ZnS薄膜参数对有机/无机复合发光器件特性的影响

半导体量子点(QDs)具有发光效率高和发光波长可调等特点。采用胶体CdSe QDs作电致发光器件的有源材料,TPD(N,N′-biphenyl-N,N′-bis-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine)作空穴传输层,ZnS作电子传输层,研究了有机/无机复合发光器件ITO/TPD/CdSe QDs/ZnS/Ag的电致发光特性。TPD和CdSe QDs薄膜采用旋涂方法、ZnS薄膜采用磁控溅射方法沉积,器件表面平整。CdSe QDs的光致发光和电致发光谱峰位波长均位于～580 nm,属于量子点的带边激子发光。我们与以前的ITO/ZnS/CdSe QDs/ZnS/Ag发光器件结构进行了对比,发现新的器件结构的电致发光谱没有观察到QDs表面态的发光,而且新器件的发光强度是ITO/ZnS/CdSe QDs/ZnS/Ag结构的～10倍。发光效率的提高归因于碰撞激发与载流子注入两种发光机制并存的结果：一方面电子经过ZnS 层加速后,碰撞激发CdSe QDs发光;另一方面,空穴从TPD层注入CdSe QDs 与QDs中激发的电子复合发光。我们进一步研究了ZnS电子加速层厚度对发光特性的影响,选择ZnS薄膜的厚度分别是80,120 和160 nm,发现随着ZnS层厚度增大,器件启亮电压升高,EL强度增大,但是击穿电压降低。EL峰位随着ZnS厚度的减小发生明显蓝移,对上述实验现象进行了机理解释。     

基于ZnSe的有机-无机异质结电致发光器件

以电子束蒸发的方法制备硒化锌(ZnSe)薄膜，研究了基于ZnSe的有机-无机异质结电致发光器件.在双层器件ITO/ZnSe(50nm)/Alq₃(12nm)/Al中看到了峰值位于578nm的ZnSe电致发光，却很难得到单层器件ITO/ZnSe(50—120nm)/Al的电致发光；在此基础上进一步引入有机空穴传输层(HTL)，通过改变器件的结构，讨论了ZnSe对有机-无机异质结器件ITO/HTL/ZnSe/Alq₃/Al电致发光特性的影响.其电致发光光谱的研究结果证实了ZnSe在器件中的作用：ZnSe既起传输电子的作用，也起到传输空穴的作用，还作为发光层.并对ZnSe的发光机理进行了讨论. 关键词： 硒化锌 有机-无机异质结 电致发光 空穴传输层     

基于Spiro-OMeTAD电子阻挡层的量子点发光二极管电荷平衡改善

针对量子点发光二极管空穴传输层和电子传输层的迁移率差异而导致的电荷不平衡问题,将具有最低未占分子轨道高能级的有机聚合物Spiro-OMeTAD薄膜放置在空穴传输层与量子点发光层之间,阻挡过剩电子由量子点发光层向空穴传输层的传输,促进器件的电荷平衡,制备出一种高效的新型绿色量子点发光二极管。结果表明:相比于传统器件,新型绿色量子点发光二极管器件的外部量子效率提升了87%,达到11.87%,亮度提升了106%,达到53055cd/m~2;阻挡过剩电子的传输可以显著改善器件中的电荷不平衡现象。     

PS-TPD空穴传输层的高亮度绿光有机电致发光器件的研究

研究了不同质量比的聚苯乙烯(PS)三苯基二胺(TPD)复合空穴传输层对有机电致发光器件(OLED)性能的影响。采用此掺杂体系作器件的空穴传输层,利用旋涂工艺制备了结构为indium-tin-oxide(ITO)/polystyrene(PS)∶N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine(TPD)/tris-(8-hydroxyquinoline)-aluminium(Alq3)/Mg∶Ag的双层有机电致发光器件。为便于比较,另直接蒸镀TPD薄膜做空穴传输层制备了相似结构的器件。利用飞行时间法对不同PS-TPD质量比例的薄膜的空穴迁移率进行了表征,并对器件的电致发光特性进行了测试。测试结果表明,掺杂薄膜的空穴迁移率比纯TPD膜的低1~2个数量级。当质量比为m(PS)∶m(TPD)=10∶90时,器件具有最高光亮度14280 cd/m2和最高流明效率1.2 l m/W。说明适当质量比PS的引入相对降低了薄膜的空穴迁移率,调节了TPD的空穴传输能力,更有效地平衡了复合区内正负载流子的数目,从而提高了器件的发光亮度和效率。     

