Catalyst-free highly vertically aligned ZnO nanoneedle arrays grown by plasma-assisted molecular beam epitaxy

This work describes the growth of highly vertically aligned ZnO nanoneedle arrays on wafer-scale catalyst-free c-plane sapphire substrates by plasma-assisted molecular beam epitaxy under high Zn flux conditions. The photoluminescence spectrum of the as-grown samples reveals strong free exciton emissions and donor-bound exciton emissions with an excellent full width at half maximum (FWHM) of 1.4 meV. The field emission of highly vertically aligned ZnO nanoneedle arrays closely follows the Fowler–Nordheim theory. The turn-on electric field was about 5.9 V/µm with a field enhancement factor β of around 793.     

Photoluminescence investigation of ZnO:P nanoneedle arrays on InP substrate by pulsed laser deposition

Phosphorus-doped ZnO nanoneedle arrays were prepared by phosphorus diffusion from InP substrate using a pulsed laser deposition (PLD) technique. The optical properties of ZnO nanoneedle were investigated by photoluminescence (PL) spectroscopy. Low-temperature photoluminescence spectrum measurements exhibited five acceptor-related emission peaks. The excitation intensity and temperature dependent photoluminescence spectra confirmed that the emission peaks corresponded to neutral-acceptor bound exciton, free electron to acceptor, donor-acceptor pairs, and their first and second photon replicas transitions. Acceptor-binding energy was determined to be 135-167 meV, which agrees well with the best-fitting result of the temperature dependent photoluminescence measurements and is reasonable in terms of theoretic prediction in ZnO.     

Field emission property of printed CNTs-mixed ZnO nanoneedles

ZnO nanoneedles were synthesized via thermal evaporation method without any catalyst. Scanning electron microscopy and transmission electron microscopy investigations showed that these products presented a nanoneedle structure. To enhance the field emission (FE) properties of screen printed ZnO nanoneedles, a given amount (0.05 g) carbon nanotubes (CNTs) mixed with (0.5 g) ZnO nanoneedles paste via screen printed method and heat-treatment at (600 °C, 500 °C and 450 °C) was presented. The CNTs-mixed ZnO nanoneedles heat-treated at 450 °C had the lowest turn-on field of 3.75 V/μm, highest field emission current of 0.16 mA at 7.5 V/μm and highest β of 830. An efficiency FE enhancement of 450 °C sample was attributed to melioration of conductance between ZnO nanoneedles and ITO surface by CNTs.     

Memristive Effect in Two-Layered Structures Based on Lithium Doped ZnO Films

The structure of Au/Li10ZnO/Li1ZnO/LaB₆ consisting of upper Au and lower LaB₆ ohmic electrodes and a p-n junction p-Li10ZnO/n-Li1ZnO, which has the resistive memory where two functions are simultaneously combined, that is, an address access and the process of reading and storing of information is investigated. The resistance ratio (R_reset/R_set = 10), the data storage time (> 3 hours) and the number of switching cycles (> 350) are improved as compared to the corresponding single-layer structures. The resistive memory is explained by the modulation effect of the Li10ZnO layer, the ferroelectric polarization of which, depending on the orientation, changes the width and height of the barrier of the p-n junction formed at the p-Li10ZnO/n-Li1ZnO contact.     

Synthesis of Cu-ZnO and C-ZnO nanoneedle arrays on zinc foil by low temperature oxidation route: Effect of buffer layers on growth, optical and field emission properties

Different densities of ZnO nanoneedle films have been prepared by pre-coated zinc foils with thin layer of copper and carbon followed by thermal oxidation at 400 °C in air. The X-ray diffraction patterns show well defined peaks, which could be indexed to the wurtzite hexagonal phase of ZnO. The scanning electron microscope images clearly reveal formation of ZnO needles on the entire substrate surface. The X-ray photoelectron spectroscopy studies indicate that Cu and C ions are incorporated into the ZnO lattice. Photoluminescence studies evaluate different emission bands originated from different defect mechanism. From the field emission studies, the threshold field, required to draw emission current density of ∼100 μA/cm², is observed to be 2.25 V/μm and 1.57 V/μm for annealed zinc foil pre-coated with copper and carbon, respectively. The annealed film with copper layer exhibits good emission current stability at the pre-set value of ∼100 μA over a duration of 4 h. The results show that buffer layer is an important factor to control the growth rate, resulting in different density of ZnO needles, which leads to field emission properties. This method may have potential in fabrication of electron sources for high current density applications.     

