拉曼光谱研究天然FeS_2晶须结构及其相变规律

利用显微激光拉曼技术研究了山西耿庄天然纳-微米FeS2晶须的结构.发现FeS2晶须中有白铁矿和黄铁矿两种结构类型.较粗的藕节状、粗柱状、串珠状等不规则形貌为白铁矿相,直线状、平直、表面光滑的品须为黄铁矿相.耿庄FeS2晶须结晶生长早期以白铁矿相为主,中期是白铁矿和黄铁矿型结构共存,晚期以黄铁矿相为主.晶须生长过程有早期白铁矿结晶向晚期黄铁矿结晶转变的趋势.而且有黄铁矿包覆白铁矿的生长现象.FeS2晶须结构相变规律与形貌、形成时间和成分特点具有关联性.     

Size, position and direction control on GaAs and InAs nanowhisker growth

The self-organized, position-controlled and parallel growth of GaAs and InAs nanowhiskers is successfully demonstrated by using a metal–organic chemical vapour deposition method. The growth takes place preferentially along the 111 As direction with the aid of the catalytic effect of Au nanodroplets, and not along 111 Ga or In directions. The diameter and length of the whisker can be controlled artificially down to 10 nm and to over 1 μm, respectively. Doping and composition control of p- or n-type such as GaAs–InAs heterostructure formation are possible along the length direction of the whisker by changing the source gases. In order to control the growth position of the whisker, positioning of a Au nanodroplet is essential and realized by a lithographic method. By choosing the [111]B direction to the substrate surface and normal to the patterned side edges, and by positioning the Au nanodroplet on the side wall, the positioned planar nanowhisker growth and bridging are successfully demonstrated. The growth mechanism of the nanowhiskers is revealed by the scanning and transmission electron microscope observations. Nanometer-size Au-alloy droplets play an important role in the growth of the whiskers. The whisker growth process is governed by the vapor–liquid–solid growth mechanism.     

由汽态还原生长金属须的机制

进行了用蒸汽还原法生长铜须和铁须的实验。研究了须的生长机制,为的是找出能够生出又粗又长而强度又极高的金属须的有效措施。实验指出,当生长槽材料的晶体结构与生长须的金属的晶体结构相同时,可以促进须的生长。由此所得的结论是,须的生长是通过沿轴线的螺型位错的机制。观测了所生的铜须和铁须在生长槽上的分布和排列取向的各种方式,由此推论到这些须是由顶端生长的。此外,实验还指出,氯化亚铜(或亚铁)蒸汽是优先在须的顶端还原的,这可能是由于螺型位错在须顶端所产生的表面台阶对于这种还原有一种催化作用。观测了直径50—120微米的大铜须的生长情况,发现了片状生长、堆垛生长和层状生长。这种特殊生长方式可能与一维和二维成核生长的交互更迭发生有关。讨论了通过适当选择和控制生长条件和方式的途径来获得基本上不含位错的大块晶体的可能性。     

Growth and kinetic studies of lead carbonate whiskers in silica gel

Lead carbonate whiskers were grown by diffusion of ammonium carbonate in the silica gel charged with lead nitrate. It is found that low pH is preferred to the whisker growth. In addition to straight whiskers gently curved whiskers are also found. Curving of whiskers is found to be maximum at high concentration of carbonate ions. Growth kinetics of whiskers are studied by changing the parameters of gel growth. It is found that the parabolic relationship between dimension and growth period is obeyed in this.     

原位生长高度定向ZnO晶须

采用大气压金属有机化合物化学气相沉积(AP-MOCVD)方法，以Zn(C₅H₇O₂)₂为原料，在玻璃基片上制备出高度定向的ZnO晶须.扫描电子显微镜观察发现晶须垂直基片取向生长，规则排列，长度、形状几乎一致.晶须直径为100nm—800nm,长径比为8—15，尖端曲率半径仅为50nm，甚至更小.x射线衍射(XRD)分析结果表明ZnO晶须为六方晶系纤锌矿结构，并沿c轴高度取向.采用热分析对反应前驱物进行了研究,同时也讨论 关键词： ZnO 取向生长 晶须 MOCVD     

