Transparent Al/WO3/Au film as anode for high efficiency organic light-emitting diodes

A transparent Al/WO₃/Au anode is introduced to fabricate high efficiency organic light-emitting devices (OLEDs). By optimizing the thicknesses of each layers of the Al/WO₃/Au structure, the transmittance of Al(7 nm)/WO₃(3 nm)/Au(13 nm) has reached over 55%. Concerning the performance of OLEDs using the optimized anode, the electroluminescence (EL) current efficiency and brightness are enhanced and the EL spectrum is greatly narrowed as compared to the OLEDs using indium-tin-oxide (ITO) as the anode. The results indicate that the metal/metal oxide/metal transparent electrode is a good structure for the anode of high performance OLEDs. In addition, Al/WO₃/Au can function as a composite transparent electrode for top-emitting OLEDs.     

Solution-processed aqueous composite hole injection layer of PEDOT:PSS+MoOx for efficient ultraviolet organic light-emitting diode

Hole injection layer (HIL) plays a crucial role in governing external quantum efficiency (EQE) of ultraviolet organic light-emitting diodes (UV OLEDs). We develop a solution-processed aqueous composite HIL of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) incorporated MoO_x (PEDOT:PSS+MoO_x) and cast successful application to UV OLEDs. PEDOT:PSS+MoO_x is characterized in detail with scanning electron microscopy, atomic force microscopy, UV–visible absorption spectra, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and impedance spectroscopy measurements. The results show that PEDOT:PSS+MoO_x features superior film morphology and exceptional electronic properties such as enhanced surface work function and promoted hole injection capacity. With PEDOT:PSS+MoO_x as HIL, the UV OLED gives maximum EQE of 4.4% and radiance of 12.2 mW/cm² as well as improved durability. The electroluminescence peaks at 376 nm with full width at half maximum of 34 nm and stable voltage-dependent spectra. Our results pave a way for exploring efficient UV OLEDs with solution-processable techniques.     

MoO3/Au/MoO3–PEDOT:PSS multilayer electrodes for ITO-free organic solar cells

The effect of the MoO₃–PEDOT:PSS composite layer in the MoO₃/Au/MoO₃–PEDOT:PSS multilayer electrode on the power conversion efficiency of ITO-free organic solar cells (OSCs) was evaluated. The MoO₃ (30 nm)/Au(12 nm)/MoO₃–PEDOT:PSS (30 nm)/PEDOT:PSS structure showed ~7% more optical transmittance than the MoO₃ (30 nm)/Au (12 nm)/MoO₃(30 nm)/PEDOT:PSS structure at 550 nm wavelength. The OSCs using MoO₃/Au/MoO₃–PEDOT:PSS multilayer electrodes as anodes showed a considerable improvement in power conversion efficiency (PCE), from 1.84% to 2.81%, comparable to ITO based OSCs with PCE of 2.89%. This improvement is attributed to the suppression of MoO₃ dissolution by the acidic hole transport layer (HTL) PEDOT:PSS on the MoO₃/Au/MoO₃–PEDOT:PSS multilayer electrode, resulting in high J_sc, V_oc and FF of the OSCs. This composite based multilayer electrode was shown to be a promising replacement in ITO-free flexible optoelectronic devices.     

ITO-free,efficient, and inverted phosphorescent organic light-emitting diodes using a WO3/Ag/WO3 multilayer electrode

We present an indium tin oxide (ITO)-free, bottom-emission inverted phosphorescent organic light-emitting diode (PHOLED) with a maximum luminance of 280,000 cd/m² at 8 V, total maximum current efficiency of 81.4 cd/A, and external quantum efficiency of 22.4%. The inverted OLED structure is composed of glass/WO₃ (30 nm)/Ag (15 nm)/WO₃ (5 nm)/BPhen:15wt% CS₂CO₃ (5 nm)/BPhen (30 nm)/CBP: 8wt% Ir(ppy)₃ (10 nm)/TAPC (50 nm)/WO₃ (5 nm)/Ag (150 nm) multilayers. In this device structure, the WO₃/Ag/WO₃ (WAW) multilayer serving as a transparent cathode demonstrates a low sheet resistance (3.5 Ω/sq) and high optical transmittance (approximately 80%) in a visible light range of 400–600 nm; this multilayer was prepared by thermal evaporation to form a relatively smooth morphology of the conductive thin film on the glass substrate. In addition, an electron-only WAW device was subjected to electrical characterization, and the results revealed that this device exhibited a more efficient electron injection property at the WAW/BPhen:CS₂CO₃ interface than the contact electrode of a standard ITO-based device.     

