Molybdenum oxide anode buffer layers for solution processed,blue phosphorescent small molecule organic light emitting diodes

In this work we present solution processed organic light emitting diodes (OLEDs) comprising small molecule, blue phosphorescent emitter layers from bis(4,6-difluorophenylpyridinato-N,C2)picolinatoiridium doped 4,4′,4″-tris(carbazol-9-yl)-triphenylamine and molybdenum trioxide (MoO₃) anode buffer layers. The latter were applied from a molybdenium(V)ethoxide precursor solution that was thermally converted to MoO₃ at moderate temperatures. The high work function MoO₃ facilitated hole injection into the emission layer. The MoO₃ layer properties were investigated by means of energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and Kelvin probe force microscopy. MoO₃ buffer layers performed superior to the commonly used poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and enabled an enhanced OLED device efficiency.     

Suppressing molecular aggregation in solution processed small molecule organic light emitting diodes

Solution processing of low-molecular weight organic materials for optoelectronic devices is a challenging task due to often strong molecular aggregation. We present a facile and universal route for suppressing the aggregation of molecules during wet-deposition of emission layers for organic light emitting diodes by incorporating electronically inactive polymers. Moderate polymer concentrations of about 10 wt.% lead to only minor changes of the electrical performance while at the same time improving the film formation and consequently the device luminance significantly. The device performance matches the performance of vacuum processed devices with the same device architecture.     

Soluble processed low-voltage and high efficiency blue phosphorescent organic light-emitting devices using small molecule host systems

We report low voltage driving and highly efficient blue phosphorescence organic light emitting diodes (PHOLEDs) fabricated by soluble process. A soluble small molecule mixed host system consisting of hole transporting 4,4’,4’’ tris(N-carbazolyl)triphenylamine (TCTA) and bipolar carrier transporting 2,6-bis(3-(carbazol-9-yl)phenyl)pyridine (26DCzPPy) exhibits high solubility with smooth surface properties. Moreover, this small molecule host shows the smoothest morphological property similar to a vacuum deposited amorphous film. A low driving voltage of 5.4 V at 1000 cd/m² and maximum external quantum efficiency 14.6% obtained in the solution processed blue PHOLEDs are useful for large area low cost manufacturing.     

Thermo-cleavable poly(fluorene-benzothiadiazole) to enable solution deposition of multi-layer organic light emitting diodes

The design of solution processable multi-layer organic light emitting diodes (OLEDs) is often hampered by the choice of solvents. To avoid the dissolution of the emission layer upon the subsequent deposition of further functional layers, we synthesize and investigate thermo-cleavage in poly[2,7-(3-(9-methyl-9H-fluorene-9-yl)propyl (2-methylhexane-2-yl) carbonate)-alt-4,7-(benzo[c][1,2,5]thiadiazole)] (c-F8BT). Employed in OLEDs, the non-cleaved polymer yields about the same current efficiency as state-of-the-art F8BT. During pyrolysis at 200 °C, the polymer releases its solubility groups, fully maintaining the device efficiency but becoming insoluble. This feature allows to enhance the OLED performance by applying an additional bathophenanthroline hole blocking layer from solution or by incorporating a low-molecular weight electron transport moiety into the affixing polymer matrix.     

Wide color-range tunable and low roll-off fluorescent organic light emitting devices based on double undoped ultrathin emitters

We demonstrated a novel wide color-range tunable, highly efficient and low efficiency roll-off fluorescent organic light-emitting diode (OLED) using two undoped ultrathin emitters having complementary colors and an interlayer between them. The OLED can be tuned to emit sky blue (0.22, 0.30), cold white (0.29, 0.33), warm white (0.43, 0.42) and yellow (0.40, 0.45) according to the Commission Internationale de L’Eclairage (CIE) 1931 (x, y) chromaticity diagram. The device fabrication was simplified by eliminating doping process in the emission layers. The influence of interlayer thickness on luminous efficiency, efficiency roll-off and color tuning mechanism is thoroughly studied. The recombination zone is greatly broadened in the optimized device, which contributes to stable energy transfer to both emitters and suppressed concentration quenching. With a threshold voltage of 2.82 V, the color tunable organic light emitting diode (CT-OLED) shows a maximum luminance of 39,810 cd/m², a peak external quantum efficiency (EQE) 6% and the efficiency roll-off as low as 11.1% at the luminance from 500 cd/m² to 5000 cd/m². This structure of CT-OLED has great advantages of easy fabrication and low reagent consumption. The fabricated CT-OLEDs are tunable from cold white (0.30, 0.36) to warm white (0.43, 0.42) with correlated color temperature (CCT) 6932 K and 3072 K, respectively, demonstrating that our proposed approach helps to meet the need for lighting with various CCTs.     

