Photoluminescence of ZnO nanowires dependent on O2 and Ar annealing

High-purity ZnO nanowires have been synthesized on Si substrates without the presence of a catalyst at 600 °C by a simple thermal vapor technique. Photoluminescence (PL) spectra of the annealed samples at 900 °C under oxygen and argon gases have been investigated. After O₂ or Ar annealing, the PL visible-emission intensity that is related to intrinsic defects (oxygen vacancies) is greatly reduced compared with as-grown ZnO nanowires because the oxygen-gas ions or oxygen interstitials diffuse into the oxygen vacancies during annealing process. The blue-band peak of the O₂- or Ar-annealed ZnO naonowires is also smaller than the green-band peak in the visible broadband because of the reduction of oxygen vacancies. Therefore, the main intrinsic defects (oxygen vacancies) of as-grown ZnO nanowires can be reduced by O₂ or Ar annealing, which is an important procedure for the development of advanced optoelectronic ZnO nanowire devices.     

Effects of temperature and atmosphere on the magnetic properties of Co-doped ZnO rods

Co-doped ZnO (Zn_0.95Co_0.05O) rods are fabricated by co-precipitation method at different temperatures and atmospheres. X-ray diffraction, Energy dispersive X-ray spectroscopy and Raman results indicate that the samples were crystalline with wurtzite structure and no metallic Co or other secondary phases were found. Raman results indicate that the Co-doped ZnO powders annealed at different temperatures have different oxygen vacancy concentrations. The oxygen vacancies play an important role in the magnetic origin for diluted magnetic semiconductors. At low oxygen vacancy concentration, room temperature ferromagnetism is presented in Co-doped ZnO rods, and the ferromagnetism increases with the increment of oxygen vacancy concentration. But at very high oxygen vacancy concentration, large paramagnetic or antiferromagnetic effects are observed in Co-doped ZnO rods due to the ferromagnetic-antiferromagnetic competition. In addition, the sample annealed in Ar gas has better magnetic properties than that annealed in air, which indicates that O₂ plays an important role. Therefore, the ferromagnetism is affected by the amounts of structural defects, which depend sensitively on atmosphere and annealing temperature.     

Electrical properties and carrier transport mechanisms of nonvolatile memory devices based on randomly oriented ZnO nanowire networks

We report reproducible bipolar resistive memory devices based on Au/ZnO nanowire networks (ZnO NWNs)/ITO, which show a high R_on/R_off ratio (～10⁴) and narrow dispersion of set and reset threshold voltages. The dominant conduction mechanisms of low resistance state and high resistance state were verified by Ohmic behavior and space charge limited current, respectively. The switching mechanism is confirmed in terms of the formation and rupture of conductive filaments, with oxygen vacancies localized on the ZnO NWNs surface involved in. The Au/ZnO NWNs/ITO devices presented in our work show potential applications in the next generation nonvolatile memory field. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Controllable Preparation of Hierarchical ZnO Nanocages and its Oxygen Vacancy through the Nanoscale Kirkendall Process

The synthesis of ZnO with tailorable shapes and point defects is important for its potential applications. Here, a facile approach is demonstrated to prepare ZnO nanocages with controllable porous shell structures though sintering a Zn‐based cyanide‐bridged coordination polymer under different temperatures. The transformation of ZnCP microspheres into ZnO nanocages is based on two types of nanoscale Kirkendall effect, which are related to low temperature solid–solid interfacial oxidation and high temperature solid–gas interfacial reaction, respectively. At low temperature (around 300 °C) and before the ZnCP decomposition, the novel “hierarchical ZnO bigger nanocages embedded with smaller nanocages with 10 nm nanocrystals” can be generated. By contrast, when coming to the total decomposition of ZnCP at 800 °C, ZnO nanocages with significantly increased sizes and large cavities are generated, and large amounts of oxygen vacancies (V_O) are created at the same time, leading to the dramatic increased luminescence intensities of the UV peak due to V_O at 540 nm. Thus, the luminescence intensities versus defect concentration in the prepared ZnO nanocages can also be controlled by tuning the sintering temperatures.     

