掺锰氧化锌的结构和光学特性

采用直流反应磁控溅射的方法,在玻璃衬底上沉积了Zn0.93Mn0.07O薄膜,研究了氧分压对薄膜结构和光学特性的影响。X射线衍射测试结果显示,Zn0.93Mn0.07O薄膜都具有高度的c轴择优取向,在氧分压为0.4的时候,薄膜的衍射峰具有最小的半峰全宽,最大的晶粒尺寸。X射线光电子能谱测试结果表明:Mn2 离子已经取代了氧化锌晶格中的部分Zn2 ,但还掺杂有少量的MnO2分子;处在1 021 eV的Zn 2p3/2能级只有单一的Zn2 ;而O2 -则来自Zn-O和Mn-O。由于伯斯坦-莫斯效应,Zn0.93Mn0.07O薄膜光吸收跃迁过程只能在价带态和费密能级附近及以上的导带空态之间发生,其吸收谱线显示,与纯ZnO薄膜吸收谱线相比,产生了蓝移现象。同时还伴随有导带尾跃迁的发生,研究表明,这是由3d5多重能级的d-d跃迁而引起的。经过计算,在氧分压为0.4的时,Zn0.93Mn0.07O薄膜的禁带宽度是最大的,这可能是由交换作用的减弱而引起的。     

高压处理对稀磁半导体Zn1-xMnxO磁性的影响

用固相反应法制备出过渡金属Mn掺杂的ZnO系列样品,并对其进行了高压处理.高压处理后的样品,通过扫描电子显微镜和X射线衍射仪进行了微观结构的表征分析.通过磁性能的测量,初步研究了压力对Mn掺杂ZnO稀磁半导体磁性能的影响.结果表明:适当的高压处理可以有效增强材料的室温铁磁性,但当压力超过一定值后,压力会使材料的磁性能下降.     

Fabrication of needle-like ZnO nanorods arrays by a low-temperature seed-layer growth approach in solution

Uniform, large-scale, and well-aligned needle-like ZnO nanorods with good photoluminescence and photocatalysis properties on Zn substrates, have been successfully fabricated using a simple low-temperature seed-layer growth approach in solution (50 °C). The formation of ZnO seed-layer by the anodic oxidation technique (AOT) plays an important role in the subsequent growth of highly oriented ZnO nanorods arrays. Temperature also proved to be a significant factor in the growth of ZnO nanorods and had a great effect on their optical properties. X-ray diffraction (XRD) analysis, selected-area electron diffraction (SAED) pattern and high-resolution TEM (HRTEM) indicated that the needle-like ZnO nanorods were single crystal in nature and that they had grown up preferentially along the [0001] direction. The well-aligned ZnO nanorods arrays on Zn substrates exhibited strong UV emission at around 380 nm at room temperature. To investigate their potential as photocatalysts, degradation of pentachlorophenol (PCP) in aqueous solution was carried out using photocatalytic processes, with comparison to direct photolysis. After 1 h, the degradation efficiencies of PCP by direct photolysis and photocatalytic processes achieved 57% and 76% under given experimental conditions, respectively. This improved degradation efficiency of PCP illustrates that ZnO nanorods arrays on Zn substrates have good photocatalytic activity. This simple low-temperature seed-layer growth approach in solution resulted in the development of an effective and low-cost fabrication process for high-quality ZnO nanorods arrays with good optical and photocatalytic properties that can be applicable in many fields such as photocatalysis, photovoltaic cells, luminescent sensors, and photoconductive sensors. PACS 81.07.Bc; 81.10.Dn; 81.15.Pq; 82.50.Hp; 85.60.Jb     

Ag-doped ZnO nanorods synthesized by two-step method

A two-step method is adopted to synthesize Ag-doped ZnO nanorods.A ZnO seed layer is first prepared on a glass substrate by thermal decomposition of zinc acetate.Ag-doped ZnO nanorods are then assembled on the ZnO seed layer using the hydrothermal method.The influences of the molar percentage of Ag ions to Zn ions(RAg/Zn) on the structural and optical properties of the ZnO nanorods obtained are carefully studied using X-ray diffractometry,scanning electron microscopy and spectrophotometry.Results indicate that Ag ions enter into the crystal lattice through the substitution of Zn ions.The<002>c-axis-preferred orientation of the ZnO nanorods decreases as RAg/Zn increases.At RAg/Zn >1.0%,ZnO nanorods lose their c-axis-preferred orientation and generate Ag precipitates from the ZnO crystal lattice.The average transmissivity in the visible region first increases and then decreases as R Ag/Zn increases.The absorption edge is first blue shifted and then red shifted.The influence of Ag doping on the average head face,and axial dimensions of the ZnO nanorods may be optimized to improve the average transmissivity at RAg/Zn <1.0%.     

