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.     

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.     

Fabrication of high efficiency and color stable white organic light-emitting diodes by an alignment free mask patterning

Small molecule based white organic light-emitting diodes were fabricated by using an alignment free mask patterning method. A phosphorescent red/green emitting layer was patterned by a metal mask without any alignment and a blue phosphorescent emitting layer was commonly deposited on the patterned red/green emitting layer. A white emission could be obtained due to separate emission of red/green and blue emitting layers. A maximum current efficiency of 30.7 cd/A and a current efficiency of 26.0 cd/A at 1000 cd/m² were obtained with a color coordinate of (0.39, 0.45). In addition, there was little change of emission spectrum according to luminance because of balanced red/green and blue emissions.     

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。     

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.     

高效率磷光与荧光相结合的白色有机发光器件

制作了一种白色有机电致发光器件(WOLED)。将红光[Ir(piq)2(acac)]及绿光[Ir(ppy)3]磷光掺杂染料分别掺入到母体CBP中,在2种磷光发光层间插入蓝光材料DPVBi,引入电子传输能力强的BPhen作为电子注入层和空穴阻挡层,通过改变蓝光发光层的厚度,得到了高效率的WOLED,最大电流效率可达17.6cd/A,最大功率效率达13.7lm/W,最大亮度达27525cd/m2,当电压从4V变化到12V时,色坐标从(0.54,0.35)变化到(0.30,0.31),基本处于白光区。器件的特点在于DPVBi的存在阻挡了2种磷光材料间的能量转移,色度可以通过简单地调整DPVBi的厚度,避免使用稀有的蓝光磷光材料和与其相匹配的母体材料,同时又可以保持较高的发光效率。     

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。     

发光性能稳定的磷光与荧光复合型白光OLED

使用荧光染料TBPe和Ir(ppy)_2acac 、R-4B两种光染料,采用蓝/红绿双发光层的结构,并结合TPBi对空穴的有效限制作用 ,制备了结构为ITO/MoO₃(X nm)/ADN:(2%)TBPe(30 nm)/CBP:Ir(ppy)_2acac(14%):R-4B(2%)(5nm)/TPBi(10 nm)/Alq₃(30nm)/LiF(1nm )/Al(100nm)的磷光与荧光复合的白光OLED,其中,MoO₃的厚 分别为0、15、20、30和40nm,通过改变MoO₃的厚度调控载流子的注入能力,使用空穴阻挡层提高光效; 通过测量其电压、电流、亮度、色坐标和电致发光(EL)光谱等参数,研究不同厚度的MoO ₃对器件发光性能的影响。结果表明,在MoO₃厚为20nm的情况下,器件的效率滚降 最为平缓。在电压分别 为8、9、10、11、12和13V时,器件的色坐标分别为 (0.31,0.33)、(0.30,0.33)、(0.29,0.33)、(0.29,0.33)、(0.29,0.33)和(0.29, 0.33),具有较高的稳定性,原因为采用 蓝/红绿双发光层结构更有利于蓝光的 出射,且使用ADN主体材料掺杂蓝色荧光染料TBPe作为蓝光发光层降低三重态-三重态 湮灭几率。 研究还发现,在电压为11V、器件的亮度为9744cd/m²和电流密度为11.50mA/cm²时,最大器件的电流效率为 7.0cd/A。     

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.     

以Liq∶Rubrene为发光层的白色有机电致发光器件的研制

以蓝色发光材料Liq为主体,以一定的比例掺入黄光染料Rubrene,研制了新型白色有机电致发光器件.调节Rubrene的掺杂比为1.1%时得到近白光器件,色坐标为(0.308,0.347),器件的启亮电压为8V,当外加电压达到25V时,器件发光亮度达3120cd/m2.     

