized device are 11294 cd/m² and 6.4 cd/A, respectively.     

Determining emissive dipole orientation in organic light emitting devices by decay time measurement

We present a method to detect anisotropy in the distribution of the transition dipole moment in organic light emitting diodes (OLEDs). The method is based on the dependency of the exciton decay rate on the optical environment and the orientation of the dipole transition moment, also called the Purcell effect. We use this method to demonstrate a preferential orientation of the small molecule emitter Ir(MDQ)₂(acac) in a TPBi matrix. The outcoupling improvement for OLEDs that could be obtained with perfectly oriented transition dipoles is estimated by simulation. For perfectly planar structures this shows an EQE in air of up to 34%.     

Thermal buffer materials for enhancement of device performance of organic light emitting diodes fabricated by laser imaging process

Laser Induced Thermal Imaging (LITI) is a laser addressed thermal patterning technology with unique advantages such as an excellent uniformity of transfer film thickness, a capability of multilayer stack transfer and a possibility to fabricate high resolution as well as large-area display. Nevertheless, it has been an obstacle to use such a laser imaging process as a commercial technology so far because of serious deterioration of the device performances plausibly due to a re-orientation of the molecular stacking especially in the emitting layer during thermal transfer process. To improve device performances, we devised a new concept to suppress the thermal degradation during such kind of thermal imaging process by using a high molecular weight small molecular species with large steric hindrance as well as high thermostability as a thermal buffer layer to realize highly efficient LITI devices. As a result, we obtained very high relative efficiency (by EQE) up to 91.5% at 1000 cd/m² from the LITI devices when we utilize 10-(naphthalene-2-yl)-3-(phenanthren-9-yl)spiro[benzo[ij]tetraphene-7,9′-fluorene] as a thermal buffer material.     

具有凹凸界面结构的有机发光器件的性能研究

通过采用毫米尺度的凹凸界面结构实现了有机发光器件(Organic Light Emitting Device,OLED)发光效率的提高。在制备OLED器件过程中使用双狭缝模板,在发光层的界面处构建了高度为10nm的凸起,获得最大功率效率为23.9lm/W,最大电流效率为45.6cd/A,与传统的平直界面的OLED相比,分别提高了70%和36%。经过实验数据分析与理论模拟得出初步结论:OLED发光效率提高主要归因于金属界面处局域表面等离子体共振激发,提高了金属阴极界面的远场散射,从而提高OLED的出光效率;另外适当凹凸深度也改善了器件的电学性能。     

Multiple exciton generation regions in phosphorescent white organic light emitting devices

We demonstrate a white electrophosphorescent organic light emitting device (WOLED) with a three-section emission layer (EML) where excitons are formed in the multiple emission regions. The EML consists of a stepped progression of highest occupied and lowest unoccupied molecular orbital energies of the ambipolar hosts. Analysis shows that (36 ± 6)% of the excitons form in the blue emitting region, while (64 ± 6)% form in the green emitting region at 100 mA/cm². The doping of the red, green and blue phosphors, each in its own host, allows for efficient utilization of excitons formed in these multiple regions. Based on this architecture, the WOLED has an internal quantum efficiency close to unity. The WOLED has total external quantum and power efficiencies of η_ext,t = (26 ± 1)% and η_p,t = (63 ± 3) lm/W at 12 cd/m², decreasing to η_ext,t = (23 ± 1)% and η_p,t = (37 ± 2) lm/W at 500 cd/m². When an undoped electron transport layer is used, the peak efficiency is η_ext,t = (28 ± 1)%. Due to the distributed exciton formation in the EML, the WOLED exhibits higher total efficiency than monochromatic devices employing the same red, green and blue dopant–host combinations.     

Impact of temperature on the efficiency of organic light emitting diodes

Organic light emitting devices (OLEDs) are known to heat up when driven at high brightness levels required for lighting and bright display applications. This so called Joule heating can in the extreme case lead to a catastrophic failure (breakdown) of the device. In this work, we compare the effect of Joule heated and externally heated OLEDs by their electrical and optical response. A reduction in resistance is observed at elevated temperatures, both, for Joule heating, and for externally heated samples driven at low current density. In both cases, we attribute the change in resistance to a higher mobility of charge carriers at the elevated temperatures. Additionally, we observe a quenching of the emission efficiency in heated single layers as well as in OLEDs, treated with an external heat source as well as on Joule heated samples.     

Improved out-coupling efficiency of organic light emitting diodes by manipulation of optical cavity length

The relationship between thickness of electron transport layer (ETL) and device performance of organic light-emitting diodes (OLEDs) was investigated. Especially, we prepared various OLEDs by varying the thickness of ETL to investigate the difference of device performance. Very interestingly, the device efficiency of green phosphorescent organic light emitting diodes (PHOLEDs) was significantly improved when the thickness of ETL was optimized even though we did not change any materials for such devices except that we applied highly conductive Li doped ETL. This means that the only one factor which is associated with an improvement of device efficiency could be originated from the constructive optical interference. As a result, the simple modification of PHOLEDs only by changing the optical thickness condition causes a dramatic improvement of current efficiency (up to 82.4 cd/A) as well as external quantum efficiency (EQE, up to 23.8%), respectively. Those values correspond to the much more improved ones (by ∼34.4%) compared to those obtained from the normal devices with thin ETL as a reference.     

