Crystallographic shear defect in molybdenum oxides: Structure and TEM of molybdenum sub‐oxides Mo18O52 and Mo8O23

Molybdenum trioxide and molybdenum sub‐oxides are of great interests in catalysis due to their utilities as model system to elucidate the correlations between the structure and the catalytic performance. The suboxides are usually an intermediate phase during catalytic reaction in which the lattice oxygen is involved. We show the identification of the two common molybdenum sub‐oxides Mo₁₈O₅₂ and Mo₈O₂₃, derived from MoO₃ by crystallographic shearing (CS), by means of electron diffraction and High‐Resolution Transmission Electron Microscopy (HRTEM) in combination with image simulation. The coincidence of simulated electron diffraction patterns and high‐resolution images with the experimental ones indicates the feasibility of CS structure determination by these techniques.     

Synthesis of ZnO nanorods by the thermal reduction process of a mixture of ZnO and Al powder

Single‐crystalline Zinc oxide (ZnO) nanorods were firstly synthesized on gold‐coated Si substrate via a simple thermal reduction method from the mixture of ZnO and Al powder. The growth process was carried out in a quartz tube at different temperature (550‐700 °C) and at different oxygen partial pressure. Their structure properties were investigated by X‐ray diffraction (XRD), scanning electron microscope (SEM), X‐ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The length of the as‐prepared ZnO nanorods was up to several micrometers and their diameters were about 130 nm. The X‐ray diffraction patterns, transmission electron microscopic images, and selective area electron diffraction patterns indicate that the one‐dimensional ZnO nanorods are a pure Single‐crystal and preferentially oriented in the [0001] direction. The reaction mechanism of ZnO nanorods was proposed on the basis of experimental data. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

碳化气体引入温度对3C-SiC薄膜生长的影响

通过低压化学气相沉积方法,在Si(100)衬底上生长了高度择优取向的3C-SiC(100)薄膜.SiC(200)峰的摇摆曲线表明SiC薄膜的结晶质量随着丙烷气体引入温度(Tgi)的升高而增加.选区电子衍射像表明高Tgi下生长的薄膜比低Tgi下生长的薄膜具有更好的取向.典型的SiC薄膜高分辨像中观察到了孪晶和层错.表面场发射扫描电镜像表明随着Tgi的升高,SiC薄膜的表明形貌发生了改变.     

CdS纳米晶的稳定化处理及介质极性对荧光光谱的影响

用硫脲、聚乙烯吡咯烷酮、L-半胱氨酸水溶液对水热法合成的硫化镉纳米晶进行稳定化处理,发现L-半胱氨酸和聚乙烯吡咯烷酮(PVP)能有效地稳定硫化镉纳米晶,荧光发射强度比处理前增强了五十倍以上.以氯仿、氧化三(正)辛基膦(TOPO)氯仿溶液以及3-巯基丙酸为萃取(或处理)剂,对水热法合成的水溶性CdS半导体纳米晶进行处理,经过荧光光谱分析,发现介质水、氯仿、氧化三(正)辛基膦(TOPO)氯仿溶液以及3-巯基丙酸会对CdS纳米晶的最大荧光激发峰与发射峰的位置产生不同影响,极性大的水分子使得荧光峰蓝移,极性小的氯仿、氧化三(正)辛基膦(TOPO)氯仿溶液以及3-巯基丙酸使得荧光峰红移,最大位移为31nm左右.     

Preparation of crystalline fibres of codoped BaAl2O4:Eu2+:Cr3+

Phosphor material BaAl₂O₄:Eu²⁺, Cr³⁺ with varying concentrations of Cr co‐doping were prepared by solid‐state synthesis method. Crystalline fibres were obtained by controlled annealing temperature. Synthesized compositions were characterized for their phase and crystallinity by powder x‐ray diffraction. The crystalline morphology was investigated using SEM analysis. High resolution transmission electron microscopy (HRTEM) in image and diffraction modes was used to investigate the microstructure. The effect of Cr doping on quality and morphology of grown crystals was investigated. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural,microchemical and superconducting properties of ultrathin NbN films on silicon

