Fabrication of layered nanostructures by successive electron beam induced deposition with two precursors: protective capping of metallic iron structures

We report on the stepwise generation of layered nanostructures via electron beam induced deposition (EBID) using organometallic precursor molecules in ultra-high vacuum (UHV). In a first step a metallic iron line structure was produced using iron pentacarbonyl; in a second step this nanostructure was then locally capped with a 2-3 nm thin titanium oxide-containing film fabricated from titanium tetraisopropoxide. The chemical composition of the deposited layers was analyzed by spatially resolved Auger electron spectroscopy. With spatially resolved x-ray absorption spectroscopy at the Fe L? edge, it was demonstrated that the thin capping layer prevents the iron structure from oxidation upon exposure to air.     

Thermally induced transformations of amorphous carbon nanostructures fabricated by electron beam induced deposition

We studied the thermally induced phase transformations of electron-beam-induced deposited (EBID) amorphous carbon nanostructures by correlating the changes in its morphology with internal microstructure by using combined atomic force microscopy (AFM) and high resolution confocal Raman microscopy. These carbon deposits can be used to create heterogeneous junctions in electronic devices commonly known as carbon-metal interconnects. We compared two basic shapes of EBID deposits: dots/pillars with widths from 50 to 600 nm and heights from 50 to 500 nm and lines with variable heights from 10 to 150 nm but having a constant length of 6 μm. We observed that during thermal annealing, the nanoscale amorphous deposits go through multistage transformation including dehydration and stress-relaxation around 150 °C, dehydrogenation within 150-300 °C, followed by graphitization (>350 °C) and formation of nanocrystalline, highly densified graphitic deposits around 450 °C. The later stage of transformation occurs well below commonly observed graphitization for bulk carbon (600-800 °C). It was observed that the shape of the deposits contribute significantly to the phase transformations. We suggested that this difference is controlled by different contributions from interfacial footprints area. Moreover, the rate of graphitization was different for deposits of different shapes with the lines showing a much stronger dependence of its structure on the density than the dots.     

Substrate atom enriched carbon nanostructures fabricated by focused electron beam induced deposition

Carbon nanostructures fabricated using focused electron beam induced deposition (FEBID) in a residual vacuum atmosphere or in the presence of low pressure precursor gas exhibit enrichment with the atoms of the substrate element. Nanostructures having base sizes up to 100?nm and height up to 250?nm with maximum substrate atom enrichment of 50% have been fabricated. The size of the structures (nanocones) and the substrate atom enrichment depends on the electron beam current density and irradiation time. A possible explanation of the phenomenon has been sought on the basis of local temperature rise and diffusion of the substrate atoms in the nanostructure during the growth process. The phenomenon can be used to fabricate dense 2D carbon nanopatterns enriched with a desired element used as the substrate material.     

High resolution radially symmetric nanostructures from simultaneous electron beam induced etching and deposition

Electron beam induced etching (EBIE) and deposition (EBID) are promising fabrication techniques in which an electron beam is used to dissociate surface-adsorbed precursor molecules to achieve etching or deposition. Spatial resolution is normally limited by the electron flux distribution at the substrate surface. Here we present simultaneous EBIE and EBID (EBIED) as a method for surpassing this resolution limit by using adsorbate depletion to induce etching and deposition in adjacent regions within the electron flux profile. Our simulation results indicate the possibility of growth control of radially symmetric nanostructures at the sub-1 nm length scale on bulk substrates. The technique is well suited to the fabrication of ring-shaped nanostructures such as those employed in plasmonics, sensing devices, magneto-optics and magnetoelectronics.     

Fabrication and optical properties of spear-like ZnO nanostructures by chemical vapor deposition

Novel spear-like ZnO nanowires with a length of 2 μm and a width of 0.26 μm were synthesized on p-Si (100) substrates by chemical vapor deposition (CVD) method without catalysts. The crystal structures and morphographies of the products were characterized by X-ray powder diffraction (XRD) and high resolution field emission scanning electron microscope (FE-SEM). Energy dispersive X-ray spectrum (EDS) demonstrated that the spear-like microstuctures consist of element Zn and O. It indicated that the shapes of the products strongly depend on the growth conditions. The optical properties of spear-like ZnO nanostructures were investigated by temperature-depended photoluminescence (PL) measurements and all of the observed emission lines were well fitted by the Varshni formula.     