二元金属须的强度和形变特点

测量了直径20—300微米的大量的Fe鬚、Fe-Cu鬚、Fe-Co鬚、Cu鬚和Cu-Co鬚的室温和高温拉断强度,结果指出,弥散型的二元金属鬚如Fe-Cu鬚和Cu-Co鬚的强度较高于单元金属鬚,而固溶型的二元金属鬚如Fe-Co鬚则否。根据应力应变曲线的测量和金相观测的结果,认为弥散型的Fe-Cu鬚的强度所以较高,可能是由于高强度的铁铜弥散混合层的出现,而它的范性所以较好,可能是由于这种鬚具有范性较好的铜心轴。讨论了弥散型和固溶型二元金属鬚在变粗当中所包含的基本过程,以及与它们所表现的强度和形变特点的联系。并且指出,生长弥散型混合鬚的原理和方法给制备强度较高和范性较好的复合材料提供了一个值得参考的途径。 关键词：     

Effect of Cu addition on whisker formation in tin-rich solder alloys under thermal shock stress

This article focuses on the influence of thermal shocks and Cu addition on tin whiskers growth on the surface of tin-rich materials and alloys. The tests were carried out on real samples manufactured with classical PCB technology. Four Pb-free materials i.e. pure Sn, Sn99Cu1, Sn98Cu2 and Sn97Cu3 were tested from the point of view of susceptibility to whisker formation after thermal shocks. Results show that all tested materials were prone for whisker formation. Copper addition in coexistence with thermal shocks did not promote the growth of filament-like whiskers.     

Near-field optical microscope with a multiheight scanning imaging mode

A near-field scanning optical microscope has been developed to yield optical images with various gap distances between the probe and the sample surface. The microscope uses an apertureless metallic probe, the position of which is controlled by regulation of the tunneling-electron current from the probe to the sample and by computer-generated bias voltage. Experimental results of near-field optical imaging with the developed microscope at different gap distances are shown. Thirteen images at gap distances of 0 to 500nm demonstrate that the near-field image depends strongly on the gap distance. The imaging characteristics of a near-field imaging system are shown with the spatial-frequency spectra of images. Future investigation of the developed microscope is also discussed.     

Investigation of the morphology of the van der Waals surface of the InSe single crystal

The morphology of the (0001) van der Waals surfaces of the layered single crystal In_1.03Se_0.97, which were prepared using different techniques, has been investigated by scanning probe microscopy methods. It has been assumed that the van der Waals surface prepared with the use of an adhesive tape oxidizes in air due to the chemisorption of acid agents on dangling bonds of the metal and selenium. An analysis of the current-voltage characteristics of the tunneling current has shown that the composition of natural oxides represents a mixture of phases of the In₂O₃ oxide and wide-band-gap selenium oxides. In the InSe surface prepared by cleavage with subsequent exposure in air for approximately 2 min, the scanning with a tunneling microscope has revealed a surface ordering in the form of a corrugation of a complex profile with a fine structure. The last fact reflects the charge density redistribution after the chemisorption of gas molecules from air on this surface and its relaxation to the state with a minimum energy. Atoms of the basal plane are observed on the InSe(0001) van der Waals surface prepared by cleavage in an oxygen-free medium. The surface corrugation is absent. Point defects cause a disturbance of the periodic potential of the single crystal, which extends over a distance equal to four lattice spacings and appears as a shadowing. A technique has been proposed for producing In₂O₃ oxide nanostructures on the surface of the single crystal of the layered semiconductor InSe with the use of an atomic-force microscope probe as a nanoindenter. The ability of the probe to operate in gaseous and liquid media significantly extends the capabilities of the method.     

Radical graft polymerization from carbon whisker initiated by peroxyester groups introduced onto the surface

The radical graft polymerization of vinyl monomers onto carbon whiskers, i.e. vapor grown carbon fibers, initiated by tert-butyl peroxyester groups that are introduced onto the surface was investigated. The introduction of tert-butyl peroxyester groups onto the carbon whisker surface was achieved by the reaction of acyl chloride groups on the surface with tert-butyl hydroperoxide. The carbon whisker having acyl chloride groups was prepared by the following three methods: (1) reaction of surface carboxyl groups with thionyl chloride, (2) reaction of surface phenolic hydroxyl groups with succinyl dichloride, and (3) reaction of surface phenolic hydroxyl groups with phthaloyl dichloride. The carbon whiskers having tert-butyl peroxyester groups prepared from these three methods were abbreviated as CW-POE 1, 2, and 3, respectively. The peroxyester group content of CW-POE 1, 2, and 3 was determined to be 0.06, 0.05, and 0.17 mmol/g, respectively. It was found that the radical polymerization of vinyl monomers such as methyl methacrylate, styrene, and N-vinylcarbazole was successfully initiated in the presence of CW-POE 2 and 3, and the corresponding polymers were grafted onto the surface. However, CW-POE 1 failed to initiate the radical graft polymerization, because surface phenyl radicals formed by the thermal decomposition of the tert-butyl peroxyester groups are stabilized by the aromatic rings of the carbon whisker surface.     

