Efficiency Improvement in Polymer Light‐Emitting Diodes by “Far‐Field” Effect of Gold Nanoparticles

The “far‐field” effect of metal nanoparticles (NPs), when chromophores localized nearby metal NPs (typically the distance >λ/10), is an important optical effect to enhance emission in photoluminescence. The far‐field effect originates mainly from the interaction between origin emission and mirror‐reflected emission, resulting in the increased irradiative rate of chromophores on the mirror‐type substrate. Here, the far‐field effect is used to improve emission efficiency of polymer light‐emitting diodes (PLEDs). A universal performance improvement is achieved for the full visible light (red, green, blue) PLEDs, utilizing gold (Au) NPs to modify the indium tin oxide (ITO) substrates; this is shown by experimental and theoretical simulation to mainly come from the far‐field effect. The optimized distance, between the NPs and chromophores with visible light emission ranging from 400 to 700 nm, is 80–120 nm. Thus the scope of the far‐field may overlap the light‐emitting profile very well to enhance the efficiency of optoelectronic devices. The 30–40% enhancement is obtained for different color‐emitting materials through distance optimization. The far‐field effect is demonstrated to enhance device performance for materials in the full‐visible spectral range, which extends the optoelectric applications of Au NPs.     

白色有机发光器件及其稳定性

报道了一种稳定的白色有机薄膜电致发光器件.电流效率6cd/A,在电流密度20mA/cm²驱动下,亮度为1026cd/m²;最高亮度21200cd/m²,色度(x=0.32,y=0.40).该器件具有较平稳的效率电流关系,即具有弱的电流荧光猝灭.初始亮度100cd/m²下,半亮度寿命达22245h.     

高效率共轭聚合物主体绿光磷光发光二极管

因电致发光效率高和器件制备工艺简单,聚合物为主体的绿色磷光电致发光成为一个研究热点.共轭聚合物的三线态能级一般低于绿色磷光材料的三线态能级,易对磷光的发光引起猝灭导致低的发光效率,所以较少被用作绿色磷光材料的主体.通过增加聚乙烯基咔唑（PVK）作为空穴传输层,获得了高发光效率的共轭聚合物聚芴（PFO）作主体绿色磷光发射,甚至高于相同条件下以PVK为主体的绿色磷光发射.究其原因,PVK的电子阻挡作用使发光中心靠近PVK与PFO的界面,界面处PVK因为其高的三线态能级增强了绿色磷光的发光.当三-（2-苯基吡啶）-Ir（Ir（ppy）₃）掺杂浓度为2％时得到了最高的亮度效率24.8 cd/A,此时的电流密度为4.65 mA/cm²,功率效率为11 lm/W,最高亮度达到35054 cd/m²,色坐标是（0.39,0.56）. 关键词： 共轭聚合物 磷光 绿光发光     

ITO‐free top emitting organic light emitting diodes with enhanced light out‐coupling

Bottom emitting organic light emitting diodes (OLEDs) can suffer from lower external quantum efficiencies (EQE) due to inefficient out‐coupling of the generated light. Herein, it is demonstrated that the current efficiency and EQE of red, yellow, and blue fluorescent single layer polymer OLEDs is significantly enhanced when a MoO_x(5 nm)/Ag(10 nm)/MoO_x(40 nm) stack is used as the transparent anode in a top emitting OLED structure. A maximum current efficiency and EQE of 21.2 cd/A and 6.7%, respectively, was achieved for a yellow OLED, while a blue OLED achieved a maximum of 16.5 cd/A and 10.1%, respectively. The increase in light out‐coupling from the top‐emitting OLEDs led to increase in efficiency by a factor of up to 2.2 relative to the optimised bottom emitting devices, which is the best out‐coupling reported using solution processed polymers in a simple architecture and a significant step forward for their use in large area lighting and displays.     