ITO-free flexible organic light-emitting diode using ZnS/Ag/MoO3 anode incorporating a quasi-perfect Ag thin film

The multi-layer electrode (ZnS/Ag/MoO₃) was optimized by investigating the formation of a continuous Ag thin film according to the base layer. The aggregation of the Ag atom was strictly limited on the ZnS layer, which showed the best thermal stability for Ag. The thermally evaporated 7-nm-thick Ag film with surface coverage of 99.6% was achieved on the ZnS layer. We fabricated the ZnS (25 nm)/Ag (7 nm)/MoO₃ (5 nm) (Z25A7M5) multi-layer electrode, optimized through the numerical calculation. The transmittance of 83% at λ = 550 nm and sheet resistance of 9.6 Ohm/sq were recorded from the Z25A7M5 electrode. These results were mainly attributed to the uniform film-like morphology of the Ag thin film. The flexible OLEDs, based on the Z25A7M5 anode also showed feasible I–V–L characteristics compared to those of ITO-based devices.     

Deep blue/ultraviolet microcavity OLEDs based on solution-processed PVK:CBP blends

There is an increasing need to develop stable, high-intensity, efficient OLEDs in the deep blue and UV. Applications include blue pixels for displays and tunable narrow solid-state UV sources for sensing, diagnostics, and development of a wide band spectrometer-on-a-chip. With the aim of developing such OLEDs we demonstrate an array of deep blue to near UV tunable microcavity (μc) OLEDs (λ ∼373–469 nm) using, in a unique approach, a mixed emitting layer (EML) of poly(N-vinyl carbazole) (PVK) and 4,4′-bis(9-carbazolyl)-biphenyl (CBP), whose ITO-based devices show a broad electroluminescence (EL) in the wavelength range of interest. This 373–469 nm band expands the 493–640 nm range previously attained with μcOLEDs into the desired deep blue-to-near UV range. Moreover, the current work highlights interesting characteristics of the complexity of mixed EML emission in combinatorial 2-d μcOLED arrays of the structure 40 nm Ag/x  nm MoO_x/∼30 nm PVK:CBP (3:1 weight ratio)/y  nm 4,7-diphenyl-1,10-phenanthroline (BPhen)/1 nm LiF/100 nm Al, where x = 5, 10, 15, and 20 nm and y = 10, 15, 20, and 30 nm. In the short wavelength μc devices, only CBP emission was observed, while in the long wavelength μc devices the emission from both PVK and CBP was evident. To understand this behavior simulations based on the scattering matrix method, were performed. The source profile of the EML was extracted from the measured EL of ITO-based devices. The calculated μc spectra indeed indicated that in the thinner, short wavelength devices the emission is primarily from CBP; in the thicker devices both CBP and PVK contribute to the EL. This situation is due to the effect of the optical cavity length on the relative contributions of PVK and CBP EL through a change in the wavelength-dependent emission rate, which was not suggested previously. Structural analysis of the EML and the preceding MoO_x layer complemented the data analysis.     

Highly efficient two component phosphorescent organic light-emitting diodes based on direct hole injection into dopant and gradient doping

A series of two component phosphorescent organic light-emitting diodes (PHOLEDs) combing the direct hole injection into dopant strategy with a gradient doping profile were demonstrated. The dopant, host, as well as molybdenum oxide (MoO₃)-modified indium tin oxide (ITO) anode were investigated. It is found that the devices ITO/MoO₃ (0 or 1 nm)/fac-tris(2-phenylpyridine)iridium [Ir(ppy)₃]:1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi) (30 → 0 wt%, 105 nm)/LiF (1 nm)/Al (100 nm) show maximum external quantum efficiency (EQE) over 20%, which are comparable to multi-layered PHOLEDs. Moreover, the systematic variation of the host from TPBi to 4,7-diphenyl-1,10-phenanthroline (Bphen), dopant from Ir(ppy)₃ to bis(2-phenylpyridine)(acetylacetonate)iridium [Ir(ppy)₂(acac)], and anodes between ITO and ITO/MoO₃ indicates that balancing the charge as well as controlling the charge recombination zone play critical roles in the design of highly efficient two component PHOLEDs.     

