Vertical growth and resonator properties of hexagonally shaped zinc oxide nanonails

We synthesized vertically aligned nail-shaped ZnO nanocrystal arrays on silicon substrates via a combination of a carbothermal reduction method and textured ZnO seeding layers that were precoated on silicon substrates by thermally decomposing zinc acetate, and studied their optical properties using cathodoluminescence (CL) and photoluminescence techniques. The ZnO nanonails show a sharp band-gap edge UV emission and a defect-related broad green emission. Monochromatic CL images of an individual ZnO nanonail show variations in spatial distributions of respective CL bands that had different origins. We attribute the spatial variation of CL images to an uneven distribution of luminescent defects and/or a structure-related light out-coupling from hexagonal ZnO nanostructures. The most distinct CL feature from the hexagonal head of an individual ZnO nanonail was the occurrence of a series of distinct resonant peaks within the visible wavelength range. It appeared that the head of a nanonail played the role of a hexagonal cavity so that polarization-dependent whispering gallery modes were stimulated by electron beam excitation.     

Conversion process of ZnO nano-/micro-rods into nano-/micro-tubes and cathodoluminescence characterization

A simple two-steps method has been successfully developed to synthesize ZnO nanotubes. The alkaline etching process was investigated in detail using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The formation of ZnO nanotube structures was due to the preferential dissolution of the defect-rich top (polar) faces. Cathodoluminescence (CL) was performed on both top and side surfaces of the ZnO tubes. Only the near-band-edge UV emission was observed, implying that the as-grown ZnO nanotubes have a very low concentration of defects. This CL result also provides evidence for explanation of ZnO tubular structure growth.     

Effect of long-term electrical degradation on the distribution of donor impurities in ZnO varistor ceramics

The effect of long-term electrical degradation on the distribution of donor impurities in ZnO varistor ceramics and their electrical properties was examined. The results are consistent with the views that, in the initial stages of the process, the degradation is due mainly to local Joule heating at intergranular barriers, while at longer degradation times, the major mechanism of degradation is the redistribution of donors in the bulk of ZnO grains owing to their migration in the electric field of the barriers.     

Spatially resolved luminescence properties of ZnO tetrapods

ZnO tetrapods were prepared by Zn-vapour deposition at 740 °C in Argon and subsequent oxidation in air for 1–30 min. The photoluminescence (PL) and cathodoluminescence (CL) spectra were measured from ZnO particles collected at various distances from the Zn source representing decreasing dimensions. The ZnO tetrapods showed a green emission centred at 516 nm (2.40 eV) band and the exciton emission at 387 nm (3.20 eV). The measured data suggested that the green emission is strongly increased for particle sizes below 500 nm, whereas the exciton emission is dominant for particle size larger than 500 nm. Spatially resolved CL-measurement on individual tetrapod legs showed, that the green emission increases with decreasing ZnO leg diameter. To our knowledge, the local CL spectroscopic measurements were correlated with the dimensions of the individual ZnO tetrapods for the first time.     

Particle size distribution study by small-angle X-ray scattering technique and photoluminescence property of ZnO nanoparticles

ZnO nanoparticles have been synthesised by thermal decomposition of zinc acetate at ～800°C. The structural characteristics and size distribution of ZnO nanoparticles have been investigated by X-ray powder diffraction (XRD) and small-angle X-ray scattering (SAXS), respectively. SAXS study reveals nanoparticles are of different sizes: namely 23 wt% of 8 nm, 19 wt% of 21 nm and 58 wt% of 51 nm. These ZnO nanoparticles possess yellow visible emission at 552 nm. The polydispersity and single emission peak at 552 nm in ZnO nanoparticles suggest that the yellow emission might be a bulk property instead of having a surface origin in nanostructured ZnO. The surface impurities are characterised by Fourier-transform infrared spectroscopy. The quenching of band edge emission in ZnO nanoparticles seems due to the presence of surface impurities.     

The structural and optical properties of ZnO nanowire arrays prepared by hydrothermal synthesis method

ZnO nanowire arrays have been grown on the ZnO film-coated silicon (100) substrates by hydrothermal method, and the deposited nanowires are found to have a uniform size distribution with sharp hexagonal-shaped tips. The structural and optical properties of the nanowires were investigated using atomic force microscopy (AFM), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and cathodoluminescence (CL) techniques. The XRD and SEM results demonstrate that the well-aligned ZnO nanowires are single crystalline structure formed along the c-axis orientation. TEM analysis further confirms that the ZnO nanowires are highly preferred grown along the (002) crystal plane. The spacing between adjacent (002) lattice planes is estimated as 0.52 nm. The optical properties of the nanowires were measured using CL after annealing in oxygen and nitrogen atmospheres at 550 °C for various times. The CL spectra in the visible spectrum exhibit two weak deep-level emission bands that may be attributed to the intrinsic or extrinsic defects. It can be observed that the ZnO nanowires show different optical behaviors after various annealing times. The dependence of the optical properties on the annealing conditions is also discussed.     