Electron beam induced deposition of silicon nanostructures from a liquid phase precursor

This work demonstrates electron beam induced deposition of silicon from a SiCl(4) liquid precursor in a transmission electron microscope and a scanning electron microscope. Silicon nanodots of tunable size are reproducibly grown in controlled geometries. The volume of these features increases linearly with deposition time. The results indicate that secondary electrons generated at the substrate surface serve as the primary source of silicon reduction. However, at high current densities the influence of the primary electrons is observed to retard growth. The results demonstrate a new approach to fabricating silicon nanostructures and provide fundamental insights into the mechanism for liquid phase electron beam induced deposition.     

Growth of doped silicon nanowires by pulsed laser deposition and their analysis by electron beam induced current imaging

Doped silicon nanowires (NWs) were epitaxially grown on silicon substrates by pulsed laser deposition following a vapour-liquid-solid process, in which dopants together with silicon atoms were introduced into the gas phase by laser ablation of lightly and highly doped silicon target material. p-n or p(++)-p junctions located at the NW-silicon substrate interfaces were thus realized. To detect these junctions and visualize them the electron beam induced current technique and two-point probe current-voltage measurements were used, based on nanoprobing individual silicon NWs in a scanning electron microscope. Successful silicon NW doping by pulsed laser deposition of doped target material could experimentally be demonstrated. This doping strategy compared to the commonly used doping from the gas phase during chemical vapour deposition is evaluated essentially with a view to potentially overcoming the limitations of chemical vapour deposition doping, which shows doping inhomogeneities between the top and bottom of the NW as well as between the core and shell of NWs and structural lattice defects, especially when high doping levels are envisaged. The pulsed laser deposition doping technique yields homogeneously doped NWs and the doping level can be controlled by the choice of the target material. As a further benefit, this doping procedure does not require the use of poisonous gases and may be applied to grow not only silicon NWs but also other kinds of doped semiconductor NWs, e.g. group III nitrides or arsenides.     

Fabrication and characterization of Ni-YSZ anode functional coatings by electron beam physical vapor deposition

Two kinds of NiO-YSZ (yttria-stabilized zirconia) coatings, respectively with uniform and gradient distributions of NiO content along the coating thickness direction, were prepared by electron beam physical vapor deposition (EB-PVD) via adjusting electron beam currents. Then uniform and graded Ni-YSZ coatings were obtained from corresponding NiO-YSZ coatings after a reduction treatment. For uniform Ni-YSZ coating, the composition and porosity distributions along the coating thickness were uniform. The specific surface area and total pore volume for this coating could reach up to 4.330  m² g ^− 1 and 0.0346  cm³ g ^− 1 respectively. The area specific resistance (ASR) of this coating kept increasing with the rise in temperature and an ASR of 2.1 × 10 ^− 5Ω cm² was obtained at 600 °C. For graded Ni-YSZ coating, a gradient in Ni content and porosity was realized along the coating thickness. A high porosity of up to 33% was achieved in the part of the coating close to the substrate, while a low porosity of 10% was obtained in the part close to coating surface.     

电子束蒸发沉积制备高度晶体取向的CeO2薄膜

为了得到CeO2为埋层的新型SOI(Silicon On Insulator)材料,采用电子束蒸发沉积及后期退火处理的方法制备得到了高度(111)、(311)晶体取向的CeO2薄膜,为进一步外延制备SOI材料打下了良好的基础.同时,从热力学角度就退火对CeO2薄膜晶体取向的影响机理进行了初步的探讨.由于CeO2(11)、(311)面为密排面和次密排面,在结晶化过程中所需克服的能垒最低和次低,所以,退火后形成了(111)、(311)结构的CeO2薄膜.     

Fabrication and characterization of solid oxide fuel cell electrolyte films by electron beam vapor deposition

Thin films of SDC for SOFC electrolyte were prepared using electron beam deposition technique. The influence of annealing temperature, substrate temperature and e-beam gun power on the structure and surface morphology of the thin films was examined. It was found that the SDC thin films annealed at 800 degrees C consisted of a single cubic phase and the main crystal structure of the thin films represented those of evaporated electrolyte powders. The crystal orientation of the SDC films increased with substrate temperature and decreased with e-beam gun power. The higher XRD peak intensity was observed for the SDC films deposited on NiO-YSZ substrate compared with those on SiO2 substrate due to the polycrystalline structure of the NiO-YSZ substrate. A good adhesion to the substrate and a columnar structure were observed by the fractured cross-sectional view of the SDC films on NiO-YSZ anode substrate. Electrical conductivity of SDC film with 5 microm thickness was observed to be 2.31 x 10(-3) Sm(-1) at 800 degrees C.     