Effects of polyethylenimine on morphology and property of ZnO films grown in aqueous solutions

Morphologies and properties of well-aligned ZnO films were controlled using zinc nitrate-hexamethylenetetramine aqueous solutions with the addition of polyethylenimine as a surfactant. Porous and dense ZnO films were fabricated with and without polyethylenimine, respectively. The addition of polyethylenimine proceeded to form porous ZnO whiskers film by preferential adsorption to nonpolar crystal faces and modifications of the surface free energy and growth rate. Dense ZnO film showed high transmittance of 80%, and low intensity of fluorescence and photo-induced current. Porous ZnO whiskers film showed low transmittance of 70%, while high intensity of fluorescence and high photo-induced current were detected because the porous ZnO nanowhisker film possessed a large interior surface area which can capture large amounts of DNA molecules labeled with dye molecules on the surface of ZnO crystals. High performance dye-sensitized sensors can be produced using ZnO whisker films prepared from an aqueous solution.     

High-resolution transmission electron microscopy on silicon carbide whiskers

SiC whiskers were grown from the reaction of silicon monoxide (SiO) with activated carbon containing iron impurities. Growth proceeds through a VLS growth mechanism with SiO and CO as reacting gases. HRTEM combined with EDS shows that the SiC whisker is topped by a Fe₃Si catalyst droplet. The SiC whisker is found to be one-dimensionally disordered along the [111] growth direction of an fcc crystal structure. Although the catalyst droplet is usually larger than the top face of the whisker, we observed a number of situations where the diameter of the droplet was smaller. The study of the SiC-Fe₃Si interface showed that the growth is nucleated from the edges.     

Near-Field Evaluation of a Quantum Size Effect in Self-Aligned GaN Whiskers Fabricated Using Photochemical Etching

We fabricated nanoscale GaN whiskers using photochemical etching. The fabricated GaN whiskers were conjugated and aligned perpendicular to the incident light polarization used for photochemical etching in a self-assembling manner. Their far-field photoluminescence spectra exhibited a blue-shifted photoluminescence peak at 3.60eV. Near-field photoluminescence spectra of individual GaN whiskers were obtained, for the first time. The evaluation of the near-field spectra identified several peaks from individual whiskers, corresponding to a diameter range of 5–10 nm, and revealed a stepwise change in the diameter along the axis of individual whisker.     

Measurement of electron density distribution in the probe of a low voltage SEM

A method for measuring the electron density distribution in the probe of a low voltage scanning electron microscope is described. It is shown that the focused electron probe of an S 4800 scanning electron microscope at the electron energy of 200 eV has a Gaussian shape of the electron density with the effective diameter of the probe of 20 nm.     

Radical graft polymerization initiated by azo groups introduced onto the surface of carbon whisker

The radical graft polymerization of vinyl monomers onto carbon whisker, i.e. vapor grown carbon fiber, initiated by azo groups introduced onto the surface has been investigated. The introduction of azo groups onto the surface is achieved by (1) the reaction of 4,4'-azobis(4-cyanopentanoic acid) with isocyanate groups on the surface, which are introduced by the treatment of surface carboxyl and phenolic hydroxyl groups with tolylene-2,4-diisocyanate and (2) the reaction of 2,2'-azobis(2-cyano-n-propanol) with acyl chloride groups on the surface, which are introduced by the treatment of surface phenolic hydroxyl groups with terephthaloyl dichloride. The carbon whiskers having azo groups prepared from the above two methods are abbreviated as CW-Azo 1 and 2, respectively. The azo group content of CW-Azo 1 and 2 is determined to be 0.04 and 0.07 mmol/g, respectively. It is found that the radical polymerization of methyl methacrylate and styrene is initiated by the surface azo groups to give the corresponding polymer-grafted carbon whisker. The polymer-grafted carbon whisker gives a stable colloidal dispersion in good solvents for grafted polymer.     

