Realization of exceeding 80% external quantum efficiency in organic light-emitting diodes using high-index substrates and highly horizontal emitters

Although both high-index substrates and horizontal-dipole emitters have been shown to be facile approaches for enhancing OLED (organic light emitting diode) light extraction, the full benefits and potential of their combination for OLED optical out-coupling have not been thoroughly studied and explored. Simulation studies indicate that very high optical coupling efficiency into substrates ϕ_sub (and perhaps similarly high OLED external quantum efficiencies) of ~90% can be possibly obtained with both high-index substrates (refractive index >1.8–1.9) and highly horizontal-dipole emitters (horizontal dipole ratio >85%), together with adoption of low-index or index-matching carrier transport layers and optimization of organic layer and transparent electrode thicknesses. With these judicious device design conditions, all waveguided modes and surface plasmon modes in devices can be effectively suppressed for optimal optical out-coupling. Finally, combining the sapphire substrate having high index of n~1.78, the recently developed OLED emitters having high horizontal emitting dipole ratio of up to 87%, and simple external extraction lens, OLED devices having external quantum efficiency of over 80% was successfully realized.     

Efficient simplified orange and white phosphorescent organic light-emitting devices with reduced efficiency roll-off

Efficient orange phosphorescent organic light-emitting devices based on simplified structure with maximum efficiencies of 46.5 lm/W and 51.5 cd/A were reported. One device had extremely low efficiency roll-off with efficiencies of 50.6 cd/A, 45.0 cd/A and 39.2 cd/A at 1000 cd/m², 5000 cd/m² and 10,000 cd/m² respectively. The reduced efficiency roll-off was attributed to more balanced carrier injection and broader recombination zone. The designed simplified white device showed much lower efficiency roll-off than the control one based on multiple emitting layers. The efficiency of simplified white device was 40.8 cd/A at 1000 cd/m² with Commission Internationale de I’Eclairage coordinates of (0.39, 0.46).     

Cover Picture: White Electroluminescence from a Single‐Polymer System with Simultaneous Two‐Color Emission: Polyfluorene as the Blue Host and a 2,1,3‐Benzothiadiazole Derivative as the Orange Dopant (Adv. Funct. Mater. 7/2006)

New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized by Wang and co‐workers on p. 957. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue and orange emission from the corresponding emitting species. A single‐layer device has been fabricated that has performance characteristics roughly comparable to those of organic white‐light‐emitting diodes with multilayer device structures. New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue (λ_max = 421 nm/445 nm) and orange emission (λ_max = 564 nm) from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light‐emitting diodes (PLEDs) based on the single‐polymer systems has been investigated. The introduction of the highly efficient 4,7‐bis(4‐(N‐phenyl‐N‐(4‐methylphenyl)amino)phenyl)‐2,1,3‐benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single‐layer device fabricated in air (indium tin oxide/poly(3,4‐ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure‐white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m^–2, luminance efficiency of 7.30 cd A^–1, and power efficiency of 3.34 lm W^–1 can be obtained. This device is approximately two times more efficient than that utilizing a single polyfluorene containing 1,8‐naphthalimide moieties, and shows remarkable improvement over the corresponding blend systems in terms of efficiency and color stability. Thermal treatment of the single‐layer device before cathode deposition leads to the further improvement of the device performance, with CIE coordinates of (0.35,0.34), turn‐on voltage of 3.5 V, luminance efficiency of 8.99 cd A^–1, power efficiency of 5.75 lm W^–1, external quantum efficiency of 3.8 %, and maximum brightness of 12 680 cd m^–2. This performance is roughly comparable to that of white organic light‐emitting diodes (WOLEDs) with multilayer device structures and complicated fabrication processes.     

