Synthesis and photoluminescence of aligned straight silica nanowires on Si substrate

Aligned straight silica nanowires (NWs) have been synthesized on Si wafer by thermal evaporation of mixed powders of zinc carbonate hydroxide and graphite at 1100 °C and condensation on Si substrate without using any catalyst. The straight silica NWs have diameters ranging from 50 to 100 nm, and lengths of several micrometers, with cone-shaped tips at their ends. High deposition temperature and relatively high SiO_x vapor concentration near the growth substrate would be beneficial to the formation of the aligned straight silica NWs. Different morphologies of silica nanostructures have also been obtained by varying the deposition temperature and the vapor concentration of the SiO_x molecules. Room temperature photoluminescence measurements on the oriented silica NWs show that two green emission bands at 510 and 560 nm, respectively, revealing that the aligned straight silica NWs might have potential applications in the future optoelectronic devices.     

Silicon monoxide clusters: the favorable precursors for forming silicon nanostructures

Using density-functional calculations, we show that the energetically favorable configurations of silicon monoxide clusters (SiO)n for n> or =5 facilitate the nucleation and growth of silicon nanostructures as the clusters contain sp3 silicon cores surrounded by silicon oxide sheaths. The frontier orbitals of (SiO)n clusters are localized to a significant degree on the silicon atoms on the surface, providing high reactivity for further stacking with other clusters. The oxygen atoms in the formed larger clusters prefer to migrate from the centers to the exterior surfaces, leading to the growth of sp3 silicon cores.     

Effect of titanium powder assisted surface pretreatment process on the nucleation enhancement and surface roughness of ultrananocrystalline diamond thin films

A superior, easy and single-step titanium (Ti) powder assisted surface pretreatment process is demonstrated to enhance the diamond nucleation density of ultrananocrystalline diamond (UNCD) films. It is suggested that the Ti fragments attach to silicon (Si) surface form bond with carbon at a faster rate and therefore facilitates the diamond nucleation. The formation of smaller diamond clusters with higher nucleation density on Ti mixed nanodiamond powder pretreated Si substrate is found to be the main reason for smooth UNCD film surface in comparison to the conventional surface pretreatment by only nanodiamond powder ultrasonic process. The X-ray photoelectron spectroscopic study ascertains the absence of SiC on the Si surface, which suggests that the pits, defects and Ti fragments on the Si surface are the nucleation centers to diamond crystal formation. The glancing-incidence X-ray diffraction measurements from 100 nm thick UNCD films evidently show reflections from diamond crystal planes, suggesting it to be an alternative powerful technique to identify diamond phase of UNCD thin films in the absence of ultra-violet Raman spectroscopy, near-edge X-ray absorption fine structure and transmission electron microscopy techniques.     

Study of iron-alumina cluster catalysts for synthesis of alkylaromatic hydrocarbons from CO and H2

New selective catalysts for alkylaromatic synthesis from CO and H₂ were studied. The catalysts were obtained by the hydrolysis of Fe(acac)₃ with Al(OR)₃ with the following activation in O₂ and H₂. The selective catalysts were found to contain tiny ferromagnetic clusters indiscernible by Mössbauer spectroscopy. The formation of the larger metallic clusters led to the alkan production.     

Oscillating cracks in glassy films on silicon substrates

Cracks that propagate with near-perfect sinusoidal form are reported in amorphous silicon-rich silica films deposited onto (001) silicon substrates by plasma-enhanced chemical vapour deposition and subjected to thermal annealing. The cracks are shown to result from high tensile stresses that develop in the film during thermal annealing at temperatures in the range up to 700°C, a process shown to be correlated with the loss of hydrogen from the films. Two distinct modes of crack propagation are reported: straight cracks that propagate along directions parallel to [100] cube-edge directions in the substrate, and oscillating cracks that propagate with sinusoidal form parallel to [110] diagonal directions. Sections through the cracks show that the oscillating cracks have a complex three-dimensional structure that extends through the glassy film and into the underlying silicon substrate. This involves a correlated oscillation between the crystallographic orientation of the crack in the surface plane and that of the crack extension into the substrate. Whereas a complete theoretical treatment of this behaviour would be extremely complicated, a simple theory is developed to demonstrate that an oscillating crack has a minimum energy per unit length for a particular wavelength and amplitude that depends upon the physical parameters of both film and substrate. The energy at this minimum is shown to be lower than that of a straight crack for certain parameter ranges so that the oscillating geometry is preferred.     