超声处理对ZnO薄膜光致发光特性的影响

对于结晶状态好的ZnO薄膜，测量了其光致发光(PL)光谱，发射光谱中只发现了峰值波长约389 nm的近紫外光.样品进行超声处理后，发射谱中不仅观察到近紫外峰，又观察到波长约508 nm的绿光峰.绿光峰的强度比近紫外光的强度强得多，且近紫外峰红移.进一步的热处理使绿光峰大大增强.超声处理改变了ZnO薄膜的质量和结晶状态，使晶格中产生氧空位.处理过程中的热效应使得薄膜晶格振动加剧.当晶格振动加剧到一定程度，晶格中的氧脱离格点形成氧空位.510 nm左右的绿色发光峰是ZnO晶体中的氧空位产生的.薄膜的温度越高， 关键词： ZnO薄膜 超声 光致发光     

Dark current suppression of amorphous selenium based photosensors by the ZnO hole blocking layer

To study the influence of defects in the hole blocking layer (HBL) on the dark current of amorphous selenium (a-Se) based photosensors, we prepared ZnO thin films by reactive sputter deposition (RSD) for the use as the HBL of the photosensors. The ZnO HBL layers prepared with different oxygen flow rates were characterized by X-ray photoelectron spectroscopy, Raman scattering analysis and photoluminescence, indicating that the density of oxygen vacancies in the ZnO thin films is significantly affected by the oxygen flow rate. The deep level transient spectroscopy measurement reveals two hole trap levels present in the RSD deposited ZnO thin films; one is at 0.94 eV and the other at 0.24 eV above the valence band edge. The electrical performance of the a-Se photosensor is largely influenced by the amount of oxygen vacancies in the ZnO thin film. The a-Se photosensor with the ZnO HBL of the most oxygen vacancies has the lowest dark current and demonstrates the highest breakdown field.     

Emerging of Ag particles on ZnO nanowire arrays for blue-ray hologram storage

Noble-metal/metal-oxide-semiconductor nanostructures as an important material platform have been applied in massive data storage. ZnO exhibits excellent optical modulation ability. However, plasmon induced charge separation effect in Ag/ZnO systems is very weak due to the low chemical activity on surface of the oxide. Herein, we prepare ZnO nanowire arrays via the hydrothermal method, and measure their absorption spectra, photoluminescence spectra and electron paramagnetic resonance, proving the existence of oxygen defects in ZnO. Accordingly, an idea of "electron reverse transfer" is proposed such that blue-ray (403.4 nm) induces reduction of Ag⁺ ions through the excitation of ZnO. Rod-like and spherical silver nanoparticles emerge on the surface and in the gap of ZnO nanowire arrays, respectively, after the visible light stimulus. It is found that nanowire density, oxygen defects and surface roughness are dependent on hydrothermal time. The optimized diffraction efficiency of 0.08% is obtained for reconstructing hologram in the nanocomposite film. This work provides a bright way for construction of ZnO-based optoelectronic integrated devices.     

Great influence of the oxygen vacancies on the ferromagnetism in the Co-doped ZnO films

The ZCO (Co-doped ZnO) films were prepared by using submolecule-doping technique, where the magnetic sputtering of Co and ZnO were alternatively performed onto silicon substrates. The prepared ZCO films were then annealed at different temperatures, and the dependence of the ferromagnetism on annealing temperature was studied. It is found that the saturation magnetization of our samples decreases with the increase of annealing temperature. This behavior is possibly due to the decrease of oxygen vacancies with the increase of the annealing temperature.     

Surface effects on photoluminescence of single ZnO nanowires

The influence of surface effects on the temperature dependent photoluminescence (PL) spectra from individual ZnO nanowires has been studied. It is found that the surface effects of the nanowire are very important in both ultraviolet (UV) and visible emission. We propose a new luminescence mechanism based on the recombination related to oxygen vacancies to explain the temperature dependent visible emission, which is significantly influenced by the carrier depletion and band bending caused by surface effects. In addition, the observed attenuation of UV emission with increasing temperature is ascribed to the decreasing depletion region and the increasing surface states related nonradiative recombination.     

Effective control of photoluminescence from ZnO nanowires by a-SiN_x:H decoration

The a-SiN_x:H with a large bandgap of 3.8 eV was utilized to decorate ZnO nanowires. The UV emission from the a-SiN_x:H-decorated ZnO nanowires are greatly enhanced compared with the undecorated ZnO nanowire. The deep-level defect emission has been completely suppressed even though the sample was annealed at temperatures up to 400 °C. The incorporation of H and N is suggested to passivate the defect states at the nanowire surface and thus result in the flat-band effect near ZnO surface as well as reduction of the nonradiative recombination probability.     

