Morphology-controlled one-dimensional ZnO nanostructures with customized Ga-doping

Enhanced functionality of the nanostructure-based devices can be achieved by customizing the doping, thereby managing the electrical properties of the nanostructures. We have optimized the synthesis condition of the ZnO nanowires (NWs) using hot-walled pulsed laser deposition (HW-PLD) that features the facilitated kinetic energy control of the laser-ablated particles. The electrical properties of the NWs have been managed by doping control while maintaining the NW morphologies. 1, 3, and 5 wt.% Ga concentration in the NWs is evaluated directly with energy dispersive spectrometer (EDS), and the exciton peak shifts are measured with room temperature photoluminescence (PL) to find the correlation between the concentration and the shifts. n-type Ga-doping status has been verified with low temperature PL to find the donor-bound exciton peaks. As for the morphology diversification, we have acquired both zigzag-shaped NWs and nanohorns using the same HW-PLD.     

Influence of Sn doping on ZnO sensing properties for ethanol and acetone

Nanostructured pure ZnO (PZO) and Sn doped ZnO (SZO) were deposited on glass templates by chemical deposition method. Before the deposition, electrically conductive silver paste was pasted at the two ends of the glass templates as electrodes. The gas sensing properties of the nanostructured PZO and SZO were systematically investigated by our home-made system, and the results show that Sn doping decreases the response to tested gases. However, it remarkably shortens the response time and recovery time of the sensor. Both PZO and SZO show higher response to acetone than to ethanol, while the response time and recovery time of PZO and SZO to ethanol are shorter than those to acetone, which indicates that the selectivity of ZnO nanostructures to ethanol and acetone are different.     

Direct observation of enhanced cathodoluminescence emissions from ZnO nanocones compared with ZnO nanowire arrays

We report, for the first time, direct observation of enhanced cathodoluminescence (CL) emissions from ZnO nanocones (NCs) compared with ZnO nanowires (NWs). For direct and unambiguous comparison of CL emissions from NWs and nanocones, periodic arrays of ZnO NW were converted to nanocone arrays by our unique HCl [aq] etching technique, enabling us to compare the CL emissions from original NWs and final nanocones at the same location. CL measurements on NW and nanocone arrays reveal that emission intensity of the nanocone at ～ 387 nm is over two times larger than that of NW arrays. The enhancement of CL emission from nanocones has been confirmed by finite-difference time-domain simulation of enhanced light extraction from ZnO nanocones compared to ZnO NWs. The enhanced CL from nanocones is attributed to its sharp morphology, resulting in more chances of photons to be extracted at the interface between ZnO and air.     

均匀沉淀法制备ZnO、Fe/ZnO光催化剂

以六水合硝酸锌、九水合硝酸铁和CO(NH2)2为原料,采用均匀沉淀法并且改变实验条件制备了纯纳米ZnO和纳米Fe/ZnO光催化剂。通过X射线衍射(XRD)和扫描电子显微镜(SEM)对所有样品进行表征,并对部分样品进行了X射线能谱分析仪(EDS)测试。结果显示所有样品均为六方纤锌矿结构。此外,所有样品均由小颗粒聚集在一起而形成了形状、大小各不相同的团聚物或颗粒膜。而且随煅烧温度和Fe掺杂浓度的改变,Fe/ZnO样品的晶粒尺寸和表面形貌也随之变化。以甲基橙溶液作为污染物,在高压汞灯的照射下进行了光降解实验,实验结果表明:Fe掺杂Fe/ZnO样品的光催化性能相较纯纳米ZnO样品得到了改善。当Fe掺杂量为1.5%时Fe/ZnO样品的光催化性能最好;另外,适当煅烧温度也使Fe/ZnO样品的光催化活性得到了提升,其中最适煅烧温度为500℃。无论是Fe的掺杂浓度还是煅烧温度,适当的Fe的掺杂浓度和煅烧温度都有利于改善Fe/ZnO样品光催化剂的性能。     

Structural, electrical and optical properties of Si doped ZnO films grown by atomic layer deposition