Preparation and characterization of oriented silica nanowires

Large-scale of oriented closely packed silica nanowire bunches have been synthesized by using large size (1-10 μm in diameter), low melting point tin droplets as catalyst on silicon wafers at 980 °C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses show that the amorphous silica nanowires have lengths of 50-100 μm and diameters of 100-200 nm. Unlike any previous observed results using high melting point metal (such as gold and iron) as catalyst, the Sn catalyst growth exhibits many interesting phenomena. Each Sn ball can simultaneously catalyze the growth of many silica nanowires, which is quite different from the conventional vapor-liquid-solid process.     

Influence of Al Preflow Time on Surface Morphology and Quality of AlN and GaN on Si(111) Grown by MOCVD

We investigate the influence of Al preflow time on surface morphology and quality of AIN and GaN. The AIN and GaN layers are grown on a Si(111) substrate by metal organic chemical vapor deposition. Scanning electron microscopy, atomic force microscopy, x-ray diffraction and optical microscopy are used for analysis. Consequently,we find significant differences in the epitaxial properties of AIN buffer and the GaN layer, which are dependent on the Al preflow time. Al preflow layers act as nucleation sites in the case of AIN growth. Compact and uniform AIN nucleation sites are observed with optimizing Al preflow at an early nucleation stage, which will lead to a smooth AIN surface. Trenches and AIN grain clusters appear on the AIN surface while melt-back etching occurs on the GaN surface with excessive Al preflow. The GaN quality variation keeps a similar trend with the AIN quality, which is influenced by Al preflow. With an optimized duration of Al preflow, crystal quality and surface morphology of AIN and GaN could be improved.     

Direct local epitaxy of diamond on Si(100) and surface-roughening-induced crystal misorientation

A direct diamond epitaxy on the silicon substrate is demonstrated not only at the interface formed during the growth process but also at the nucleation sites. The small (001) terraces with dimensions of several atomic distances at the site of nucleation are formed due to the roughening of silicon surface and lead to the grain misorientation. A model is presented which attempts to explain the initial stages of diamond growth. Predictions are made for methods of improving the nucleation of epitaxial diamond crystallites.     

Luminescent defects in nanostructured silica

The spectral and kinetic properties of excited states of luminescent defects (oxygen-deficient centers) in SiO₂ ceramics are studied using pulsed cathodoluminescence and time-resolved photoluminescence. It is found that, in nanostructured samples prepared by thermal decomposition of polysilazane in air, there can exist modifications of oxygen-deficient centers in the form of surface analogs of either neutral oxygen monovacancies ≡Si-Si≡ (≡Ge-Ge≡) or twofold-coordinated silicon atoms =Si: (=Ge:). Photoluminescence of these centers is efficiently excited in the optical absorption bands of E′_s surface centers and silicon clusters ≡SiSiSi≡ and can be associated with the intercenter energy transfer in the course of their nonradiative relaxation. The photoluminescence and excitation spectra indicate thermally induced conversion of different types of oxygen-deficient centers. The specific features of the thermally induced changes in the luminescence characteristics of the defects due to the transformation of the structure of the silica samples from amorphous to partially crystalline are revealed from analyzing the spectral composition and decay kinetics of pulsed cathodoluminescence.     

Nucleation and initial growth of diamond by biased hot filament chemical vapour deposition

6 cm^-2 for non-scratched silicon. The maximum value of the nucleation density was over 10¹¹ cm^-2 on mirror-polished Si(100) at -300 V. The transportation process of the ion flux from the filament to the substrate is discussed in detail for biased substrates. The nucleation enhancement by the positive bias is believed to be a result of the increased impingement of the electrons emitted from the filament to the substrate surface. The studies have shown that electron emission from diamond plays a key role in negative-bias-enhanced nucleation by accelerating the dissociation of molecular hydrogen and hydrocarbon species into various free radicals and causing a plasma to be ignited near the substrate surface. The negative bias pretreatment is also a critical step in growing heteroepitaxial diamond films: the enlargement of the area of diamond clusters in contact with the substrate enhances the orientated growth of the films. Received: 18 October 1996/Accepted: 4 February 1997     

How can we make stable linear monoatomic chains? Gold-cesium binary subnanowires as an example of a charge-transfer-driven approach to alloying

On the basis of first-principles calculations of clusters and one dimensional infinitely long subnanowires of the binary systems, we find that alkali-noble metal alloy wires show better linearity and stability than either pure alkali metal or noble metal wires. The enhanced alternating charge buildup on atoms by charge transfer helps the atoms line up straight. The cesium doped gold wires showing significant charge transfer from cesium to gold can be stabilized as linear or circular monoatomic chains.     