Effect of MgO on the enhancement of ultraviolet photoluminescence in ZnO

By glycine-nitrate combustion route and followed by 900 °C annealing in air, ZnO-MgO nanocomposite with heterojunction-like structures between ZnO and MgO phase was successfully produced. The ultraviolet photoluminescence band from ZnO is enhanced by the incorporation of MgO, as compared to the pure ZnO synthesized via the similar route. The charge transfer required by electronic equilibrium across the junction creates an electron depletion region in ZnO phase, which greatly changes the electron states of visible emission-related defects, as a result, the band-edge emission is enhanced while the visible emission in ZnO is suppressed. This mechanism may provide an effective way to modify the emission property of nanomaterials.     

Analysis of effective spin-polarized transport through a ZnO based magnetic p–n junction at room temperature

ZnO based magnetic semiconductors (MSs) are prominent candidates for the spintronic devices because of their high Curie temperatures and low conductance mismatches. In this paper the spin-polarized transport in MS/nonmagnetic semiconductor (NMS) p–n junction is investigated. A model is established based on semiconductor drift–diffusion theory and continuity equation. Boundary conditions are obtained from the quasi-chemical potential (QCP) relations at the junction interface. For a ZnO based magnetic p–n junction, we calculate the distributions of carrier/spin density and spin polarization at room temperature. It is demonstrated that by choosing proper parameters, effective spin-polarized injection from ZnO based MS into ZnO can be achieved at room temperature without external spin-polarized injection (ESPI) or large bias.     

新型ZnO纳米针的双光子激射特性

室温下采用640nm的飞秒脉冲激光泵浦ZnO纳米针得到双光子诱导的光致发光谱。结合单光子下的研究结果,实验分析了双光子泵浦下样品随着受激能量增强产生的三种紫外发射行为并归结为自由激子自发辐射,激子-激子散射和电子空穴等离子体复合。双光子泵浦下ZnO纳米针的受激阈值是4.82GW/cm2,远小于其他ZnO微纳材料的双光子阈值(TW/cm2)。结果表明:这种新型的ZnO纳米针结构能更有效地产生双光子激射,这在纳米激光器方面将会有很大的应用前景。     

N2掺杂p型ZnO及ZnO同质p-n结LED的制备

采用射频等离子体辅助分子束外延方法,以N₂作为掺杂源,以O₂作为辅助分解的气体和氧源,通过等离子体光谱的实时监测来控制掺杂源中各组分的含量,制备了p型ZnO薄膜及同质p-n结。I-V曲线显示该p-n结具有整流特性,直流驱动下获得了稳定的室温电致发光,包括位于420nm附近的发光峰和500~700nm的发光带。     

Radiation-induced formation of ZnO nanoparticles on the ZnSe single-crystal surface

The possible formation of ZnO nanocrystals was studied as a result of radiolysis of a ZnSe crystal surface exposed to zinc vapor and irradiated with gamma rays and in producing ZnSe-ZnO heterostructures. Under ⁶⁰Co gamma radiation in air, nanocrystals ～27 nm in size are formed from nanoscopic ZnO nuclei. Under a mixed flux of gamma rays and thermal-neutron radiation, a twin structure is formed in the host ZnSe lattice and ZnO is removed. The oxide layer is also destroyed under proton irradiation in vacuum. It is found that the growth of ZnO nanocrystallites causes a manyfold increase in the luminescence intensity in the ～600-nm band and in microhardness and also a decrease in the resistance and blocking and threshold voltages irrespective of polarity. Thus, gamma irradiation brings about the formation of light-emitting ZnSe-ZnO: Zn semiconductor structures with a p-n junction.     

Novel W-shaped and straight porous ZnO nanobelts

Novel W-shaped porous ZnO nanobelt with the periodical junction angles of about 118° and straight porous ZnO nanobelt have been successfully synthesized. The W-shaped structure growth changes from [0 0 0 1] to periodically. The straight nanobelt grows along [0 0 0 1] direction. Both of the structures have smooth surfaces with high porous density. Based on our X-ray diffraction (XRD), electron microscopy and photoluminescence (PL) spectrum study, the growth mechanism of the special ZnO nanostructures is discussed, emphasizing the effect of alteration of the reactant concentration for two different morphologies.     

