Improving hole injection ability using a newly proposed WO3/NiOx bilayer in solution processed quantum dot light-emitting diodes

We propose a novel device structure with a WO₃/NiO_x bilayer to improve the hole injection ability in QLEDs fabricated mainly by a solution-based process. First, we employed a spin-coated NiO_x thin film as a hole injection layer (HIL) to replace Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) PEDOT:PSS which corrodes indium tin oxide (ITO) used as an anode in QLEDs. We showed a simply optimized annealing process, instead of a rather complicated process like doping, can improve the electrical conductivity of the NiO_x thin film. The reason for the dependency of conductivity on the post-metallization annealing is because of the change of the total amount of Ni vacancy in the NiO_x thin film as a function of annealing temperature: The electrical conductivity of the NiO_x thin film annealed at 275 °C was the best in this work. Second, we inserted the WO₃ thin film in between ITO electrode and NiO_x HIL to form an ITO/WO₃/NiO_x structure which reduces the hole injection barrier to 0.35 eV, resulting in the excellent characteristic in view of charge balance. Finally, we measured the properties of QLEDs with the WO₃/NiO_x bilayer to check the effects of the proposed device structure and showed the substantial improvement of the electrical conductivity of NiO_x, the luminance, and the current efficiency of the QLEDs.     

Improvement of the electron transport behavior in quantum-dot light-emitting diodes using a low-temperature processable ZnO

Zinc oxide (ZnO) is a commonly used electron transport layer in quantum-dot light-emitting diodes (QLEDs). In this study, we used a highly conductive ZnO film via a low-temperature process to improve the electron transport behavior of the QLEDs. The electron transport behavior of ZnO film was investigated from the electron only device, and the origin of high conductivity was figured out using x-ray photoelectron spectroscopy. We found that the oxygen vacancy, which can improve the carrier transport in ZnO film, was increased according to reduce the process temperature of ZnO. Meanwhile, the hydroxyl group, which contribute to the quenching effect, was decreased according to reduce the process temperature of ZnO. Therefore, high-performance QLEDs were fabricated using the low-temperature processed ZnO, and it showed an improved luminance and current efficiency in a full current range. The maximum luminance and current efficiency of the devices were measured as 65,391 Cd/m² and 2.48 Cd/A, respectively. Moreover, the lifetime of the device was improved due to the low-temperature process. Therefore, we suggest that a highly conductive ZnO film could be formed through a low-temperature process, and it can improve the performance of QLEDs.     

Sub-10 nm V2O5 Crystals on Carbon Nanosheets for Advanced All-Solid-State Lithium Metal Batteries

V₂O₅, as a lithium-free cathode material, has inherent defects such as sluggish kinetics and volume change and, at the same time, requires a lithium metal anode that tends to form dendrites in liquid electrolytes. Both the lithium dendrite and the flammable electrolyte solvent bring longtime safety issues. This work introduces nonflammable inorganic–organic composite solid electrolyte to inhibit the growth of the lithium dendrite and suppress the instability caused by V₂O₅ nanometerization. However, the long-term cycling and rate performances are still insufficient even when reducing V₂O₅ size to about 50 nm. As an improvement, sub-10 nm V₂O₅/C nanosheets are designed and prepared using corn stalks as precursors through simple impregnation and calcination process. The V₂O₅/C offers a much better electrode/electrolyte contact and interface stability than bulk V₂O₅ and commercial V₂O₅ in the inorganic–organic composite solid electrolyte. The discharge capacity is 228 mAh g⁻¹ at 0.1 C after 50 cycles and ≈110 mAh g⁻¹ at 2.0 C.     