Realizing improved performance of down-conversion white organic light-emitting diodes by localized surface plasmon resonance effect of Ag nanoparticles

Down-conversion structure white organic light-emitting diodes (WOLEDs), in which white light is generated by a blue emission organic light-emitting diodes (OLEDs) in combination with a color conversion layer (CCL) outside the substrate, has attracted extensive interest due to its significant advantages in low cost and stabilized white-light emissions. However, low color-conversion efficiency of CCL is still a bottleneck for the performance improvement of down-conversion WOLEDs. Here, we demonstrate an approach to enhance the color-conversion efficiency of CCL-WOLEDs by localized surface plasmon resonance (LSPR) effect. In this approach, a blend of Ag nanoparticles and polyvinyl alcohol (PVA) is solution-deposited between the blue organic light emitting diodes and color-conversion layer. Based on the LSPR effect of this modified structure, the color conversion efficiency has improved 32%, from 45.4% to 60%, resulting a 14.4% enhancement of the current efficiency, from 9.73 cd/A to 11.14 cd/A. Our work provides a simple and low-cost way to enhance the performance of down-conversion WOLEDs, which highlights its potential in illumination applications.     

白光有机电致发光器件发光稳定性研究

基于红绿/蓝双发光层,制作了结构为ITO/MoO ₃(10nm)/NPB(40nm)/TCTA(10nm)/CBP:R-4B(2%):GIR1(14%,X nm)/mCP:Firpic(8%,Y nm/BCP(10nm)/Alq₃(40nm)/LiF(1nm)/Al( 100nm)的白色全磷光有机电致发光器件(OLED),通过 调节红绿发光层的厚度X与蓝光发光层的厚度Y,研究了不同发光层厚度器件发 光性能的影响。研究发现:当X 为23nm、Y为7nm时,器件的光效和色坐标都具有 很高的稳定性,在电压分别为5、 10和15V时,色坐标分别为(0.33,0.37)、(0.33,0. 37)和(0.34,0.38);在电压为 5V时,电流密度为0.674mA,亮度为158.7cd ,最大电流效率为26.87cd/A;利用电子阻 挡材料TCTA和空穴阻挡材料BCP能够显著提高载流子的复合效率。分析认为:发光层顺序 为红绿/蓝时,更有利于蓝光的出射,从而使白光的色坐标更稳定。     

一种新的多发光层白色有机电致发光器件

采用多发光层结构,将一种新型的黄橙色荧光染料2-溴-4-氟苯乙烯-8-羟基喹啉锌(BFHQZn,(E)-2-(2-bronw-4-fluorostyryl)quinolato-Zinc)与蓝色9,10-二-2-蔡蔥(ADN)组合在一起实现白光.研究了插入4,4-N,N-二咔唑联苯(CBP)对器件色度的影响,通过改变发光...     

Organic light emitting devices employing non-doped structure

11H(1)-benzopyropyrano(6,7-8-i,j)quinolizin-11-one (C545T) with different thicknesses of 0.05 nm, 0.10 nm and 0.20 nm. For comparing, a doped WOLED was also fabricated, in which C545T and DCM2 are codoped into DPVBi layer to provide blue, green and red emission for obtaining white emission. The maximum luminance and power efficiency of the doped WOLED are 5 765 cd/m2 at 16 V and 5.23 lm/W at 5 V, respectively, and its Commission Internationale de l’Eclairage (CIE) coordinate changes from (0.393 7, 0.445 3) at 5 V to (0.300 7, 0.373 8) at 12 V. When the thickness of the ultrathin C545T layer in non-doped WLEDs increases, the emission luminance increases, but all non-doped devices are in the yellow white region. The device with 0.10-nm-thick C545T has a maximum efficiency of 15.23 cd/A at 8 V and a maximum power efficiency of 6.51 lm/W at 7 V, and its maximum luminance is 10 620 cd/m2 at 16 V. CIE coordinates of non-doped WLEDs with C545T thickness of 0.05 nm, 0.10 nm and 0.20 nm are (0.447 3, 0.455 6), (0.464 0, 0.473 1) and (0.458 4, 0.470 0) at 8 V, respectively. This work has been supported by the Major Project of Science and Technology Office of Fujian Province of China (No.2014H0042), the Natural Science Foundation of Fujian Province of China (No.2015J01664), the Project of Science and Technology Research of Quanzhou in Fujian Province of China (Nos.2013Z125 and 2014Z137), and the 2016 Annual National or Ministries of the Quanzhou Normal University Prepare Research Foundation Project (No.2016YYKJ21).E-mail:lishuangw@126.com      