面向彩色有机微显示的有机白光顶发射器件

以比铝、银等金属材料透光性更好的铜作为白光有机顶发射器件的顶电极,将其应用到基于Al底电极的蓝、黄互补色顶发射白光有机电致发光器件(TEWOLED),通过合理设计器件结构,制备出的器件具有较低的驱动电压和较高的效率,4V下亮度超过1 000cd/m2、功率效率达到28.5lm/W,效率滚降较小。我们利用p型电学掺杂结构和电子注入缓冲层结构分别解决了铝和铜电极功函数同空穴传输层的HOMO能级和电子传输层的LUMO能级不匹配问题,并通过TcTa光学覆盖层的调节作用使器件具有较好的光谱稳定性。基于Cu顶电极的TEWOLED与采用Al作为互连金属的CMOS工艺兼容,我们将该器件与硅基CMOS驱动电路结合,获得了SVGA白光有机微显示器件,为彩色有机发光微显示的实现奠定了基础。     

Improved efficiency of solution processed small molecules organic solar cells using thermal annealing

A solution processable A-D-A-D-A structure small molecule DCAEH5TBT using a BT unit as the core has been designed and synthesized for application in BHJ solar cells. The device employing DCAEH5TBT/PC₆₁BM as active layer shows PCE of 2.43% without any post treatment. After thermal annealing (150 °C, 10 min), the PCE of this molecule based device increased to 3.07%, with J_sc of 7.10 mA/cm², V_oc of 0.78 V and FF of 55.4%, which indicates that high performance of solution processed small molecule based solar cells can be achieved using thermal annealing by carefully design molecule structure.     

Modification effect of hole injection layer on efficiency performance of wet-processed blue organic light emitting diodes

We examined the performance of solution-processed organic light emitting diodes (OLEDs) by modifying the hole injection layer (HIL), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS). Atomic force microscopy (AFM) showed morphological changes with surface roughness (R_RMS) of 1.47, 1.73, and 1.37 nm for pristine PEDOT: PSS, PEDOT: PSS modified with a 40 v% deionized water and with a 30 v% acetone, respectively. The surface hydrophobicity of the acetone modified PEDOT:PSS HIL layer was decreased by 34% as comparing with the water modified counterpart. Electrical conductivity was increased to two orders of magnitude for the water and acetone modified PEDOT:PSS as compared to pristine. We observed a low refractive index and high transmittance for the modified HILs. We fabricated and explored electroluminescent properties of bis[2-(4,6-difluorophenyl)pyridinato-C2,N](picolinato)iridium(III) (FIrpic) based sky blue device by utilizing HIL with and without modification. The changes in electrical conductivity, surface roughness, refractive index, and transmittance of the modified HILs strongly influenced the performance of devices. By utilizing a 30% acetone modified HIL, the power efficiency was increased from 14.2 to 24.2 lm/W, an increment of 70% and the EQE from 8.5 to 13.1% at 100 cd/m², an increment of 54%. The maximum luminance also increased from 11,780 to 18,190 cd/m². The findings revealed herein would be helpful in designing and fabricating high efficiency solution processed OLEDs.     

Tunable chromaticity stability in solution-processed organic light emitting devices

Efficient solution-processed color-stable and color-tunable white organic light emitting diodes (OLEDs) have been realized by judicious selection of the host materials for the emission layers. The color-tunable OLED demonstrates the unique characteristic of modulating the electroluminescence by using the applied voltage of the device and displays color temperatures ranging from 1600 K to 4600 K around the daylight locus, with a peak external quantum efficiency of 13.6% and a peak current efficiency of 22.5 cd A⁻¹. On the other hand, the chromaticity-stable device shows a negligible color change, from 300 to 2000 nits. The manipulation of chromaticity is attributed to the energy transfer dynamics of the hosts and dopants under different electric fields.     