新型稀土铕配合物Eu(o-BBA)3(phen)电致发光研究

研究了一种新的稀土配合物邻苯甲酰苯甲酸-1,10-菲咯啉-铕(Eu(o-BBA)3(phen))的电致发光特性.采用不同的电子传输层材料,制备了多种结构的有机电致发光器件及有机无机复合器件.比较了单层电致发光器件A:ITO/PVK:Eu/Al与有机无机复合器件B:ITO/PVK:Eu/ZnS/Al发光性能的不同.分析了采用无机半导体材料ZnS作为电子传输层的优点.研究结果表明采用无机的电子传输层,能有效地避免激基复合物的形成,提高器件的亮度同时保持稀土离子发光的色纯性.     

纳米ZnO薄膜对有机电致发光器件性能的影响

由于有机电致发光器件(Organic light-emitting devices,OLEDs)的主动发光、高亮度等优点,在显示和照明领域有极大的应用前景。报道了纳米ZnO薄膜对这种发光器件性能的影响。在普通有机电致发光器件空穴传输层和发光层之间直接蒸镀一层纳米ZnO薄膜,当纳米ZnO薄膜的厚度为1nm时,器件的电流效率可达3.26cd/A,是没有纳米ZnO薄膜同类器件的1.24倍。适当厚度的纳米ZnO薄膜降低了发光层空穴的浓度,提高了电子和空穴的平衡,从而提高了器件的效率。     

以联苯乙烯衍生物为发光层的蓝色有机发光二极管特性的研究

以一种新型联苯乙烯衍生物NPVBi作为发光层，制备了结构为：ITO／TPD／NPVBi/Alq3/LiF/Al的有机薄膜电致发光器件，其中TPD厚度保持为50nm,NPVBi与Alq3厚度之和保持为50nm。通过调节NPVBi与Alq3的厚度，获得了色纯度较好的NPVBi蓝色电致发光，最高亮度为708cd/m^2，最大流明效率为1.13lm/W。结果表明，发光层NPVBi和电子传输层Alq3的厚度对器件的发光特性有显著的影响。     

利用氧等离子体处理阳极银实现高效率顶发射有机电致发光

主要报道在器件结构为玻璃衬底/Ag(阳极)/NPB(空穴传输层)/Alq3(电子传输及发光层)/Sm(半透明阴极)/Alq3的顶发射有机电致发光器件中,利用氧等离子体对阳极银的表面进行处理来降低阳极和空穴传输层(Ag/NPB)界面处的空穴注入势垒,提高顶发射有机电致发光器件的性能。主要研究了氧等离子体处理时间对阳极银和顶发射有机电致发光器件光电特性的影响。紫外光电子能谱表明,氧等离子体处理能有效降低Ag/NPB界面处的空穴注入势垒。通过优化处理时间获得最佳器件性能,优化后的器件最大效率可达6.14cd/A。     

以ZnO为电子传输层PPV的发光

以Ⅱ-Ⅵ族无机半导体ZnO为电子传输层,PPV为空穴传输层和发光层,得到的电致发光器件比单层PPV器件的发光亮度和效率都高.器件结构为ITO/PPV/ZnO/Al的电致发光光谱同单层PPV器件的光谱基本相同,但是启亮电压明显比单层器件低,最大亮度大约比单层器件高6倍左右,同时工作电流也比单层器件小.通过PPV层自吸收现象可判断出发光区域在PPV/ZnO界面处.电流-电压曲线表明,这种器件具有空间电荷限制电流特性,即J∝Vn,这里n大约为2,这器件的电流主要受到空穴的限制.     

