微腔调色法实现有机发光器件三基色的研究

用微腔调色法来实现有机发光器件的三基色，有利于减少光损失，并提高器件的色饱和度和效率.以多波长的白光器件为基构成了微腔顶发射器件.顶发射器件以Ag作为全反射阳极，ITO为光程调节层，Al/Ag为半透明复合阴极，Alq：DCJTB/TBADN：TBPe/Alq：C545为白光发光层.通过调节ITO厚度，改变微腔光程以及器件的颜色，分别得到红、蓝、绿三基色的器件，器件发光峰值分别为475，538和603nm，色坐标分别为(0.133，0.201)，(0.335，0.567)和(0.513，0.360).半高宽分别为30，48，70nm. 关键词： 有机发光 顶发射 微腔效应 三基色     

A very simple method of constructing efficient inverted top-emitting organic light-emitting diode based on Ag/Al bilayer reflective cathode

A comparative study on top-emitting organic light-emitting diodes (TOLEDs) with normal and inverted structures is briefly investigated. In comparison with the normal TOLED having Ag reflective anode, the inverted device with monolayer Al reflective cathode shows low efficiency as a result of lower reflectance of Al and inferior electron injection. Using Ag/Al bilayer reflective cathode is demonstrated to be a simple and effective method of enhancing efficiency in inverted TOLED. With tris(8-hydroquinoline) aluminum (Alq₃) as emitter the luminous efficiency reaches 5.9±0.6 cd/A, which is much higher than those of the corresponding normal TOLED (～5.1 cd/A) and inverted TOLED with monolayer Al reflective cathode (～4 cd/A). The improved performance is attributed to the enhanced reflectance and significant microcavity effect. The electron-injection barrier height of ～0.1 eV from Al to Alq₃ via an ultrathin LiF is estimated in the tunneling process for both normal and inverted devices.     

微腔结构顶发射有机发光器件

以Ag/ITO为全反射阳极，以Al/Ag为半透明复合阴极，制备了绿色、蓝色两种微腔结构顶发射有机发光器件，研究了微腔效应对顶发射器件颜色的影响，通过调节光程，实现了用同一种有机发光层制备出不同波长的发射.Alq基顶发射器件得到波长峰值从500 nm到584 nm的不同颜色的器件，发光光谱半高宽由传统器件的100 nm窄化到20—40 nm，最高电流效率1.77 cd/A.蓝光顶发射器件发光峰值从464 nm变化到532 nm，半高宽由传统器件的65 nm窄化到17—21 nm，并得到色坐标为(0.141，0.049)的深蓝色顶发射有机发光器件. 关键词： 有机发光 顶发射 微腔效应     

Model and simulation on the efficiencies of microcavity OLEDs

This paper presents simple calculation models of the external quantum efficiency and power efficiency for the microcavity OLEDs. The models take into account the energy spatial distribution of the device and provide a rough estimate of the efficiencies for the planar surface emitting devices, by which the integrating sphere and monochrometer were saved. The external quantum efficiency and luminous current efficiency from the structures of glass/DBR/ITO/NPB/Alq: C545T/Alq/LiF/Al and glass/ITO/NPB/Alq: C545T/Alq/LiF/Al were calculated based on these models and the measured data. Comparing with conventional OLED, the external quantum efficiency and luminous current efficiency of the MOLED were improved 3.1% and 8% at low current density (< 10 mA/cm², corresponding to the display brightness range), respectively.     