Efficient White OLEDs Employing Phosphorescent Sensitization

We have investigated white-emitting organic light-emitting devices (WOLEDs) making use of both blue-phosphor-sensitized orange-red fluorescence and the residual blue phosphorescence. By carefully adjusting the concentrations the phosphor and the fluorophore in the emitting layer and choosing the carrier-transport layers in the device structure, WOLEDs containing a single phosphor-sensitized emitting layer (type-I devices) can give colors close to the equal-energy white (0.33, 0.33), CRI up to 75, and efficiencies up to (10%, 23 cd/A, 13.4lm/W). Furthermore, by doping a green phosphor into the poorly emitting electron-transport layer (type-II devices) to recycle excitons formed there, the EL efficiencies can be further enhanced up to (12.1%, 35.3 cd/A, 23.9lm/W). In both types of devices, the phosphor sensitization reduces population of triplet excitons in the emitting region and substantially mitigates the efficiency roll-off with the driving current or brightness that is often observed in all-phosphor OLEDs. At the brightness of 1000 cd/m², both types of devices retain quantum and cadmium per ampere (cd/A) efficiencies similar to their peak values     

Highly efficient pure white phosphorescent organic light-emitting diodes using a deep blue phosphorescent emitting material

A high efficiency pure white phosphorescent organic light-emitting diode was developed by combining a deep blue emitting phosphorescent dopant material with red/green phosphorescent emitting materials. A simple stack structure of blue/red:green was used and tris((3,5-difluoro-4-cyanophenyl)pyridine) iridium was used as a deep blue emitting phosphorescent dopant. A pure white emission with a color coordinate of (0.29, 0.31) and a very high current efficiency of 28 cd/A was obtained after managing the device architecture of the all phosphorescent white devices.     

White Electroluminescence from a Single‐Polymer System with Simultaneous Two‐Color Emission: Polyfluorene as the Blue Host and a 2,1,3‐Benzothiadiazole Derivative as the Orange Dopant

New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue (λ_max = 421 nm/445 nm) and orange emission (λ_max = 564 nm) from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light‐emitting diodes (PLEDs) based on the single‐polymer systems has been investigated. The introduction of the highly efficient 4,7‐bis(4‐(N‐phenyl‐N‐(4‐methylphenyl)amino)phenyl)‐2,1,3‐benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single‐layer device fabricated in air (indium tin oxide/poly(3,4‐ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure‐white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m^–2, luminance efficiency of 7.30 cd A^–1, and power efficiency of 3.34 lm W^–1 can be obtained. This device is approximately two times more efficient than that utilizing a single polyfluorene containing 1,8‐naphthalimide moieties, and shows remarkable improvement over the corresponding blend systems in terms of efficiency and color stability. Thermal treatment of the single‐layer device before cathode deposition leads to the further improvement of the device performance, with CIE coordinates of (0.35,0.34), turn‐on voltage of 3.5 V, luminance efficiency of 8.99 cd A^–1, power efficiency of 5.75 lm W^–1, external quantum efficiency of 3.8 %, and maximum brightness of 12 680 cd m^–2. This performance is roughly comparable to that of white organic light‐emitting diodes (WOLEDs) with multilayer device structures and complicated fabrication processes.     

基于DOPPP的高效白光OLED器件

采用真空热蒸镀的方法,以荧光染料1-(2,5-d imethoxy-4-(1-pyrenyl)-phenyl)pyrene (DOPPP)为蓝发光 层,5,6,11,2-Tetraphenylnaphthacene (Rubrene)为黄发光层,制备了结构为ITO/m-M TDATA(10nm)/NPB(30nm)/ Rubrene (0.2nm)/ DOPPP (x nm)/TAZ(10nm)/Alq₃(30nm)/LiF(0.5nm)/Al的双发光层的高效白色有机电 致发光器件(OLED)。通过调整DOPPP层的厚度,研究器件的发光性能。当DOPPP层厚小 于25nm时,器件以 黄光发射为主;当DOPPP层厚为25nm时器件的性能最佳,在电流密度为209.18mA/cm²时,获得最 大亮度为9232cd/m²,在电流密度为103.712mA/cm²时获得最大电流效率4.68cd/A, 并随着驱动电压 的升高,器件的色坐标从(0.366,0.365)变化到(0.384,0.399),都在白光的范围之内;当DOPPP层厚度超过25nm时,器件的效率和亮度 都开始下降。     

Voltage independent white emission from all solution processed polymer light-emitting diode with dual emitting layers spaced by an alcohol soluble conjugated polymer as interlayer

