新型苯乙烯衍生物掺杂的蓝色及白色有机电致发光器件

研究了新型高效蓝色掺杂剂EBDP的电致发光性能. 分别以EBDP为掺杂剂制备了结构为氧化铟 锡(ITO)/酞菁铜(CuPc)/N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺(NPB)/2- 叔丁基-9,10-二-(2-萘基)蒽(TBADN):EBDP/8-羟基喹啉铝(Alq₃)/LiF/Al 与ITO /CuPc/NPB/TBADN:EBDP: 4-二氰亚甲基-2-叔丁基-6-(1,1,7,7-四甲基久咯呢定基-9-烯基)- 4H-吡喃/Alq_{3 关键词： 有机电致发光 蓝色掺杂剂 蓝色电致发光器件 白色电致发光器件}     

Deep blue organic light emitting diode based on anthracene derivative as a dopant

This letter presents a deep blue organic light emitting diode which was fabricated by using 9,10-di(2-naphthyl)anthracene as a dopant and 4,4′-N,N′-dicarbazole-biphenyl as a host. The Commission Internationale de l’Eclairage coordinates of (0.1516, 0.0836) were achieved in the cell, which is very close to the National Television Standards Committee standard of (0.14, 0.08). Meanwhile, maximum luminance over 6500 cd/cm² and maximum current efficiency of 3.5 cd/A were also obtained.     

Transparent manganite films as hole injectors for organic light emitting diodes

Organic light-emitting diodes (OLEDs) are nowadays one of the most attractive devices based on organic semiconductors due to their successful application in the display technology. Electroluminescence in OLEDs is mainly governed by the fluorescence from excited singlet states, which have large transition probabilities providing the major radiative pathway. The “forbidden” triplet state emission can be activated by increasing spin–orbit coupling via dye doping. The singlet–triplet exciton formation statistics is usually given by 1:3 partition due to the quantum constrains.

Injection of carriers with finite spin polarisation should influence and modify the recombination statistics and can be used for tuning of the device efficiency. In this context, the development of a new class of electrodes able to guarantee both efficient charge and spin injection becomes of paramount importance. We show that strongly spin polarised colossal magnetoresistance manganite La_0.7Sr_0.3MnO₃ (LSMO) can successfully substitute conventional ITO electrodes in OLEDs. Highly transparent, metallic and ferromagnetic LSMO layers were used in combination with standard Al and spin polarised Co top electrodes. Electrical and optical characterisations of the OLEDs with spin polarised electrodes indicate the applicability of the new manganite electrodes for organic light-emitting devices.     

Surface and edge emission in organic light emitting devices

We report the studies on photoluminescence (PL) and electroluminescence (EL) spectra of organic light emitting diodes (OLED) based on most widely used light emitting material, i.e., Tris-(8-hydroxyquinoline) aluminum (Alq₃). PL studies from the edges and top surface were carried out on different thicknesses of single layer of Alq₃ coated on glass substrate and the PL intensity from the edges was found to be more than that from the top surface. On the other hand EL emission intensity from the surface was found to be larger than that from the edges of the OLED device. The discrepancy in the PL and EL emission from edge and the top surfaces is discussed. The effect of the thickness of Alq₃ layer on the PL intensity and the emission spectra are also investigated.     

3,4,9,10-Perylenetetracarboxylicdiimide as an interlayer for ultraviolet organic light emitting diodes

Ultraviolet organic light emitting diodes with 3,4,9,10-perylenetetracarboxylicdiimide (PTCDI) interlayer have been achieved. The emission spectrum and intensity were strongly dependent on the thickness of PTCDI interlayer, in spite of the fact that PTCDI has neither much lower HOMO nor much higher LUMO level, which is considered necessary for efficient charge blocking layers. The influence of PTCDI layer was investigated in three different device configurations and obtained results are discussed. For optimal device configuration, OLED with emission centered at 370 nm and turn-on voltage of 4.5 V is obtained.     