利用p型掺杂技术制备的高效有机电致发光器件

利用氧化钼(MoO_x)作为p型掺杂剂,以掺杂层4,4'-bis(carbazol-9-yl)biphenyl(CBP):MoO_x作为空穴注入层,制备了一种结构为ITO/MoO_x/CBP:MoO_x/CBP/CBP:tris(2-phenylpyridine)iridium(III)(Ir(ppy)₃)/4,7-diphenyl-1,10-phenanthroline(Bphen)/LiF/Al的有机电致发光器件.器件中CBP同时作为空穴注入层、空穴传输层以及发光层母体材料,这种结构具有结构简单同时能有效降低空穴注入势垒等优点.研究发现,随着空穴注入层厚度的增加,器件的电流密度增加,表明p型掺杂层的引入能够有效增强空穴的注入;通过优化器件空穴注入层与空穴传输层厚度,器件性能有所提高,最大电流效率为29.8 cd/A,可以认为合理的优化空穴注入层和空穴传输层的厚度,使载流子在发光层中的分布更加平衡是提高器件发光效率的主要原因.值得指出的是,从电流效率最大值到亮度为 20 000 cd/m²时,优化后器件的效率衰减仅为17.7%,而常规器件的效率衰减则为62.1%,优化后器件效率衰减现象得到了明显的改善.分析认为优化后的器件中未掺杂的CBP有助于展宽激子形成区宽度,进而减弱了三线态-三线态湮灭、三线态-极化子淬灭现象,激子形成区的展宽是改善效率衰减的主要原因.     

Tailoring of electrochemical properties of V2O5 thin films grown on flexible substrates using plasma-assisted activated reactive evaporation

The vanadium pentoxide (V₂O₅) thin films have been deposited using home built activated reactive evaporation technique on indium tin oxide-coated flexible Kapton substrates and investigated their microstructural and electrochemical properties. X-ray diffraction pattern displayed predominant (001) orientation designating the orthorhombic structure of the films deposited at optimised growth conditions. The surface of the films is observed to be composed of vertical elliptical-shaped grains of size 98 nm distributed uniformly over the surface of the films provided with root mean square surface roughness of 9 nm as evidenced from atomic force microscopy studies. As-deposited V₂O₅ thin films demonstrated constant discharge capacity of about 60 μAh/(cm² _?μm) for 10 cycles at room temperature in the potential window of 4.0–2.5 V. The influence of silver (Ag) interlayer on electrochemical properties of V₂O₅ films was investigated and observed appreciable improvement in electrochemical performance of ‘V₂O₅/Ag/V₂O₅’ films. The multilayered V₂O₅/Ag/V₂O₅ films exhibited a discharge capacity of about 75 μAh/(cm² _?μm) provided with enhanced cycliability.     

Fabrication and Li+-intercalation properties of V2O5-TiO2 composite nanorod arrays

A capillary-enforced template-based method has been applied to fabricate V₂O₅-TiO₂ composite nanorod arrays via filling mixture of VOSO₄ and TiOSO₄ solutions into the pores of polycarbonate membrane. For comparison purposes, pure V₂O₅ nanorod arrays were prepared through the similar template-based method with V₂O₅ sol and the sol was synthesized through the V₂O₅-H₂O₂ route. The nanorods covered completely a large area and projected from the surface of ITO substrate. The addition of TiO₂ to V₂O₅ has demonstrated to greatly affect the Li⁺ intercalation capacity of V₂O₅. For example, V₂O₅-TiO₂ nanorod array with molar ratio V/Ti=75/25 delivered 1.5 times discharge capacity of V₂O₅ nanorods at a current density of 92 mA/g. Such improvement in the intercalation properties was ascribed to the change of crystallinity and possible modification in lattice structure and interaction forces between adjacent layers in V₂O₅. PACS 81.05.Je; 82.45.Yz; 81.10.Dn; 81.20.Fw; 82.47.Aa     