Spatial control of recombination zone in multilayer white polymer light emitting diode (WPLED) is highly desirable for stable white-light emission. In this work, the utilization of 18-crown-6 (Cn6)-grafted polyfluorene (PFCn6) as an interlayer in between two emitting layers is demonstrated to control the recombination zones for the multilayer WPLED with β-phase and rubrene doped poly(9,9-di-n-octylfluorene) (PFO) as blue- and yellow-emitting layers, respectively. The device gives the maximum brightness of 15,695 cd/m² and maximum efficiency 5.43 cd/A, accompanying with voltage-independent electroluminescence spectrum having invariant Commission Internationale de L’Eclairage (CIE) coordinates of (0.32, 0.36). The performance with the luminance efficiency 5.43 cd/A and voltage independent white emission is the highest record among the reported multilayer WPLED.     

High-efficiency blue and white organic light-emitting devices by combining fluorescent and phosphorescent blue emitters

High-efficiency blue and white organic light-emitting devices (OLEDs) combined fluorescent and phosphorescent blue emitters were reported. The hybrid blue OLED showed better color purity than that of all phosphorescent device without sacrificing efficiency. The maximum power efficiency of the blue device could reach 23.5 lm/W with the CIE coordinates of (0.163, 0.325). High-efficiency white OLED with maximum power efficiency of 50.6 lm/W was obtained by combined such hybrid blue device and ultrathin phosphorescent yellow emitter. At the practical brightness of 1000 cd/m², the power efficiency of the white device was 28.3 lm/W with a low voltage of 3.37 V and CIE coordinates of (0.40, 0.44). The excitons recombination zone was adjusted by the introduction of the fluorescent blue emitter which resulting a relative high color rendering index and power efficiency of the white device.     

High efficiency phosphorescent white organic light-emitting diodes with an ultra-thin red and green co-doped layer and dual blue emitting layers

Phosphorescent white organic light emitting diodes (WOLEDs) with a multi-layer emissive structure comprising two separate blue layers and an ultra-thin red and green co-doped layer sandwiched in between have been studied. With proper host and dopant compositions and optimized layer thicknesses, high-performance WOLEDs having a power efficiency over 40 lm/W at 1000 cd/m² with a low efficiency roll-off have been produced. Through a systematic investigation of the exciton confinement and various pathways for energy transfer among the hosts and dopants, we have found that both the ultra-thin co-doped layer and two blue emitting layers play a vital role in achieving high device efficiency and controllable white emission.     

采用DCJTB作为色彩转换膜实现白色有机电致发光的研究

采用橙红色荧光材料4-(二氰基亚甲基)-2-叔丁基-6-(1,1,7,7-四甲基久罗尼定基-4-乙烯基)-4H-吡喃(DCJTB)作为色彩转换材料,结合蓝色有机电致发光器件实现了较好的白光发射。分别通过真空蒸镀和旋转涂覆两种不同的工艺进行色彩转换膜(CCL)的制备,发现不同的转换膜制备工艺对白光器件的性能影响不明显。当采用浓度比例为20mg/ml的DCJTB溶液通过旋涂方法制备CCL后,所得到白光器件的起亮电压为3.4V,在12V时达到最大亮度为1 939cd/m2,且该器件的最大电流效率为1.34cd/A(在电流密度为3.23mA/cm2时)。当驱动电压从5V增加到9V时,该白光器件的色坐标仅从(0.36,0.33)变化到(0.33,0.31)。表现出良好的色纯度和色稳定性。     

2-TNATA对蓝与黄二基色分离的堆叠式白色有机发光器件性能的影响(英文)

研究了2-TNATA厚度对蓝与黄二基色分离的堆叠式白色有机发光器件性能的影响。器件结构为:2-TNATA(xnm)/NPB(25nm)/ADN(30nm)∶TBPE(2%)∶DCJTB(1%)/Alq3(20nm)/LiF(1nm)/Al(100nm)。根据实验结果,2-TNATA的厚度对载流子的注入、色稳定性、热稳定性影响明显。发光器件的颜色可以通过改变加入的2-TNATA层的厚度来改变。这种器件使用2-TNATA作为空穴注入层显示出了色纯度高的白光发射,CIE色坐标x=0.3197,y=0.3496,亮度能够达到12230cd/m2。     

