Catalyst-free growth of well-aligned arsenic-doped ZnO nanowires by chemical vapor deposition method

ZnO nanowires with different arsenic concentration were grown on Si (1 0 0) substrates by chemical vapor deposition method without using catalyst. Zn/GaAs mixed powders were used as Zn and As source, respectively. Oxygen was used as oxidant. The images of scanning electron microscope show that the arsenic-doped ZnO nanowires with preferred c-axial orientation were obtained, which is in well accordance with the X-ray diffraction analysis. The arsenic related acceptor emission was observed in the photoluminescence spectra at 11 K for all arsenic-doped ZnO samples. This method for the preparation of arsenic-doped ZnO nanowires may open the way to realize the ZnO nanowires based light-emitting diode and laser diode.     

Comparison between ZnO nanowires grown by chemical vapor deposition and hydrothermal synthesis

Vertically aligned zinc oxide nanowires (NWs) were synthesized by two different techniques: chemical vapor deposition (CVD) and hydrothermal synthesis. To compare the effects of different growth conditions, both F-doped SnO₂ (FTO) coated-glass and silicon wafers were used as substrates. Before NWs growth, all the substrates were covered with a ZnO seed layer film obtained with the same procedure, which acts as nucleation site for the subsequent growth of the nanowires both during CVD and hydrothermal synthesis. We studied the influence of the two synthesis techniques and the growth duration on the final morphology, orientation, and density of the ZnO NWs using electron microscopy and X-ray diffraction, while the NWs optical quality was addressed by UV–Vis spectroscopy. By discussing advantages and disadvantages of both synthesis methods, we finally show that the application purpose often drives the choice of the NWs growth process and the substrate to be used.     

Novel phase transformation in ZnO nanowires under tensile loading

We predict a previously unknown phase transformation from wurtzite to a graphitelike (P6(3)/mmc) hexagonal structure in [0110]-oriented ZnO nanowires under uniaxial tensile loading. Molecular dynamics simulations and first principles calculations show that this structure corresponds to a distinct minimum on the enthalpy surfaces of ZnO for such loading conditions. This transformation is reversible with a low level of hysteretic dissipation of 0.16 J/m3 and, along with elastic stretching, endows the nanowires with the ability to recover pseudoelastic strains up to 15%.     

High-performance InGaN/GaN MQW LEDs with Al-doped ZnO transparent conductive layers grown by MOCVD using H_2O as an oxidizer

In this study,the high performance of InGaN/GaN multiple quantum well light-emitting diodes(LEDs) with Aldoped ZnO(AZO) transparent conductive layers(TCLs) has been demonstrated.The AZO-TCLs were fabricated on the n~+-InGaN contact layer by metal organic chemical vapor deposition(MOCVD) using H_2O as an oxidizer at temperatures as low as 400 ℃ without any post-deposition annealing.It shows a high transparency(98%),low resistivity(510 ~4 Ω·cm),and an epitaxial-like excellent interface on p-GaN with an n+-InGaN contact layer.A forward voltage of 2.82 V @ 20 mA was obtained.Most importantly,the power efficiencies can be markedly improved by 53.8%@20 mA current injection and 39.6%@350 mA current injection compared with conventional LEDs with indium tin oxide TCL(LED-Ⅲ),and by28.8%@20 mA current injection and 4.92%@350 mA current injection compared with LEDs with AZO-TCL prepared by MOCVD using O_2 as an oxidizer(LED-Ⅱ),respectively.The results indicate that the AZO-TCL grown by MOCVD using H_2O as an oxidizer is a promising TCL for a low-cost and high-efficiency GaN-based LED application.     

A wet chemical preparation of transparent conducting thin films of Al-doped ZnO nanoparticles

A wet chemical deposition method for preparing transparent conductive thin films on the base of Al-doped ZnO (AZO) nanoparticles has been demonstrated. AZO nanoparticles with a size of 7 nm have been synthesised by a simple precipitation method in refluxed conditions in ethanol using zinc acetate and Al-isopropylate. The presence of Al in ZnO was revealed by the EDX elemental analysis (1.8 at.%) and UV–Vis spectroscopy (a blue shift due to Burstein–Moss effect). The obtained colloid solution with the AZO nanoparticles was used for preparing by spin-coating thin films on glass substrates. The film demonstrated excellent homogeneity and transparency (T > 90%) in the visible spectrum after heating at 400 °C. Its resistivity turned to be excessively high (ρ = 2.6 Ω cm) that we ascribe to a poor charge percolation due to a high film porosity revealed by SEM observations. To improve the percolation via reducing the porosity, a sol–gel solution was deposited “layer-by-layer” in alternation with layers derived from the AZO colloid followed by heating. As it was shown by optical spectroscopy measurements, the density of thus prepared film was increased more than twice leading to a significant decrease in resistivity to 1.3 × 10⁻² Ω cm.     