Synthesis and Characteristics of Electrodeposited CoxZn1-x Nanorods

CoxZn1-x nanorod arrays were fabricated by electrodeposition in porous anodic aluminum oxide templates at different electric potentials. X-ray diffraction and transmission electron microscopy indicate that highly-ordered and uniform nanorods have been fabricated. The amounts of Co and Zn contents are investigated using energy dispersive spectroscopy, which demonstrates that the atom ratio of the alloy nanorods changes with the deposition potential. In addition, magnetic measurements show that the magnetic isotropy Co-rich CoZn nanorods will change to magnetic anisotropy nanorods with the easy axis parallel to the rod long axis with decreasing Co content.     

氧化锌纳米棒的生长过程研究

利用高分子聚乙烯吡咯烷酮(PVP)和乙酸锌的配合物作为前驱体,在300 ℃温度下煅烧,并制备了氧化锌纳米棒。生成的产物用XRD,TEM,SAED等测试方法进行了表征。为了研究氧化锌纳米棒的生长过程,我们通过控制制备前驱体所需原料的比例不变,改变在300 ℃温度下煅烧的时间,分别为0.5, 3, 12和24 h,来观察生成产物的形貌特征。实验发现在110 ℃温度下干燥的前驱体中已经有氧化锌微晶生成;在300 ℃温度下煅烧0.5 h后就出现了明显的由几个纳米大小的微晶所组成的氧化锌纳米棒;煅烧3 h后的产物是结构非常完整的径直单晶ZnO纳米棒;12和24 h煅烧前驱体生成的ZnO纳米棒长度有所增加,ZnO的量基本保持不变。实验发现氧化锌的生长是沿着c轴方向,但是在横向也有生长方向。     

Effect of zinc nitrate concentration on the structural and the optical properties of ZnO nanostructures

ZnO nanorods and nanodisks were formed on indium-tin-oxide-coated glass substrates by using an electrochemical deposition method. Scanning electron microscopy images showed that the ZnO nanorods were transformed into nanodisks with increasing Zn(NO₃)₂ concentration. X-ray diffraction patterns showed that the ZnO nanostructures had wurzite structures. The full widths at half maxima of the near band-edge emission peak of photoluminescence spectra at 300 K for ZnO nanorods were small, indicative of the high quality of the nanorods. These results indicate that the structural and the optical properties of ZnO nanostructures vary by changing Zn(NO₃)₂ concentration.     

Effect of ultrasonic treatment before and after hydrothermal process on the morphologies and formation mechanism of ZnO nanorods

ZnO nanorods were fabricated by ultrasonic treatment before and after a hydrothermal process. The morphology and structure of the nanorods were individually characterized by scanning electron microscopy and X-ray diffraction. The results show that before the hydrothermal process, fore-ultrasonic treatment can directly gain ZnO nanorods which mainly experienced four conversion stages from initial bulk Zn(OH)₂, a coexisting phase of bulk Zn(OH)₂ with ZnO nanoslices, ZnO nanoslices with flower-like ZnO nanorods and finally to purely flower-like ZnO nanorods. After the hydrothermal process, the post-ultrasonic treatment mainly influences the aggregation degree of the ZnO nanorods. The formation mechanism of ultrasonic treatment on ZnO nanorods is also discussed.     

Preparation of 3D ZnSe novel structure

Samples of ZnSe with a novel 3D structure have been successfully synthesized by chemical vapour deposition method, simply using Zn and Se powder sources without any catalysts. The ZnSe nanorods grew on the facets of ZnSe particles and their length increases with the growth time increasing. The ZnSe samples grew on the inner wall of the alumina crucible with Zn source. The morphologies and structures of nanorods and particles were characterised by a scanning electron microscopy, high-resolution transmission electron microscopy and X-ray diffraction, and their photoluminescence properties were also measured at different temperatures. Results show that the nanorods are single crystals and the particles are also crystalline materials. The ZnSe samples show two emission bands at 467 and 605 nm, respectively.     

