使用PTB7作为阳极修饰层提高有机发光二极管的性能

采用poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl][3-?uoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]](PTB7)作为有机发光二极管器件的阳极修饰层,制备了结构为indium tin oxide(ITO)/PTB7(不同浓度)/N,N’-Bis(naphthalen-1-yl)-N,N’-bis(phenyl)benzidine(NPB,40 nm)/8-hydroxyquinoline(Alq3,60 nm)/LiF(1 nm)/Al的系列器件,同时研究了不同浓度的PTB7对器件性能的影响.PTB7的最佳浓度为0.25 mg/mL,器件性能得到明显的改善,起亮电压为4.3 V.当驱动电压为14.6 V时,最大亮度为45800 cd/m2,最大电流效率为9.1 cd/A.与没有PTB7修饰的器件相比,其起亮电压降低了1.9 V,最高亮度提升了78.5%.器件性能提高归因于PTB7的插入使得空穴注入和传输能力大大改善.     

The visible and ultraviolet organic light-emitting diodes with germanium dioxide as facile solution-processed anode buffer layer

Germanium dioxide (GeO₂) aqueous solutions are facilely prepared and the corresponding anode buffer layers (ABLs) with solution process are demonstrated. Atomic force microscopy, X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy measurements show that solution-processed GeO₂ behaves superior film morphology and enhanced work function. Using GeO₂ as ABL of organic light-emitting diodes (OLEDs), the visible device with tris(8-hydroxy-quinolinato)aluminium as emitter gives maximum luminous efficiency of 6.5 cd/A and power efficiency of 3.5 lm/W, the ultraviolet device with 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole as emitter exhibits short-wavelength emission with peak of 376 nm, full-width at half-maximum of 42 nm, maximum radiance of 3.36 mW/cm² and external quantum efficiency of 1.5%. The performances are almost comparable to the counterparts with poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) as ABL. The current, impedance, phase and capacitance as a function of voltage characteristics elucidate that the GeO₂ ABL formed from appropriate concentration of GeO₂ aqueous solution favors hole injection enhancement and accordingly promoting device performance.     

Organic light-emitting diode performance enhancement via indium tin oxide glass surface modification

A self-assembly monolayer (SAM), with phenyl-triethoxysilane (PTES), was used to modify the indium tin oxide anode for an organic light-emitting diode (OLED) in order to improve the OLED performance. The enhancement of OLED performance is attributed to the blockage of excessive hole injection by PTES, balancing the hole and electron injection numbers. The result indicates that the SAM process reaction time duration greatly affects the OLED performance outcomes. If the reaction time is too long, it will impact on the optical efficiency due to molecular aggregates accumulated on the SAM layers, thus reducing the performance of the OLEDs. The electrical and optical characteristics of the OLEDs are modeled by using the modified Shockley equation. Modified Shockley parameters are extracted to interpret the experimental data with excellent accuracy. Those parameters, both electrical and optical, can be used as the DC level modeling parameters for OLED product design simulations.     

Improved performances in top-emitting organic light-emitting diodes based on a semiconductor zinc oxide buffer layer

Electroluminescence performances are improved by inserting a semiconductor zinc oxide (ZnO) buffer layer into the emissive tris-(8-hydroxyquinoline)aluminum (Alq₃) layer and the semitransparent Al/Ag cathode in top-emitting organic light-emitting diodes (TEOLEDs) with structures of Si/SiO₂/Ag/Ag₂O/4,4′, 4″-tris(3- methylphenylphenylamino)triphenylamine/ 4,4′-bis[N-(1-naphthyl-1-)-N-phenyl- amino]-biphenyl/Alq₃/ZnO/Al/Ag. The thermal deposition of ZnO layer onto Alq₃ results in Alq₃ anion formation, which is beneficial to electron injection by generating some new energy levels in the forbidden band of Alq₃. In addition, a large hole-injection barrier of 2 eV at the interface of Alq₃/ZnO effectively blocks hole injection into Al/Ag cathode, leading to more carrier recombination in the emissive region.     