Control growth of catalyst-free high-quality ZnO nanowire arrays on transparent quartz glass substrate by chemical vapor deposition

ZnO nanowire arrays have been successfully synthesized on transparent quartz glass substrate by chemical vapor deposition technique. Our work demonstrates the critical role of the growth temperature and the buffer layer on the effective control of the morphology of ZnO nanowires. A proper growth temperature and the thicker buffer layer could promise the good alignment and high density of the nanowires. The room-temperature photoluminescence spectrum shows that the buffer layer has also great effects on optical properties of ZnO nanowire arrays. The integrated intensity ratio [I_UV/I_{Visible band}] of the ZnO UV emission peak to visible band emission decreases with the increase of the thickness of the buffer layers. The obtained nanowire arrays have transmittance of above 50% in the visible region.     

PECVD制备AZO（ZnO:Al）透明导电薄膜

采用PECVD（等离子体增强化学气相沉积）工艺在普通玻璃和Si基上制备出了方块电阻低至89 Ω,可见光透过率高达79%,对基体附着力强的多晶态的AZO（ZnO:Al）薄膜.采用PECVD法制备AZO薄膜是一种有益的尝试,AZO透明导电薄膜不仅具有与ITO（透明导电薄膜,如In₂O₃:Sn）可比拟的光电特性,而且价格低廉、无毒,在氢等离子体环境中更稳定,所获结果对实际工艺条件的选择具有一定借鉴作用和参考价值. 关键词： AZO（ZnO:Al） 等离子体增强化学气相沉积 透明导电薄膜     

Highly flexible,transparent, conductive and antibacterial films made of spin-coated silver nanowires and a protective ZnO layer

We prepared highly flexible, transparent, conductive and antibacterial film by spin coating a silver nanowire suspension on a poly (ethylene terephthalate) (PET) substrate. The ZnO layer covered the conductive silver nanowire (AgNW) network to protect the metal nanowires from oxidization and enhance both wire-to-wire adhesion and wire-to-substrate adhesion. It is found that the number of AgNW coatings correlates with both the sheet resistance (R_s) and the transmittance of the AgNW/ZnO composite films. An excellent 92% optical transmittance in the visible range and a surface sheet resistance of only 9 Ω sq⁻¹ has been achieved, respectively. Even after bending 1000 times (5 mm bending radius), we found no significant change in the sheet resistance or optical transmittance. The real-time sheet resistance measured as a function of bending radius also remains stable even at the smallest measured bending radius (1 mm). The AgNW/ZnO composite films also show antibacterial effects which could be useful for the fabrication of wearable electronic devices.     

Surface defects on ZnO nanowires: implications for design of sensors

Surface defects are commonly believed to be fundamentally important to gas-sensor performance. We examine the effect of gas coverage and ethanol orientation on its adsorption on the stoichiometric and oxygen deficient (101(-)0) nanowire surface. Our density functional theory calculations show that ethanol adsorbs in multiple stable configurations at coverages between 1/4 and 1 ML, highlighting the ability of ZnO to detect ethanol. Ethanol prefers to bind to a surface Zn via the adsorbate oxygen atom and, if a surface oxygen atom is in close proximity, the molecule is further stabilized by formation of a hydrogen bond between the hydrogen of the hydroxyl group and the surface oxygen. Two primary adsorption configurations were identified and have different binding strengths that could be distinguished experimentally by the magnitude of their OH stretching frequency. Our findings show that ethanol adsorbed on the oxygen deficient ZnO(101(-)0) surface has a reduced binding strength. This is due to either the lack of a hydrogen bond (due to a deficiency in surface oxygen) or to surface reconstruction that occurs on the defect surface that weakens the hydrogen bond interaction. This reduced binding on the oxygen deficient surface is in contrast to the defect enhanced gas-sensor interaction for other gases. Despite this difference, ethanol still acts as a reducing gas, donating electrons to the surface and decreasing the band gap. We show that multiple adsorbed ethanol molecules prefer to be orientated parallel to each other to facilitate the hydrogen bonding to the defect-free surface for enhanced interaction.     

Room-temperature deposition of transparent conducting Al-doped ZnO films by RF magnetron sputtering method

Transparent conductive Al-doped zinc oxide (AZO) films with highly (0 0 2)-preferred orientation were deposited on quartz substrates at room temperature by RF magnetron sputtering. Optimization of deposition parameters was based on RF power, Ar pressure in the vacuum chamber, and distance between the target and substrate. The structural, electrical, and optical properties of the AZO thin films were investigated by X-ray diffraction, Hall measurement, and optical transmission spectroscopy. The 250 nm thickness AZO films with an electrical resistivity as low as 4.62 × 10⁻⁴ Ω cm and an average optical transmission of 93.7% in the visible range were obtained at RF power of 300 W, Ar flow rate of 30 sccm, and target distance of 7 cm. The optical bandgap depends on the deposition condition, and was in the range of 3.75-3.86 eV. These results make the possibility for light emitting diodes (LEDs) and solar cells with AZO films as transparent electrodes, especially using lift-off process to achieve the transparent electrode pattern transfer.     