Structural, chemical and superconducting properties of thin NbN films used for development of fast and sensitive hot‐electron bolometer (HEB) detectors for wide spectra range are reported. The thin NbN films with a thickness between 4 and 10 nm were deposited on the (001)Si substrates by magnetron sputtering. In order to investigate the film morphology and microchemistry, diffraction‐contrast and high‐resolution transmission electron microscopy (TEM) in combination with scanning TEM and electron energy loss spectroscopy (EELS) were performed. In addition, the zero‐resistance critical temperature of the NbN films was measured and correlated to their thickness. The interrelations between fabrication conditions, crystalline and superconducting properties of the differently thick NbN films are discussed. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Size effect in X-ray and electron diffraction patterns from hydroxyapatite particles

High-resolution transmission electron microscopy (HRTEM), electron microdiffraction, and X-ray diffraction were used to study hydroxyapatite specimens with particle sizes from a few nanometers to several hundreds of nanometers. Diffuse scattering (without clear reflections in transmission diffraction patterns) or strongly broadened peaks in X-ray diffraction patterns are characteristic for agglomerated hydroxyapatite nanocrystals. However, HRTEM and microdiffraction showed that this cannot be considered as an indication of the amorphous state of the matter but rather as the demonstration of size effect and the morphological and structural features of hydroxyapatite nanocrystals.     

Structure and thermal stability of MOCVD ZrO2 films on Si (1 0 0)

The structure and thermal stability of ZrO₂ films grown on Si (1 0 0) substrates by metalorganic chemical vapor deposition have been studied by high-resolution transmission electron microscopy, selected area electron diffraction and X-ray energy dispersive spectroscopy. As-deposited films consist of tetragonal ZrO₂ nanocrystallites and an amorphous Zr silicate interfacial layer. After annealing at 850°C, some monoclinic phase is formed, and the grain size is increased. Annealing a 6 nm thick film at 850°C in O₂ revealed that the growth of the interfacial layer is at the expense of the ZrO₂ layer. In a 3.0 nm thick Zr silicate interfacial layer, there is a 0.9 nm Zr-free SiO₂ region right above the Si substrate. These observations suggest that oxygen reacted with the Si substrate to grow SiO₂, and SiO₂ reacted with ZrO₂ to form a Zr silicate interfacial layer during the deposition and annealing. Oxygen diffusion through the tetragonal ZrO₂ phase was found to be relatively easier than through the monoclinic phase.     

Channeling‐enhanced EDX for polarity resolved crystal orientation determination

Using channeling‐enhanced energy‐dispersive X‐ray spectroscopy (EDX), we demonstrate polarity sensitive orientation determination of a non‐centrosymmetric crystal in the scanning electron microscope. The authors observe a characteristic asymmetry in the channeling‐enhanced, angle‐dependent EDX data of a GaAs sample, which is in good agreement to simulations using the dynamical theory of diffraction for the incident electron beam. This allows us to assign the orientation of the GaAs crystal according to the non‐centrosymmetric point group. The method shown here overcomes the limitation of a reduced point‐group sensitivity of electron backscatter diffraction patterns and electron channeling patterns for crystalline phases that contain atoms of approximately equal electron scattering cross sections.     

Twinning of quasicrystals and related crystals

Electron microscopy and electron diffraction have been employed to bring out the intimate relationship between icosahedral quasicrystal and various types of crystalline phases with emphasis on aluminium transition metal alloys. The relationship between quasicrystal and twinned rational approximant structures will be treated in the context of irrational twinning. The twinned aggregates show an icosahedral like symmetry in electron diffraction patterns. The crystallography of irrational twins has been discussed in terms of various ways of representing a twin relationship in a cubic lattice.     

CdS纳米晶的制备及其荧光研究

以醋酸镉、L-半胱氨酸为主要原料,采用水热法制备了尺寸小于10nm、具有强光致荧光的纤锌矿结构CdS半导体纳米晶.水热法可以将晶核形成与晶体生长阶段较好地分开,加之提供的高温熟化条件,可以得到粒度小而均匀、结构良好的纳米晶.用高分辨透射电镜(HRTEM)、XRD对产品的晶体大小、结构进行了详细地表征,分析了影响纳米晶尺寸的因素,用相关性较好的荧光激发与发射光谱研究了硫化镉纳米晶的光致荧光性能.制备的硫化镉(CdS)纳米晶结构良好、粒度均匀、荧光激发专一,最大激发波长在338nm,其发射荧光的波长位于419nm,发射强度大.     