Enhancing the efficiency of simplified red phosphorescent organic light emitting diodes by exciton harvesting

High efficiency red phosphorescent organic light emitting diode (PHOLED) employing co-doped green emitting molecule bis(2-phenylpyridine)(acetylacetonate)iridium(III) [Ir(ppy)₂(acac)] and red emitting molecule bis(2-methyldibenzo[f,h]quinoxaline)(acetylacetonate)iridium(III) [Ir(MDQ)₂(acac)] into 4,4′-bis(carbazol-9-yl)biphenyl (CBP) host in a simplified wide-bandgap platform is demonstrated. The green molecule is shown to function as an exciton harvester that traps carriers to form excitons that are then efficiently transferred to the Ir(MDQ)₂(acac) by triplet-to-triplet Dexter energy transfer, thereby significantly enhancing red emission. In particular, a maximum current efficiency of 37.0 cd/A and external quantum efficiency (EQE) of 24.8% have been achieved without additional out-coupling enhancements. Moreover, a low efficiency roll-off with the EQE remaining as high as 20.8% at a high luminance of 5000 cd/m² is observed.     

基于无线指挥的有机电致发光器件的特性及实验

深入探究了多层有机电致发光器件的特性及优势。理论上分析了器件的电场与局域态的特性关系,设计了类似夹层式的两次堆叠双层有机层的实验结构,采用了电子传输材料Bphen来进行相关器件的制作。实验结果表明:叠层器件的开启电压几乎高出单层器件的开启电压值的一倍;叠层器件相比单层器件的电流效率高出1.5倍以上;叠层器件会产生微腔效应,设计内部连接层结构十分便捷有效。上述结果对于有机半导体器件的在无线指挥中的发展具有一定的理论和实践意义。     

以iridium磷光为红绿蓝染料的白光器件研究

以磷光染料iridium (III) bis [(4,6-di-fluoropheny)-pyridinato-N,C2′] picolinate(Flrpic)掺在4.4′-bis (9-carbazolyl)-2,2′-dimethyl-biphenyl(CDBP)中作为蓝光发光层,tris (2-Phenylpyridine) iridium(Irlppy)3和bis (1-phenyl-isoquinoline) acetylacetonate iridium (III)(Ir(piq)2)(acac)共掺在4,4′-N,N′-dicarbazole-biphenyl(CBP)中作为绿光和红光发光层,制备了高效白光器件.通过控制染料的浓度和发光层的厚度调节颜色,实现白光发射.器件的最大亮度为17 V时37 100 cd/m2,最大效率为5 V时7.37 lm/W.当亮度从1 000 cd/m2 到30 000 cd/m2色坐标由(0.41,0.42) 变到(0.37,0.39).     

High efficiency and non-color-changing orange organic light emitting diodes with red and green emitting layers

We report a high performance orange organic light-emitting diode (OLED) where red and green phosphorescent dyes are doped in an exciplex forming co-host as separate red and green emitting layers (EMLs). The OLED shows a maximum external quantum efficiency (EQE) of 22.8%, a low roll-off of efficiency with an EQE of 19.6% at 10,000 cd/m², and good orange color with a CIE coordinate of (0.442, 0.529) and no color change from 1000 to 10,000 cd/m². The exciplex forming co-host system distributes the recombination zone all over the EMLs and reduces the triplet exciton quenching processes.     

High contrast flexible organic light emitting diodes under ambient light without sacrificing luminous efficiency

We demonstrate a polarizer free high contrast ratio (CR) flexible top emitting organic light emitting diode (TOLED) using a periodic metal/dielectric anti-reflection (AR) cathode structure. The AR cathode was designed to have an asymmetric reflectance for the inward (low reflectance) and outward (high reflectance) directions of the OLED. The flexible AR-TOLED showed a sufficiently low luminous reflectance (6%), very high efficiency (86% of the TOLED without the AR structure), 1.75 times higher than the TOLED employing a circular polarizer, and extremely high durability upon repeated bending with a bending radius of 0.7 cm up to 10,000 times.     

Enhanced organic light emitting diode and solar cell performances using silver nano-clusters

Silver nano-clusters (NCs) were incorporated into organic light emitting diodes (OLED) and solar cells by means of thermal evaporation. Silver NCs enhance the efficiency of both OLEDs and polymer solar cells under tailored device architecture. In tris-(8-hydroxyquinoline) aluminum (Alq₃) based small molecule OLEDs, silver NCs were deposited under the Al cathode. The electron injection from the cathode to organic layer is promoted significantly owing to silver NCs induced lightning rod effect, the Alq₃ OLEDs luminous efficiency is increased up to a factor of 6. In poly(3-hexylthiophene) (P3HT) polymer solar cells, the active layer absorption is enhanced in the presence of silver NCs, which can be ascribed to NCs induced light scattering effect as well as to plasmon enhanced local electric field effect. As a result, photocurrent of the solar cells is increased and the power conversion efficiency (PCE) is improved up to 20%. The comparative study of surface plasmon effects in different organic optoelectronic devices reveals interesting features of the surface plasmon and allows optimization of optoelectronic devices from a novel point of view.