Focused ion beam preparation of atom probe specimens containing a single crystallographically well-defined grain boundary

Needle-shaped atom probe specimens containing a single grain boundary were produced using the focused ion beam (FIB) of a two-beam FIB/SEM (scanning electron microscope) system. The presented specimen preparation approach allows the unprecedented study of a grain boundary which is well characterised in its crystallographic orientation by means of the field ion microscope (FIM) and the tomographic atom probe (TAP). The analysis of such specimens allows in particular the determination of solute excess atoms at this specific grain boundary and hence the investigation of the segregation behaviour. The crucial preparation steps are discussed in detail in the present study for the Sigma 19 a {331} 110 grain boundary of a 40 at.ppm-Bi doped Cu bi-crystal. Transmission electron microscope (TEM) images and TAP analyses of the atom probe tips demonstrate unambiguously the presence of the selectively prepared grain boundary in the apex region of some of the specimens.     

On the general regularities of the growth of micro-and nanoscale si whiskers

On the basis of the investigations of the processes of synthesis nano-and microscale silicon whiskers, general regularities of their quasi-one-dimensional growth are established: the presence of the catalyst drop liquid at the top, the same preferred orientation <111> of the growth axis, presence of pedestal in the whisker base, decrease in radius over the crystal length (conicity), branching and formation of bends, flat crystallization front under the drop, two-stage character of the process (axial and radial growth), etc. Some individual features, inherent in the nanocrystal growth, are also established.     

受限钠盐水溶液孔外结晶现象

多孔材料内含盐水溶液中离子的析出结晶是造成多孔结构破坏的重要因素, 因此在建筑保护和地貌学研究中受到了极大关注. 现有研究主要集中于微孔介质中盐的孔内结晶行为. 本文对比研究了限制于纳孔硅胶颗粒孔隙内的NaCl, NaNO₃, Na₂SO₄三种盐溶液在蒸发过程中盐的孔外结晶行为. 利用扫描电子显微镜对所形成晶体的形貌进行了表征. 实验结果表明: 1) 随孔径从2 nm增加至15 nm, NaCl和NaNO₃在硅胶颗粒表面的结晶由晶粒转变为晶须形态, 而Na₂SO₄则由晶须转变为晶粒形态; 2) NaCl和NaNO₃晶须的生长主要沿垂直于颗粒表面的方向, 而Na₂SO₄晶须则在硅胶颗粒表面斜向生长, 后一种生长方式对硅胶颗粒产生横向的应力, 从而对孔结构具有更强的破坏作用; 3) NaNO₃的细长晶须所具有的分支和珠链结构表明其在结晶过程中发生了Plateau-Rayleigh失稳.     

Composites of Hydroxyapatite Whiskers/poly(L-lactide-co-glycolide) with High Tensile Plasticity

Hydroxyapatite whiskers (HAW) with a maximum aspect ratio of 20 were employed to improve the toughness of poly(L-lactide-co-glycolide) (PLGA). 3-Aminopropyltriethoxysilane (AMEO) was grafted on the surface of the hydroxyapatite whiskers (g-HAW) to improve its wetting in the PLGA matrix. Composites based on HAW, g-HAW, and PLGA were prepared. The structure and properties of the composites were subsequently investigated by powder X-ray diffraction (XRD), scanning electron microscopy, differential scanning calorimetry, and tensile testing. The g-HAW were distributed homogenously in the PLGA matrix because of improved wetting of g-HAW while the HAW were aggregated. The stronger interfacial bonding also gave rise to improved mechanical properties of the g-HAW/PLGA composites. The HAW/PLGA and g-HAW/PLGA composites failed in a tough manner with intensive plastic deformation. The g-HAW/PLGA composite (5 wt% g-HAW) failed at a maximum elongation of 366%, although the tensile strength dropped slightly. The g-HAW/PLGA composite (1 wt% g-HAW) maintained the initial tensile strength of neat PLGA but failed at an equally high elongation of 347%, whereas PLGA failed at an elongation of 11%.     

Interaction between neighbouring phase-slip centers in a superconducting Zn whisker

We fabricated multi-potential-probe samples with a Zn whisker as measuring whisker and four Sn whiskers as potential probes and investigated the interaction effect between two neighbouring phase-slip centers in the Zn whisker. An active phase-slip center changes the critical current of a neighbouring phase-slip center. This change depends on the temperature and the relative polarity of the currents through the influencing and influenced phase-slip center. An interpretation of the observed effect is proposed.