不同结构镍纳米线阵列的制备及其磁性

采用直流电沉积在多孔有序氧化铝模板中制备了不同结构的有序镍纳米线阵列。采用SEM和TEM对所制备的镍纳米线的形貌和结构进行了表征。研究了镍纳米线不同结构对镍纳米线阵列磁性性能的影响规律．当电沉积电压为2．5V时制备的镍纳米线为多晶结构；电沉积电压4V时，镍纳米线为沿[220]择优取向的单晶结构；电沉积电压＞5V时，择优取向由[220]转为[111]方向．磁滞回线结果表明，单晶镍纳米线阵列与多晶纳米线阵列相比具有更高的矩形度，沿[111]择优取向的单晶纳米线相比沿[220]取向的单晶镍纳米线具有更大的矩形度，表现出显著的磁各向异性。     

Fabrication and characterization of nanostructures on insulator substrates by electron-beam-induced deposition

Abstract

The fabrication, characterization, and decoration with metallic nanoparticles of nanostructures such as nanowhiskers, nanodendrites, and fractal-like nanotrees on insulator substrates by electron-beam-induced deposition (EBID) are reviewed. Nanostructures with different morphologies of whiskers, dendrites, or trees are fabricated on insulator (Al₂O₃ or SiO₂) substrates by EBID in transmission electron microscopes by controlling the irradiation conditions such as the electron beam intensity. The growth of the nanostructure is related to the accumulation of charges on the surface of a substrate during electron-beam irradiation. A high concentration of the target metallic element and nanocrystal grains of the element are contained in the fabricated nanostructures. The process of growth of the nanostructures is explained qualitatively on the basis of mechanisms in which the formation of the nanostructures is considered to be related to the nanoscaled unevenness of the charge distribution on the surface of the substrate, the movement of the charges to the convex surface of the substrate, and the accumulation of charges at the tip of the grown nanostructure. Novel composite structures of Pt nanoparticle/tungsten (W) nanodendrite or Au nanoparticle/W nanodendrite are fabricated by the decoration of W nanodendrites with metallic elements. Because they have superior features, such as a large specific surface area, a freestanding structure on substrates, a typical size of several nanometers of the tip or the branch, and high purity, the nanostructures may have applications in technologies such as catalysts, sensors, and electron emitters. However, there are still some subjects that should be further studied before their application.     

Fabrication and characterization of nanostructures on insulator substrates by electron-beam-induced deposition

The fabrication, characterization, and decoration with metallic nanoparticles of nanostructures such as nanowhiskers, nanodendrites, and fractal-like nanotrees on insulator substrates by electron-beam-induced deposition (EBID) are reviewed. Nanostructures with different morphologies of whiskers, dendrites, or trees are fabricated on insulator (Al₂O₃ or SiO₂) substrates by EBID in transmission electron microscopes by controlling the irradiation conditions such as the electron beam intensity. The growth of the nanostructure is related to the accumulation of charges on the surface of a substrate during electron-beam irradiation. A high concentration of the target metallic element and nanocrystal grains of the element are contained in the fabricated nanostructures. The process of growth of the nanostructures is explained qualitatively on the basis of mechanisms in which the formation of the nanostructures is considered to be related to the nanoscaled unevenness of the charge distribution on the surface of the substrate, the movement of the charges to the convex surface of the substrate, and the accumulation of charges at the tip of the grown nanostructure. Novel composite structures of Pt nanoparticle/tungsten (W) nanodendrite or Au nanoparticle/W nanodendrite are fabricated by the decoration of W nanodendrites with metallic elements. Because they have superior features, such as a large specific surface area, a freestanding structure on substrates, a typical size of several nanometers of the tip or the branch, and high purity, the nanostructures may have applications in technologies such as catalysts, sensors, and electron emitters. However, there are still some subjects that should be further studied before their application.     

Fabrication of nickel nanocontacts using nanostencils and electron beam assisted SiO2 deposition

Nickel nanocontacts for studying ballistic magnetoresistance have been fabricated by sputtering through FIB prepared nanostencil masks and by using electron beam assisted deposition of SiO2 to reduce the size of FIB milled pores through silicon nitride membranes. These two methods are discussed in terms of the nanocontact sizes, fabrication, and yield. The smallest size of the nanocontacts prepared using the nanostencil method was 40 nm and by the filling method was 1-2 nm. The maximum magnetoresistance measured was 1% and no evidence of a large ballistic magnetoresistance was observed.     

Hydrothermal synthesis and gas sensing properties of different titanate nanostructures

Anatase TiO₂ nanoparticles and other three different morphologies of titanate nanostructures such as nanotubes, nanosheets and nanowires were successfully prepared by hydrothermal method. The structures and morphologies of the final products were characterized with field-emission scanning electron microscopy (FE-SEM). Phase analysis was carried out using X-ray diffraction (XRD). A novel formation mechanism from anatase TiO₂ nanoparticles to titanate nanowires is proposed based on FE-SEM. The gas sensing properties to ethanol were also investigated. The results indicate that nanotubes, nanosheets, nanowires show much less resistance and larger response than nanoparticles.     