Si doped ZnO (SZO) films with various Si concentrations were deposited by atomic layer deposition at 300 °C using triethyzinc, tris(dimethylamino)silane and H₂O₂ as the precursors. The influences of Si doping concentration on structural, electrical and optical properties of ZnO films have been investigated. All the films exhibited a highly preferential c-axis orientation. A minimum resistivity of 9.2 × 10^?4 Ω cm, with a carrier concentration of 4.3 × 10²⁰ cm^?3 and a Hall mobility of 15.8 cm²/Vs, was obtained for SZO film prepared with the Si concentration of 2.1 at%. The increase of conductivity with Si doping was attributed to the presence of Si in +3 valence state acting as donor in ZnO and the increases of oxygen vacancies with Si concentration as proven by XPS measurements. The optical bandgap of SZO films initially increased from 3.25 to 3.55 eV with increasing of Si concentration to 2.1 at%, then decreased with further increase of Si concentration. The blue shift of band gap of SZO films with increasing carrier concentration can be explained by the Burstein-Moss (B-M) effects.     

ZnO nanowire arrays with and without cavity tops

We report a new bubble-assisted growing and etching method for constructing ZnO nanowire (NW) arrays with cavity tops. Firstly, a ZnO NW array structure was formed on a ZnO-seed-layer-patterned Si substrate by combining e-beam lithography and a wet chemical method. Secondly, a new kind of ZnO NW array with cavity tops could be formed by a subsequent bubble-assisted growing and etching. These ZnO NW array structures with different morphologies exhibited different photoluminescence properties, showing their potential applications in lasing cavities, stimulated emitters, nanogenerator, photocatalysis and light-emitting diodes. The bubble-assisted etching method will open a new door for morphology design of ZnO and other semiconductor nanowire arrays at special sites.     

Effect of Ag doping on the performance of ZnO thin film transistor

Ag-doped zinc oxide (SZO) thin film transistors (TFTs) have been fabricated using a back-gate structure on thermally oxidized and heavily doped p-Si (100) substrate. The SZO thin films were deposited via pulsed laser deposition (PLD) from a 1, 3, and 5 wt.% Ag-doped ZnO (1SZO, 3SZO, and 5SZO, respectively) target using a KrF excimer laser (λ, 248 nm) at oxygen pressure of 350 mTorr. The deposition carried out at both room-temperature (RT) and 200 °C. The SZO thin films had polycrystalline phase with preferred growth direction of (002) as well as a wurtzite hexagonal structure. Compare with ZnO thin films, the SZO thin films were characterized by confirming the shift of (002) peak to investigate the substitution of Ag dopants for Zn sites. The as-grown SZO TFTs deposited at RT and 200 °C showed insulator characteristics. However the SZO TFTs annealed at 500 °C showed good n-type TFT performance because Ag was diffused from Zn lattice site and bound themselves at the high temperature, and it caused generation of electron carriers. The post-annealed 5SZO TFT deposited at 500 °C exhibited a threshold voltage (V_th) of 11.5 V, a subthreshold swing (SS) of 2.59 V/decade, an acceptable mobility (μ_SAT) of 0.874 cm²/V s, and on-to-off current ratios (I_on/off) of 1.44 × 10⁸.     

退火条件对Sn掺杂ZnO薄膜光电性能的影响

采用溶胶-凝胶法在普通载玻片上制备Sn掺杂ZnO薄膜(SZO薄膜)。研究空气退火、低真空退火、高真空退火、氮气退火、三高退火、循环退火6种不同退火条件对SZO薄膜光电性能的影响。结果表明:6种不同的退火条件制备的SZO薄膜均为纤锌矿结构且具有c轴择优取向生长的特性。高真空退火下,SZO薄膜的结晶状况和电学性质最优,最低电阻率可达到5.4×10~(-2)Ω·cm。薄膜的可见光区平均透过率均大于85%。薄膜在390nm和440nm附近(325nm光激发下)都出现光致发光峰,在空气、氮气、低真空中退火后薄膜440nm处发光强度最为显著。     

Comparative investigation on nanocrystal structure,optical, and electrical properties of ZnO and Sr-doped ZnO thin films using chemical bath deposition method