Optoelectronic characterisation of an individual ZnO nanowire in contact with a micro-grid template

Optoelectronic characterisation of an individual ZnO nanowire in contact with a micro-grid template has been studied.The low-cost micro-grid template made by photolithography is used to fabricate the ohmic contact metal electrodes.The current increases linearly with the bias,indicating good ohmic contacts between the nanowire and the electrodes.The resistivity of the ZnO nanowire is calculated to be 3.8 ·cm.We investigate the photoresponses of an individual ZnO nanowire under different light illumination using light emitting diodes(λ = 505 nm,460 nm,375 nm) as excitation sources in atmosphere.When individual ZnO nanowire is exposured to different light irradiation,we find that it is extremely sensitive to UV illumination;the conductance is much larger upon UV illumination than that in the dark at room temperature.This phenomenon may be related to the surface oxygen molecule adsorbtion,which indicates their potential application to the optoelectronic switching device.     

过渡金属元素X(X=Mn,Fe,Co,Ni)掺杂对ZnO基阻变存储器性能的影响

实验表明掺杂是一种改善阻变存储器性能的有效手段,但其物理机理鲜有研究.本文采用第一性原理方法系统研究了过渡金属元素X(X=Mn,Fe,Co,Ni)掺杂对ZnO基阻变存储器中氧空位迁移势垒和形成能的影响.计算结果表明Ni掺杂可同时有效降低+1和+2价氧空位在掺杂原子附近的迁移势垒,X掺杂均减小了氧空位的形成能,特别是掺杂Ni时氧空位的形成能减小最为显著(比未掺杂时减少了64%).基于该结果制备了未掺杂和Ni掺杂ZnO阻变存储器,研究表明通过掺杂控制体系中氧空位的迁移势垒和形成能,可以有效改善器件的初始化过程、操作电压、保持性等阻变性能.研究结果有助于理解探究影响阻变的微观机制,并可为掺杂提高阻变存储器性能提供一定的理论指导.     

单晶ZnO纳米线的合成和生长机理研究

用化学气相输运(CVT)方法合成了直径在20～120nm呈单晶结构的ZnO纳米线.利用场发射扫描电 镜(FESEM)、高分辨透射电镜(HRTEM)以及选区电子衍射(SAED)等技术对ZnO纳米线的生长机理和结构进行 了系统研究,结果表明,纳米线的成核与Au Zn合金催化颗粒的饱和度有直接的关系,先饱和的颗粒上纳米线首 先成核.纳米线顶端合金颗粒组成的变化是导致纳米线生长终止的重要原因,大量纳米线的生长不是同时进行 的.本工作提供了支持纳米线气液固(V L S)生长机理的新实验证据,提出了氧化物纳米线的生长机理.     

单根ZnO纳米线低温条件下的电子输运及光敏性质

用化学气相沉积的方法合成了ZnO纳米线，采用微栅模板法制得电极从而获得欧姆接触的单根ZnO纳米线半导体器件。通过研究60~300 K范围内的电阻变化情况，发现在整个温度区间内存在热激活和近程跳跃两种传输机制。在300，200，100 K的条件下分别测试了器件的紫外光响应和恢复情况，结果表明：低温下器件对紫外光的敏感性提高，电流的恢复时间随着温度的降低而延长。     

Zinc Oxide Thin Films for Memristive Devices: A Review

Zinc Oxide (ZnO) thin films have been addressed as promising candidates for the fabrication of Resistive Random Access Memory devices, which are alternative to conventional charge-based flash memories. According to the filamentary conducting model and charge trapping/detrapping theory developed in the last decade, the memristive behavior of ZnO thin films is explained in terms of conducting filaments formed by metallic ions and/or oxygen vacancies, and their breaking through electrochemical redox reactions and/or recombination of oxygen vacancies/ions. A comparative review of the memristive properties of ZnO thin films grown by sputtering, atomic layer deposition (ALD), pulsed laser deposition (PLD), and sol-gel methods is here proposed. Sputtered ZnO thin films show promising resistive switching behaviors, showing high on/off ratios (10–10⁴), good endurance, and low operating voltages. ALD is also indicated to be useful for growing conformal ZnO layers with atomic thickness control, resulting in important resistive switching characteristics, such as relatively high on/off ratios and low operating voltages. High insulating epitaxial ZnO thin films can be obtained by PLD, showing reliable switching properties at low voltages and with good retention. On the contrary, the sol-gel approach generally results in ZnO thin films with poor resistive switching behaviors. Nevertheless, thin films derived from ZnO NPs show improved switching performances, with higher on/off ratios and lower operating voltages. Independently of the synthetic approach, doped ZnO thin films exhibit better resistive switching behaviors than pristine ones, coupling a strong increase of the on/off ratio with a more stable switching response.     