Ligand effect on the performance of organic light-emitting diodes based on europium complexes

A series of europium complexes were synthesized and their electroluminescent (EL) characteristics were studied. It was found by comparison that the different substituted groups, such as methyl, chlorine, and nitryl, on ligand 1,10-phenanthroline affect significantly the EL performance of devices based on these complexes. The more methyl-substituted groups on ligand 1,10-phenanthroline led to higher device efficiency. A chlorine-substituted group showed the approximate EL performance as two methyl-substituted groups, whereas a nitryl substituent reduced significantly the EL luminous efficiency. However, β-diketonate ligand TTA and DBM exhibited similar EL performance. The improved EL luminous efficiency by proper substituted groups on the 1,10-phenanthroline was attributed to the reduction of the energy loss caused by light hydrogen atom vibration, as well as concentration quenching caused by intermolecular interaction, and the match of energy level between the ligand and Eu³⁺.     

Solution-processed p-doped hole-transport layer and its application in organic light-emitting diodes

We investigate p-type doping poly(9-vinylcarbazole) (PVK) hole-transport layer (HTL) with tetrafluoro-tetracyano-quinodimethane introduced via cosolution. We found that the performances of devices with doped HTLs are significantly improved. The efficiency and lifetime of the p-doped device are 2.3 and 3.7 times as large as that of the control device with pure PVK as a HTL. Furthermore, the turn-on voltage of the device is reduced from 9.5 to 3.6 V by using a p-doped HTL. These improved properties are attributed to the formation of the charge-transfer complex in the HTL, which increases hole injection and conductivity of p-doped films considerably.     

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     

Multiple roles of bathocuproine employed as a buffer-layer in organic light-emitting diodes

Efficiency and brightness and carriers injection have been obviously improved by using bathocuproine (BCP) as a buffer-layer in organic light-emitting diodes. Compared with the bufferless device, the quantum efficiency of device ITO/NPB (10 nm)/Alq₃ (10 nm)/BCP (2.4 nm)/Al has increased four times at the same current density (32 mA/cm²). Moreover, the buffer layer has changed the current-voltage properties and the turn-on voltage has obviously decreased. Considering BCP and Al³⁺ can react conveniently under room temperature, we suggest that a complex cathode structure of BCP/[(Al)_x(BCP)_y]^3x+/Al has formed under electric field and the new cation [(Al)_x(BCP)_y]^3x+ at the BCP/Al interface has improved the internal electric field and then enhanced the electrons injection. we conclude that: for a very thin (<1 nm) BCP buffer layer, improving electron injection will principally responsible to the improvement of the performance of the OLEDs; for a thicker BCP layer, there will be a synthetic function of BCP: improving electron injection, hole-blocking and electron-transporting.     

Color tunable high efficiency microcavity organic light-emitting diodes

Color tunable microcavity organic light-emitting diodes (OLEDs) with structure of distributed Bragg reflectors (DBR)/indium-tin-oxide (ITO)/N,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB)/tris(8-hydroxyquinoline) aluminum (Alq₃)/LiF/Al were fabricated. Orange red and green light emissions with full width at half maximum (FWHM) of less than 20 nm were obtained through simply changing the thickness of NPB layer. Furthermore, due to the effective modification of the spontaneous emission within microcavity, the brightness and electroluminescent (EL) efficiency of the microcavity OLEDs were significantly enhanced. The maximum brightness and current efficiency, respectively, reached 31000 cd/m² at a current density of 480.0 mA/cm² and 8.3 cd/A at a current density of 110.0 mA/cm² for green devices, and 9700 cd/m² at a current density of 180.0 mA/cm² and 6.6 cd/A at a current density of 36.4 mA/cm² for red devices, which are over 1.5 times higher than those of noncavity OLEDs.      

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.     

Improved performance of P3HT：PCBM solar cells by both anode modification and short-wavelength energy utilization using Tb（aca）3phen

The performance of P3HT:PCBM solar cells was improved by anode modification using spin-coated Tb(aca)3phen ultrathin films. The modification of the Tb(aca)3phen ultrathin film between the indium tin oxide(ITO) anode and the PEDOT:PSS layer resulted in a maximum power conversion efficiency(PCE) of 2.99% compared to 2.66% for the reference device, which was due to the increase in the short-circuit current density(Jsc). The PCE improvement could be attributed to the short-wavelength energy utilization and the optimized morphology of the active layers. Tb(aca)3phen with its strong down-conversion luminescence properties is suitable for the P3HT:PCBM blend active layer, and the absorption region of the ternary blend films is extended into the near ultraviolet region. Furthermore, the crystallization and the surface morphology of P3HT:PCBM films were improved with the Tb(aca)3phen ultrathin film. The ultraviolent–visible absorption spectra,atomic force microscope(AFM), and X-ray diffraction(XRD) of the films were investigated. Both anode modification and short-wavelength energy utilization using Tb(aca)3phen in P3HT:PCBM solar cells led to about a 12% PCE increase.     