Zn-catalyzed growth processes and ferromagnetism of Mn-doped ZnO nanorods on Si substrate

Well-aligned ZnO nanorods and Mn-doped ZnO nanorods are fabricated on Si (1 0 0) substrate according to the contribution of Zn metal catalysts. Scanning electron microscopy and high-resolution transmission electron microscopy images indicate that the influence of Zn catalyst on the properties of ZnO can be excluded and the growth of ZnO nanorods follows a vapor-liquid-solid and self-catalyzed model. Mn-doped ZnO nanorods show a typical room temperature ferromagnetic characteristic with a saturation magnetization (M_S) of 0.273μ_B/Mn. Cathodoluminescence suggests that the ferromagnetism of Mn-doped ZnO nanorods originates from the Mn²⁺-Mn²⁺ ferromagnetic coupling mediated by oxygen vacancies. This technique provides exciting prospect for the integration of next generation Si-technology-based ZnO spintronic devices.     

联合体驱使生长法制备ZnO纳米棒及其表征

在常压环境下采用联合体驱使生长(Aggregation-driven growth)法在镀有ZnO纳米薄膜的医用盖玻片衬底和锌箔上制备了不同直径、高取向、密集生长的ZnO纳米棒阵列结构,发现平均直径与生长时间呈线性关系。X射线衍射(XRD)谱图中出现了较强的(002)峰,表明制备的纳米棒阵列具有高度c轴择优生长取向;高分辨透射电子显微镜(HRTEM)和选区电子花样衍射图谱(SAED)结果表明我们得到的单根纳米棒为沿(002)生长的单晶结构。分析确定盖玻片上的纳米棒阵列是以ZnO纳米薄膜缓冲层上的ZnO种子颗粒为成核点生长形成的。     

Growth of ZnO nanorods by a simple chemical method

ZnO nanorods were grown by a near-room-temperature, simple, chemical solution method on large-area Zn foils and substrate materials such as silicon, and zinc oxide thin films on silicon and glass. Study of the ZnO nanorods on the different substrates by electron microscopy methods shows that the morphology and size of the ZnO nanorods can be tuned varying the growth parameters and the substrates used. The growth mechanism is briefly discussed. Photoluminescence experiments at room temperature reveal a major emission peak of the nanorods at around 385 nm, which is attributed to the band edge transition of ZnO and weaker defect-related visible band peaks. PACS 81.05.Dz; 78.55.Et; 81.07.-b     

The growth mechanism of ZnO single-crystal nanorods synthesized by polymer complexing with zinc salts

The growth mechanism of single-crystal ZnO nanorods synthesized by the method of polymer complexing with zinc salts is investigated. The annealing temperature is controlled at about the decomposition temperature of dihydrate zinc acetate (Zn(O₂CCH₃)₂·2H₂O) of 573 K. By changing the annealing time, the ZnO nanostructures can be modified from nanoparticles to nanorods. As a result, the formation of single-crystal ZnO nanorods can be observed. Through investigating the Fourier transform infrared spectra of (a) polyvinyl pyrrolidone (PVP), (b) Zn(O₂CCH₃)₂·2H₂O and (c) the mixture of PVP and Zn(O₂CCH₃)₂(H₂O)₂, the interaction between PVP and Zn(O₂CCH₃)₂·2H₂O can be observed. PVP plays an important role in the growth of the single-crystal ZnO nanorods. We analyze the growth process of ZnO nanorods by observing their TEM images at different moments. Consequently, our results indicate that the single-crystal ZnO nanorods were formed by self-assembling the ZnO nanoparticles. PACS 61.46.Hk; 61.46.Df; 78.30.-j; 81.07.-b; 81.16.Be     

Synthesis and field-emission properties of roselike ZnO nanostructures

Self-assembled roselike ZnO nanostructures were synthesized via thermal evaporation of zinc powders without catalytic assistance at the relatively low temperature of 550 °C. The roselike structures consist of a large number of ZnO nanorods that uniformly arrange into hexagonal multilayers. The spontaneous nanoindentation effects under geometric constraints can be used to explain the structures. The cathodoluminescence spectra show a wide visible emission band related to Zn interstitials and oxygen vacancies. Field emission measurements demonstrate that the roselike ZnO nanostructures possess good electron emission characteristics with a turn-on field of 4.3 V/μm. PACS 68.70.+w; 78.55.Cr; 81.05.Cy     

电沉积法制备ZnO纳米柱及其机制研究

采用阴极还原方法,以Zn(NO₃)₂水溶液为电解液制备ZnO纳米柱。分析了不同沉积电位和不同沉积时间的缓冲层对ZnO纳米柱的密度、形貌及取向的影响。通过分析缓冲层在不同沉积时间下的电流密度变化,研究了缓冲层对ZnO纳米柱密度影响的机理。利用扫描电子显微镜(SEM)和X射线衍射(XRD)分析了样品的表面形貌及结构。研究结果表明,缓冲层能够增加ZnO纳米柱的密度及c轴的取向性,当缓冲层的沉积时间为60 s时,可以得到密度最大、取向最好的ZnO纳米柱。     

Co掺杂ZnO纳米棒的共振拉曼光谱和发光特性

采用X射线衍射(XRD)和透射电子显微镜(TEM)手段对微乳液法合成的Zn0.9Co0.1O纳米棒进行了表征.通过室温下的共振拉曼光谱和光致发光光谱手段,研究了所合成纳米材料的共振拉曼光谱和发光特性,并与体相ZnO的研究结果对比,发现合成的材料具有四阶声子紫外共振拉曼散射,而体相材料只有两阶,并观察到在紫外和可见区域所...     

