The influence of exciton behavior on luminescent characteristics of organic light-emitting diodes

We used N,N′-bis-(1-naphthyl)-N,N′-1-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB), 4,4′-N,N′-dicarbazole-biphenyl (CBP) and tris(8-hydroxyquinoline) aluminum (Alq₃) to fabricate tri-layer electroluminescent (EL) device (device structure: ITO/NPB/CBP/Alq₃/Al). In photoluminescence (PL) spectra of this device, the emission from NPB shifted to shorter wavelength accompanying with the decrease of its emission intensity and moreover the emission intensity of Alq₃ increased relatively with the increase of reverse bias voltage. The blue-shifted emission and the decrease in emission intensity of NPB were attributed to the polarization and dissociation of NPB excitons under reverse bias voltage. The increase of emission intensity of Alq₃ benefited from the recombination of electrons (produced by the dissociation of NPB exciton) and holes (injected from the Al cathode).     

Modeling of transient electroluminescence overshoot in bilayer organic light-emitting diodes using rate equations

When a voltage pulse is applied under forward biased condition to a spin-coated bilayer organic light-emitting diode (OLED), then initially the electroluminescence (EL) intensity appearing after a delay time, increases with time and later on it attains a saturation value. At the end of the voltage pulse, the EL intensity decreases with time, attains a minimum intensity and then it again increases with time, attains a peak value and later on it decreases with time. For the OLEDs, in which the lifetime of trapped carriers is less than the decay time of the EL occurring prior to the onset of overshoot, the EL overshoot begins just after the end of voltage pulse. The overshoot in spin-coated bilayer OLEDs is caused by the presence of an interfacial layer of finite thickness between hole and electron transporting layers in which both transport molecules coexist, whereby the interfacial energy barrier impedes both hole and electron passage. When a voltage pulse is applied to a bilayer OLED, positive and negative space charges are established at the opposite faces of the interfacial layer. Subsequently, the charge recombination occurs with the incoming flux of injected carriers of opposite polarity. When the voltage is turned off, the interfacial charges recombine under the action of their mutual electric field. Thus, after switching off the external voltage the electrons stored in the interface next to the anode cell compartment experience an electric field directed from cathode to anode, and therefore, the electrons move towards the cathode, that is, towards the positive space charge, whereby electron–hole recombination gives rise to luminescence. The EL prior to onset of overshoot is caused by the movement of electrons in the electron transporting states, however, the EL in the overshoot region is caused by the movement of detrapped electrons. On the basis of the rate equations for the detrapping and recombination of charge carriers accumulated at the interface expressions are derived for the transient EL intensity I, time t_m and intensity I_m corresponding to the peak of EL overshoot, total EL intensity I_t and decay of the intensity of EL overshoot. In fact, the decay prior to the onset of EL overshoot is the decay of number of electrons moving in the electron transporting states. The ratio I_m/I_s decreases with increasing value of the applied pulse voltage because I_m increases linearly with the amplitude of applied voltage pulse and I_s increases nonlinearly and rapidly with the increasing amplitude of applied voltage pulse. The lifetime τ_t of electrons at the interface decreases with increasing temperature whereby the dependence of τ_t on temperature follows Arrhenius plot. This fact indicates that the detrapping involves thermally-assisted tunneling of electrons. Using the EL overshoot in bilayer OLEDs, the lifetime of the charge carriers at the interface, recombination time of charge carriers, decay time of the EL prior to onset of overshoot, and the time delay between the voltage pulse and onset time of the EL overshoot can be determined. The intense EL overshoot of nanosecond or shorter time duration may be useful in digital communication, and moreover, the EL overshoot gives important information about the processes involving injection, transport and recombination of charge carriers. The criteria for appearance of EL overshoot in bilayer OLEDs are explored. A good agreement is found between the theoretical and experimental results.     

Efficiency improvement of red organic light-emitting diodes using a blue phosphorescent exciton blocking layer

Quantum efficiency of red organic light-emitting diodes was improved using a blue phosphorescent emitting layer as an exciton blocking layer. Compared with 8.1% quantum efficiency of standard devices without an exciton blocking layer, high quantum efficiency of 14.1% was obtained using a blue phosphorescent emitting layer between the hole transport layer and the red emitting layer.     