This paper reports on the comparative investigation of structural and optical properties of nano thin films of ZnO and Sr-doped ZnO (SZO) onto glass substrates synthesized by a two-step chemical bath deposition (CBD) technique. The mode of crystallization, structural properties, and morphologies have been investigated. The films are polycrystalline in nature with hexagonal phase having (002) preferential orientation. The typical crystallite size is also estimated and found to be around 30–80 nm. The shifts in optical band gap of the SZO films are estimated to be ∼3.25–3.27 eV with respect to the ZnO film and the refractive index is 2.35. The room temperature resistivity is of the order of ∼2,000 Ωcm. Thermoemf measurements show that films are of n-type. The sensitivity of the films was studied as a function of their temperature 275–575 K for a fixed ethanol concentration (400 ppm). The films have been tested for cross sensitivity for different gases and it has been confirmed that these are highly sensitive and selective for ethanol vapors around 200 °C in air atmosphere.     

Synthesis of different architectures like stars, multipods, ellipsoids and spikes of zinc oxide by surfactantless precipitation

Zinc oxide with different morphologies like stars, multipods, ellipsoids and spikes was synthesized using zinc nitrate and sodium hydroxide in the absence of surfactants. Seed mediation was found to be essential for the formation of ZnO nanospikes. Synthesized ZnO samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), UV-visible diffuse reflectance spectroscopy (UV-vis-DRS) and energy dispersive analysis by X-rays (EDAX) techniques. The predominant c-axis growth of hexagonal lattice was observed in ZnO anisotropic particles. TEM analysis revealed the formation of two types of ZnO ellipsoid particles. Concentration of the reactants was found to have a role in controlling the morphology of the resulting ZnO. Mechanism of formation of varying morphologies of ZnO particles has been proposed.     

Triangle-shape ZnO prepared by thermal decomposition

Using oleic acid as surfactant, triangle-shape ZnO with an average diameter of 250 nm can be synthesized by thermal decomposition of precursor zinc acetate (Zn(CH₃CH₂COO)₂) in the high boil-point solvent trioctylamine (TOA). Fundamental characterizations including transmission electron microscopy, X-ray diffraction, high-resolution transmission electron microscopy, scanning electron microscopy and photoluminescence were conducted for the as-synthesized ZnO particles. The effects of refluxing time and the content of surfactant on size and morphology of ZnO particles were studied. It is found that the shape of ZnO particles changes from round-shape, disk-shape to triangle-shape. Based on experimental observations and surface and attachment energies simulation for various crystallographic planes, a possible growth mechanism was put forward to explain the formation of triangle-shape ZnO particles.     

Structural and optical properties of individual GaP/ZnO core–shell nanowires

Structural and optical properties of ZnO–GaP core–shell nanowires were studied by means of electron microscopy and microphotoluminescence. A thin ZnO shell layer was deposited by RF sputtering on GaP nanowires, which were grown on GaP (111)B substrates under vapour–liquid–solid mode by MOVPE. The SEM and TEM characterization showed that the ZnO shells fully covered the surface of the NWs from top to bottom. Each GaP NW core is composed of many well-defined twinned segments with the planes of twinning oriented in perpendicular to the growth direction. This was contradicted in kinked GaP NWs: their growth direction was initially perpendicular to the twinning planes, but once the NW had kinked, it changed to lie within the twinning planes. The ZnO shell deposited on the GaP core has a columnar morphology. The columns are inclined at a positive angle close to 70° with respect to the GaP growth axis. All observed columns were tilted at this angle to the growth direction. Micro-photoluminescence study showed that thermal annealing improved the quality of the ZnO crystallographic structure; the annealing made observable the photoluminescence peak related to the band-to-band transition in ZnO.     

Controllable synthesis of ZnO with various morphologies by hydrothermal method

ZnO microstructures with various morphologies have been controllably synthesized by hydrothermal route using different precipitant and zinc source in liquid solution. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the ZnO2, Zn(OH)2 and ZnO structures to understand the role of precipitant and precursors in the growth of various morphologies. The nucleation and growth process can regulate by changing the precipitant. When H2O2 was used as precipitant, ZnO particles with a rather uniform particle size of -500 nm and a rather rough surface was obtained. While, ZnO synthesized in this polyvinyl pyrrolidone (PVP) solution has the same granular morphology with particle size of 300-1000 nm. In contrast, ZnO sunflower and polyhedron aggregates composed of several smaller polyhedron were formed, when ammonium hydroxide and NH4HCO3 was applied, respectively. Meanwhile, precursors play an important role in the determination of the morphology of ZnO. Sunflower and dumbbell like ZnO composed of nanosheets were obtained, when different centrifugal component of Zn(OH)2 suspension was applied as zinc source. In contrast, sunflower and dumbbell like ZnO composed of nanorods and ZnO rods were obtained, when different centrifugal components of ZnO2 suspension were used as zinc sources. The growth mechanism of ZnO nanostructures fabricated by the hydrothermal process using different zinc sources was tentatively investigated.     