Near-white emitting QD-LED based on hydrophilic CdS nanocrystals

In this work we report fabrication of a nanocrystal (NC)-based hybrid organic–inorganic LED with structure of ITO/PEDOT:PSS/PVK/CdS-NCs/(Al or Mg:Ag). The hydrophilic CdS NCs were synthesized using a novel aqueous thermochemical method at 80 °C and sizes (around 2 nm) were controlled by thioglycolic acid (TGA) as the capping agent. The favorite feature of these NCs is their relatively high emission intensity and broad, near-white emission. The hydrophilic CdS NCs were successfully spin coated using Triton X-100 as the wetting agent. The fabricated LEDs demonstrated a turn on voltage about 7 V for Al metallic contact. The electroluminescence was a broad spectrum at 540 and 170 nm width, which was about 50 nm red shifted compared to photoluminescence spectra. The CIE color coordinates of the LED at (0.33, 0.43) demonstrated a near white light LED with an emission on green–yellow boundary of white. Annealing of the device up to 190 °C had a positive effect on the performance, possibly due to better contacts between layers. Replacing Al contacts with Mg:Ag reduced the turn-on voltage to 6 V and changed CIE color coordinate to (0.32, 0.41). The EL peak was also shifted to 525 nm, with a brightness of 15 Cd/m² at working voltage of 15 V. The current efficiency and external quantum efficiency of device were 0.08 Cd/A and 0.03% at current densities higher than 10 mA/cm².     

微腔有机电致发光白光器件设计及制作

用一种宽谱带材料Alq₃作为发光层,设计并制作白色有机微腔电致发光器件。器件结构:Glass/DBR/ITO(194 nm)/NPB(93 nm) /Alq₃(49 nm)/MgAg(150 nm),得到了位于蓝(488 nm)和红(612 nm)光区域的两个腔发射模式,并通过颜色匹配获得了白光。器件的最大电致发光亮度16 435 cd/m²,最大效率11.1 cd/A,典型亮度值100 cd/m²时的发光效率、电压、电流密度分别是9 cd/A,6 V和1.2 mA/cm²,CIE 色坐标为(0.32, 0.34)。在不同的驱动电压下,器件的发光颜色稳定,说明了微腔是一种制作白光OLED的有效结构。     

Fabrication of blue top-emitting organic light-emitting devices with highly saturated color

Blue top-emitting organic light-emitting devices (TOLEDs) with highly saturated color were developed by microcavity effect. The device structure studied was glass/reflective silver/indium-tin oxide (ITO)/organic electroluminescent stack/semi-transparent cathode (calcium/silver). By changing the thicknesses of ITO and organic layers in the microcavity structure device doped with p-bis(p-N, N-di-phenyl-aminostyryl)benzene (DSA-ph), highly saturated color with Commission Internationale de L'Eclairage chromaticity coordinates (CIE_x,y) of (0.14, 0.08) was obtained.     

Highly efficient and stable organic light-emitting diode by balancing drift current of charge

Highly efficient and stable OLED device in which hole-drift current and electron-drift current are balanced was fabricated. Drift current characteristics according to the thickness of organic layer were examined using the device with ITO/m-MTDATA/NPB/Al structure that can only move the hole and the device with Al/LiF/Alq₃/LiF/Al structure that can only move the electron. Using the result of such examination, green device with balanced drift current was produced. Device with the structure of m-MTDATA (80 nm)/NPB (20 nm)/C-545T (3%) doped Alq₃ (5 nm)/Alq₃ (59 nm)/LiF (1 nm)/Al (200 nm) showed color purity of (0.309, 0.643) and high efficiency of 7.0 lm/W (14.4 cd/A). Most of light emission was observed inside the green emitting layer. Through the result of EL spectrum for the device also including red emitting layer, same result could be obtained. The device with balanced drift current also showed half life-time of 175 h for initial luminance of 3000 cd/m², which is more stable in comparison to the device without balanced drift current.     

The effect of Ag layer thickness on the properties of WO3/Ag/MoO3 multilayer films as anode in organic light emitting diodes