Probing the electronic structure of ZnO nanowires by valence electron energy loss spectroscopy

Valence electron energy loss spectroscopy in a transmission electron microscope is employed to investigate the electronic structure of ZnO nanowires with diameter ranging from 20 to 100 nm. Its excellent spatial resolution enables this technique to explore the electronic states of a single nanowire. We found that all of the basic electronic structure characteristics of the ZnO nanowires, including the 3.3 eV band gap, the single electron interband transitions at approximately = 9.5, approximately = 13.5,and approximately = 21.8 eV, and the bulk plasmon oscillation at approximately 18.8 eV, resemble those of the bulk ZnO. Momentum transfer resolved energy loss spectra suggest that the 13.5 eV excitation is actually consisted of two weak excitations at approximately = 12.8 and approximately = 14.8 eV, which originate from transitions of two groups of the Zn 3d electrons to the empty density of states in the conduction band, with a dipole-forbidden nature. The energy loss spectra taken from single nanowires of different diameters show several size-dependent features, including an increase in the oscillator strength of the surface plasmon resonance at approximately = 11.5 eV, a broadening of the bulk plasmon peak, and splitting of the O 2s transition at approximately = 21.8 eV into two peaks, which coincides with a redshift of the bulk plasmon peak, when the nanowire diameter decreases. All these observations can be well explained by the increased surface/volume ratio in nanowires of small diameter.     

Synthesis and functionalization study of hierarchical ZnO nanowires for potential nitroaromatic sensing applications

In this work, we synthesize hierarchical ZnO nanowires in a customized atmospheric CVD furnace and investigate their surface modification behavior for prospective nitroaromatic sensing applications. The morphology and crystal structure of pristine nanowires are characterized through FE-SEM, TEM, X-ray diffraction and EDAX studies. Photoluminescence behavior of pristine nanowires is also reported. Surface modification behavior of synthesized nanowires on a ZnO–oleic acid system is studied by utilizing Raman and FT-IR spectroscopy. Based on these findings, 1-pyrenebutyric acid (PBA) has been identified as an appropriate fluorescent receptor for sensing p-nitrophenol. Fluorescence quenching experiments on a PBA–p-nitrophenol system are reported and a detection limit of up to 28 ppb is envisaged for PBA-grafted ZnO nanowire-based optical sensor.     

Growth study of indium-catalyzed silicon nanowires by plasma enhanced chemical vapor deposition

Indium was used as a catalyst for the synthesis of silicon nanowires in a plasma enhanced chemical vapor deposition reactor. In order to foster the catalytic activity of indium, the indium droplets had to be exposed to a hydrogen plasma prior to nanowire growth in a silane plasma. The structure of the nanowires was investigated as a function of the growth conditions by electron microscopy and Raman spectroscopy. The nanowires were found to crystallize along the <111>, <112> or <001> growth direction. When growing on the <112> and <111> directions, they revealed a similar crystal quality and the presence of a high density of twins along the {111} planes. The high density and periodicity of these twins lead to the formation of hexagonal domains inside the cubic structure. The corresponding Raman signature was found to be a peak at 495 cm⁻¹, in agreement with previous studies. Finally, electron energy loss spectroscopy indicates an occasional migration of indium during growth.     

Comment on "Investigation on optical properties of ZnO nanowires by electron energy-loss spectroscopy"

Recently, Zhang et al. have published a paper [Zhang, Z.H., Qi, X.Y., Jian, J.K., Duan, X.F., 2006. Micron 37, 229–233] in which – among others – the determination of the optical properties of a semiconductor by use of electron energy-loss spectroscopy (EELS) is performed with 200 keV electrons and a collection angle of only 0.3 mrad. The authors do not take into account relativistic effects such as Čerenkov losses (CL) before performing Kramers–Kronig Analysis (KKA) on the EELS spectra obtaining erroneous results. Although the positions of features within the optical properties are consistant with the simulated ones, the relative hights or absolute values differ a lot.     