Strain Mismatch Induced Tilted Heteroepitaxial (000l) Hexagonal ZnO Films on (001) Cubic Substrates

A novel strain mismatch induced tilted epitaxy method has been demonstrated for producing high quality (000l) hexagonal films on (001) cubic substrates. Highly oriented hexagonal (000l) ZnO films are grown on cubic (001) MgO substrates using Sm_0.28Zr_0.72O_{2? δ} (SZO) as a template. The large lattice mismatch of >13% between the obvious crystallographic matching directions of the template and substrate means that cube‐on‐cube epitaxy is energetically unfavorable, leading to growth instead of two high index, low energy compact planes, close to the {111} orientation. These planes give three different in‐plane orientations resulting from coincidence site lattice matching (12 in‐plane orientations in total) and provide a pseudo‐hexagonal symmetry surface for the ZnO to grow on. The texture of the ensuing (000l) ZnO layer is markedly improved over the template. The work opens up both a new avenue for growing technologically important hexagonal structures on a range of readily available, (001) cubic substrates, as well as showing that there are wide possibilities for heteroepitaxial growth of a range of dissimilar materials.     

Highly sensitive and selective trimethylamine sensor using one-dimensional ZnO-Cr2O3 hetero-nanostructures

Highly selective and sensitive detection of trimethylamine (TMA) was achieved by the decoration of discrete p-type Cr(2)O(3) nanoparticles on n-type ZnO nanowire (NW) networks. Semielliptical Cr(2)O(3) nanoparticles with lateral widths of 3-8 nm were deposited on ZnO NWs by the thermal evaporation of CrCl(2) at 630 °C, while a continuous Cr(2)O(3) shell layer with a thickness of 30-40 nm was uniformly coated on ZnO NWs at 670 °C. The response (R(a)/R(g): R(a), resistance in air; R(g), resistance in gas) to 5 ppm TMA of Cr(2)O(3)-decorated ZnO NWs was 17.8 at 400 °C, which was 2.4 times higher than that to 5 ppm C(2)H(5)OH and 4.3-8.4 times higher than those to 5 ppm p-xylene, NH(3), benzene, C(3)H(8), toluene, CO, and H(2). In contrast, both pristine ZnO and ZnO (core)-Cr(2)O(3) (shell) nanocables (NCs) showed comparable responses to the different gases. The highly selective and sensitive detection of TMA that was achieved by the deposition of semielliptical Cr(2)O(3) nanoparticles on ZnO NW networks was explained by the catalytic effect of Cr(2)O(3) and the extension of the electron depletion layer via the formation of p-n junctions.     

Helium droplet assisted synthesis of plasmonic Ag@ZnO core@shell nanoparticles

Plasmonic Ag@ZnO core@shell nanoparticles are formed by synthesis inside helium droplets with subsequent deposition and controlled oxidation. The particle size and shape can be controlled from spherical sub-10 nm particles to larger elongated structures. An advantage of the method is the complete absence of solvents, precursors, and other chemical agents. The obtained particle morphology and elemental composition have been analyzed by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS). The results reveal that the produced particles form a closed and homogeneous ZnO layer around a 2–3 nm Ag core with a uniform thickness of (1.33 ± 0.15) nm and (1.63 ± 0.31) nm for spherical and wire-like particles, respectively. The results are supported by ultraviolet photoelectron spectroscopy (UPS), which indicates a fully oxidized shell layer for the particles studied by STEM. The plasmonic properties of the produced spherical Ag@ZnO core@shell particles are investigated by two-photon photoelectron (2PPE) spectroscopy. Upon excitation of the localized surface plasmon resonance in Ag at around 3 eV, plasmonic enhancement leads to the liberation of electrons with high kinetic energy. This is observed for both Ag and Ag@ZnO particles, showing that even if a Ag cluster is covered by the ZnO layer, a plasmonic enhancement can be observed by photoelectron spectroscopy.