发光层厚度对联苯乙烯衍生物蓝色有机发光器件性能的影响

本文制备了联苯乙烯衍生物(4, 4'-bis(2, 2'-diphenylvinyl)-1, 1'-biphenyl, DPVBi) 为发光层的蓝色有机电致发光器件. 器件性能随发光层厚度变化而变. 在DPVBi厚度为10---50 nm范围内, 同样电流密度下器件亮度及效率随DPVBi厚度增加先增后减, 40 nm时最佳, 最高亮度达到15840 cd/m², 最高外量子效率达到3.2%, 器件色坐标(Commission Internationale de l'Eclairage (CIE) co-ordinates) 为(0.15, 0.15). DPVBi厚度超过40 nm时器件发光光谱出现红移而致色度变差, 其原因可归于微腔效应所致. 同时, 通过实验结果分析表明DPVBi中激子扩散长度位于20---30 nm范围.     

Investigation of carrier injection mechanism in small molecular organic light emitting device with a mixed single organic layer

Injection properties of electrons and holes in a mixed single layer organic light emitting device with mixed small molecules tris-(8-hydroxy-quinoline) aluminum (Alq₃), 2,5-bis(6′-(2′,2″-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (PyPySPyPy), 4′-bis[N-(1-napthyl)-N-phenyl-amino]biphenyl (α-NPD), and 5,6,11,12-tetraphenylnaphthacene (rubrene) were investigated using Au/MoO₃ as hole and Al alloy as electron injection electrodes. On the basis of measuring the temperature dependence of currents through the interface between the electrodes and the mixed single organic layer, the carrier injection mechanism was primarily ascribed to the Schottky thermionic emission with the barrier height of 0.25 eV for holes and 0.67 eV for electrons. By adding the dopant material rubrene and the electron transport material PyPySPyPy into the mixed single layer, the barrier height of electrons could be reduced. The interfacial state analysis demonstrated that the electron barrier height was also dependent on the interfacial conditions of the device.     

A triphenylamine derivative as an efficient organic light color-conversion material for white LEDs

A novel efficient (Φ=0.44) organic yellow-emitting dye, 3-(4-(diphenylamino)phenyl)-1-phenylprop-2-en-1-one (DPPO), was synthesized. The compound was characterized by means of ¹H NMR and differential scanning calorimetry (DSC) and analyzed by quantum chemistry method. It was found that DPPO could be effectively excited by the InGaN-based blue LED. Photo-durability data of DPPO were studied. Bright white light of Commission International del’ Eclairage (CIE) x=0.30, y=0.33 was obtained by using DPPO as a light color-conversion material (CCM).     

Blue organic electroluminescent devices based on a distyrylarylene derivative as emitting layer and a terbium complex as electron-transporting layer

With a blue distyrylarylene derivative, 4,4′-bis(2,2-di(2-methoxyphenyl)ethenyl)-1,1′-biphenyl (CBS) as emitting material, double-layer and triple-layer electroluminescent (EL) devices were fabricated. For the device using tris-(1-phenyl-3-methyl-4-isobutyryl-5-pyrozolone)-bis(triphenyl phosphine oxide) terbium (Tb(PMIP)₃(TPPO)₂) as the electron-transporting layer, blue EL emission with a maximum luminance of 253 cd/m² was achieved at 19 V. The difference of Tb(PMIP)₃(TPPO)₂ and tris(8-hydroxyquinolinate)aluminum (AlQ) as the electron-transporting materials in these devices were compared and discussed.     

两种谐振腔长度的微腔有机电致发光器件模拟

微腔的谐振腔长度直接影响微腔有机电致发光器件(MOLED)的发光特性,根据微腔器件的相关计算公式运用传输矩阵法,分别对微腔长度L=λ/2和L=λ(λ:中心波长)时,在微腔内不同位置激子复合发光的电致发光谱(EL)进行模拟计算和比较。发现:微腔长度为L=λ/2时,峰值均为520nm,半峰全宽均为17nm,激子处在微腔的中心位置时,峰值强度和积分强度均为最大。L=λ时,激子在腔内不同位置时,峰值均为520nm,半峰全宽均12nm,在腔的中心区域时,与L=λ/2时正好相反,峰值强度和积分强度最小。分析后判断是因为两种长度的微腔内电场强度分布不同,激子位于腔内电场的最大值处发光性能最好。说明要制作出高效率的MOLED,要区别不同谐振腔长度,并使激子处于腔内电场最大处。     