White LED based on polyfluorene Co-polymers blend on plastic substrate

We report on high-performance, white light emission from polyfluorene co-polymers blend and study of the opto-electrical properties of polymer blend light-emitting devices (PLEDs) fabricated on plastic substrate. Our results show that efficient white light emission via energy transfer, producing higher device efficiencies and luminance in comparison with the conventional single PLEDs, can be realized by blending carrier donor (host) and acceptor (guest) organic polyfluorene co-polymers. A maximum luminance of /spl sim/7400 cd/m/sup 2/ was achieved at 13 V with Internationale de L'Eclairage coordinates of (0.33, 0.33). Maximum emission efficiency of /spl sim/2.0 cd/A and power efficiency of /spl sim/1.1 lm/W are obtained for white light PLEDs on plastic substrate.     

Toward Highly Efficient Solid‐State White Light‐Emitting Electrochemical Cells: Blue‐Green to Red Emitting Cationic Iridium Complexes with Imidazole‐Type Ancillary Ligands

Using imidazole‐type ancillary ligands, a new class of cationic iridium complexes ( 1 – 6 ) is prepared, and photophysical and electrochemical studies and theoretical calculations are performed. Compared with the widely used bpy (2,2′‐bipyridine)‐type ancillary ligands, imidazole‐type ancillary ligands can be prepared and modified with ease, and are capable of blueshifting the emission spectra of cationic iridium complexes. By tuning the conjugation length of the ancillary ligands, blue‐green to red emitting cationic iridium complexes are obtained. Single‐layer light‐emitting electrochemical cells (LECs) based on cationic iridium complexes show blue‐green to red electroluminescence. High efficiencies of 8.4, 18.6, and 13.2 cd A^?1 are achieved for the blue‐green‐emitting, yellow‐emitting, and orange‐emitting devices, respectively. By doping the red‐emitting complex into the blue‐green LEC, white LECs are realized, which give warm‐white light with Commission Internationale de L'Eclairage (CIE) coordinates of (0.42, 0.44) and color‐rendering indexes (CRI) of up to 81. The peak external quantum efficiency, current efficiency, and power efficiency of the white LECs reach 5.2%, 11.2 cd A^?1, and 10 lm W^?1, respectively, which are the highest for white LECs reported so far, and indicate the great potential for the use of these cationic iridium complexes in white LECs.     

Blue top-emitting organic light-emitting devices using Alq3 as phase shift adjustment layer

Blue top-emitting organic light-emitting devices (TEOLEDs) are demonstrated by employing Alq3 as phase shift adjustment layer (PSAL) to increase the phase shift on reflection of the top electrode within a range, which also improves the light out-coupling. By adjusting the thickness of PSAL, the CIEx,y of devices, which utilize 2, 7-Di-pyrenyl-9, 9-spiro-bifluorene (DPSF) as emitting layer, changes from (0.16, 0.50) to (0.18, 0.37). The maximum current efficiency of 7.1 cd/A is acquired under 4.5 V with an increasing luminance of 139 cd/m2. Compared with adjusting the total thickness of organic layer, it is more beneficial for achieving blue TEOLEDs with high efficiency.     

Improved efficiency in fluorescent blue organic light emitting diode with a carrier confining structure

A blue organic light emitting device (OLED) with improved efficiency and good color purity is reported. The highest occupied molecular orbital (HOMO) level of the hole transport layer (HTL) and that of the emissive layer (EML) differs by 0.3 eV. This energy level mismatch confines the carriers at the HTL/EML interface. Conventional devices have only one HTL/EML interface, with a current efficiency of 2.9 cd/A. Without adding a separate hole blocking layer, incorporating multi-layers of the same HTL and EML increases this efficiency to 5.8 cd/A, with only a small increase in operating voltage yielding increased power efficiency also. But, there are an optimum number of layers, beyond which efficiency loss results. Also, including the multilayer structure simultaneously improves the blue color co-ordinates. To gain insight into the role of multilayer structures in modifying charge transport and recombination zone a simulator was developed. The simulated results could qualitatively explain the experimental observations.     