Characterization of ZnO nanorods grown on Si substrates coated with NiCl2

ZnO nanorods were synthesized on NiCl₂‐coated Si substrates via a chemical vapor deposition (CVD) process. The as‐fabricated nanorods with diameters ranging from 150 nm to 200 nm and lengths up to several tens of micrometers grew preferentially arranged along [0001] direction, perpendicular to the (0002) plane. The clear lattice fringes in HRTEM image demonstrated the growth of good quality hexagonal single‐crystalline ZnO. Room temperature photoluminescence (PL) spectra illustrated that the ZnO nanorods exhibit strong UV emission peak and green emission peak, peak centers located at 388 nm and 506 nm. A possible growth mechanism based on the study of our X‐ray diffraction (XRD), electron microscopy and PL spectroscopy was proposed, emphasizing the effect of NiCl₂ solution (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Facile morphology‐controlled hydrothermal synthesis of flower‐like self‐organized ZnO architectures

Flower‐like self‐organized crystalline ZnO architectures were obtained through a facile and controlled hydrothermal process. As‐synthesized products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), X‐ray diffraction (XRD), electron diffraction and UV‐Vis spectroscopy. XRD and electron diffraction results confirmed the obtained materials are pure wurtzite ZnO. The effects of different ratios of starting materials and solvent on the morphologies of ZnO hydrothermal products were also evaluated by SEM observations. It is suggested that the use of water, rather than ethanol as the solvent, as well as employing a precursor of Zn(Ac)₂ and 2NaOH (v/v) in hydrothermal reactions are responsible for the generation of specific flower‐like self‐assembled ZnO structures. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the structure of nanorods and nanowires with pentagonal cross-sections

Here, we present a comprehensive study on the structure of multi-twinned decahedral-based nanorods and nanowires (Dh-NWs), specifically for the case of silver. We have demonstrated that their high-resolution transmission electron images (HRTEM) can be interpreted as a Moire pattern contrast based on a multi-twinned decahedron, and that their selected-area electron diffraction (SAED) patterns can be also completely generated through the same multi-twinned decahedron basis. We propose that the structure of these nanowires can be interpreted as a chain of decahedra joined along the vertex, which is parallel to the five-fold symmetry axis. This chain can be generated through [1 1 1] growth for FCC structures.     

Structural and optical properties of vapour‐etching based porous silicon

The structural and optical properties of porous silicon (PS) layers prepared by Vapour‐Etching (VE) of moderately and heavily boron‐doped Si substrates are investigated. The VE technique produces rough PS layers that are essentially formed of interconnected cluster‐like structures. Optical investigations indicate that this surface roughness enables the PS layers to be used as antireflection coatings in silicon based devices. These optical characteristics are investigated by optical reflectivity and light scattering. The local chemical state and the microstructure of the PS layers are studied by electron energy loss spectroscopy (EELS) in transmission electron microscopy (TEM), and are correlated to the red photoluminescence (PL). TEM studies point out that the cluster‐like interconnected structures are composed of luminescent nanocrystallites. PL measurements display that both quantum confinement and surface passivation determine the electronic states of the silicon nanocrystallites. The complex dielectric function is calculated from the experimental single‐scattering distribution spectrum using a Kramers Kronig analysis. The first resonance peak in the imaginary part is observed at 2.3 eV; two other broadened features appear at 4.7 and 8.8 eV. The latter is generally related to an interface plasmon resulting from the silicon‐silicon oxide interface. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of PbS nano‐microcrystals with different morphologies and their optical properties

PbS nano‐microcrystals were prepared from Pb(OAc)₂·3H₂O and sulfur in a solution without any surfactant using the solvothermal process. Different morphologies, mainly including polyhedron microcrystals and sphere‐like assemblies, were characterized using a scanning electron microscope (SEM) and a transmission electron microscope (TEM). PbS nano‐microcrystals with cubic crystal structure were detected using X‐ray diffraction (XRD), electron diffraction (ED) and high resolution transmission electron micrograph (HRTEM) techniques. The optical properties were investigated by ultraviolet‐visible (UV‐vis) spectroscopy, and photoluminescence spectroscopy (PL). The UV‐vis absorption peaks of PbS exhibited a large blue‐shift and the PL spectra had a strong and broad emission bands centered at 408 nm. The crystal growth mechanism of PbS was also discussed.     