     

Mechanical properties of ZnO nanowires under different loading modes

A systematic experimental and theoretical investigation of the elastic and failure properties of ZnO nanowires (NWs) under different loading modes has been carried out. In situ scanning electron microscopy (SEM) tension and buckling tests on single ZnO NWs along the polar direction [0001] were conducted. Both tensile modulus (from tension) and bending modulus (from buckling) were found to increase as the NW diameter decreased from 80 to 20 nm. The bending modulus increased more rapidly than the tensile modulus, which demonstrates that the elasticity size effects in ZnO NWs are mainly due to surface stiffening. Two models based on continuum mechanics were able to fit the experimental data very well. The tension experiments showed that fracture strain and strength of ZnO NWs increased as the NW diameter decreased. The excellent resilience of ZnO NWs is advantageous for their applications in nanoscale actuation, sensing, and energy conversion.      

Dual gas-bubble-assisted solvothermal synthesis of magnetite with tunable size and structure

We present a facile solvothermal approach by employing ammonium bicarbonate (NH4HCO3) and ammonium acetate (NH4Ac) as dual gas-bubble-generating structure-directing agent to produce of magnetite (Fe3O4) particles with tunable size ranging from 90 nm to 400 nm and controllable structures including porous and hollow construction. The size, morphology and structure of the final products are achieved by simple adjustment of the molar ratio of NH4HCO3 and NH4Ac, ammonium ion concentration and the reaction time. The results reveal that the molar ratio of NH4HCO3 and NH4Ac strongly influenced the morphology and size of magnetite particles, even could decide the kind of architecture including solid, hollow and porous to form. Particularly, ammonium ion molar concentration plays a significant role in controlling size and magnetic property for magnetite particles. Simultaneously, prolonging the reaction time is beneficial to the magnetite particles growth and inner space escalation with altered reaction time at a certain concentration of ammonium and molar ratio of NH4HCO3 and NH4Ac. Such a design conception of dual gas-bubble-assistance used here is promisingly positive and significant for hollow magnetic particles fabrication and may be extended to other nano-scale hollow construction.     

Near UV LEDs made with in situ doped p-n homojunction ZnO nanowire arrays

Catalyst-free p-n homojunction ZnO nanowire (NW) arrays in which the phosphorus (P) and zinc (Zn) served as p- and n-type dopants, respectively, have been synthesized for the first time by a controlled in situ doping process for fabricating efficient ultraviolet light-emitting devices. The doping transition region defined as the width for P atoms gradually occupying Zn sites along the growth direction can be narrowed down to sub-50 nm. The cathodoluminescence emission peak at 340 nm emitted from n-type ZnO:Zn NW arrays is likely due to the Burstein-Moss effect in the high electron carrier concentration regime. Further, the electroluminescence spectra from the p-n ZnO NW arrays distinctively exhibit the short-wavelength emission at 342 nm and the blue shift from 342 to 325 nm is observed as the operating voltage further increasing. The ZnO NW p-n homojunctions comprising p-type segment with high electron concentration are promising building blocks for short-wavelength lighting device and photoelectronics.     

Synthesis of sealed sponge ZnO nanospheres through a novel NH(3)-evaporation method

Sealed sponge ZnO nanospheres are prepared through a novel NH(3)-evaporation method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and N(2) physisorption analysis show that the samples obtained are ZnO nanospheres with hexagonal wurtzite structure. The particle size is in the range 80-130?nm and the pores inside are estimated to be in the range 2-35?nm. During the preparation process, the carboxyls derived from the polyacrylamide hydrolyzation tend to attach to the particle surface and bring about the interaction between particles by hydrogen bonding. Results show that the polyacrylamide and alcohol are crucial to the formation of the sealed sponge ZnO, by forming a diffusion layer around the particle. The formation mechanism is considered to be controlled by the diffusion of Zn(2+) through the diffusion layer, and the mass transmission between the initial particles.