Effects of Pt junction on electrical transport of individual ZnO nanorod device fabricated by focused ion beam

The electrical transport of individual ZnO nanorod devices manufactured by focused ion beam (FIB) was investigated by the direct measurement of electrical resistance at electrode junctions of cross-sectioned devices using two nanoprobes. The cathodoluminescence (CL) measurements were also performed to evaluate the crystallinity at the center and edge of the cross-sectioned ZnO nanorods. The electrical transport of the individual ZnO nanorod device depends strongly on the crystallinity of the ZnO nanorod itself and the carbon contents at Pt junctions. The ZnO-Au junction of the device acted as the fastest path for electrical transport.     

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.     

扩散诱导的锌间隙相关施主缺陷对ZnO纳米棒结构及光电特性的影响

采用射频磁控溅射技术和水浴法在SiO2单晶衬底上生长了Zn纳米颗粒/ZnO纳米棒复合材料(Zn/ZnO)。后期热处理促使Zn/ZnO界面之间发生元素相互扩散,直接向ZnO纳米棒中引入额外锌杂质,从而获得了富锌的ZnO纳米棒材料。借助扫描电子显微镜、X射线衍射仪、霍尔测试仪、分光光度计和拉曼光谱仪研究了富锌ZnO纳米棒的形貌、结构以及光电特性。结果表明,所有ZnO纳米棒均呈整齐的六角纤锌矿结构,相比ZnO纳米棒,富锌纳米棒具有相对较差的结晶质量,较好的导电性,较低的透射率和较窄的禁带宽度。拉曼光谱研究表明,通过扩散法向ZnO纳米棒引入的锌间隙相关施主缺陷,是其拉曼光谱中出现异常的275 cm^-1振动模的来源,也是导致富锌ZnO纳米棒微结构以及光电特性显著变化的主要原因。     

Synthesis of ZnO nanotube arrays and heterostructures of Cu-ZnO coaxial nanotubes by electrodeposition-oxidation method

Semiconductor ZnO nanotube arrays and heterostructures of Cu-ZnO coaxial nanotubes have been synthesized by electrodeposition into porous anodic alumina membranes and subsequent oxidation. Scanning electron microscopy and transmission electron microscopy indicate that the ZnO nanotubular arrays and Cu-ZnO coaxial nanotubular arrays are of large-area and highly ordered. X-ray diffraction patterns show that the nanotubes are polycrystalline. Photoluminescence spectra of the Cu-ZnO nanotubes show that a violet peak, a blue peak and a green peak are centered at 422 nm, 480 nm and 537 nm, respectively. The ordered ZnO nanotube arrays and heterostructures of Cu-ZnO coaxial nanotubes may have promising potential applications in nanodevices.     

两步法实现ZnO纳米结构的集成及光学性质研究

通过简单的两步热蒸发方法成功地实现了ZnO纳米管和纳米棒的集成.SEM结果表明,大量的纳米线以层层生长的机理从约200℃低温Si基片表面生长出来.EDS和XRD结果进一步表明第一步所制备的样品主要是由大量Zn和少量Zn的氧化物组成.第二步所制备样品的SEM和TME图像证实了在高温下以第一步所制备的样品作为第二步的基片,可实现纳米管和纳米棒的集成.TEM图像表明,纳米管的表面所生长的纳米棒是单晶的.通过改变工作气压,可调控纳米管表面纳米棒的尺寸和形貌,实现ZnO纳米结构可控生长.室温光致发光谱表明,样品的光学性质可通过可控的形貌来调制.     

Growth and properties of ZnO nanowires synthesized by a simple hydrothermal method

Hexagonal ZnO nanowires were synthesized on pre-seeded silicon (100) substrates by a simple hydrothermal method at a relatively low temperature of 95 °C without any catalyst or template. The pre-seeded layer was produced using the sol–gel spin coating technique with 1 M zinc acetate in ethanol and ethanolamine. The structural properties of the nanowires were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD pattern indicated that the as-grown ZnO nanowires had the single-phase wurtzite structure, formed along the c-axis. SEM revealed that the nanostructure thin film had wire textures and the synthesis processes importantly influence the final size and shape of the ZnO nanowires. High-resolution transmission electron microscopy (HRTEM) provided further insight into the structure of ZnO nanostructures. The obtained HRTEM image was of the tip of an individual nanowire. The ZnO nanowires highly preferentially grew in the (002) crystal plane. The lattice spacing between adjacent (002) lattice planes was calculated to be 0.52 nm. The optical characteristics of the nanowires were determined from cathodoluminescence (CL) spectra. The CL revealed a fairly high surface state density of ZnO nanowires that grew at reaction concentrations of 0.01–0.25 M.     