同时掺杂磷光和荧光染料的白色有机电致发光器件性能研究

以磷光染料Ir(piq)₂(acac)作为发光掺杂剂,掺入空穴传输性主体材料NPB中得到红色发光层,荧光材料TBP掺入到主体CBP中作为蓝色发光层,制备了结构为ITO/NPB/NPB：Ir(piq)₂(acac)/CBP/CBP：TBPe/BCP/ALq/Mg：Ag的双发光层白色有机电致发光器件.其中ALq₃、未掺杂的NPB和CBP及BCP层分别作为电子传输层、空穴传输层和激子阻挡层.实验中通过调节发光层厚度及Ir(piq)_{2关键词： 磷光 激子阻挡层 有机电致发光}     

Creation and Investigation of Organic Light-Emitting Structures Containing Arrays of Colloidal Quantum Dots

We have created organic electroluminescent structures—ITO/TPD/Alq3/Al and ITO/PEDOT:PSS/TPD/Alq3/Al—which are organic light-emitting diodes (OLEDs). Experiments on the incorporation of CdSe/ZnS colloidal quantum dots into the active layer of the structure have been performed. The parameters of the created structures have been determined using optical-spectroscopy methods. The appropriateness of using the method of high-speed vacuum thermal deposition as a main method for the deposition of structural layers has been demonstrated, and the possibility of accelerated formation of layers of the material without disturbing its chemical structure has been shown. By measuring the photoluminescence spectra at different points in samples, we have determined the quality of the obtained structures and plotted maps of the radiation power distribution of the material and of its thickness. Recommendations for the creation of upper contacts and other regions of light-emitting structures have been formulated. We have created organic structures with ITO/PEDOT:PSS/TPD/TPD + CQD’s CdSe/Alq3/Al colloidal quantum dots, in which electroluminescence of CdSe/ZnS quantum dots has been obtained for a wide range of applied voltages. It has been shown that the introduction of colloidal quantum dots into the structure leads to a significant modification of its electroluminescence spectrum.     

ZnO作为电子传输层的绿光胶体CdSe量子点LED(QD-LED)的制备与表征

通过调节作为发光层的量子点的尺寸,可以制作出覆盖可见光(380～780 nm)以及近红外光谱的量子点LED(QD-LED),其光谱范围很窄且半高宽可达30 nm。然而量子点LED的寿命、亮度以及效率需要进一步提高才能满足商业化的需求。为了研究QD-LED器件的特性,本文采用523 nm波长的CdSe/ZnS核壳型量子点为发光层、poly-TPD为空穴传输层、ZnO为电子传输层,制备了绿光量子点LED,并表征了器件的特性。     

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).     

Simulation of electroluminescence of quantum dot-based microcavity light-emitting device

We present a detailed analysis and computations of the emitted radiation spectrum for quantum dots (QDs) microcavity light-emitting device, where the total physical thickness of the cavity spacer was kept at 254 nm which corresponds to the wavelength of the mode number (m) = 1 resonant mode of the cavity. Our calculation gives good results for QD diameter only from 1.2 to 6.4 nm. The computations are used to examine how the emitted radiation spectrum can be optimized by varying the position of the light-emitting layer, the type of cathode material, the choice of hole transport layer material, and the thickness of electron transport layer, QD layer, and hole transport layer. These studies showed that the variation of layers geometry and the position of the light-emitting layer will optimize the output intensity and the radiation spectrum and varying the ETL and QD layer thickness will have a more effect on the emitted spectrum than varying HTL thickness. In addition, we have examined the effect of using different quantum dots sizes in emission layer. On the other hand, we have investigated the difference between the electroluminescence (EL) emissions for microcavity device in comparison with the non-cavity device, and we have found that the full width at half maximum (FWHM) of the EL is reduced from 45 nm for the QD non-cavity LED to 30 nm for the output of a resonant microcavity device. Finally, we have investigated the compatibility between our calculation and the experimental results and found a fairly good agreement between them.     

聚对苯乙炔(PPV)的薄膜电致发光特性

聚对苯乙炔[poly(p-phenylene vinylene),缩写为PPV]是一种典型的线性共轭高分子.早在1968年,美国化学家Wessling就宣布合成出了PPV[1],但由于当时对该材料的应用前景不清,故未能引起科学界的重视.80年代中期,Murase等用AsF5及其它多种掺杂剂成功地对PPV进行了掺杂导电研究[2],使其电导率提高了16个数量级,由绝缘体变成了导体.     