Air-gap embedding GaN template for enhanced emission from light-emitting diodes

Selective growth by metal-organic chemical vapor deposition (MOCVD), and electrochemical etching of a heavily Si-doped GaN (n⁺-GaN) interlayer were employed to obtain air-gaps embedded in a u-GaN layer. As confirmed by Raman spectroscopy, the introduction of an n⁺-GaN, which was later etched to obtain air-gaps, also enhanced the strain-compliance of GaN epilayer on sapphire substrate. An enhanced electroluminescence emission was observed from the light-emitting diodes (LEDs) fabricated on the air-gap embedding template. Using theoretical LED simulation, it was discerned that the increase in optical emission from the LED was caused predominantly by the redirection of photons at GaN/air-gap interface. Finite-difference time domain (FDTD) simulation method was employed to understand the mechanism of optical emission enhancement and its spatial variation over the LED surface.     

Improving the color purity and efficiency of blue organic light-emitting diodes (BOLED) by adding hole-blocking layer

This work demonstrates the fabrication of a bright blue organic light-emitting diode (BOLED) with good color purity using 4,4′-bis(2,2-diphenylvinyl)-1,1′-biphenyl (DPVBi) and bathocuproine (BCP) as the emitting layer (EML) and the hole-blocking layer (HBL), respectively. Devices were prepared by vacuum deposition on indium tin oxide (ITO)-glass substrates. The thickness of DPVBi used in the OLED has an important effect on color and efficiency. The blue luminescence is maximal at 7670 cd/m² when 13 V is applied and the BCP thickness is 2 nm. The CIE coordinate at a luminance of 7670 cd/m² is (0.165, 0.173). Furthermore, the current efficiency is maximum at 4.25 cd/A when 9 V is applied.     

Phosphorescent white organic light-emitting diodes with stable white color depending on luminance

We fabricated simple and color-stable phosphorescent white organic light-emitting diodes (OLEDs) without an interlayer using a single host of 1,3-bis(9-carbazolyl)benzene with iridium(III) bis[(4,6-difluorophenyl) pyridinato-N,C2’]picolinate and bis(1-phenylisoquinoline)(acetylacetonate) iridium(III) as blue and red phosphorescent emitters, respectively. The CIE 1931 color coordinate difference of the white OLEDs is (0.008, 0.007) when the luminance of the device is increased from approximately 265 cd/m² to 9156 cd/m², which is regarded as visually indistinguishable in practice. In addition, we also measured the decay time of excitons to investigate the emission mechanism in this device using transient photoluminescence and electroluminescence techniques.     

有机薄膜晶体管驱动聚合物发光二极管研究

研究了有机薄膜晶体管(OTFT)与聚合物发光二极管(PLED)集成制备技术和相关物理问题.OTFT结构为栅极钽(Ta)/绝缘层五氧化二钽(Ta2O5)/有源层并五苯(Pentacene)/源漏极金(Au);PLED器件结构为ITO/PEDOT:PEO(polyethylene oxide)/P-PPV或MEH-PPV/Ba/Al.PEDOT:PEO,P-PPV和MEH-PPV薄膜层均采用丝网印刷技术,实现了OTFT与PLED器件集成发光.其中OTFT器件的阈值电压为-7V,迁移率为0.91cm2/(V.s),并通过OTFT驱动得到以P-PPV和MEH-PPV为发光层的PLED器件的发光亮度分别达到124和26cd/m2,电流效率分别为12.4和1.1cd/A.利用丝网印刷技术可以有效控制高分子薄膜的沉积区域,实现功能器件的集成.     

The performance enhancement in organic light-emitting diode using a semicrystalline composite for hole injection

A semicrystalline composite, 3, 4, 9, 10 perylenetetracarboxylic dianhydride （PTCDA） doped N,N＇-di（1-naphthyl）- N,N＇-diphenylbenzidine （NPB）, has been fabricated and characterized. An organic light-emitting diode using such a composite in hole injection exhibits the improved performance as compared with the reference device using neat NPB in hole injection. For example, at a luminance of 2000 cd/m2, the former device gives a current efficiency of 2.0cd/A, higher than 1.6cd/A obtained from the latter device. Furthermore, the semicrystalline composite has been shown thermally to be more stable than the neat NPB thin film, which is useful for making organic light emitting diodes with a prolonged lifetime.     