The electric field gradient at111Cd in vanadium oxides

The electric field gradient (efg) of¹¹¹Cd in polycrystalline V₂O₅ was studied using perturbed angular correlation (PAC) spectroscopy, with the¹¹¹In activity ion-implanted at 400 keV. Between the individual steps of an isochronal annealing program, a distinct efg (v _Q 1=88.1(3) MHz, ₁=0.62(2)) was recorded the contribution of which increased with annealing temperature up to 74% at 870 K. Corresponding X-ray analysis of inactive V₂O₅ samples, which underwent the same annealing treatment, proved that the sample always stayed as V₂O₅. Since V₂O₅ has only one equivalent cation site, it is concluded that this efg belongs to¹¹¹Cd at this site. Oxidation of a vanadium foil atT=675 and 800 K at =200 mbar also yielded this efg. From PAC measurements in VO₂, two well-defined efg's were found above and below the metal-semiconductor transition at 340 K, which are tentatively attributed to the monoclinic and the tetragonal phase.Supported by Deutsche Forschungsgemeinschaft and DAAD.On leave from the University of Durban-Westville, South Africa.     

Vertical aligned V<Subscript>2</Subscript>O<Subscript>5</Subscript> nanoneedle arrays grown on Ti substrate as binder-free cathode for lithium-ion batteries

V₂O₅ nanoneedle arrays were grown directly on titanium (Ti) substrate by a facile solvothermal route followed with calcination at 350 °C for 2 h. The as-prepared V₂O₅ nanoneedles are about 50 nm in diameter and 800 nm in length. The electrochemical behavior of V₂O₅ nanoarrays as binder-free cathode for lithium-ion batteries (LIBs) was evaluated by cyclic voltammetry and galvanostatic discharge/charge tests. Compared with V₂O₅ powder electrode, V₂O₅ nanoneedle arrays electrode exhibited improved electrochemical performance in terms of high discharge capacity of 262.5 mA h g^?1 between 2.0 and 4.0 V at 0.2 C, and high capacity retention up to 77.1% after 100 cycles. Under a high current rate of 2 C, a discharge capacity of about 175.6 mA h g^?1 can be maintained. The enhanced performance are mainly due to the intimate contact between V₂O₅ nanoneedle active material and current collector, which enable shortened electron transfer pathway and improved charge transfer kinetics, demonstrating their potential applications in high rate electrochemical storage devices.     

Flexible metal–insulator–metal (MIM) devices for plastic film AM-LCD

We developed new flexible metal–insulator–metal (MIM) devices subject to plastic film substrate. The structure of the MIM device is that a Ta₂O₅ insulator is covered with two flexible Al electrodes on both sides. The flexible structure of the MIM device was successfully fabricated applying our own etch-free process.     

Morphological transformations of vanadium oxide films during low-temperature reduction in hydrogen electron cyclotron resonance plasma

Morphological transformations of amorphous vanadium oxide films obtained by the sol-gel method and polycrystalline V₂O₅ films are studied during their low-temperature (295–623 K) reduction in a hydrogen electron cyclotron resonance plasma. The morphology of films is analyzed using atomic force microscopy and high-resolution electron microscopy. It is found that a homogeneous amorphous film during the reduction process transforms to an island film and then bulk amorphous islands of a regular shape appear. These islands resemble microcrystals, and their concentration depends on the temperature and the reduction time. The low-temperature reduction of polycrystalline V₂O₅ films leads to their amorphization; however, the microcrystals in the polycrystalline film do not change their shape in this process. A mechanism of the reduction process is proposed. This mechanism explains the regularities of morphological transformations in amorphous sol-gel films of vanadium oxides based on the suggestion of a competition between the ion-stimulated nucleation and growth of nuclei of the crystalline phase and the amorphization of the growing nuclei.     

X-RAY PHOTOELECTRON SPECTROSCOPY STUDY ON ELECTROCHROMIC V2O5 THIN FILM

Nanocrystalline V₂O₅ thin films were reactively radio-frequency magnetron-sputtered under optimal deposition parameters. Their electrochemical and electrochromic characteristics were investigated by cyclic voltammetry and in-situ monochromatic transmittance measurements. Upon lithium intercalation, V₂O₅ thin films showed a double electrochromic behavior depending on the wavelength and the intercalation extent. X-ray photoelectron spectroscopy results showed that part of the V⁵⁺ in V₂O₅ was reduced to V⁴⁺ during the Li⁺ intercalation process.     