Blade coating of Tris(8-hydroxyquinolinato)aluminum as the electron-transport layer for all-solution blue fluorescent organic light-emitting diodes

Organic light-emitting diodes (OLEDs) with a low driving voltage and efficient blue fluorescence were fabricated through blade coating. Tris(8-hydroxyquinolinato)aluminum (Alq₃) is a relatively stable electron-transporting material commonly used in evaporation. However, depositing Alq₃ through a solution process is difficult because of its extremely low solubility organic solvents, a result of its symmetrical molecular structure. In this study, Alq₃ was successfully deposited through blade coating at a very low concentration below 0.1wt%. The OLEDs contained co-dopants BUBD-1 and p-bis(p-N,N-diphenyl-aminostyryl)benzene (DSA-Ph), and a high-band-gap host 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN) as the emission layer with the following structure: ITO/PEDOT:PSS (40 nm)/VB-FNPD (30 nm)/MADN:2% BUBD-1:1% DSA-Ph (50 nm)/TPBI (30 nm)/LiF (0.8 nm)/Al (100 nm)or ITO/PEDOT:PSS (40 nm)/VB-FNPD (30 nm)/MADN:3% BUBD-1 (50 nm)tris(8-hydroxyquinolinato)aluminum (Alq₃; 10 nm)/LiF (0.8 nm)/Al (100 nm). 2,7-disubstituted fluorene-based triaryldiamine(VB-FNPD)is the cross-linking transporting material. The device exhibited a peak current efficiency of 5.67 cd/A for Alq₃ and 5.76 cd/A for TPBI. The device with Alq₃ has operated lifetime seven times higher than the device with TPBI.     

Effect of oxygen plasma treatment on air exposed MoOx thin film

Oxygen plasma (OP) treatment on air exposed molybdenum oxide (MoO_x) has been investigated with ultraviolet photoemission spectroscopy (UPS) and angle resolved X-ray photoemission spectroscopy (AR-XPS). It was found that the work function (WF) reduction of MoO_x by air exposure can be recovered partially by OP treatment on the surface. The overall recovery was measured to be slightly more than 64%, which was adequate to provide a hole extraction layer to many hole-conducting organic materials. The incompleteness of the WF recovery could be attributed to the formation of a very thin layer of oxygen rich absorbents on top of the evaporated MoO_x film after OP treatment. AR-XPS showed that OP treatment shifted the core levels of oxygen and molybdenum about 0.1 eV toward the lower binding energy (BE), and confirmed the existence of oxygen deficiency in the evaporated MoO_x film. We also investigated the electronic energy level evolution of copper phthalocyanine (CuPc) on MoO_x/ITO by UPS. With the deposition of CuPc on OP treated MoO_x we observed band bending and the highest occupied molecular orbital (HOMO) level of CuPc was almost pinned to the Fermi level, which indicates the possibility of efficient hole injection with the OP treated MoO_x film.     

MoO3–Au composite interfacial layer for high efficiency and air-stable organic solar cells

Efficient and stable polymer bulk-heterojunction solar cells based on regioregular poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PC₆₁BM) blend active layer have been fabricated with a MoO₃–Au co-evaporation composite film as the anode interfacial layer (AIL). The optical and electrical properties of the composite MoO₃–Au film can be tuned by altering the concentration of Au. A composite film with 30% (weight ratio) Au was used as the AIL and showed a better performance than both pure MoO₃ and PEDOT:PSS as AIL. The surface morphology of the MoO₃–Au composite film was investigated by atomic force microscopy (AFM) and showed that the originally rough ITO substrate became smooth after depositing the composite film, with the root mean square roughness (RMS) decreased from 4.08 nm to 1.81 nm. The smooth surface reduced the bias-dependent carrier recombination, resulting in a large shunt resistance and thus improving the fill factor and efficiency of the devices. Additionally, the air stability of devices with different AILs (MoO₃–Au composite, MoO₃ and PEDOT:PSS) were studied and it was found that the MoO₃–Au composite layer remarkably improved the stability of the solar cells with shelf life-time enhanced by more than 3 and 40 times compared with pure MoO₃ layer and PEDOT:PSS layer, respectively. We argue that the stability improvement might be related with the defect states in MoO₃ component.     