Investigation of the fill factor of dye-sensitized solar cell based on ZnO nanowire arrays

The fill factor of dye-sensitized solar cells based on the ZnO nanowire array is very low, which is usually ascribed to a rapid charge recombination. In this article, the influence on the fill factor of ZnO nanowire array cell is investigated and discussed by comparing dark current and decay rate of open circuit potential of the ZnO nanowire array cell with those of the ZnO nanoparticle cell, TiO₂ nanoparticle cell and TiO₂-coated ZnO nanowire array cell. The results demonstrate that the low fill factor of the ZnO nanowire array cell is largely caused by a rapid decrease of electron injection efficiency rather than a rapid charge recombination, which is decided by the absorption nature of Ru-complexed dye molecules on ZnO surface and repellency of radial electric field. The fill factor of the ZnO nanowire array cell can be improved by coating ZnO nanowires with a wide band gap semiconductor material or metal oxide insulator.     

紫外光表面处理对ZnO纳米粒子的晶体结构与光学性质的影响

利用溶胶凝胶法制备了ZnO纳米粒子,用紫外光照射对其进行表面处理.探讨了表面处理对ZnO纳米粒子晶体结构与光学性质的影响.结果显示:在晶体结构方面,紫外光照射会降低ZnO纳米粒子的团聚现象,缩短晶格常数,使其所受应力由压缩应力释放变为伸张应力,增大表面能,使能量最佳化并稳定而导致ZnO纳米粒子形成再构.在光学性质方面,紫外光照射会使ZnO纳米粒子表面产生较多的氧空位,而氧空位又会使其表面容易吸附羟基,使得ZnO纳米粒子变得更加亲水.     

紫外光表面处理对ZnO纳米粒子的晶体结构与光学性质的影响

利用溶胶凝胶法制备了ZnO纳米粒子,用紫外光照射对其进行表面处理。探讨了表面处理对ZnO纳米粒子晶体结构与光学性质的影响。结果显示：在晶体结构方面,紫外光照射会降低ZnO纳米粒子的团聚现象,缩短晶格常数,使其所受应力由压缩应力释放变为伸张应力,增大表面能,为使能量最佳化并稳定而导致ZnO纳米粒子形成再构。在光学性质方面,紫外光照射会使ZnO纳米粒子表面产生较多的氧空位,而氧空位又会使其表面容易吸附羟基,使得ZnO纳米粒子变得更加亲水。     

ZnO薄膜的性质对水热生长ZnO纳米线阵列的影响

用水热法在ZnO薄膜上制备了直径、密度及取向可控的ZnO纳米线阵列。ZnO薄膜是通过原子层沉积(ALD)方法制备并在不同温度下退火处理得到的,退火温度对ZnO薄膜的晶粒尺寸、结晶质量和缺陷性质有很大的影响。而ZnO薄膜的性质对随后生长的ZnO纳米线的直径、密度及取向能起到调节控制的作用。通过扫描电子显微镜(SEM)、X射线衍射(XRD)仪和光致发光(PL)测试对ZnO薄膜和ZnO纳米线进行了表征。最后得到的垂直取向的ZnO纳米线阵列适合在发光二极管和太阳能电池等领域使用。     

低能质子辐照对ZnO白漆光学性能退化的影响

 通过光致荧光光谱解谱和X射线光电子能谱（XPS）分析,研究了ZnO白漆经受能量低于200 keV低能质子辐照过程中氧空位缺陷的形成与演化过程。XPS解析表明质子辐照后晶格氧减少,光致荧光光谱解析表明锌空位减少,说明ZnO白漆中氧空位数量增加,且双电离氧空位能够捕获价带中的电子转变为单电离氧空位,使单电离氧空位逐渐成为辐照产生的主要缺陷。质子辐照使ZnO白漆中氧空位数量增加,而氧空位易捕获电子形成色心,从而导致光学性能下降。