Highly efficient all phosphorescent white organic light-emitting diodes for solid state lighting applications

We report highly efficient all phosphorescent white organic light-emitting diodes (OLEDs) with an exciton-confinement structure. By stacking two emissive layers (EMLs) with different charge transporting properties, effective charges as well as exciton confinements were achieved. Accordingly, efficient blue OLEDs with a peak external quantum efficiency (EQE) over 22% and power efficacy (PE) over 50 lm/W were developed by using iridium(III) bis(4,6-(difluorophenyl) pyridinato-N,C2′)picolinate (FIrpic) as an electro-phosphorescent dopant. When the optimized orange and red EMLs were sandwiched between the stacked two blue EMLs, white OLEDs with an EQE and PE of 24.3% and 45.9 lm/W at a luminance of 1000 cd/m² were obtained without the use of any out-coupling techniques. In addition, these white OLEDs exhibit a color rendering index (CRI) value of 84 with high efficacy.     

The effect of electric field strength on electroplex emission at the interface of NPB/PBD organic light-emitting diodes

Organic light-emitting diode (OLED) based on two kinds of blue emission materials N,N′-bis(1-naphthyl)-N,N′-diphenyl-l,l′-diphenyl-4,4′-diamine (NPB) and 2-(4-biphenylyl)-5(4-tert-butyl-phenyl)-1,3,4-oxadiazole (PBD) was fabricated. There is only one emission peak in photoluminescence (PL) spectrum which originates from NPB exciton emission. And the electroluminescence (EL) emission peaks have an apparent red-shift with the increase of driving voltage. The red-shift emission from exciplex emission could be ruled out. Thus, by the method of Gaussian fitting it should be ascribed to the overlap of exciton emission and electroplex emission which occurs at the interface between NPB and PBD. The formation of the electroplex emission under high electric field is analyzed.     

有机发光二极管的光致磁电导效应

制备了结构为ITO/CuPc/NPB/Alq₃/LiF/Al的常规有机发光二极管, 之后对器件采用波长为442 nm和325 nm的激光线进行照射产生激子, 并在小偏压下(保证器件没有开启)对激子的演化过程进行控制, 同时测量器件的光致磁电导(photo-induced magneto-conductance, PIMC). 实验发现, 不同于电注入产生激子的磁电导效应, PIMC在正、反小偏压下表现出明显不同的磁响应结果. 当给器件加上正向小偏压时, 器件的PIMC在0-40 mT范围内迅速上升; 随着磁场的进一步增大, 该PIMC增加缓慢, 并逐渐趋于饱和. 反向小偏压时, 器件的PIMC随着磁场也是先迅速增大(0-40 mT), 但达到最大值后却又逐渐减小. 通过分析外加磁场对器件光生载流子微观过程的影响, 采用'电子-空穴对'模型和超精细相互作用理论对正向偏压下的PIMC进行了解释; 反向偏压下因各有机层的能级关系, 为激子与电荷相互作用提供了必要条件, 运用三重态激子与电荷的反应机制可以解释PIMC出现高场下降的实验现象.     

Dependence of charge trapping of fluorescent and phosphorescent dopants in organic light-emitting diodes on the dye species and current density

This paper utilizes multilayer organic light-emitting diodes with a thin layer of dye molecules to study the mechanism of charge trapping under different electric regimes. It demonstrates that the carrier trapping was independent of the current density in devices using fluorescent material as the emitting molecule while this process was exactly opposite when phosphorescent material was used. The triplet--triplet annihilation and dissociation of excitons into free charge carriers was considered to contribute to the decrease in phosphorescent emission under high electric fields. Moreover, the fluorescent dye molecule with a lower energy gap and ionized potential than the host emitter was observed to facilitate the carrier trapping mechanism, and it would produce photon emission.     

Charge trapping phenomena in high-efficiency metal-oxide-silicon light-emitting diodes with ion-implanted oxide

This work is a comparative study of the processes of charge trapping in silicon dioxide layers doped with different rare-earth (RE) impurities (Gd, Tb, Er) as well as with Ge. Diode SiO₂-Si structures incorporating such oxide layers exhibit efficient electroluminescence (EL) in the spectral range of UV to IR. Ion implantation was performed over a wide dose range with the implant profiles peaking in the middle of the oxide. Charge trapping was studied using an electron injection technique in constant current regime with simultaneous measurements of the EL intensity (ELI). High-frequency C/V characteristics were used to monitor the net charge in the oxides.Analysis of the charge trapping and the variation of the EL intensity during electron injection shows that the current density range can be divided in three portions: (i) low injection level, where electron/hole capture at traps with large capture cross-sections and low ELI occurs; (ii) medium injection level corresponding to the main operation mode of the devices (odd hole trapping depending on the injected current level is observed); and (iii) high injection level (electrical quenching of the EL that correlates with electron capture at traps of extremely small capture cross-sections takes place). The nature of specific hole trapping at the medium injection level in RE-doped devices is discussed. Mechanisms of EL quenching at the high injection level are proposed.     