高效暖白光器件的廉价制备及其相关材料研究

低色温光源由于其对抗黑变激素具有较低的抑制作用而成为生理友好照明的首选。同时,高的能量效率对于节能也至关重要。本课题采用温和的溶液旋涂方法分别制备了含互补色、三基色和四基色磷光染料的单层有机白光二极管(WOLED)。经过优化WOLED的结构,实现了宽亮度范围内100~10 000cd/m2的低色温(low-CCT)白光发射。CCT低至2 500K以下、显示指数(CRI)高达到83、电流效率在亮度为1 000cd/m2时达到了17.8cd/A,与传统的白炽灯功效相当。高发光性能、廉价制备成本及生理友好的特性表明,本工作制备的器件是益于人类健康的照明光源尤其是夜间照明光源的理想选择。     

Determining emissive dipole orientation in organic light emitting devices by decay time measurement

We present a method to detect anisotropy in the distribution of the transition dipole moment in organic light emitting diodes (OLEDs). The method is based on the dependency of the exciton decay rate on the optical environment and the orientation of the dipole transition moment, also called the Purcell effect. We use this method to demonstrate a preferential orientation of the small molecule emitter Ir(MDQ)₂(acac) in a TPBi matrix. The outcoupling improvement for OLEDs that could be obtained with perfectly oriented transition dipoles is estimated by simulation. For perfectly planar structures this shows an EQE in air of up to 34%.     

High open circuit voltage in efficient thiophene-based small molecule solution processed organic solar cells

We have synthesized and fully characterized an oligothiophene small organic molecule for its use as electron donor moiety in solution processed bulk-heterojunction organic solar cells. Our results show that device solvent annealing process of the conjugated oligothiophene molecule leads to a light-to-energy conversion efficiency of 3.75% under standard illumination conditions. The solar cell presents open-circuit voltage and fill factors as high as 1.01 V and 63.05% respectively, which are among the highest values obtained for small molecule solution processed organic solar cells.     

Efficient and stable red organic light emitting devices from a tetradentate cyclometalated platinum complex

An efficient and stable red phosphorescent organic light emitting diode was developed using a tetradentate cyclometalated platinum complex. Devices employing the phosphorescent molecule, platinum(II)-9-(4-methylpyridin-2-yl)-2-(3-(quinolin-2-yl)phenoxy)-9H-carbazole (PtON11Me), yielded high external quantum efficiencies and high operational lifetimes. A maximum EQE of 12.5% and color coordinates CIE (x = 0.61, y = 0.36) was achieved in devices employing efficient hole blocking and transporting materials and a high operational lifetime of T_0.97 ∼ 3200 h was achieved in devices utilizing electrochemically stable hole blocking and transporting materials.     

High efficiency warm white phosphorescent organic light emitting devices based on blue light emission from a bipolar mixed-host

In this study, we demonstrate a high-efficiency and low turn-on voltage warm white phosphorescent organic light emitting devices (PH-WOLEDs) based on a blue mixed-host emission layer (EML) and an orange ultrathin layer. The device has a simple structure and would simplify the fabrication process and reduce fabrication costs. The concept is based on the design a high-efficiency blue mixed-host EML, using an electron-transport material, 4,6-Bis(3,5-di(pyridin-4-yl) phenyl)-2-(3-(pyridin-3-yl) phenyl) pyrimidine (B4PYMPM) to enhance the carrier balance ability of the hole-transport material 1,3-Bis(carbazol-9-yl) benzene (MCP) which operates as the mixed-host and when the MCP: B4PYMPM ratio in the mixed-film was 4:1 got better effects. Based on the blue EML, we realized WOLEDs, characterized by a peak power efficiency of 71.3 lm/W at 3.1 V and a low turn-on voltage of 2.65 V. The mixed-host blue EML exhibited a much higher performance compared to the MCP host. Stable warm white light emission with Commission International de L'Eclairage (CIE) coordinates from (0.37, 0.45) to (0.38, 0.47) for a luminance value ranging from 1000 to 10,000 cd/m² was obtained.     

Realization of solution processed multi-layer bulk heterojunction organic solar cells by electro-spray deposition

Electro-spray deposition (ESD) was applied to fabricate solution processed donor–acceptor bulk heterojunction organic photovoltaic devices with multi-layer structure. Solvent effect was observed when using different organic solvents. Power conversion efficiency (PCE) of the devices prepared from dichlorobenzene increased dramatically comparing to the ones from chloroform, owing to improved homogeneity of the films. ESD enabled us to fabricate solution processed multi-layer (donor/donor:acceptor/acceptor) devices with simple successive deposition steps. Energy Dispersive X-ray Reflectometry analysis confirmed distinct three layered structure of the active layers. Solar cell device parameters of the trilayer devices were compared to single layer devices and those of spin coated devices with the same donor:acceptor ratio and film thickness. Post-thermal treatment results showed that after annealing at 125 °C, trilayer devices exhibited best performance with the maximum PCE of 2.17%.     