基于新型空穴传输材料的有机电致发光器件的研究

利用真空蒸镀方法以N2,N7-二(间甲苯胺基)-N2,N7-二苯基-2,7-二胺基-9,9-二甲基芴[2,7-bis(pmethoxyphenyl-m'-tolylamino)9,9-dimethylfluorene,TPF-OMe]为空穴传输层、8-羟基喹啉铝[tris(8-hydroxyquinolinato)aluminum,Alq3)]作为发光层及电子传输层,制备了双层器件.与制作的典型双层结构N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺[N,N'-biphenyl-N,N'-bis-(3-methylphenyl)-1,1'-biphenyl-4,4'diamine,TPD/Alq3]器件相比,电流密度较大,发光效率低,发光谱峰为516 nm,色坐标为(0.30,0.53),为Alq3材料发光.以TPF-OMe为发光层兼空穴传输层,2,9-二甲基-4,7-二苯基-1,10-菲罗啉(2,9-dimethyl-4,7-diphenyl-l,10-phenanthroline,bathocuproine或BCP)为空穴阻挡层,Alq3为电子传输层,制作三层有机电致发光器件.结果表明,光谱峰值在414 nm,色坐标为(0.20,0.24),为蓝色光,是TPF-OMe材料本身发光,器件在15 V电压下电流密度为1137 mA/cm2,亮度为900 cd/m2,在3 V偏压下有最大流明效率,为0.11 lm/W.基于TPF-OMe材料的器件的击穿温度比基于TPD材料的器件高近20℃,原因可能在于TPF-OMe材料比TPD材料高19℃的玻璃化转变温度(Tg).     

Organic‐inorganic hybrids based on phenanthrene‐functionalized gold nanoparticles for OLEDs

The electroluminescence intensity of the phenanthrene‐functionalized gold nanoparticles, PMPT‐Au nanoparticles/CPB: Ir(PIA)₂ (acac) film, was increased by 4.9 times compared with control device, CPB: Ir(PIA)₂ (acac) due to coupling between the excitons of emissive layer and localized surface plasmonic resonance of PMPT‐Au NPs. The maximum luminous efficiencies of devices II to IV with PMPT‐Au NPs were 39.2 cd A^?1 (11.8 V), 40.1 cd A^?1 (10.5 V), and 43.1 cd A^?1 (9.0 V), respectively. The increment of current efficiency with PMPT‐Au NP coated devices was strongly related to the energy transfer between the radiated light generated from CBP: Ir(PIA)₂ (acac) emissive layer and localized surface plasmonic resonance excited by PMPT‐Au NP layer.     

Improved efficiencies of hybrid organic light‐emitting diodes using efficient electron injection layer

Hybrid organic‐inorganic light‐emitting diodes were developed with pristine ZnO (2.0 wt%) and Cu‐doped ZnO (2.0 wt%) as electron injection layer and iridium(III)‐bis‐2‐(4‐fluorophenyl)‐1‐(naphthalen‐1‐yl)‐1H‐phenanthro[9,10‐d]imidazole (acetylacetonate) [Ir(fpnpi)₂ (acac)] as green emissive layer (521 nm). The pristine ZnO and Cu‐doped ZnO are deposited at indium tin oxide cathode and emissive layer interface. The electroluminescent performances increased by electron injection layer–Cu‐doped ZnO compared with ZnO‐based device because Cu‐doped ZnO injects electron efficiently result in balanced h⁺ ? e^? recombination in emissive layer than ZnO‐based device. The Cu‐doped ZnO (2.0 %) device shows luminance (L) of 10 982 cd/m² at 23.0 V (ZnO, 1450 cd/m² at 23.0 V).     

利用p型掺杂技术制备的高效有机电致发光器件

利用氧化钼(MoO_x)作为p型掺杂剂,以掺杂层4,4'-bis(carbazol-9-yl)biphenyl(CBP):MoO_x作为空穴注入层,制备了一种结构为ITO/MoO_x/CBP:MoO_x/CBP/CBP:tris(2-phenylpyridine)iridium(III)(Ir(ppy)₃)/4,7-diphenyl-1,10-phenanthroline(Bphen)/LiF/Al的有机电致发光器件.器件中CBP同时作为空穴注入层、空穴传输层以及发光层母体材料,这种结构具有结构简单同时能有效降低空穴注入势垒等优点.研究发现,随着空穴注入层厚度的增加,器件的电流密度增加,表明p型掺杂层的引入能够有效增强空穴的注入;通过优化器件空穴注入层与空穴传输层厚度,器件性能有所提高,最大电流效率为29.8 cd/A,可以认为合理的优化空穴注入层和空穴传输层的厚度,使载流子在发光层中的分布更加平衡是提高器件发光效率的主要原因.值得指出的是,从电流效率最大值到亮度为 20 000 cd/m²时,优化后器件的效率衰减仅为17.7%,而常规器件的效率衰减则为62.1%,优化后器件效率衰减现象得到了明显的改善.分析认为优化后的器件中未掺杂的CBP有助于展宽激子形成区宽度,进而减弱了三线态-三线态湮灭、三线态-极化子淬灭现象,激子形成区的展宽是改善效率衰减的主要原因.     