基于金属卤化物钙钛矿材料的高效发光二极管

金属卤化物钙钛矿半导体既在光伏器件研究中获得巨大进展,又在发光应用中体现出明显优势。金属卤化物钙钛矿半导体的荧光转化效率高、发光峰形窄、发射光谱可调控并可覆盖整个可见光范围,从而使得该类材料所制备的发光二极管有望满足下一代显示技术应用的性能要求。文章在简要叙述发光二极管基本原理的基础上,分别介绍了钙钛矿材料的结构和荧光特性、钙钛矿发光二极管的电致发光特性,以及钙钛矿发光二极管进入实际应用所必须解决的器件寿命、离子迁移和光谱不稳定性等主要技术问题,最后讨论了钙钛矿发光技术所面临的机遇和挑战。     

基于Alq3的有机发光二极管的磁电导效应

制备了结构为 ITO/CuPc/NPB/Alq₃/LiF/Al 的有机发光二极管,并在300,260,220和180 K 四个温度测量了器件在恒压偏置下注入电流的磁场效应(磁电导效应).在注入电流从双极电流过渡到单极电流的过程中,随电流减小,器件的磁电导呈现先上升后下降的变化趋势.当温度降低,磁电导的值下降.但在任何测量条件下,器件的磁电导始终为正,没有出现如文献报道的磁电导从正到负的变化.实验结果表明,有机发光二极管中正负磁电导现象的产生,并非仅取决于注入电流是单极电流还是双极电流,它还与有机材料、器件结构等密切相关.利用受磁场调控的“电子-空穴对”机理与“双极化子”模型,分别解释了器件双极电流和单极电流的正磁电导效应. 关键词： 有机发光二极管 磁电导 双极化子     

Influence of capacitance effect on alternating-current organic light-emitting diodes

The capacitance effect on ITO/poly[2-methoxy-5-[(2′-ethylhexyl)oxy]-p-phenylenevinylene] (MEH-PPV)/Al is studied by impedance spectroscopy technology, and the electroluminescence (EL) mechanism of this device driven by a sinusoidal alternating-current (AC) bias is suggested. By calculating the RC time constant of the device, we find that it is in good agreement with the lag-time between the EL and applied AC bias. Also, the influence of operating frequency on the EL intensity of the device is presented and it is concluded that a low operating frequency is good for a high device performance.     

高场作用下有机双层器件的场致复合发光

以在高场作用下载流子对三角势垒的Fowler Nordheim隧穿理论为基础 ,建立了双层有机电致发光器件载流子的输运与复合发光模型。求出了稳态下电荷载流子的复合发光与电压和界面势垒的函数关系式 ,计算并讨论了所加电压和阳极区与阴极区厚度之比 (Lh/Le)对复合发光的影响。该理论模型很好地解释了电场对复合区域的调制作用。     

Temperature-dependent electrical properties of organic light-emitting diodes depending on cathodes

We have studied temperature-dependent electrical properties of organic light-emitting diodes with a variation of cathode materials; Al, LiAl, and LiF/Al. The organic light-emitting diodes emit a light by a recombination of injected charge carriers such as holes and electrons. Thus, the charge transport is affected by the injection barrier at the interface. By varying the cathode materials, the electron injection at the interface could be controlled because of the work-function change at the cathode. Temperature-dependent current–voltage luminance characteristics of the organic light-emitting diodes were measured in the temperature range from 10 to 300 K. The current-voltage characteristics were analyzed in terms of Fowler–Nordheim tunneling model, and the energy-barrier height was obtained. A measured lifetime of device with LiF/Al cathode is relatively longer than the other cathodes at room temperature: 4.5 h for Al cathode, 12.4 h for LiAl, and 29.6 h for LiF/Al. The device with LiAl and LiF/Al cathode, in the aspect of lifetime and luminous efficiency, is superior to one of other cathodes.     

量子阱结构对有机电致发光器件效率的影响

实验中共制备了五种有机量子阱结构电致发光器件,分别对这五种量子阱结构器件的电致发光特性进行了研究,分析了量子阱结构的周期数和势垒层的厚度对器件电学性能的影响.实验结果表明适当周期数的量子阱结构器件的亮度和电流效率比传统的三层结构器件的要大,主要原因是量子阱结构对电子和空穴的限制作用,这种限制作用提高了电子和空穴在发光层中形成激子和复合的概率,从而提高了发光的亮度和效率.当改变阱结构器件中势阱层的厚度时,也会对器件的亮度和效率产生影响,采用适当的势阱层厚度能够提高器件的亮度和效率. 关键词： 量子阱结构 电致发光 电流效率 光谱     

Exciplex formation and electroluminescent absorption in ultraviolet organic light-emitting diodes

We investigated the formation of exciplex and electroluminescent absorption in ultraviolet organic light-emitting diodes(UV OLEDs) using different heterojunction structures.It is found that an energy barrier of over 0.3 eV between the emissive layer(EML) and adjacent transport layer facilitates exciplex formation.The electron blocking layer effectively confines electrons in the EML,which contributes to pure UV emission and enhances efficiency.The change in EML thickness generates tunable UV emission from 376 nm to 406 nm.In addition,the UV emission excites low-energy organic function layers and produces photoluminescent emission.In UV OLED,avoiding the exciplex formation and averting light absorption can effectively improve the purity and efficiency.A maximum external quantum efficiency of 1.2%with a UV emission peak of 376 nm is realized.     