Binaphthyl‐Containing Green‐ and Red‐Emitting Molecules for Solution‐Processable Organic Light‐Emitting Diodes

Strong intermolecular interactions usually result in decreases in solubility and fluorescence efficiency of organic molecules. Therefore, amorphous materials are highly pursued when designing solution‐processable, electroluminescent organic molecules. In this paper, a non‐planar binaphthyl moiety is presented as a way of reducing intermolecular interactions and four binaphthyl‐containing molecules ( BNCM s): green‐emitting BBB and TBT as well as red‐emitting BTBTB and TBBBT , are designed and synthesized. The photophysical and electrochemical properties of the molecules are systematically investigated and it is found that TBT , TBBBT , and BTBTB solutions show high photoluminescence (PL) quantum efficiencies of 0.41, 0.54, and 0.48, respectively. Based on the good solubility and amorphous film‐forming ability of the synthesized BNCM s, double‐layer structured organic light‐emitting diodes (OLEDs) with BNCM s as emitting layer and poly(N‐vinylcarbazole) (PVK) or a blend of poly[N,N′‐bis(4‐butylphenyl)‐N,N′‐bis(phenyl)benzidine] and PVK as hole‐transporting layer are fabricated by a simple solution spin‐coating procedure. Amongst those, the BTBTB based OLED, for example, reaches a high maximum luminance of 8315 cd · m⁻² and a maximum luminous efficiency of 1.95 cd · A⁻¹ at a low turn‐on voltage of 2.2 V. This is one of the best performances of a spin‐coated OLED reported so far. In addition, by doping the green and red BNCM s into a blue‐emitting host material poly(9,9‐dioctylfluorene‐2,7‐diyl) high performance white light‐emitting diodes with pure white light emission and a maximum luminance of 4000 cd · m⁻² are realized.     

Novel Blue Bipolar Thermally Activated Delayed Fluorescence Material as Host Emitter for High‐Efficiency Hybrid Warm‐White OLEDs with Stable High Color‐Rendering Index

A novel thermally activated delayed fluorescence (TADF) molecule, PHCz2BP, is synthesized and used to construct high performance organic light‐emitting diodes (OLEDs) in this work. PHCz2BP is not only the neat emitting layer for efficient sky‐blue OLED, with very high peak external quantum efficiency/power efficiency (EQE/PE) values of 4.0%/6.9 lm W^?1, but also acts as a host to sensitize high‐luminance and high‐efficiency green, orange, and red electrophosphorescence with the universal high EQEs of >20%. More importantly, two hybrid white OLEDs based on the double‐layer emitting system of PHCz2BP:green phosphor/PHCz2BP:red phosphor are achieved. To the best of the knowledge, this is the first report for three‐color (blue–green–red) white devices that adopt a TADF blue host emitter and two phosphorescent dopants without any other additional host. Such simple emitting systems thus realized the best electroluminescent performance to date for the WOLEDs utilizing the hybrid TADF/phosphor strategy: forward‐viewing EQEs of 25.1/23.6% and PEs of 24.1/22.5 lm W^?1 at the luminance of 1000 cd m^?2 with the color rendering indexes of 85/87 and warm‐white Commission Internationale de L'Eclairage coordinates of (0.41, 0.46)/(0.42, 0.45), indicating its potential to be used as practical eye‐friendly solid‐state lighting in future.     