Point defects in ZnO: an approach from first principles

Abstract

Recent first-principles studies of point defects in ZnO are reviewed with a focus on native defects. Key properties of defects, such as formation energies, donor and acceptor levels, optical transition energies, migration energies and atomic and electronic structure, have been evaluated using various approaches including the local density approximation (LDA) and generalized gradient approximation (GGA) to DFT, LDA+U/GGA+U, hybrid Hartree–Fock density functionals, sX and GW approximation. Results significantly depend on the approximation to exchange correlation, the simulation models for defects and the post-processes to correct shortcomings of the approximation and models. The choice of a proper approach is, therefore, crucial for reliable theoretical predictions. First-principles studies have provided an insight into the energetics and atomic and electronic structures of native point defects and impurities and defect-induced properties of ZnO. Native defects that are relevant to the n-type conductivity and the non-stoichiometry toward the O-deficient side in reduced ZnO have been debated. It is suggested that the O vacancy is responsible for the non-stoichiometry because of its low formation energy under O-poor chemical potential conditions. However, the O vacancy is a very deep donor and cannot be a major source of carrier electrons. The Zn interstitial and anti-site are shallow donors, but these defects are unlikely to form at a high concentration in n-type ZnO under thermal equilibrium. Therefore, the n-type conductivity is attributed to other sources such as residual impurities including H impurities with several atomic configurations, a metastable shallow donor state of the O vacancy, and defect complexes involving the Zn interstitial. Among the native acceptor-type defects, the Zn vacancy is dominant. It is a deep acceptor and cannot produce a high concentration of holes. The O interstitial and anti-site are high in formation energy and/or are electrically inactive and, hence, are unlikely to play essential roles in electrical properties. Overall defect energetics suggests a preference for the native donor-type defects over acceptor-type defects in ZnO. The O vacancy, Zn interstitial and Zn anti-site have very low formation energies when the Fermi level is low. Therefore, these defects are expected to be sources of a strong hole compensation in p-type ZnO. For the n-type doping, the compensation of carrier electrons by the native acceptor-type defects can be mostly suppressed when O-poor chemical potential conditions, i.e. low O partial pressure conditions, are chosen during crystal growth and/or doping.     

Improvement of green cathodoluminescence of zinc oxide stacked films prepared by high-power excimer laser irradiation of sol-gel-derived precursors

Zinc oxide (ZnO) stacked films were prepared by repeating a procedure involving KrF excimer laser irradiation at various energy fluences (E_f) of sol-gel-derived precursors. All the stacked films are wurtzite-type and highly c-axis oriented on glass substrates. The green cathodoluminescence (CL) efficiency of the films is strongly influenced by the preparation conditions. Especially, laser E_f and stacking number are important control factors. The stacked film prepared under optimized preparation conditions consists of large grains and indicate low electric resistivity. The green CL efficiency of the stacked film is 0.0139 lm/W, which is higher than those of ZnO thin films prepared by a single stacking.     

热蒸发法制备Zn1-xCdxO纳米管及其生长机制研究

采用热蒸发纯Zn粉和Cd粉, 在湿反应气氛中氧化制备得到掺Cd的ZnO纳米管, 其Cd含量为3.3at%. 场发射扫描电镜(FESEM)及高分辨透射电镜(HRTEM)分析表明, 大部分纳米管外径约80~150nm, 长度达数微米, 壁厚约20nm. 通过与相同条件下制备的ZnO纳米结构的室温光致发光谱(PL) 进行对比发现, 由于Cd的掺入, Zn_1-xCd_xO纳米管的紫外近带边峰(UV NBE)从3.26eV红移到3.20eV附近.分析认为,Zn_1-xCd_xO纳米管遵循气液固(VLS)生长机制, 并在此基础上提出Zn_1-xCd_xO纳米管生长过程, 同时指出Kirkendall效应可能对纳米管的形成起到了重要作用.     