Modification of anode surface in organic light-emitting diodes by chalcogenes

Influence of thin chalcogen X (S, Se, Te) interlayer between anode (indium-tin oxide, ITO) and a layer of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) used as a hole-transport layer (HTL) on the operating characteristics of organic light-emitting diodes (OLEDs) of composition ITO/X/TPD/Alq₃/Yb (Alq₃ - aluminum 8-quinolinolate) has been investigated. It was found that the sulphur layer decreases operating voltage and enhances operating stability of a device while the selenium or tellurium interlayers impair these characteristics.     

有机层界面对双层有机发光二极管复合效率的影响

建立了双层有机发光二极管中载流子在有机层界面复合的无序跳跃理论模型.由于有机分子材料的空间及能带结构的无序性，采用刚体模型处理有机层界面问题是不恰当的，而采用无序跳跃模型比较合理.复合效率及复合电流由载流子跳跃距离、有机层界面的有效势垒高度及该界面处的电场强度分布所决定：在双层器件ITO/α-NPD/Alq₃/Al中，当所加电压小于19.5V时，复合效率随着载流子跳跃距离的增加而增加，而大于19.5V时，复合效率随着其距离的增加而减少；复合效率随着有机层界面有效势垒高度的增加而增加； 关键词： 有机层界面 双层有机发光二极管 复合效率 有效势垒高度 无序跳跃模型     

High-efficiency organic light-emitting diodes based on ultrathin blue phosphorescent modification layer

Yellow organic light-emitting devices(YOLEDs) with a novel structure of ITO/MoO_3(5 nm)/NPB(40 nm)/TCTA(15 nm)/CBP:(tbt)_2Ir(acac)(x%)(25 nm)/FIrpic(y nm)/TPBi(35 nm)/Mg:Ag are fabricated. The ultrathin blue phosphorescent bis[(4,6-difluorophenyl)-pyridi-nato-N,C2■](picolinate) iridium(Ⅲ)(FIrpic) layer is regarded as a highperformance modification layer. By adjusting the thickness of FIrpic and the concentration of (tbt)_2Ir(acac), a YOLED achieves a high luminance of 41618 cd/m~2, power efficiency of 49.7 lm/W, current efficiency of 67.3 cd/A, external quantum efficiency(EQE) of 18%, and a low efficiency roll-off at high luminance. The results show that phosphorescent material of FIrpic plays a significant role in improving YOLED performance. The ultrathin FIrpic modification layer blocks excitons in EML. In the meantime, the high triplet energy of FIrpic(2.75 eV) alleviates the exciton energy transport from EML to FIrpic.     

GaN基多量子阱发光二极管的极化效应和载流子不均匀分布及其影响

制备了GaN基绿光发光二极管.利用耦合法求解了在自发极化和压电极化效应影响下的GaN/InGaN量子阱的极化电场强度.考虑载流子在量子阱间的不均匀分布，模拟计算了系统的一维薛定谔方程、稳态速率方程和泊松方程，得到了载流子在各个阱间的分布比值和辐射复合速率.同时还得到了不同电流下电致发光(EL)谱的峰值波长、谱峰半高宽及EL谱强度的变化情况.发现当测试电流由10 mA 增加到70 mA时，理论结果与实验结果能很好符合. 关键词： 极化 载流子不均匀分布 复合速率     

Improvement in electroluminescence performance of n-ZnO/Ga_2O_3 /p-GaN heterojunction light-emitting diodes

n-ZnO/p-GaN heterojunction light-emitting diodes with and without a Ga2O3 interlayer are fabricated. The electroluminescence （EL） spectrum of the n-ZnO/p-GaN displays a single blue emission at 430 nm originating from GaN, while the n-ZnO/Ga2O3/p-GaN exhibits a broad emission peak from ultraviolet to visible. The broadened EL spectra of n-ZnO/Ga2O3/p-GaN are probably ascribed to the radiative recombination in both the p-GaN and n-ZnO, due to the larger electron barrier （ΔEC=1.85 eV） at n-ZnO/Ga2O3 interface and the much smaller hole barrier （ΔEV=0.20 eV） at Ga2O3/p-GaN interface.