Effects of substrate topography on current injection and light emission properties of organic light emitting devices

Substrate topography plays a critical role in the function of nano-scale materials and devices. We study small molecular organic light emitting devices (OLEDs) deposited onto non-planar substrates, where the substrate’s radius of curvature in some regions approaches the thickness of the active device layers. As a result, the electric field profile inside the organic charge transport layers is modified, influencing carrier injection, transport, and light emission properties. Experiments and numerical modeling suggest that charge balance and electroluminescence efficiency potentially can be improved in electron injection-limited OLED architectures via substrate geometry. These findings elucidate the optoelectronic behavior (and degradation) of OLEDs on imperfect substrates, and suggest a strategy based on substrate topography for controlling device behavior.     

Oligothiophene based small molecules with a new end group for solution processed organic photovoltaics

Two oligothiophene based small molecules (DINER5T and DINER7T) with a new end group INER were synthesized as the donors for organic solar cells, and their photovoltaic performance was studied and compared with the corresponding compounds (DRHD7T and DIN7T) with the same backbone structure but different end groups. Both of the new molecules exhibit broad and red shift absorption compared with DRHD7T and DIN7T, with very low band gaps of 1.47 eV and 1.34 eV, respectively. The devices based on DINER5T:PC₇₁BM and DINER7T:PC₇₁BM blend films gave PCEs of 4.22% and 4.02%, respectively, through a solvent vapor annealing (SVA) process with CH₂Cl₂.     

Analysis of alternating current driven electroluminescence in organic light emitting diodes: A comparative study

The alternating current (AC) responses of double-injection and double-insulated organic light-emitting diodes (OLEDs) were investigated and compared. To reveal the electroluminescent (EL) processes in these devices, the AC voltage and frequency dependence of the EL intensity and capacitive current were studied in the time domain with a focus on phase difference analysis. It was found that the voltage-dependent transit time and frequency-dependent carrier distribution were important for the AC-driven performance of the double-injection OLEDs. In contrast, although the double-insulated OLEDs shared some similarities with the double-injection OLEDs, they had some unique characteristics, which were the absence of resistive current and phase shift of EL profiles. It was revealed that the EL in the double-insulated OLEDs was driven by the displacement current generated by the ionization of the doped layers, which, however, formed space charge regions and undermined the EL emission. The space charge redistributed the electric field across the devices after the initiation of EL, making the EL maintain for a limited time interval. This effect was significant under low frequency and high AC voltage. Comparing the phase difference between both devices, it was indicated that the space charge effect was responsible for the observed EL phase shift and the asymmetric EL profiles at low frequency and high AC voltage in the double-insulated OLEDs. The proposed model was also of help to understand the EL saturation phenomena with AC frequency and voltage in those devices.     

Synthesis and characterization of triphenylamine flanked thiazole-based small molecules for high performance solution processed organic solar cells

Two new small molecules, 5,5-bis(2-triphenylamino-3-decylthiophen-2-yl)-2,2-bithiazole (M1) and 2,5-bis(2-triphenylamino-3-decylthiophen-2-yl)thiazolo[5,4-d]thiazole (M2) based on an electron-donor triphenylamine unit and electron-acceptor thiophene-thiazolothiazole or thiophene-bithiazole units were synthesized by a palladium(0)-catalyzed Suzuki coupling reaction and examined as donor materials for application in organic solar cells. The small molecules had an absorption band in the range of 300-560 nm, with an optical band gap of 2.22 and 2.25 for M1 and M2, respectively_. As determined by cyclic voltammetry, the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of M1 were −5.27 eV and −3.05 eV, respectively, which were 0.05 eV and 0.02 eV greater than that of M2. Photovoltaic properties of the small molecules were investigated by constructing bulk-heterojunction organic solar cell (OSC) devices using M1 and M2 as donors and fullerene derivatives, 6,6-phenyl-C61-butyric acid methyl ester (PC₆₁BM) and 6,6-phenyl-C71-butyric acid methyl ester (PC₇₁BM) as acceptors with the device architecture ITO/PEDOT:PSS/M1 or M2:PCBM/LiF/Al. The effect of the small molecule/fullerene weight ratio, active layer thickness, and processing solvent were carefully investigated to improve the performance of the OSCs. Under AM 1.5 G 100 mW/cm² illumination, the optimized OSC device with M1 and PC₇₁BM at a weight ratio of 1:3 delivered a power conversion efficiency (PCE) of 1.30%, with a short circuit current of 4.63 mA/cm², an open circuit voltage of 0.97 V, and a fill factor of 0.29. In contrast, M2 produced a better performance under identical device conditions. A PCE as high as 2.39% was recorded, with a short circuit current of 6.49 mA/cm², an open circuit voltage of 0.94 V, and a fill factor of 0.39.