Enhanced efficiency and brightness in organic light- emitting devices with MoO3 as hole-injection layer

The organic light-emitting devices (OLEDs) using 4,4’,4’’-tris{N-(3-methylphenyl)-N-phenylamin}triphenylamine (m-MTDATA) and MoO3 or 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-tetrachloride (TAPC) and MoO3 as the hole-injection layer (HIL) were fabricated. MoO3 can be expected to be a good injection layer material and thus enhance the emission performance of OLED. The highest occupied molecular (HOMO) of MoO3 is between those of m-MTDATA or TAPC and N,N’-bis-(1-naphthyl)-N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB), which reduces the hole-injection barrier and improves the luminance of the OLEDs. The current efficiency is improved compared with that of the device without the MoO3 layer. The highest luminous efficiency of the device with 2-nm-thick MoO3 as HIL is achieved as 5.27 cd/A at 10 V, which is nearly 1.2 times larger than that of the device without it. Moreover, the highest current efficiency and power efficiency of the device with the structure indium-tin oxide (ITO)/TAPC (40 nm)/MoO3 (2 nm)/TcTa:Ir(ppy)3 (10%, 10 nm)/ tris-(8-hydroxyquinoline) aluminium (Alq) (60 nm)/LiF (1 nm)/Al are achieved as 37.15 cd/A and 41.23 lm/W at 3.2 V and 2.8 V, respectively.     

Top illuminated organic photodetectors with dielectric/metal/dielectric transparent anode

The top illuminated organic photodetectors (OPDs) with a Dielectric/Metal/Dielectric (DMD) transparent anode are fabricated. The transparent electrode is composed of molybdenum trioxide (MoO₃)/silver (Ag)/MoO₃ layers and zinc oxide (ZnO)/aluminum (Al) is used for bottom cathode. The optimized DMD electrode has an optical transmittance of 85.7% at the wavelength of 546 nm and sheet resistance of ∼6 Ω/sq. The fabricated OPDs exhibit a high detectivity and wide range linearity.     

MoO3修饰氧化石墨烯作为空穴注入层影响研究

研究了MoO₃修饰氧化石墨烯(GO)作为空穴注入层的影响。采用旋涂的方法制备了GO, 再真空蒸镀修饰层MoO₃,得到了空穴注入能力强和透过率高的复合薄膜。MoO₃的厚分 别采用0、3、5和8nm。通过优化MoO₃的厚度发现,当MoO₃的厚为5nm时,复合薄膜 的透过率达到最大值,在 550nm的光波长下透光率为88%,且此时采用 复合薄膜作为空穴注入层制备的结构为 ITO/GO/MoO₃(5nm)/NPB(40nm)/Alq₃(40nm)/LiF(1nm)/Al(100nm)的有机电致发光器件(OLED)性能 最佳。通过对OLED进一步的优化,改变Alq₃的厚度,分别取50、60和70nm,测量其电压 、电流、亮度、色坐标和电致发光(EL)光谱等参数发现,当Alq₃的厚为50nm时器件性能最 佳。最终制备了结构为ITO/GO/MoO₃(5nm)/NPB(50nm)/Alq₃(50nm)/LiF(1nm)/Al(100 nm)的OLED,在电压为10V时,最大电流效率达到5.87cd/A,与GO单独作为空穴注入层制备的器件相比,提高了50%。     

Reflectivity and Abnormal Absorption at ITO/Al Interface

The electrical and optical thermal stability of indium tin oxide (ITO)/Al bilayers are investigated in this study. The electrical resistivity of ITO and ITO/Al multilayers, both about 1 × 10⁻³ Ω cm after annealing at 300°C for 1 min, are measured by the four-probe measurement method. In addition to the electrical measurements, we also observe the rapid initial diffusion of Al atoms into the ITO thin films. When the diffusing elemental Al atoms occupy interstitial sites they tend to form defects, causing a serious decrease in the reflectance of the a-ITO/Al bilayer in the wavelength region from 400 nm to 600 nm.     

Solution-processed MoOx hole injection layer towards efficient organic light-emitting diode

Low cost, high throughout and large scale production techniques, such as roll-to-roll, printing and doctor blading, boost the favorite of electronic devices with all solution process. While MoO_x are conventionally formed via high temperature and vacuum deposition, we develop a novel, lower-temperature, solution-processable MoO_x hole injection layer (HIL) and cast successful application in organic light-emitting diodes (OLEDs). The characterization of MoO_x is presented in detail using X-ray diffraction, atomic force microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and impedance spectroscopy measurements. The results show MoO_x features amorphous phase structure, superior film morphology and exceptional electronic properties. With solution-processed MoO_x as HIL, highly efficient OLED is demonstrated. The luminous efficiency has been enhanced by 56% in comparison with that of the counterpart using evaporated MoO_x. The main reasons for the substantially improved performance are the tailored surface work function and appropriate hole injection capacity correspondingly result in optimizing carrier balance in OLED. Our results pave a way for advancing MoO_x-based organic electronic devices with solution-processable techniques.     