Fabrication, microstructure, and mechanical properties of tin nanostructures

Vertically aligned, cylindrical tin nanopillars have been fabricated via an electron beam lithography and electroplating method. Characterization by a non-destructive synchrotron X-ray microdiffraction (μSXRD) technique revealed that the tin nanostructures are body-centered tetragonal and are likely single-crystalline, or consist of a few large grains. The mechanical properties of tin nanopillars with average diameters of 920 nm, 560 nm, and 350 nm were studied by uniaxial compression in a nanoindenter outfitted with a flat punch diamond tip. The results of compression tests reveal strain rate sensitivity for nanoscale tin deformation, which matches closely to the previously reported bulk tin values. However, unlike bulk, tin nanopillars exhibit size-dependent flow stresses where smaller diameter specimens exhibit greater attained strengths. The observed size-dependence matches closely to that previously reported for single-crystalline face centered cubic metals at the nanoscale. μSXRD data was used to compare the dislocation density between as-fabricated and deformed tin nanopillars. Results of this comparison suggest that there is no measurable accumulation of dislocations within deformed tin nanopillars.     

Synthesis of Fe-group metal oxide nanostructures by thermal oxidation and their magnetic properties

In this paper, we review the preparation of Fe-group metal oxide nanostructures by the thermal oxidation method developed in our lab. By this method, we have prepared several kinds of nanostructures, including nanowires and nanoleaves. The magnetic properties of these nanostructures have also been studied. By carefully controlling the reacting time, temperature, and humidity, we have prepared alpha-Fe2O3, gamma-Fe2O3, Fe3O4, and Co3O4 nanowires and alpha-Fe2O3 nanoleaves by heating the substrates in proper atmosphere. The alpha-Fe2O3 and Co3O4 nanowires are produced by directly oxygenating pure metal at 550 to approximately 650 degrees C and 480-520 degrees C, separately. The gamma-Fe2O3 and Fe3O4 nanowires are produced by reducing as-prepared alpha-Fe2O3 nanowires in a mixture of N2 and H2. The nanowires are about 10-20 microm, with diameter of about 20 to approximately 100 nm. Most of the nanowire arrays are grown vertically from the surface of the substrate at a high surface density (10(8)-10(9) cm(-2)). Compared with the nanowires prepared by hydrothermal process and template method, Most of our nanowires are structurally uniform and single crystallites. The magnetic properties of these nanostructures are also studied, and demonstrate some novel properties.     

Synthesis of PbSe nanostructures with different size and morphology and their electrochemical properties

Four different mediums have been developed for the synthesis of PbSe nanostructures, with different size and morphology. The particles were obtained in solid state medium with size of only 60 nm on average which are much smaller than those gained in liquid and molten state mediums. The growth mechanisms of these PbSe nanostructures were discussed. Results show that the state of medium have a direct impact on the size of PbSe nanostructures and the alkalinity of environment plays a key part in the formation of PbSe nanocubes. On the other hand, the electrochemical property of two typical nanostructures was studied. In the CV curves, there are four reaction peaks corresponding to oxidation of the PbSe and Pb(OH)₂, and the reduction of PbO₂ and Pb(OH)₂. Otherwise, nanorods with size of only 60 nm have greater structural stability than nanocubes.     

Synthesis and growth mechanism of CuO nanostructures and their gas sensing properties

CuO nano-particles, nano-rods, nano-sheets and nano-flowers were synthesized by the hydrothermal routes with copper salts under different additions. The obtained samples were characterized by X-ray diffraction and scanning electron microscopy. We investigated the effects of precursors on the formation of CuO with different morphologies and proposed their possible formation mechanisms. In addition, the obtained CuO nano-flowers are found to show better sensing performances than the other three low-dimensional CuO nanostructures. Our results also demonstrate that gas sensing properties of nanocrystals can be significantly improved by tailoring shape and morphology of the nanocrystals. The CuO nano-flowers may hold substantial promise in low-dimensional gas-sensing applications.     

Transport of a high-current relativistic electron beam by magnetic multipoles

With the aid of moments of the distribution function a system of differential equations is obtained to describe the dynamics of a Gaussian high-current electron beam in magnetic fields with quadrupole and octupole symmetries. Results of its numerical solution are reported. Research Institute for Nuclear Problems at the Belarusian State University, Minsk, Belarus; Institute of Mathematics of the Academy of Sciences of Belarus, Minsk, Belarus. Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 70, No. 5, pp. 776–782, September-October, 1997.