Light outcoupling efficiency enhancement in organic light emitting diodes using an organic scattering layer

Crystallized 4,7‐diphyenyl‐1,10‐phenanthroline (BPhen) films deposited by convenient vacuum thermal evaporation technique have been found to be an efficient means to extract the substrate wave guided light in organic light emitting diodes (OLEDs). The optimized BPhen film working as organic scattering layer was successfully used with OLEDs for light outcoupling efficiency improvement. Enhancement of 26%, 15% and 6% in efficiency of the blue, green and red OLEDs were obtained, respectively. The achievement was found to be advantageous in terms of simplicity of fabrication method and feasibility for large area OLED applications. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Improved outcoupling of light in organic light emitting devices, utilizing a holographic DFB-structure

In this work organic light emitting devices (OLEDs) were fabricated implementing gratings, in order to extract waveguided electroluminescence (EL). The gratings were recorded by exposing thin films of the molecular azo glass N, N′-bis (4-phenyl)-N, N′-bis [(4-phenylazo)-phenyl] benzidine (AZOPD) to holographic light patterns. The photopatterned AZOPD serves as hole transport material for devices with aluminum-tris(8-hydroxyquinoline) doped with 1% of 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (Alq₃:DCM) as emissive/electron transport layer. The corrugated devices showed enhanced emission in the forward direction. The emitted light is polarized preferably parallel to the grating lines. In addition, we have found a doubling in the total luminance with respect to the unstructured device.     

Electronic properties of phenanthrimidazoles as hole transport materials in organic light emitting devices and in photoelectron transfer to ZnO nanoparticles

Phenanthrimidazoles as hole transport materials have been synthesized, characterized, and applied as nondoping emitters in organic light emitting devices. The synthesized molecules possess high fluorescent quantum yield and thermal properties and display film forming abilities. The highest occupied molecular orbital (HOMO) energies of these materials are shallower than the reported tris(8‐hydroxyquinoline)aluminum (Alq₃), which enables the hole transport ability of these phenanthrimidazoles. Taking advantage of the thermal stability and hole transporting ability, these compounds can be used as a functional layer between NPB [4,4‐bis(N‐(1‐naphthyl)‐N‐phenylamino)biphenyl] and Alq₃ layers and show that these phenanthrimidazoles can be alternatively used as novel hole transport materials and to improve the device performances. Geometrical, optical, electrical, and electroluminescent properties of these molecules have been probed. Further, natural bond orbital, nonlinear optical materials (NLO), molecular electrostatic potential, and HOMO–lowest unoccupied molecular orbital (LMO) energy analysis have been made by density functional theory (DFT) method to support the experimental results. Hyperpolarizability analysis reveals that the synthesized phenanthrimidazoles possess NLO behavior. The chemical potential, hardness, and electrophilicity index of phenanthrimidazoles have also been computed by DFT method. Photoinduced electron transfer explains the enhancement of fluorescence by nanoparticulate ZnO, and the apparent binding constant has been obtained. Adsorption of the fluorophore on ZnO nanoparticle lowers the HOMO and LUMO energy levels of the fluorophore. The strong adsorption of the phenanthrimidazoles on the surface of ZnO nanocrystals is likely due to the chemical affinity of the nitrogen atom of the organic molecule to Zn(II) on the surface of nanocrystal. Copyright © 2013 John Wiley & Sons, Ltd.     

磁场对基于Co铁磁薄膜的有机发光器件效率和电流的影响

制备结构为ITO/Co/NPB/Alq₃/LiF/Al的有机发光器件,测量了室温下磁场对器件发光效率和电流的影响.发现磁场强度小于80 mT时,器件发光效率随磁场强度的增加而增大,最大为18.8%,随磁场强度的继续增加发光效率的增强趋于饱和.效率的增加是Co的自旋极化的注入和磁场效应共同作用的结果,其中自旋极化注入起主要作用.在磁场强度小于60 mT时电流随磁场增强而增加,最大为6.9%,随磁场强度的进一步增加电流的增加有所减弱.产生这种现象的原因可归结为磁场相关的单线态极化子对的解 关键词： 有机电致发光 自旋极化 磁场效应     

Advantages of an InGaN-based light emitting diode with a p-InGaN/p-GaN superlattice hole accumulation layer