Control of diameter of ZnO nanorods grown by chemical vapor deposition with laser ablation of ZnO

We made a study of controlling diameters of well-aligned ZnO nanorods grown by low-pressure thermal chemical vapor deposition combined with laser ablation of a sintered ZnO target, which was developed by us. Until now, it has been impossible to control diameters of ZnO nanorods, while the growth orientation was maintained well-aligned. In this study we developed a multi-step growth method to fabricate well-aligned nanorods whose diameters could be controlled. Metal Zn vapor and O₂ are used as precursors to grow ZnO nanorods. N₂ is used as a carrier gas for the precursors. A substrate is an n-Si (111) wafer. A sintered ZnO target is placed near the substrate and ablated by a Nd–YAG pulsed laser during ZnO nanorod growth. The growth temperature is 530 C and the pressure is 66.5 Pa. A vertical growth orientation of ZnO nanorods to the substrate is realized in the first-step growth although the diameter cannot be controlled in this step. When an O₂ flow rate is 1.5 sccm, well-aligned nanorods with 100 nm diameter are grown. Next, the second-step nanorods are grown on only the flat tip of the first-step nanorods. The diameters of the second-step nanorods can be controlled by adjusting the O₂ flow rate, and the growth direction is kept the same as that of the first-step nanorods. When the O₂ flow rate in second-step growth is smaller than 0.6 sccm, the diameter of the second-step nanorods is 30–50 nm. When the O₂ flow rate is between 0.75 and 3.0 sccm, the diameter is almost same as that of the first-step nanorods. When the O₂ flow rate is larger than 4.5 sccm, the diameter is increased with increasing O₂ flow rate. Further, the third-step ZnO nanorods with gradually increased diameters can be grown on the second-step nanorods with 1.5 sccm O₂ flow rate and without laser ablation.     

Light-induced reversible hydrophilicity of ZnO structures grown by aqueous chemical growth

ZnO wurtzite microrods and flowerlike structures were deposited on glass and ITO substrates by the aqueous chemical growth (ACG) technique at mild temperature (95 °C). Wettability studies revealed that the as-deposited structures are hydrophilic and super-hydrophilic for short and long growth times, respectively. The hydrophilic ZnO surfaces could be reversibly switched to super-hydrophilic by alternation of UV illumination and dark storage. Our results demonstrate that ACG at low temperatures can be efficiently employed to deposit transparent photosensitive ZnO structures exhibiting reversible wettability changes.     

直流反应磁控溅射制备掺铟ZnO透明导电薄膜的研究

本文介绍了掺铟ZnO透明导电膜的制备工艺.并应用半导体物理理论分析了薄膜的导电机理,用Drude理论建立了物理模型,分析与计算了薄膜从可见到红外光波段的光学性能,结果表明,理论计算与实测值两者符合得较好.     

Low-temperature deposition of transparent conducting ZnO:Zr films on PET substrates by DC magnetron sputtering

Transparent conducting zirconium-doped zinc oxide (ZnO:Zr) films were firstly deposited on polyethylene terephthalate (PET) substrates with ZnO buffer layers by DC magnetron sputtering at room temperature. Dependence of physical properties of ZnO:Zr films on deposition pressure was systematically studied. All the deposited films were polycrystalline and (1 0 0) oriented. When deposition pressure increases from 1 to 2.5 Pa, the crystallinity of the films improves and the resistivity decreases. While deposition pressure increases from 2.5 to 3.5 Pa, the crystallinity of the films deteriorates and the resistivity increases. The lowest resistivity of 1.8 × 10⁻³ Ω cm was obtained for the films deposited at the optimum deposition pressure of 2.5 Pa. All the films present a high transmittance of above 86% in the wavelength range of the visible spectrum.     

A study on defect formation and magnetic properties of nitrogen-doped ZnO nanowires by the first principles

Theoretical calculation based on density functional theory (DFT) and generalized gradient approximation (GGA) has been carried out in studying defect formation energies, ionizing energies and ferromagnetism of nitrogen-doped ZnO nanowires. The result shows that N_O is deep acceptor, which make it hard to ionize. Ferromagnetic (FM) and antiferromagnetic (AFM) coupling between N atoms are also investigated. The results show that FM coupling between N atoms is more stable than AFM coupling. The FM coupling mechanism is explained by the interaction of N energy level. In addition, zinc and oxygen vacancies affecting FM coupling is also discussed. It is found that zinc and oxygen vacancies are unfavorable for stabilizing FM coupling of nitrogen-doped ZnO nanowires.     

化学气相沉积法制备Zn2GeO4纳米线及其发光性质的研究

利用化学气相沉积法（CVD）,气-液-固（VLS）生长法则在表面溅有金属Au催化剂层的1 cm×1 cm的Si片上制备三元Zn₂GeO₄纳米线。X射线衍射仪（XRD）测试结果表明,锌源与锗源质量比为8：1时可成功制备出Zn₂GeO₄纳米结构;扫描电子显微镜（SEM）测试结果表明,Zn₂GeO₄纳米线直径为100 nm,长度为10~11 μm;光致发光（PL）测试结果表明,Zn₂GeO₄纳米线在432和480 nm处具有两个发光峰,最后对其生长机理进行了分析。