New double graded structure for enhanced performance in white organic light emitting diode

This study presents a new design that uses a combination of a graded hole transport layer (GH) structure and a gradually doped emissive layer (GE) structure as a double graded (DG) structure to improve the electrical and optical performance of white organic light-emitting diodes (WOLEDs). The proposed structure is ITO/m-MTDATA (15 nm)/NPB (15 nm)/NPB: 25% BAlq (15 nm)/NPB: 50% BAlq (15 nm)/BAlq: 0.5% Rubrene (10 nm)/BAlq: 1% Rubrene (10 nm)/BAlq: 1.5% Rubrene (10 nm)/Alq₃ (20 nm)/LiF (0.5 nm)/Al (200 nm). (m-MTDATA: 4,4′,4″ -tris(3-methylphenylphenylamino)triphenylamine; NPB: N,N′-diphenyl-N,N′-bis(1-naphthyl-phenyl)-(1,1′-biphenyl)-4,4′-diamine; BAlq: aluminum (III) bis(2-methyl-8-quinolinato) 4-phenylphenolate; Rubrene: 5,6,11,12-tetraphenylnaphthacene; Alq₃: tris-(8-hydroxyquinoline) aluminum). By using this structure, the best performance of the WOLED is obtained at a luminous efficiency at 11.8 cd/A and the turn-on voltage of 100 cd/m² at 4.6 V. The DG structure can eliminate the discrete interface, and degrade surplus holes, the electron-hole pairs are efficiently injected and balanced recombination in the emissive layer, thus the spectra are unchanged under various drive currents and quenching effects can be significantly suppressed. Those advantages can enhance efficiency and are immune to drive current density variations.     

Excitation cross-section and lifetime of the excited state of erbium ions in avalanching light-emitting Si : Er : O diodes

Electroluminescence (EL) characteristics of avalanching silicon diodes fabricated by Er and O co-implantation and subsequent annealing have been studied. Saturation of the Er-related EL intensity is achieved under the avalanche regime at current density an order of magnitude lower than that under the tunnel regime. Under avalanche regime at 300 K, the effective cross-section for excitation of Er³⁺ ions is equal to 2.3×10⁻¹⁶ cm² and the lifetime of the excited state is equal to 380 μs being four times higher than these values in tunneling diodes.     

Solution-processed WOx hole injection layer for efficient fluorescent blue organic light-emitting diode

Solution-processed tungsten oxide (s-WO_x) interfacial layer for efficient hole injection in fluorescent blue organic light-emitting diode (OLED) is demonstrated. The OLED using 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN) as emitter shows luminous efficiency of 3.3 cd/A, power efficiency of 2.5 lm/W and external quantum efficiency of 4.6% with Commission Internationale d'Eclairage (CIE) color coordinates of (0.154, 0.102). Using MADN doped 1-4-di-[4-(N,N-diphenyl)amino]styryl-benzene as emitter, luminous efficiency of 10.8 cd/A, power efficiency of 6.4 lm/W and external quantum efficiency of 7.2% with CIE color coordinates of (0.167, 0.283) are achieved. Atomic force microscopy and X-ray photoelectron spectroscopy show that s-WO_x features superior film morphology and non-stoichiometry with slight oxygen deficiency. Current-voltage characteristics and impedance spectroscopy analysis indicate that s-WO_x behaves slightly enhanced hole injection and accordingly contributes to improved device performance in comparison with conventional vacuum thermal evaporation WO_x. Our results pave an alternative way for broadening WO_x application with solution process and advancing fluorescent blue OLEDs.     

利用发光层梯度掺杂改善顶发射白光有机发光二极管光谱的稳定性

在具有顶发射结构的白光有机发光二极管(TWOLED)中, 稳定的纯白光比较难以实现. 本文在蓝光/红光/蓝光三发光层基础上, 进一步采用了红光层梯度掺杂的方式提高TWOLED的性能. 制备了一系列的梯度掺杂器件, 通过与均匀掺杂器件的对比, 详细分析了梯度掺杂对发光层中载流子漂移以及激子扩散的影响, 解释了白光稳定性提高的物理机理. 此外, 顶发射器件中的微腔效应也是影响白光光谱的一个重要因素, 本文利用微腔理论计算分析了微腔共振对器件光谱的影响.