Highly Efficient and Fully Solution‐Processed White Electroluminescence Based on Fluorescent Small Molecules and a Polar Conjugated Polymer as the Electron‐Injection Material

Highly efficient and fully solution‐processed white organic light‐emitting diodes (WOLEDs) based on fluorescent small molecules and a polar conjugated polymer as electron‐injection material are reported. The emitting layer in the WOLEDs is a blend of new blue‐, green‐, and red‐fluorescent small molecules, with a blending ratio of 100:0.4:0.8 (B/G/R) by weight, and a methanol/water soluble conjugated polymerpoly[(9,9‐bis(30‐(N,N‐dimethylamino)propyl)‐2,7‐fluorene)‐alt‐2,7‐(9,9‐dioctylfluorene)] (PFN) acts as the electron‐injection layer (EIL). All the organic layers are spin‐coated from solution. The device exhibits pure white emission with a maximum luminous efficiency of 9.2 cd A^?1 and Commission Internationale d'Eclairage Coordinates of (0.35, 0.36). PFN acting as the EIL material plays a key role in the improvement of the device performance when used in solution‐processed small‐molecule WOLEDs.     

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.     

m‐Indolocarbazole Derivative as a Universal Host Material for RGB and White Phosphorescent OLEDs

The host materials designed for highly efficient white phosphorescent organic light‐emitting diodes (PhOLEDs) with power efficiency (PE) >50 lm W^‐1 and low efficiency roll‐off are very rare. In this work, three new indolocarbazole‐based materials (ICDP, 4ICPPy, and 4ICDPy) are presented composed of 6,7‐dimethylindolo[3,2‐a]carbazole and phenyl or 4‐pyridyl group for hosting blue, green, and red phosphors. Among this three host materials, 4ICDPy‐based devices reveal the best electroluminescent performance with maximum external quantum efficiencies (EQEs) of 22.1%, 27.0%, and 25.3% for blue (FIrpic), green (fac‐Ir(ppy)₃), and red ((piq)₂Ir(acac)) PhOLEDs. A two‐color and single‐emitting‐layer white organic light‐emitting diode hosted by 4ICDPy with FIrpic and Ir(pq)₃ as dopants achieves high EQE of 20.3% and PE of 50.9 lm W^?1 with good color stability; this performance is among the best for a single‐emitting‐layer white PhOLEDs. All 4ICDPy‐based devices show low efficiency roll‐off probably due to the excellent balanced carrier transport arisen from the bipolar character of 4ICDPy.     

Organic Light‐Emitting Diodes with a White‐Emitting Molecule: Emission Mechanism and Device Characteristics

The unique and unprecedented electroluminescence behavior of the white‐emitting molecule 3‐(1‐(4‐(4‐(2‐(2‐hydroxyphenyl)‐4,5‐diphenyl‐1H‐imidazol‐1‐yl)phenoxy)phenyl)‐4,5‐diphenyl‐1H‐imidazol‐2‐yl)naphthalen‐2‐ol (W1), fluorescence emission from which is controlled by the excited‐state intramolecular proton transfer (ESIPT) is investigated. W1 is composed of covalently linked blue‐ and yellow‐color emitting ESIPT moieties between which energy transfer is entirely frustrated. It is demonstrated that different emission colors (blue, yellow, and white) can be generated from the identical emitter W1 in organic light‐emitting diode (OLED) devices. Charge trapping mechanism is proposed to explain such a unique color‐tuned emission from W1. Finally, the device structure to create a color‐stable, color reproducible, and simple‐structured white organic light‐emitting diode (WOLED) using W1 is investigated. The maximum luminance efficiency, power efficiency, and luminance of the WOLED were 3.10 cd A^?1, 2.20 lm W^?1, 1 092 cd m^?2, respectively. The WOLED shows white‐light emission with the Commission Internationale de l′Eclairage (CIE) chromaticity coordinates (0.343, 0.291) at a current level of 10 mA cm^?2. The emission color is high stability, with a change of the CIE chromaticity coordinates as small as (0.028, 0.028) when the current level is varied from 10 to 100 mA cm^?2.