MgF2缓冲层对蓝光OLED性能的影响

为了提高蓝光有机电致发光器件(OLED)的发光性能,将MgF2缓冲层插入ITO阳极与空穴传输层NPB之间,通过优化MgF2的厚度,制备了结构为ITO/MgF2(x nm)/NPB(50nm)/DPVBi:DSA-ph(30nm)/Alq3(30nm)/LiF(0.6nm)/Al(100nm)的高性能蓝光器件。实验结果表明,MgF2厚为1.0nm时,器件性能最佳,对应的器件最大电流效率达到5.51cd/A,最大亮度为23 290cd/m2(10.5V),与没有MgF2缓冲层的标准器件相比,分别提高47.3%和25.2%。对ITO表面的功函数测量结果表明,MgF2缓冲层可以有效修饰ITO表面,降低ITO与NPB之间的势垒高度差,改善空穴的注入效率,从而导致电子和空穴的注入更加平衡,激发机制更高效,实现了高性能的蓝光发射,为实现高效而稳定的全彩显示和白光照明奠定了基础。     

The role of molybdenum oxide as anode interfacial modification in the improvement of efficiency and stability in organic light-emitting diodes

It has been experimentally found that molybdenum oxide (MoO₃) as the interfacial modification layer on indium-tin-oxide (ITO) in organic light-emitting diodes (OLEDs) significantly improves the efficiency and lifetime. In this paper, the role of MoO₃ and MoO₃ doped N,N′-di(naphthalene-1-yl)–N,N′-diphenyl-benzidine (NPB) as the interface modification layer on ITO in improvement of the efficiency and stability of OLEDs is investigated in detail by atomic force microscopy (AFM), polarized optical microscopy, transmission spectra, ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). The studies on the energy level and the morphology of the films treated at different temperatures clearly show that the MoO₃ and MoO₃:NPB on ITO can reduce the hole injection barrier, improve the interfacial stability and suppress the crystallization of hole-transporting NPB, leading to a higher efficiency and longer lifetime of OLEDs.     

蓝绿色磷光OLED的制备及发光性能研究

以mCP为主体发光材料,蓝绿色磷光染料BGIr1作 为掺杂剂,制备了6种不同BGIr1掺杂量的蓝绿色磷光有机电致发光器件(OLED),研究了不 同掺杂量对蓝绿色磷光OLED器件发光特性的影 响。制得器件的结构为ITO/MoO₃(20nm)/NPB(40nm)/mCP:BGIr1(x%,30nm)/BCP(10nm)/Alq₃(20 nm)/LiF/Al(100nm),其中x%为发光层中磷光染料BGIr1的掺杂量(质量分数)。结果表明,BGIr1掺杂量 为18%时,获得器件的发光性能最佳。18% BGIr 1掺杂器件在488nm和 512nm处获得两个主发射峰,当电 流密度为26.5mA/cm²时,获得最大发光效率为6.2cd/A;在15V驱动电压下,获得最大亮度为6970cd/cm², CIE坐标为(0.17,0.31)。这说明,BGI r1掺杂改善了器件的发光亮度和色纯度,提高了器件的发光效率。     

Highly Transparent and Flexible Organic Light‐Emitting Diodes with Structure Optimized for Anode/Cathode Multilayer Electrodes

In this study, a dielectric layer/metal/dielectric layer (multilayer) electrode is proposed as both anode and cathode for use in the fabrication of transparent and flexible organic light‐emitting diodes (TFOLEDs). The structure of multilayer electrodes is optimized by systematic experiments and optical calculations considering the transmittance and efficiency of the device. The details of the multilayer electrode structure are [ZnS (24 nm)/Ag (7 nm)/MoO₃ (5 nm)] and [ZnS (3 nm)/Cs₂CO₃ (1 nm)/Ag (8 nm)/ZnS (22 nm)], as anode and cathode, respectively. The optimized TFOLED design is fabricated on a polyethylene terephthalate (PET) substrate, and the device shows high transmittance (74.22% around 550 nm) although the PET substrate has lower transmittance than glass. The TFOLEDs operate normally under compressive stress; degradation of electrical characteristics is not observed, comparable to conventional OLEDs with ITO and Al as electrodes. In addition, because the fabricated TFOLEDs show a nearly Lambertian emission pattern and a negligible shift of Commission International de l'Eclairage (CIE) coordination, it is concluded that the fabricated TFOLEDs are suitable for use in displays.