Concentration quenching effect of organic light‐emitting devices using DCM1‐doped tetraphenylgermole

We examine the concentration quenching of a 4‐(dicyanomethylene)2‐methyl‐6‐(p‐dimethylaminostyryl)‐4H‐pyran (DCM1)‐doped 1,1‐bis(2‐phenylethynyl)‐2,3,4,5‐tetraphenylgermole (HPAG)‐based light‐emitting diode. Originally, HPAG emits in the ~500‐nm (green) region, which can be converted to a red‐emission material by using DCM1 doping. As the DCM1 concentration increased from 1 to 10 wt%, the electroluminescence peak positions are red‐shifted from 604 to 644 nm, respectively. Increasing doping density not only shows the red‐shift but also shows decreasing luminance efficiency. Förster energy transfer between the HPAG host material and the DCM1 guest material is responsible for the strong red‐emission behavior. The calculated Förster radius (4.0 nm) for excellent Förster energy transfer characteristics with increasing doping concentration of DCM1 is consistent with experimental results. The maximum luminance efficiency was 6.64 cd/A at 11.0 mA/cm². The HPAG germole compound shows excellent red‐emission host–guest system properties for red organic light‐emitting device applications. Copyright © 2011 John Wiley & Sons, Ltd.     

新型高色纯度弱电流猝灭性蓝色有机发光器件

以ADN为基质,分别以不同掺杂剂制备了四种蓝色有机发光器件,器件结构为:CuPc(12 nm)/NPB(40 nm)/AND∶Dopant(50 nm)/Alq(12 nm)/LiF(4 nm)/Al。掺杂剂有:BCzVB(amino-substituted distyrylarylenederivatives)、TBPe、BCzVBi和DSA-ph四种。研究了最佳掺杂浓度以及器件的亮度、电流密度、效率和色坐标等电学特性和光学特性。其中掺杂BCzVB制备了色纯度高、低电流猝灭性的蓝色有机发光器件,色坐标达到x=0.146,y=0.162,最大亮度为11600 cd/m2(15 V),电流效率为2.8 cd/A,流明效率为1.79 lm/W;以ADN为基质,分别以TBPe、BCzVBi和DSA-ph为掺杂剂,制备了另外三种对比器件。器件ADN∶TBPe色坐标为x=0.162,y=0.222(蓝绿光),效率随电流的增加而降低很快;器件ADN∶BczVBi有较好的色纯度(色坐标:x=0.164,y=0.146),但电流效率较低:2.03 cd/A,效率随电流的增加降低幅度也较快。器件ADN∶DSA-ph效率较高为8 cd/A,效率随电流增加变化幅度不大,但色纯度比较差(x=0.153,y=0.306),适合于做白色有机发光器件。     

Highly efficient blue fluorescent OLEDs with doped double emitting layers based on p—n heterojunctions

We fabricate a kind of novel efficient blue fluorescent organic light emitting device(OLED) based on p-n heterojunctions composed of hole transporting layer(HTL) N,N ’-bis(naphthalen-1-yl)-N,N ’-bis(phenyl)-benzidine(NPB) and electron transporting layer(ETL) 4,7-diphnenyl-1,10-phenanthroline(BPhen),into which a new blue material,DNCA(a derivation of N 6,N 6,N 12,N 12-tetrap-tolylchrysene-6,12-diamine),is partially doped simultaneously,and double emitting layers are configured.With a turn-on voltage of 2.6 V at 1 cd/m 2,this type of OLED presents a maximum luminance efficiency(η max) of 8.83 cd/A at 5.818 mA/cm 2 and a maximum luminance of over 40000 cd/m 2.Meanwhile,the Commission Internationale De L’Eclairage(CIE) coordinates of this device change slightly from(0.13,0.27) to(0.13,0.23) as the driving voltage increases from 3 V to 11 V.This improvement in the electroluminescent characteristics is attributed mainly to the ideal p-n heterojunction which can confine and distribute excitons evenly on two sides of the heterojunction interface so as to improve the carrier combination rate and expand the light-emitting region.     

Multi‐peak and chromaticity‐stable top‐emitting white organic light‐emitting diodes using single blue emitter

We have fabricated multi‐peak and chromaticity‐stable top‐emitting white organic light‐emitting diodes (TEWOLEDs) using single blue emitter. Besides the intrinsic emission of blue emitter, the additional emission can be well realized by simply adjusting the thickness of hole transporting layer (HTL), thus modifying the optical cavity length to obtain different resonant wavelengths. The detailed variation process for multi‐peak spectra with the increase of HTL thickness is studied, which provides a guidance for the design of microcavity TEWOLEDs.