Studies of luminescence properties of ZnO and ZnO:Zn nanorods prepared by solution growth technique

Pyramidal ZnO nanorods with hexagonal structure having c-axis preferred orientation are grown over large area silica substrates by a simple aqueous solution growth technique. The as-grown nanorods were studied using XRD, SEM and UV-vis photoluminescence (PL) spectroscopy for their structural, morphological and optical properties, respectively. Further, the samples have also been annealed under different atmospheric conditions (air, O₂, N₂ and Zn) to study the defect formation in nanorods. The PL spectra of the as-grown nanorods show narrow-band excitonic emission at 3.03 eV and a broad-band deep-level emission (DLE) related to the defect centers at 2.24 eV. After some mild air annealing at 200 °C, fine structures with peaks having energy separation of ∼100 meV were observed in the DLE band and the same have been attributed to the longitudinal optical (LO) phonon-assisted transitions. However, the annealing of the samples under mild reducing atmospheres of N₂ or zinc at 550 °C resulted in significant modifications in the DLE band wherein high intensity green emission with two closely spaced peaks with maxima at 2.5 and 2.7 eV were observed which have been attributed to the V_O and Zn_i defect centers, respectively. The V-I characteristic of the ZnO:Zn nanorods shows enhancement in n-type conductivity compared to other samples. The studies thus suggest that the green emitting ZnO:Zn nanorods can be used as low voltage field emission display (FED) phosphors with nanometer scale resolution.     

Thermo-electrochemical selective growth of ZnO nanorods on any noble metal electrodes

Selective growth of ZnO nanorods has been successfully performed on the patterned Au/Ti metal electrode regions on a glass substrate by using a seeded thermo-electrochemical method in an acidic growth solution. The selective growth mechanism of the thermo-electrochemical method was proposed by using a series of chemical reactions for the first time. The thermo-electrochemical selective ZnO growth was performed on the cathode electrode at a temperature below 90 °C. A ZnO seed layer was precoated and selectively etched away from the non-metal regions in order to create the patterned selective nucleation sites on which the precursors are transferred and crystallized into ZnO nanorods. Both the dimensions and the placements of the ZnO nanorods have been simultaneously controlled. Energy dispersive X-ray spectrometry showed that the selectively grown ZnO nanorods consist of only Zn and O, indicating that the selectively grown ZnO nanorods are pure and contamination free. XRD and electron diffraction patterns revealed that the obtained ZnO nanorods have a wurtzite single-crystal structure.     

Synthesis of ZnO hollow spherical structures with different surface-to-volume ratios

ZnO hollow spherical structures with different surface-to-volume ratios were prepared using solid Zn microspheres as template via a simple oxygen-controlled thermal evaporation approach. The results of scanning electron microscopy testify that ZnO hollow spherical structures with different morphologies can be realized by changing oxygen supply. The corresponding transmission electron microscopy images further reveal that the prepared spherical structures are hollow, and nanorods epitaxially grow from the surface of the sphere shell along the [0001] direction. A series of experiments indicates that the formation of hollow spherical structures involves the oxidization on the surface of Zn microspheres, sublimation of Zn, and growth of ZnO nanorods.     

Self-catalytic ZnSe nanorods on grains synthesized using thermal evaporation method

In this paper, ZnSe nanorods grown on in-situ synthesized ZnSe grains are reported. The ZnSe products are synthesized through thermal evaporation of elementary materials of Zn and Se powders in a horizontal resistance furnace. It is interesting to note that the ZnSe nanorods of nearly the same diameter and length are obtained, and they grow in the same direction on a facet of the ZnSe grain. The ZnSe grains are random in shape, with well-defined bounded facets. The ZnSe grains can be synthesized in various growth conditions while the ZnSe nanorods can be synthesized on the ZnSe grains with the fulfillment of the Zn enriched condition. The growth of ZnSe nanorods can be described by the self-catalytic vapor–liquid–solid (VLS) mechanism. PACS 73.21.-b; 78.55.Et; 61.10.Nz; 61.46.+w; 68.65.-k