Transparent conductive WO₃/Ag/MoO₃ (WAM) multilayer electrodes were fabricated by thermal evaporation and the effects of Ag layer thickness on the optoelectronic and structural properties of multilayer electrode as anode in organic light emitting diodes (OLEDs) were investigated using different analytical methods. For Ag layers with thickness varying between 5 and 20 nm, the best WAM performances, high optical transmittance (81.7%, at around 550 nm), and low electrical sheet resistance (9.75 Ω/cm²) were obtained for 15 nm thickness. Also, the WAM structure with 15 nm of Ag layer thickness has a very smooth surface with an RMS roughness of 0.37 nm, which is suitable for use as transparent conductive anode in OLEDs. The current density?voltage?luminance (J?V?L) characteristics measurement shows that the current density of WAM/PEDOT:PSS/TPD/Alq₃/LiF/Al organic diode increases with the increase in thickness of Ag and WO₃/Ag (15 nm)/MoO₃ device exhibits a higher luminance intensity at lower voltage than ITO/PEDOT:PSS/TPD/Alq₃/LiF/Al control device. Furthermore, this device shows the highest power efficiency (0.31 lm/W) and current efficiency (1.2 cd/A) at the current density of 20 mA/cm², which is improved 58% and 41% compared with those of the ITO-based device, respectively. The lifetime of the WO₃/Ag (15 nm)/MoO₃ device was measured to be 50 h at an initial luminance of 50 cd/m², which is five times longer than 10 h for ITO-based device.     

An organic electroluminescent device made from a gadolinium complex

A gadolinium ternary complex, tris(1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone) (phenanthroline) gadolinium [Gd(PMIP)₃(Phen)] was synthesized and used as a light emitting material in the organic electroluminescent (EL) devices. The triple layer device with a structure of indium tin oxide (ITO)/N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine (TPD) (20 nm)/Gd(PMIP)₃(Phen) (80 nm)/2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (bathocuproine or BCP) (20 nm)/Mg: Ag(200 nm)/Ag(100 nm) exhibited green emission peaking at 535 nm. A maximum luminance of 230 cd/m² at 17 V and a peak power efficiency of 0.02 lm/w at 9 V were obtained.     

Enhanced power efficiency of ZnO based organic/inorganic solar cells by surface modification

We present series of strategies to enhance efficiency of ZnO nanorods based organic/inorganic solar cells with spin-coated P3HT:PCBM blend as active layer. The performance of the as-fabricated devices is improved by controlling the size of ZnO nanorods, annealing temperature and time of active layer, surface modification of ZnO with PSBTBT. Optimized device of ITO/ZnO nanorod/P3HT:PCBM/Ag device with PSBTBT surface modification and air exposure reaches an efficiency of 2.02% with a short-circuit current density, open-circuit voltage and fill factor of 13.23 mA cm⁻², 0.547 V and 28%, respectively, under AM 1.5 irradiation of 100 mW m⁻², the increase in efficiency is 7-fold of the PSBTBT surface modified ITO/ZnO nanorods/P3HT:PCBM/Ag device compared with the unmodified one, which is own to the increased interface contact, expanded light absorption, tailored band alignment attributed to PSBTBT. We found exposure to air and surface modification is crucial to improve the device performance, and we discussed the mechanisms that affect the performance of the devices in detail.     

Synthesis and characterization of PPV-based light-emitting copolymer with alkylsilylphenyloxy pendant group for light-emitting diode applications

A novel light-emitting copolymer with high brightness and luminance efficiency was synthesized using the Gilch polymerization method, and its electro-optical properties were investigated. A polymer light-emitting diode (PLED) was fabricated in ITO/PEDOT/light-emitting copolymer/Ca/Al configuration. The turn-on voltage of the PLED was about 5.0 V with maximum brightness and luminance efficiency up to 1420 cd/m² at 16.2 V and 0.5 cd/A at 6.8 V, respectively.     

Ohmic contact and space-charge-limited current in molybdenum oxide modified devices

The effect of indium-tin oxide (ITO) surface treatment on hole injection of devices with molybdenum oxide (MoO₃) as a buffer layer on ITO was studied. The Ohmic contact is formed at the metal/organic interface due to high work function of MoO₃. Hence, the current is due to space charge limited when ITO is positively biased. The hole mobility of N, N′-bis-(1-napthyl)-N, N′-diphenyl-1, 1′biphenyl-4, 4′-diamine (NPB) at various thicknesses (100–400 nm) has been estimated by using space-charge-limited current measurements. The hole mobility of NPB, 1.09×10⁻⁵ cm²/V s at 100 nm is smaller than the value of 1.52×10⁻⁴ cm²/V s at 400 nm at 0.8 MV/cm, which is caused by the interfacial trap states restricted by the surface interaction. The mobility is hardly changed with NPB thickness for the effect of interfacial trap states on mobility which can be negligible when the thickness is more than 300 nm.     