P-InGaN/p-GaN superlattices (SLs) are developed for a hole accumulation layer (HAL) of a blue light emitting diode (LED). Free hole concentration as high as 2.6×1018 cm-3 is achieved by adjusting the Cp2Mg flow rate during the growth of p-InGaN/p-GaN SLs. The p-InGaN/p-GaN SLs with appropriate Cp 2 Mg flow rates are then incorporated between the multi-quantum well and AlGaN electron blocking layer as an HAL, which leads to the enhancement of light output power by 29% at 200 mA, compared with the traditional LED without such SL HAL. Meanwhile, the efficiency droop is also effectively alleviated in the LED with the SL HAL. The improved performance is attributed to the increased hole injection efficiency, and the reduced electron leakage by inserting the p-type SL HAL.     

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.     

LiF插层对有机发光二极管磁场效应的调控

制备了有LiF插层的有机发光二极管,以八羟基喹啉铝（Alq₃）作为电子传输层,N, N′-二苯基-N, N′-二(1-萘基)-1,1′-联苯-4,4′-二胺（NPB）作为空穴传输层.通过改变Alq₃与NPB间LiF插层的厚度,研究了不同温度下器件的光电特性及电致发光的磁场效应.测量结果表明:LiF插层可以影响器件内部载流子的输运和激发态的形成.较厚的插层阻碍了空穴的传输,使器件的电流效率变低.但实验中发现, 关键词： LiF插层结构 磁场效应 三重态激子     

Composition-dependent phase separation effects of organic solar cells using P3HT:PCBM as active layer and chromium oxide as hole transporting layer

Phase separation of the poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) active layer (ATL) was investigated by varying their relative ratio in the organic solar cells (OSCs). With the help of the UV/visible spectrophotometer, optical microscopy and scanning electron microscope, we found that the cluster of PCBM at the interface or surface was affected by Al cathode, the composition of the blends and thermal annealing. The disc-like shape crystals of PCBM substituted for the needle-like ones at higher PCBM compositions at the ATL/Al interface, which led to stronger contacts and bigger contact area. It could make short circuit current density increase, but may affect the blend morphology and result in parallel resistance and open circuit voltage decreased with the PCBM ratio increasing from 40 to 60%. The microstructure of the P3HT:PCBM ATL, determined by the composition dependent phase separation, supported the optimized performance of the OSCs with the composition of 40-50% PCBM.     

Improvement in semiconductor laser printing using a sacrificial protecting layer for organic thin-film transistors fabrication

Laser-induced forward transfer (LIFT) has been used to deposit pixels of an organic semiconductor, distyryl-quaterthiophenes (DS4T). The dynamics of the process have been investigated by shadowgraphic imaging for the nanosecond (ns) and picosecond (ps) regime on a time-scale from the laser iradiation to 1.5 μs. The morphology of the deposit has been studied for different conditions. Intermediate sacrificial layer of gold or triazene polymer has been used to trap the incident radiation. Its role is to protect the layer to be transferred from direct irradiation and to provide a mechanical impulse strong enough to eject the material.     

Increased performance of an organic light-emitting diode by employing a zinc phthalocyanine based composite hole transport layer

We demonstrate that the electroluminescent performances of organic light-emitting diodes are significantly improved by employing a zinc phthalocyanine （ZnPc）-based composite hole transport layer （c-HTL）. The optimum ris-（8-hydroxyquinoline）aluminum （Alq3）-based organic light-emitting diode with a c-HTL exhibits a lower turn-on voltage of 2.8 V, a higher maximum current efficiency of 3.40 cd/A and a higher maximum power efficiency of 1.91 lm/W, which are superior to those of the conventional device （turn-on voltage of 3.8 V, maximum current efficiency of 2.60 cd/A, and maximum power efficiency of 1.21 lm/W）. We systematically studied the effects of different kinds of N’-diphenyl-N,N’-bis（1-naphthyl）（1,1’-biphenyl）-4,4’diamine （NPB）：ZnPc c-HTL. Meanwhile, we also investigate their mechanisms different from that in the case of using ZnPc as buffer layer. The specific analysis is based on the absorption spectra of the hole transporting material and current density–voltage characteristics of the corresponding hole-only devices.