     

Efficiency enhancement of fluorescent blue organic light-emitting diodes using doped hole transport and emissive layers

The electroluminescent characteristics of blue organic light-emitting diodes(BOLEDs) fabricated with doped charge carrier transport layers are analyzed. The fluorescent blue dopant BCzVBi is doped in an emissive layer,hole transport layer(HTL) and electron transport layer(ETL), respectively, to optimize the probability of exciton generation in the BOLEDs. The luminance and luminous efficiency of BOLEDs made with BCzVBi-doped HTL and ETL increase by 22% and 17% from 11,683 cd/m2 at 8.5 V and 6.08 cd/A at 4.0 V to 14, 264 cd/m2 at8.5 V and 7.13 cd/A at 4.0 V while CIE coordinates of(0.15, 0.15) of both types of BOLEDs remained unchanged. The electron mobility of BCzVBi is estimated to be 1.02 x 10_o cm2/Vs by TOF.     

Bandgap engineering of GaxZn1–xO nanowire arrays for wavelength‐tunable light‐emitting diodes

Wavelength‐tunable light‐emitting diodes (LEDs) of Ga_xZn_1–xO nanowire arrays are demonstrated by a simple modified chemical vapor deposition heteroepitaxial growth on p‐GaN substrate. As a gallium atom has similar electronegativity and ion radius to a zinc atom, high‐level Ga‐doped Ga_xZn_1–xO nanowire arrays have been fabricated. As the x value gradually increases from 0 to 0.66, the near‐band‐edge emission peak of Ga_xZn_1–xO nanowires shows a significant shift from 378 nm (3.28 eV) to 418 nm (2.96 eV) in room‐temperature photoluminescence (PL) measurement. Importantly, the electroluminescence (EL) emission of Ga_xZn_1–xO nanowire arrays LED continuously shifts with a wider range (∼100 nm), from the ultraviolet (382 nm) to the visible (480 nm) spectral region. The presented work demonstrates the possibility of bandgap engineering of low‐dimensional ZnO nanowires by gallium doping and the potential application for wavelength‐tunable LEDs.     

Simplified hybrid white organic light‐emitting diodes with efficiency/efficiency roll‐off/color rendering index/color‐stability trade‐off

A high‐performance hybrid white organic light‐emitting diode (WOLED) based on a simple structure has been developed. The resulting device exhibits a maximum total current efficiency and power efficiency of 35.7 cd/A and 30.6 lm/W, respectively. Even at a high luminance of 1000 cd/m², a current efficiency of 32.0 cd/A and a power efficiency of 19.4 lm/W are obtained, suggesting that the device exhibits a low efficiency roll‐off. Besides, the device shows excellent color‐stability during a wide range of luminance and a high color rendering index (CRI) of 83 is obtained. Moreover, the origin of the superior properties is explored comprehensively. Such achieved results demonstrate that high efficiency, low efficiency roll‐off, stable color and high CRI can be simultaneously realized in a simplified hybrid WOLEDs. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Bottom‐Up Synthesis of Carbon Quantum Dots With High Performance Photo‐ and Electroluminescence

Although carbon quantum dots (CQDs) are of great interest because of cost effectiveness and environmental compatibility with the facile tunability of their optical properties, poor photo‐ and electroluminescence (EL) of CQDs limits further implementation. Here, a novel bottom‐up synthetic route for fabricating highly crystalline CQDs suitable for high‐brightness blue light‐emitting diodes is demonstrated. The two‐step solution process is based on time‐controlled thermal carbonization of citric acid, followed by ligand exchange of the CQDs with oleylamine (OA) in solution. Carbonization allows for the nucleation and growth of crystalline CQDs, while OA treatment disperses the CQDs and stabilizes the solution, giving rise to CQDs with low structural defects and uniform sizes. The systematic study reveals the origin of the light emission of OA‐treated CQDs by photoluminescence (PL) analysis, which yields a high quantum efficiency of ≈30%. The photoluminescence‐optimized OA‐treated CQDs exhibit excellent blue EL performance with a low turn‐on voltage of ≈4 V and high brightness of 308 cd m⁻²; a negligible voltage‐dependent color shift when they are employed to an inverted light‐emitting diode.     