Crystal orientation effects on electronic and optical properties of wurtzite ZnO/MgZnO quantum well lasers

Crystal orientation effects on electronic and optical properties of ZnO/MgZnO QW structures are investigated by taking into account the non-Markovian gain model with many-body effects. These results are compared with those for GaN-based QW structures. In a range of small crystal angles, ZnO/MgZnO QW structures have a lower internal field than GaN/AlGaN and InGaN/GaN QW structures. However, ZnO/MgZnO QW structures show a larger internal field than GaN-based QW structures at crystal angles near ${\theta =50^{\circ}}$ . The WZ ZnO/MgZnO QW structures are shown to have much larger optical gain than the GaN-based QW structures for small crystal angles. This is because WZ ZnO/MgZnO QW structures have larger matrix element and smaller effective masses than InGaN/GaN QW structures near the (0001) crystal orientation. On the other hand, in the case of the (10 ${\bar{1}}$ 0) crystal orientation, the optical gain of ZnO/MgZnO QW structures becomes smaller than that of InGaN/GaN QW structures due to the increase of the effective mass. In addition, the ZnO/MgZnO QW structures have a maximum in the optical gain near ${\theta =50^{\circ}}$ , which can be explained by the fact that the average hole effective mass increases although the matrix element at high carrier density is improved with increasing crystal angle.     

Influence of mesoporous substrate morphology on the structural, optical and electrical properties of RF sputtered ZnO layer deposited over porous silicon nanostructure

Morphological, optical and transport characteristics of the RF sputtered zinc oxide (ZnO) thin films over the mesoporous silicon (PS) substrates have been studied. Effect of substrate porosity on the grain growth and transport properties of ZnO has been analyzed. Physical and optical properties of ZnO-PS structures were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), and photoluminescence (PL) spectroscopy. Our experimental results indicate that on changing porosity of the PS substrates, regularity of the spatial distribution of the ZnO nanocrystallites can be controlled. While the morphology and grain size of ZnO depended strongly on the morphology and pore size of the PS substrates, the rectifying factors of the metal semiconductor junction were found to be different by a factor of 3. The deposition of semiconducting oxides on such mesoporous substrates/templates offers the possibility to control their properties and amplify their sensing response.     

Fabrication and characteristics of a surface acoustic wave UV sensor based on ZnO thin films grown on a polycrystalline 3C-SiC buffer layer

Zinc oxide (ZnO) thin films were deposited onto a polycrystalline (poly) 3C-SiC buffer layer for surface acoustic wave (SAW) ultraviolet (UV) sensing using a magnetron sputtering system. X-ray diffraction (XRD) and photoluminescence (PL) spectra showed that the ZnO film grown on 3C-SiC/Si had a dominant c-axis orientation, a lower residual stress, and higher intensity of luminescence at 380 nm of ZnO thin film. The SAW resonator UV detector were fabricated on ZnO/Si structures with a 3C-SiC buffer layer. The SAW resonator exposed under UV illumination had a linear response with sensitivity of 85 Hz/(μW/cm²) in ZnO/3C-SiC/Si structures, as compared to 25 Hz/(μW/cm²) in ZnO/Si structures with UV intensity varied until 600 μW/cm².     

Photoluminescence properties of nitrogen-doped ZnO films deposited on ZnO single crystal substrates by the plasma-assisted reactive evaporation method

Photoluminescence (PL) spectra of nitrogen-doped ZnO films (ZnO:N films) grown epitaxially on n-type ZnO single crystal substrates by using the plasma-assisted reactive evaporation method were measured at 5 K. In PL spectra, free exciton emission at about 3.375 eV was very strong and emissions at 3.334 and 3.31 eV were observed. These two emissions are discussed in this paper. The nitrogen concentration in ZnO:N films measured by secondary ion mass spectroscopy was 10^19-20 cm⁻³. Current-voltage characteristics of the junction consisting of an n-type ZnO single crystal substrate and ZnO:N film showed good rectification. Also, ultraviolet radiation and visible light were emitted from this junction under a forward bias at room temperature. It is therefore thought that ZnO:N films have good crystallinity and that doped nitrogen atoms play a role as acceptors in ZnO:N films to form a good pn junction. From these phenomena and the excitation intensity dependency of PL spectra, emissions at 3.334 and 3.31 eV were assigned to neutral acceptor-bound exciton (A⁰X) emission and a donor-acceptor pair (DAP) emission due to doped nitrogen, respectively.     

Excitation wavelength dependent photoluminescence intensity of six faceted prismatic ZnO microrods

This article presents the investigation on the large-scale synthesis of ZnO microrods with a simple low temperature hydrothermal method without using surfactants, organic solvents, or catalytic reagents. The synthesized ZnO powder is characterized with different techniques. The X-ray diffraction study reveals the excellent crystal quality of the ZnO product possessing the hexagonal (wurtzite-type) crystal structure. The scanning electron microscope observation confirms the formation of six faceted prismatic hexagonal ZnO microrods with the aspect ratio of 10. It also reveals that the ZnO microrods grow along the (0 0 0 1) direction and finally emerge with a sharp tip because of the existence of polar faces. The UV–vis spectrum shows a sharp absorption peak centered at 370 nm, which is in a good agreement with the equivalent bulk band gap value. The strong UV absorption peak implies the excellent crystal quality of the synthesized ZnO microrods. Room temperature photoluminescence spectroscopic study of the ZnO microrods with different excitation wavelengths reveals a strong band edge emission peak centered at 398 nm and a defect related visible blue emission peak at 460 nm. The decrease in photoluminescence intensity with negligible red shift in peak position is observed with increasing excitation wavelength.     