Highly efficient and stable organic light-emitting diodes employing MoO3-doped perylene-3, 4, 9, 10-tetracarboxylic dianhydride as hole injection layer

We report highly efficient and stable organic light-emitting diodes (OLEDs) with MoO₃-doped perylene-3, 4, 9, 10-tetracarboxylic dianhydride (PTCDA) as hole injection layer (HIL). A green OLED with structure of ITO/20 wt% MoO₃: PTCDA/NPB/Alq₃/LiF/Al shows a long lifetime of 1012 h at the initial luminance of 2000 cd/m², which is 1.3 times more stable than that of the device with MoO₃ as HIL. The current efficiency of 4.7 cd/A and power efficiency of 3.7 lm/W at about 100 cd/m² have been obtained. The charge transfer complex between PTCDA and MoO₃ plays a decisive role in improving the performance of OLEDs.     

Effect of vanadium-containing activating additives on the oxidation of aluminum powders

The effect of vanadium-containing activating additives on the oxidation of an ASD-4 aluminum powder subjected to low-rate heating in the air is studied. The tests are conducted for a number of activators introduced by impregnating the metal powder with vanadium-containing gels with the following compositions: Li₂V₁₂O₃₁ · nH₂O, Na₂V₁₂O₃₁ · nH₂O, Na₂MoV₁₁O₃₁ · nH₂O, V₂O₅ · nH₂O, and 6V₂O₅ · B₂O₃ · nH₂O. A gel-preparation method based on the instantaneous cooling of melts of the respective reagents in cold water is proposed. It is found that the oxidation of the activated powders is shifted to a low-temperature region.     

Photocatalytic performance of TiO2/V2O5 nanocomposite powder prepared by DC arc plasma

TiO₂/V₂O₅ nanocomposite powder was synthesized by the DC arc plasma, and its photocatalytic activity was examined by decompositions of Rhodamine B solution and toluene gas. In the synthesis of TiO₂/V₂O₅ nanocomposite powder, TiCl₄ and VOCl₃ precursors were introduced into thermal plasma flame with argon carrier gases through separated two gas bubblers. They were decomposed by Ar–N₂ thermal plasma generating Ti and V vapors, followed by the formation of oxides with the injection of additional oxygen into a plasma reactor. Nanocomposite composed of relatively small size V₂O₅ nanoparticles on a spherical TiO₂ nanoparticle which was about 250 nm in diameter was identified by X-ray diffractometry, electronic microscopy, and energy dispersive spectroscopy when the ratio of carrier gas flow rates for TiCl₄ to VOCl₃ was 1:4 or 1:5. In ultraviolet–visible absorption spectroscopy, the absorbed wavelength of light for synthesized TiO₂/V₂O₅ nanocomposite powder was wider than that for commercially available TiO₂ nanopowder. Therefore, Rhodamine B solution exposed to visible light was decomposed by TiO₂/V₂O₅ nanocomposite, whereas it was not decomposed by TiO₂ nanopowder. In addition, toluene decomposition in a dielectric barrier discharge reactor was carried out with nano-sized photocatalysts of TiO₂ nanopowder and TiO₂/V₂O₅ nanocomposite. Relatively higher removal rate of toluene was found in the case of TiO₂/V₂O₅ nanocomposite in virtue of improved photocatalytic performance.     

Laser-induced forward transfer technique for maskless patterning of amorphous V2O5 thin film

A laser-induced forward transfer technique has been applied for the maskless patterning of amorphous V₂O₅ thin films. A sheet beam of a frequency doubled (SHG) Q-switched Nd:YAG laser was irradiated on a transparent glass substrate (donor), the rear surface of which was pre-coated with a vacuum-deposited V₂O₅ 180 nm thick film was either in direct contact with a second glass substrate (receiver) or a 0.14 mm air-gap was maintained between the donor film and the receiving substrate. Clear, regular stripe pattern of the laser-induced transferred film was obtained on the receiver. The pattern was characterized using X-ray diffraction (XRD), optical absorption spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), atomic force microscopy (AFM), etc.     