Charge‐Carrier Balance and Color Purity in Polyfluorene Polymer Blends for Blue Light‐Emitting Diodes

A study of an efficient blue light‐emitting diode based on a fluorescent aryl polyfluorene (aryl‐F8) homopolymer in an inverted device architecture is presented, with ZnO and MoO₃ as electron‐ and hole‐injecting electrodes, respectively. Charge‐carrier balance and color purity in these structures are achieved by incorporating poly(9,9‐dioctylfluorene‐co‐N‐(4‐butylphenyl)‐diphenylamine (TFB) into aryl‐F8. TFB is known to be a hole‐transporting material but it is found to act as a hole trap on mixing with aryl‐F8. Luminance efficiency of ≈6 cd A^?1 and external quantum efficiency (EQE) of 3.1% are obtained by adding a small amount (0.5% by weight) of TFB into aryl‐F8. Study of charge injection and transport in the single‐carrier devices shows that the addition of a small fraction of hole traps is necessary for charge‐carrier balance. Optical studies using UV–vis and fluorescence spectroscopic measurements, photoluminescence quantum yield, and fluorescence decay time measurements indicate that TFB does not affect the optical properties of the aryl‐F8, which is the emitting material in these devices. Luminance efficiency of up to ≈11 cd A^?1 and EQE values of 5.7% are achieved in these structures with the aid of improved out‐coupling using index‐matched hemispheres.     

Highly Efficient Greenish‐Yellow Phosphorescent Organic Light‐Emitting Diodes Based on Interzone Exciton Transfer

Phosphorescent organic light emitting diodes (PHOLEDs) have undergone tremendous growth over the past two decades. Indeed, they are already prevalent in the form of mobile displays, and are expected to be used in large‐area flat panels recently. To become a viable technology for next generation solid‐state light source however, PHOLEDs face the challenge of achieving concurrently a high color rendering index (CRI) and a high efficiency at high luminance. To improve the CRI of a standard three color white PHOLED, one can use a greenish‐yellow emitter to replace the green emitter such that the gap in emission wavelength between standard green and red emitters is eliminated. However, there are relatively few studies on greenish‐yellow emitters for PHOLEDs, and as a result, the performance of greenish‐yellow PHOLEDs is significantly inferior to those emitting in the three primary colors, which are driven strongly by the display industry. Herein, a newly synthesized greenish‐yellow emitter is synthesized and a novel device concept is introduced featuring interzone exciton transfer to considerably enhance the device efficiency. In particular, high external quantum efficiencies (current efficiencies) of 21.5% (77.4 cd/A) and 20.2% (72.8 cd/A) at a luminance of 1000 cd/m² and 5000 cd/m², respectively, have been achieved. These efficiencies are the highest reported to date for greenish‐yellow emitting PHOLEDs. A model for this unique design is also proposed. This design could potentially be applied to enhance the efficiency of even longer wavelength yellow and red emitters, thereby paving the way for a new avenue of tandem white PHOLEDs for solid‐state lighting.     

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.     

High‐Color‐Rendering and High‐Efficiency White Organic Light‐Emitting Devices Based on Double‐Doped Organic Single Crystals

Organic single crystals with much higher carrier mobility and stability compared to the amorphous organic materials have shown great potential in electronic and optoelectronic devices. However, their applications in white organic light‐emitting devices (WOLEDs), especially the three‐color‐strategy WOLEDs, have been hindered by the difficulties in fabricating complicated device structures. Here, double‐doped white‐emission organic single crystals are used as the active layers for the first time in the three‐color‐strategy WOLEDs by co‐doping the red and green dopants into blue host crystals. Precise control of the dopant concentration in the double‐doped crystals results in moderately partial energy transfer from the blue donor to the green and red dopants, and thereafter, simultaneous RGB emissions with balanced emission intensity. The highest color‐rendering index (CRI) and efficiency, to the best of the authors' knowledge, are obtained for the crystal‐based WOLEDs. The CRI of the WOLEDs varies between 80 and 89 with the increase of the driving current, and the luminance and current efficiency reach up to 793 cd m^?2 and 0.89 cd A^?1, respectively. The demonstration of the present three‐color organic single‐crystal‐based WOLED promotes the development of the single crystals in optoelectronics.