Effects of oxygen partial pressure on resistive switching characteristics of ZnO thin films by DC reactive magnetron sputtering

Cu/ZnO/n⁺-Si structures were prepared by magnetron sputtering of a layer of ZnO thin film onto heavily doped silicon substrate, followed by thermal evaporation of a thin layer of metallic Cu. The resistive switching characteristics of Cu/ZnO/n⁺-Si structures were investigated as a function of oxygen partial pressure during ZnO deposition. Reproducible resistive switching characteristics were observed in ZnO thin films deposited at 20%, 33% and 50% oxygen partial pressure ratios while ZnO thin film deposited at 10% oxygen partial pressure ratio did not show resistive switching behavior. The conduction mechanisms in high and low resistance states are dominated by space-charge-limited conduction and ohmic behavior respectively, which suggests that resistive switching behaviors in such structures are related to filament formation and rupture. It is also found that the reset current decreases as oxygen partial pressure increases, due to the variation of oxygen vacancy concentration in the ZnO thin films.     

Significant Fowler–Nordheim tunneling across ZnO – Nanorod based nanojunctions for nanoelectronic device applications

We demonstrate significant Fowler–Nordheim (FN) tunneling across Al/Al₂O₃/ZnO metal–insulator–semiconductor (MIS) and Ag/ZnO metal–semiconductor (MS) nanojunctions. The transport properties of ZnO nanostructures in the form of urchins and randomly distributed nanorods were investigated in terms of various conduction mechanism. The minimum voltage necessary for triggering Fowler–Nordheim (FN) tunneling, under forward biasing, was ～1.2 V and ～3.4 V; respectively, below which only direct tunneling and thermionic emission events were evident. Mediated through Al₂O₃ layer, the FN tunneling was more prominent across MIS junction than MS one. The weak FN tunneling across MS junction was owing to interfacial charge transfer process through the atomic scale gapping between adjacent nanostructures. The extent of such type of tunneling is found to be nanostructure morphology dependent and largely rely on the free electrons donated by the native donor defects in the crystal structure of ZnO. The significant FN tunneling across the MIS and MS junctions has a direct relevance in designing nanoscale field emission devices/components working at low voltage with high throughputs.     

Fabrication and electrical characterization of nanocrystalline ZnO/Si heterojunctions

Nanocrystalline zinc oxide (nc-ZnO) films were prepared by a sol-gel process on p-type single-crystalline Si substrates to fabricate nc-ZnO/p-Si heterojunctions. The structure and morphology of ZnO films on Si substrates, which were analyzed by X-ray diffraction (XRD) spectroscopy and atomic force microscopy (AFM), showed that ZnO films consisted of 50-100 nm polycrystalline nanograins with hexagonal wurtzite structure. The electrical transport properties of the nc-ZnO/p-Si heterojunctions were investigated by temperature-dependent current-voltage (I-V) measurements and room temperature capacitance-voltage measurements. The temperature-dependent I-V characteristics revealed that the forward conduction was determined by multi-step tunneling current, and the activation energy of saturation current was about 0.26 eV. The 1/C²-V plots indicated the junction was abrupt and the junction built-in potential was 1.49 V at room temperature.     

Fast synthesis of ZnO nanostructures by laser-induced chemical liquid deposition

ZnO nanostructures were obtained by directly irradiating a small volume of a solution of precursor on a fused-quartz substrate using an unfocused continuous wave CO₂ laser for 2-30 s at laser powers ranging from 20 to 40 W. The laser-based thermochemistry approach allows rapid non-isothermal heating and convection enhanced mass transport which opens new growth mechanisms for the rapid deposition of nanomaterials at predetermined locations on a substrate. The deposits consist of a variety of ZnO nanostructure morphologies, including aggregated nanoparticles, nanorods, faceted nanocrystals and nanowires. The samples were characterized by scanning and transmission electron microscopy, X-ray diffraction and photoluminescence spectroscopy. They were found to exhibit an intense room-temperature photoluminescence, which is characterized by the presence of a strong UV peak around 390 nm and no visible emission. The relationship between the PL signal characteristics and specific ZnO nanostructures was investigated in order to point up optimal nanostructures for possible luminescent devices.