Modeling and numerical simulation of electrical and optical characteristics of a quantum dot light-emitting diode based on the hopping mobility model: Influence of quantum dot concentration

We present a comprehensive numerical framework for the electrical and optical modeling and simulation of hybrid quantum dot light-emitting diodes (QD-LEDs). We propose a model known as hopping mobility to calculate the carrier mobility in the emissive organic layer doped with quantum dots (QDs). To evaluate the ability of this model to describe the electrical characteristics of QD-LEDs, the measured data of a fabricated QD-LED with different concentrations of QDs in the emissive layer were taken, and the corresponding calculations were performed based on the proposed model. The simulation results indicate that the hopping mobility model can describe the concentration dependence of the electrical behavior of the device. Then, based on the continuity equation for singlet and triplet excitons, the exciton density profiles of the devices with different QD concentrations were extracted. Subsequently, the corresponding luminance characteristics of the devices were calculated, where the results are in good agreement with the experimental data.     

On the improvement of the electroluminescent signal of organic light emitting diodes by the presence of an ultra‐thin metal layer at the interface organic/ITO

The electroluminescent (EL) signal of organic light emitting diodes (OLEDs) based on simple “hole transporting layer/electron transporting layer” (HTL/ETL) structures has been studied as a function of the anode/HTL interface, the anode being an indium tin oxide (ITO) film. It is shown that the electroluminescent (EL) signal increases when a metal ultra‐thin layer is introduced between the anode and the HTL. Experimental results show that the work function value of the metal is only one of the factors which allow improving the EL signal via better hole injection efficiency. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Improved performance of organic light-emitting devices with plasma treated ITO surface and plasma polymerized methyl methacrylate buffer layer

Transparent indium-tin-oxide (ITO) anode surface was modified using O₃ plasma and organic ultra-thin buffer layers were deposited on the ITO surface using 13.56 MHz rf plasma polymerization technique. A plasma polymerized methyl methacrylate (ppMMA) ultra-thin buffer layer was deposited between the ITO anode and hole transporting layer (HTL). The plasma polymerization of the buffer layer was carried out at a homemade capacitively coupled plasma (CCP) equipment. N,N′-Diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine (TPD) as HTL, Tris(8-hydroxy-quinolinato)aluminum (Alq₃) as both emitting layer (EML)/electron transporting layer (ETL), and aluminum layer as cathode were deposited using thermal evaporation technique. Electroluminescence (EL) efficiency, operating voltage and stability of the organic light-emitting devices (OLEDs) were investigated in order to study the effect of the plasma surface treatment of the ITO anode and role of plasma polymerized methyl methacrylate as an organic ultra-thin buffer layer.     

二硫化钨纳米片制备及其钙钛矿太阳能电池空穴传输层应用

开发新型无机空穴传输层材料是钙钛矿电池实现商业应用的重要挑战之一。本文开展了二硫化钨纳米片制备及其钙钛矿太阳能电池空穴传输层应用研究。采用液相超声剥离法成功制备了WS 2纳米片,并将其引入钙钛矿太阳能电池中用作空穴传输层。结果表明,当WS 2纳米片溶液浓度为1 mg/mL时,制备的WS 2纳米片空穴传输层具有较合适的厚度,并且后续在其上生长的钙钛矿活性层成膜质量高、结晶性能好,电池取得6.3%的光电转换效率。结果证实WS 2纳米片可作为新型无机空穴传输层材料用于钙钛矿太阳能电池。     

效率增强的新型蓝色有机发光器件

使用一种新型空穴传输材料J003制备了不同结构、不同发光层厚度的两组蓝色发光器件,其结构为:ITO/CuPc/J003/JBEM:perylene/Al_q3/LiF/Al和ITO/CuPc/J003/JBEM:perylene/TPBi/Al_q3/LiF/Al,这里CuPc(Copper phthalocyanine)和LiF分别为空穴注入层(HIL)和电子注入层(EIL),J003为空穴传输层(HTL),JBEM(9,10-bis(3,5'-diaryl)phenylylanthracene)为发光层(EML),TPBj(1,3,5-tri(phenyl-2-benzimidazole)-benzene)为空穴阻挡层(HBL),Al_q3(tris(8-quinolinolato)aluminium complex)为电子传输层(ETL).两种结构中前者为无阻挡层的普通型结构,后者在发光层和电子传输层中加入了空穴阻挡层,是新型阻挡层结构.研究了空穴阻挡层的引入在不同厚度发光层时对器件发光性能的影响,结果表明,新型阻挡层结构能明显提高器件的亮度和效率,但依赖于发光层厚度,利用能级图分析了其中的原因.