Cathodoluminescence and its mapping of flower-like ZnO, ZnO/ZnS core-shell and tube-like ZnS nanostructures

The cathodoluminescence (CL) properties including intensity and distribution of the band to band and defect emission of the flower-like ZnO, ZnO/ZnS core-shell and tube-like ZnS nanostructures have been investigated. It is indicated that the Ultraviolet (UV) emission at 380 nm of the flower-like ZnO nanostructures due to the band to band emission is weaker than their yellow emission at 600 nm induced by interstitial oxygen. Moreover, the UV emission of the ZnO nanorods unevenly distributes from the tip to the end. The UV emission on the tip is stronger than that of others due to the waveguide. On the contrary, the yellow emission at 600 nm is uniform. Furthermore, the UV emission of ZnO has been greatly enhanced and the yellow emission has been inhibited by the formation of ZnO/ZnS core-shell nanostructures in the sulfuration process due to the elimination of interstitial oxygen. However, the polycrystalline tube-like ZnS nanostructures shows the uniform and weak defect emission due to S vacancies.     

Microscale sphere assembly of ZnO nanotubes

In this paper, we report a facile method to perform microsphere organization of ZnO nanotubes. Study shows ZnO nanotubes with diameters of 80-150 nm and lengths of 1.2-2 μm were assembled into 3-4.5 μm microsphere superstructures, the significance of these assembled ZnO nanotubes is that one-dimensional anisotropic ZnO building blocks are selectively aligned into highly symmetrical three-dimensional isotropic conformations, which may promise us new types of ZnO applications. These microsphere assemblies of ZnO nanotubes have a wide visible yellow emission at 600 cm⁻¹. The assembly mechanism was also proposed, the addition of metallic zinc species into linear poly ethylene glycol (PEG) containing ethanol and water mixed solution led to aggregation of PEG polymer coils to Zn(II)/PEG globules with a diameter of ∼500 nm, the globule turned into tube-like-structured ZnO-PEG microsphere assemblies (∼2 μm) after ultrasonic pretreatment, ZnO nanotubes were formed by the oriented attachment and Ostwald ripening of ZnO growth units onto the tube-like structures during the following hydrothermal process.     

ZnO/TiO2纳米管晶膜电极的制备及光电性能

采用水热法制备了ZnO纳米棒,以ZnO纳米棒为原料制备出ZnO/TiO2纳米管晶膜电极并应用于染料敏化太阳能电池.用扫描电镜(SEM)、X射线衍射仪(XRD)、X射线能谱仪(EDX)和N2吸脱附分析等研究了样品的结构、表面形貌和化学组成,并通过紫外可见光度计和电化学工作站探讨了煅烧温度在80~600℃范围内ZnO/TiO2纳米管电极的光电化学性能.此外,研究经TiCl4化学处理的ZnO/TiO2纳米管电极光电性能的改善情况.结果表明,600℃煅烧的ZnO/TiO2纳米管电极制备的染料敏化太阳能电池表现出较优的光电性能,其短路电流密度(Jsc)为2.28 mA/cm2,开路电压(Voc)为0.631 V,光电转换效率η为0.66%.600℃煅烧的ZnO/TiO2纳米管经TiCl4处理后的染料敏化太阳能电池的光电性能得到显著改善,其光电转换效率η提高到1.06%.     

A study of the size-dependent elastic properties of ZnO nanowires and nanotubes

We present our calculations of the Young's modulus of ZnO nanowires and nanotubes by using the empirical Buckingham-type potential. Our results indicate that the Young's moduli of ZnO nanowires increase as the diameters decrease, and the Young's moduli of ZnO nanotubes increase as the thicknesses decrease. Furthermore, we find that such size-dependent elastic properties mainly arise from the lateral facets of the nanowires and nanotubes. In particular, for a ZnO nanotube with a thin wall, the Coulomb interaction between the ions of the outer and inner atomic layers plays an important role in the Young's moduli of the surface atomic layers.     

Photoluminescence imaging of electronic-impurity-induced exciton quenching in single-walled carbon nanotubes

The electronic properties of single-walled carbon nanotubes can be altered by surface adsorption of electronic impurities or dopants. However, fully understanding the influence of these impurities is difficult because of the inherent complexity of the solution-based colloidal chemistry of nanotubes, and because of a lack of techniques for directly imaging dynamic processes involving these impurities. Here, we show that photoluminescence microscopy can be used to image exciton quenching in semiconducting single-walled carbon nanotubes during the early stages of chemical doping with two different species. The addition of AuCl(3) leads to localized exciton-quenching sites, which are attributed to a mid-gap electronic impurity level, and the adsorbed species are also found sometimes to be mobile on the surface of the nanotubes. The addition of H(2)O(2) leads to delocalized exciton-quenching hole states, which are responsible for long-range photoluminescence blinking, and are also mobile.