High performance IGZO/TiO2 thin film transistors using Y2O3 buffer layers on polycarbonate substrate

In this work, we fabricate IGZO TFT devices on flexible substrate at room temperature. The IGZO/TiO₂ TFT has small subthreshold swing of 0.16 V/dec, but suffers large gate leakage and negative threshold voltage. However, the TiO₂ TFT with Y₂O₃ buffer layers shows improved characteristics including a low threshold voltage of 0.55 V, a small sub-threshold swing of 0.175 V/decade and high field-effect mobility of 43 cm²/Vs. Such good performance can be attributed to the enhanced capacitance density and lowered gate leakage owing to the integration of large band gap Y₂O₃ and low-temperature higher-κ TiO₂.     

Effect of buffer layer on VOx film fabrication by reactive RF sputtering

Vanadium oxide VO_x films were fabricated by RF magnetron sputtering on various metal buffer layers or silica glass substrates at a substrate temperature of 400 °C. V₂O₅ film was fabricated on a silica glass substrate, and VO₂ films were fabricated on V, W, Fe, Ni, Ti, and Pt metal buffer layers. The transition temperature of the sample on the V buffer layer was 68 °C and that on the W buffer layer was 53 °C. The VO₂ film was also fabricated on the V buffer layer by non-reactive sputtering using a V₂O₅ target at a substrate temperature of 400 °C.     

Vanadium oxide thin films deposited on indium tin oxide glass by radio—frequency magnetron sputtering

Highly oriented VO₂(B), VO₂(B) + V₆O₁₃ films were grown on indium tin oxide glass by radio-frequency magnetron sputtering. Single phase V₆O₁₃ films were obtained from VO₂(B) +V₆O₁₃ films by annealing at 480℃ in vacuum. The vanadium oxide films were characterized by x-ray diffraction and x-ray photoelectron spectra (XPS). It was found that the formation of vanadium oxide films was affected by substrate temperature and annealing time, because high substrate temperature and annealing were favourable to further oxidation. Therefore, the formation of high valance vanadium oxide films was realized. The V₆O₁₃ crystalline sizes become smaller with the increase of annealing time. XPS analysis revealed that the energy position for all the samples was almost constant, but the broadening of the V_2p3/2 line of the annealed sample was due to the smaller crystal size of V₆O₁₃.     

Formation of V2O3 nanocrystals by thermal reduction of V2O5 thin films

We report the formation of homogeneous and stable V₂O₃ nanocrystals, directly from V₂O₅ thin films, at 600 °C, as observed by using in situ electron microscopy experiments. Thermally-induced reduction of V₂O₅ thin films in vacuum is remarkably different when compared to reduction of V₂O₅ single crystals and results in the formation of nanophase V₂O₃. Thermally grown V₂O₃ nanocrystals exhibit hexagon or square shape and are stable at higher temperature as well as room temperature. The formation of stable nanocrystals through the reduction process in a non-chemical environment (vacuum) could provide a basis for understanding the complex processes of vanadium oxide phase transitions and for controlling the chemical processes to produce oxide nanocrystals.     

High‐mobility flexible thin‐film transistors with a low‐temperature zirconium‐doped indium oxide channel layer

Thin film transistors (TFTs) with zirconium‐doped indium oxide (ZrInO) channel layer were successfully fabricated on a flexible PEN substrate with process temperature of only 150 °C. The flexible ZrInO TFT exhibited excellent electrical performance with a saturation mobility of as high as 22.6 cm² V^–1 s^–1, a sub‐threshold swing of 0.39 V/decade and an on/off current ratio of 2.5 × 10⁷. The threshold voltage shifts were 1.89 V and ?1.56 V for the unpassivated flexible ZrInO TFT under positive and negative gate bias stress, respectively. In addition, the flexible ZrInO TFT was able to maintain the relatively stable performance at bending curvatures larger than 20 mm, but the off current increased apparently after bent at 10 mm. Detailed studies showed that Zr had an effect of suppress the free carrier generation without seriously distorting the In₂O₃ lattice. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)