Electrical characteristics and efficiency of organic light-emitting diodes depending on hole-injection layer

In a device structure of ITO/hole-injection layer/N,N′-biphenyl-N,N′-bis-(1-naphenyl)-[1,1′-biphthyl]4,4′-diamine(NPB)/tris(8-hydroxyquinoline)aluminum(Alq₃)/Al, we investigated the effect of the hole-injection layer on the electrical characteristics and external quantum efficiency of organic light-emitting diodes. Thermal evaporation was performed to make a thickness of NPB layer with a rate of 0.5–1.0 Å/s at a base pressure of 5 × 10⁻⁶ Torr. We measured current–voltage characteristics and external quantum efficiency with a thickness variation of the hole-injection layer. CuPc and PVK buffer layers improve the performance of the device in several aspects, such as good mechanical junction, reducing the operating voltage, and energy band adjustment. Compared with devices without a hole-injection layer, we found that the optimal thickness of NPB was 20 nm in the device structure of ITO/NPB/Alq₃/Al. By using a CuPc or PVK buffer layer, the external quantum efficiencies of the devices were improved by 28.9% and 51.3%, respectively.     

Tetraalkoxylated-PPV derivative: An efficient and pure green electroluminescent polymer with good solution processability

A new solution-processable tetraalkoxy-substituted poly(1,4-phenylenevinylene) derivative, poly{[2-(3′,7′-dimethyloctyloxy)-3,5,6-trimethoxy]-1,4-phenylenevinylene} (TALK-PPV), was synthesized through a dehydrohalogenation polymerization route, and its light-emitting properties were investigated. The TALK-PPV showed highly blue-shifted UV–visible absorption and PL emission spectra compared to the dialkoxy-substituted PPV derivatives. This is because of the disturbance to the π-conjugation caused by a steric hindered structure. The TALK-PPV thin film exhibited an absorption peak at 446 nm, with an onset at 515 nm. Its PL emission maximum was at 554 nm. Cyclic voltammetric analysis showed the HOMO and LUMO energy levels of the TALK-PPV to be 5.77 and 3.36 eV, respectively. Light-emitting devices were fabricated with an ITO (indium-tin oxide)/PEDOT/polymer/Ca/Al configuration. The TALK-PPV component leads to pure green light emission with a CIE 1931 chromaticity of (0.20, 0.74) at 100 cd/m² brightness, which is very close to the standard green (0.21, 0.71) demanded by the NTSC (National Television System Committee). The maximum brightness of this device was 24,900 cd/m² with an efficiency of 1.45 cd/A.     

采用复合空穴注入层提高有机电致发光器件的性能

制备了以Ag/SAM/m-MTDATA为复合空穴注入层的NPB/Alq₃双层异质结发光器件,研究了器件的性能并与传统的器件进行了对比。考察了银膜厚度的变化对器件性能的影响。研究了光谱窄化以及微腔效应对器件的影响。研究结果表明:在ITO表面制备4-FTP自组装单分子膜修饰的5 nm厚的金属银膜,可以在保持阳极透明性的基础上,增强空穴的注入,改善界面的形貌,进而提高器件性能。制备的ITO/Ag/SAM/m-MTDATA/NPB/Alq₃/LiF/Al器件的启亮电压为4 V,最 大电流效率为6.9 cd/A, 最大亮度为34 680 cd/m²(12 V);优于以ITO为阳极的对比器件(25 300 cd/m² @12 V)。     