以蓝色发光材料DPVBi为基质的白色发光器件

白色有机发光器件是实现彩色平板显示的重要方案之一。利用蓝色发光材料DPVBi[4，4′—(2，2—苯乙烯基)—1，1′—联苯]掺杂红光染料DCJTB[4—氰甲烯基—2—叔丁基—6—(1，1，7，7—四甲基久洛尼定基—9—烯炔基—4H—吡喃)]作发光层制备了白色发光器件。研究了DPVBi掺杂不同浓度IDCJTB薄膜的光致发光性质，根据光致发光结果，制备了以DPVBi掺杂不同浓度DCJTB作发光层的电致发光器件，其结构为ITO／GuPc／NPB／DPVBi：DCJTB／Alq3／LiF／Al。当DCJTB质量分数为0．0008时，器件实现了白色发光(色度x=0．25，y=0．32)，电致发光和光致发光的掺杂比例基本相符，表明器件的白色发光主要是由基质DPVBi向掺杂剂DCJTB的能量传递产生的。研究还发现：白色器件随电压升高，光谱中蓝色成分相对于红色成分的比例略有增加，文章对此现象进行了分析。该白光器件在14V时达到最高亮度7822cd／cm^2，在20mA／cm^2电流密度下的亮度为-489cd／cm^2，最大流明效率为1．75lm／W。     

Graphene‐Based Phosphorus‐Doped Carbon as Anode Material for High‐Performance Sodium‐Ion Batteries

Graphene‐based phosphorus‐doped carbon (GPC) is prepared through a facile and scalable thermal annealing method by triphenylphosphine and graphite oxide as precursor. The P atoms are successfully doped into few layer graphene with two forms of P–O and P–C bands. The GPC used as anode material for Na‐ion batteries delivers a high charge capacity 284.8 mAh g^?1 at a current density of 50 mA g^?1 after 60 cycles. Superior cycling performance is also shown at high charge?discharge rate: a stable charge capacity 145.6 mAh g^?1 can be achieved at the current density of 500 mA g^?1 after 600 cycles. The result demonstrates that the GPC electrode exhibits good electrochemical performance (higher reversible charge capacity, super rate capability, and long‐term cycling stability). The excellent electrochemical performance originated from the large interlayer distance, large amount of defects, vacancies, and active site caused by P atoms doping. The relationship of P atoms doping amount with the Na storage properties is also discussed. This superior sodium storage performance of GPC makes it as a promising alternative anode material for sodium‐ion batteries.     

发光层掺杂对红光OLED性能影响研究

制备高效率、高亮度的红光有机发光二极管是显示器实现全彩色的关键,对高性能的红光有机发光二极管器件研究具有十分重要的意义.本文主要研究了掺杂剂(DCJTB)浓度对红光有机发光二极管性能影响.实验采用真空热蒸镀的方法,选取结构为ITO／2-TNATA(20 nm)/NPB(30 nm)/AlQ(50 nm):(X%)DCJTB／AlQ(30 nm)／LiF(0.8 nm)／Al(100 nm)的红光器件,在高准确度膜厚控制仪的监控下,实现了有机薄膜功能材料的精确蒸镀.研究表明:红光掺杂剂掺杂浓度为(2.5~3.0)%时,在12 V电压下,可以得到发光亮度最高达到8 900 cd/m²,发光效率大于2.8 cd/A,且发光光谱波长为610~618 nm较为理想的红光有机发光二极管器件.     

A new‐generation color converter for high‐power white LED: transparent Ce3+:YAG phosphor‐in‐glass

Currently, the major commercial white light‐emitting diode (WLED) is the phosphor‐converted LED made of the InGaN blue‐emitting chip and the Ce³⁺:Y₃Al₅O₁₂ (Ce:YAG) yellow phosphor dispersed in organic epoxy resin or silicone. However, the organic binder in high‐power WLED may age easily and turn yellow due to the accumulated heat emitted from the chip, which adversely affects the WLED properties such as luminous efficacy and color coordination, and therefore reduces its long‐term reliability as well as lifetime. Herein, an innovative luminescent material: transparent Ce:YAG phosphor‐in‐glass (PiG) inorganic color converter, is developed to replace the conventional resin/silicone‐based phosphor converter for the construction of high‐power WLED. The PiG‐based WLED exhibits not only excellent heat‐resistance and humidity‐resistance characteristics, but also superior optical performances with a luminous efficacy of 124 lm/W, a correlated color temperature of 6674 K and a color rendering index of 70. This easy fabrication, low‐cost and long‐lifetime WLED is expected to be a new‐generation indoor/outdoor high‐power lighting source.