Low temperature synthesis of spindle‐like ZnO nanostructures under microwave irradiation

A simple and general microwave route is developed to synthesize nanostructured ZnO using Zn(acac)₂·H₂O (acac = acetylacetonate) as a single source precursor. The reaction time has a great influence on the morphology of the ZnO nanostructures and an interesting spindle‐like nanostructure is obtained. The microstructure and morphology of the synthesized materials are investigated by X‐ray diffraction (XRD), scanning electron microscopy (SEM), field‐emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED). It is found that all of them with hexagonal wurtzite phase are of single crystalline structure in nature. Ultraviolet–visible (UV‐vis) absorption spectra of these ZnO nanostructures are investigated and a possible formation mechanism for the spindle‐like ZnO nanostructures is also proposed.     

Enhanced thermal stability of NiSi films on Si(1 1 1) substrates by a thin Pt interlayer

A thin interlayer of Pt can greatly enhance the thermal stability of NiSi films formed by rapid thermal annealing (RTA) on Si(1 1 1) substrates, as was revealed by X-ray diffraction (XRD) data and sheet resistance measurement. High-resolution transmission electron microscopy (HRTEM) reveals a well-defined interface between the Ni(Pt)Si film and the Si(1 1 1) substrate for the Ni/Pt/Si sample annealed at 640°C. The orientation relationship in this sample determined by selected area electron diffraction (SAED) was NiSi(1 0 0)||Si(1 1 1) and NiSi[0   0]||Si[0 1  ]. With the increase of temperature, the texture of NiSi films transform from NiSi(1 0 0)||Si(1 1 1) to NiSi(0 0 1)||Si(1 1 1). The reduction in the interfacial energy due to the formation of the (1 0 0) textured NiSi film is proposed as a possible reason for the improved thermal stability of NiSi and the transition in NiSi texture during high-temperature annealing. Detailed study on the XRD data combined with Auger electron spectra (AES) indicates PtSi and NiSi form a solid solution following Vegard's law, which adjusts the lattice constant ratio c/b to and may account for the texture of NiSi(1 0 0)||Si(1 1 1).     

X-ray diffraction study of the morphology and structure of pulse-anodized porous Si multilayers

Porous Si layers, obtained by pulsed electrochemical etching of n-Si(001) substrates (resistivity 0.01 Ω cm) in a 1: 1 mixture of hydrofluoric acid and ethanol, have been investigated by high-resolution X-ray diffraction and electron microscopy. The average structural parameters of the layers grown (thickness, strain, porosity, pore size) are determined. It is found that pulsed anodic oxidation leads to a decrease in the average strain of layers. It is established that, at frequencies up to 1 Hz, anodic oxidation makes obtaining porous silicon multilayers with layer thicknesses of 20–300 nm containing Si nanocrystallites possible. It is shown that X-ray diffuse scattering from pores yields information about their ordering and can be used to monitor the processes of electrochemical etching used to form porous layers.     

PMA‐b‐PAA‐controlled synthesis of one‐dimensional CaCO3 superstructures

Crystallization of calcium carbonate (CaCO₃) crystals by a gas‐liquid diffusion method has been carried out in aqueous solution using a double‐hydrophilic block copolymer (DHBC) poly(maleic anhydride)‐b‐poly(acrylic acid) (PMA‐b‐PAA). The as‐prepared products were characterized with X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), selected area electron diffraction (SAED), high‐resolution transmission electron microscopy (HRTEM) and infrared spectroscopic analysis (FT‐IR). Uniform one‐dimensional calcite micro/nanostructures with different morphologies are fabricated through an assembled process. The influence of PMA‐b‐PAA copolymer concentration on the morphology of calcite nano/microwires is investigated, which plays an important role in the morphological control of building blocks composed of one‐dimensional calcite crystals. The possible formation mechanism of one‐dimensional CaCO₃ crystals was discussed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)