Advanced ion beam technology for versatile oxide thin film formation

Various oxide films, such as SnO₂, In₂O₃, Al₂O₃, SiO₂, ZnO, and Sn-doped In₂O₃ (ITO) have been deposited on glass and polymer substrates by advanced ion beam technologies including ion-assisted deposition (IAD), hybrid ion beam, ion beam sputter deposition (IBSD), and ion-assisted reaction (IAR). Physical and chemical properties of the oxide films and adhesion between films and substrates were improved significantly by these technologies. By using the IAD method, non-stoichiometry, crystallinity, and microstructure of the films were controlled by changing assisted oxygen ion energy and arrival ratio of assisted oxygen ion to evaporated atoms. IBSD method has been carried out for understanding the growth mode of the films on glass and polymer substrate. Relationships between microstructure and electrical properties in ITO films on polymer and glass substrates were intensively investigated by changing ion energy, reactive gas environment, substrate temperature, etc. Smooth-surface ITO films (R_rms ⩽ 1 nm and R_p−v ⩽ 10 nm) for organic light-emitting diodes were developed with a combination of deposition conditions with controlling microstructure of a seed layer on glass. IAR surface treatment enormously enhanced the adhesion of oxide films to polymer substrate. In the case of Al₂O₃ and SiO₂ films, the oxygen and moisture barrier properties were also improved by IAR surface treatment. The experimental results of the oxide films prepared by the ion beam technologies and its applications will be represented in detail.     

High-efficiency organic light-emitting diodes (OLEDs) with a mixed layer structure

Improved performance of organic light-emitting diodes (OLEDs) as obtained by a mixed layer was investigated. The OLEDs with a mixed layer which were composed of N,N′-diphenyl-N,N′-bis(1-napthyl-phenyl)-1,1′-biphenyl-4,4′-diamine (NPB), tris-(8-hydroxyquinolato) aluminum (Alq₃) and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) showed the highest brightness and efficiency, which reached 19048 cd/m² at 17 V and 4.3 cd/A at 10 mA/cm², respectively. The turn-on voltage of the device is 2.6 V. Its Commission Internationale del’Eclairage (CIE) coordinate is (0.497, 0.456) at 17 V, and the CIE coordinates of the device are largely insensitive to the driving voltages, which depicts stabilized yellow color.     

高色饱和度的微腔结构蓝色顶发射有机发光器件的光谱分析

制作了具有微腔结构的蓝色有机顶发射电致发光器件。利用TBADN∶3%DSAPh为发光材料,结构为Ag/ITO/CuPc/NPB/TBADN∶3%DSAPh/Alq₃/LiF/Al(Ag)。在玻璃基片上,制备Ag为阳极反射层,CuPc作为空穴注入层,NPB作为空穴传输层,ITO为光程调节层;Al/Ag作为半透明阴极,电极的透射率在30％左右。得到了半高宽仅为17nm发光光谱,实现了窄带发射。通过改变ITO的厚度,得到了纯度较高的蓝色发光光谱,色坐标为(0.141,0.049),实现了高色饱和度的发射。在文章中,作者研究了微腔器件的发光强度,当选择合适的阴极透射率时可以使发光强度达到最大。根据相关的公式,计算出了发光强度随阴极透射率(或者反射率)变化的近似曲线。     

Preserving long-term emission stability of carbon nanotube field emitter using aluminum layer

Carbon nanotube (CNT) field emitter was fabricated, and then its emission stability was evaluated with three different anode structures; indium tin oxide (ITO)/glass, ZnS:Cu,Al(green phosphor)/ITO/glass, and Al/ZnS:Cu,Al/ITO/glass. It was found that the electron emission from CNTs to the phosphor layer degrades much faster than the emission to ITO layer does. The current decay time from 100 μA/cm² to 50 μA/cm² for ITO/glass and ZnS:Cu,Al/ITO/glass were 250 h and 20 h, respectively. Such rapid decay in emission current with the phosphor-coated anode was found to be attributed to the formation of Zn particles on CNTs during the field emission. However, the deposition of aluminum layer on the phosphor, in other words, using the anode structure of Al/ZnS:Cu,Al/ITO/glass recovered the stability that is comparable to that with an ITO/glass. The aluminum layer was found to efficiently prevent phosphor elements from being degassed, preserving the long-term emission stability of carbon nanotubes.