Imaging the elastic properties of coiled carbon nanotubes with atomic force microscopy

Coiled carbon nanotubes were produced catalytically by thermal decomposition of hydrocarbon gas. After deposition on a silicon substrate, the three-dimensional structure of the helix-shaped multiwalled nanotubes can be visualized with atomic force microscopy. Helical structures of both chiralities are present in the nanotube deposits. For larger coil diameters ( >170 nm), force modulation microscopy allows one to probe the local elasticity along the length of the coil. Our results agree with the classical theory of elasticity. Similar to the case of straight nanotubes, the Young modulus of coiled multiwalled nanotubes remains comparable to the very high Young modulus of hexagonal graphene sheets.     

Kinetic Monte Carlo simulation of the growth of metal clusters on regular array of defects on insulator

A Kinetic Monte Carlo simulation of the nucleation and growth of Pd clusters on a nanostructured alumina substrate is presented. The new Monte Carlo simulation program allows to derive the 3D shape of the growing clusters without performing a full all atoms simulation. The simulation shows, like in previous pure 2D simulations, that clusters nucleate exclusively on the defects of the nanostructure in a limited range of substrate temperature. Around 300 K, the clusters have a compact faceted shape and they grow, at not too large coverage, layer by layer. These results are in agreement with previous studies of the nucleation and growth of Pd clusters on an ultrathin alumina film on Ni₃Al (1 1 1).     

Mechanism of silicon epitaxy on porous silicon layers

The mechanism of silicon epitaxy on porous Si(111) layers is investigated by the Monte Carlo method. The Gilmer model of adatom diffusion extended to the case of arbitrary surface morphology is used. Vacancies and pendants of atoms are allowed in the generalized model, the activation energy of a diffusion hop depends on the state of the neighboring positions in the first and second coordination spheres, and neighbors located outside the growing elementary layer are also taken into account. It is shown that in this model epitaxy occurs by the formation of metastable nucleation centers at the edges of pores, followed by growth of the nucleation centers along the perimeter and the formation of a thin, continuous pendant layer. Three-dimensional images of surface layers at different stages of epitaxy were obtained. The dependence of the kinetics of the epitaxy process on the amount of deposited silicon is determined for different substrate porosities. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 7, 512–517 (10 April 1998)     

Nanowire formation by coalescence of small gold clusters inside carbon nanotubes

The coalescence of Au₁₃, Au₅₅ and Au₁₄₇ icosahedral clusters encapsulated inside single walled carbon nanotubes (CNTs) of different diameters are investigated using molecular dynamics simulation with semi-empirical potentials. Three steps needed for the formation of encapsulated nanowires are followed in detail, namely, the penetration of clusters in CNTs, the coalescence between two clusters inside CNTs and their accumulation to form wires. It is suggested that no significant energy barrier is encountered during the penetration of free clusters into CNTs provided the CNT radius is large enough, that is, about 0.3 nm larger than the cluster radius. The relative orientation of clusters imposed by the CNT favors their spontaneous coalescence. After coalescence of two clusters, the Au atoms are rearranged to form new structures of cylindrical symmetry that may be seven fold, six fold, five fold, helical or fcc depending on the CNT diameter. The thermal stability of these structures is discussed and the structural properties of nanowires formed by accumulation of many clusters in CNTs are analyzed in detail. A geometrical method is presented which allows the prediction of the structure of multi-shell helical wires, when knowing only the CNT radius. These modeling results suggest the possibility of synthesizing metallic nanowires with controlled diameter and structure by embedding clusters into nanotubes with suitable diameters.     

硅基二氧化硅厚膜材料的快速生长

采用火焰水解法在Si片上快速淀积SiO₂厚膜材料,材料膜厚达到40μm以上,生长速率达8μm/min.然后将该材料分别在真空中/空气气氛中高温致密化处理,获得了各种形态的二氧化硅厚膜材料,包括平整度好、光滑透明的玻璃态SiO₂厚膜材料.并利用XRD、电子显微镜等仪器对SiO₂膜的表面和膜厚进行了测试分析.     

Influence of nucleation on the kinetics of boron precipitation in silicon

A study of the precipitation of boron implanted into pre-amorphized silicon has been carried out following several thermal processes in the temperature range between 550 and 900 °C. It will be shown that the formation of inactive boron takes place even during a low-temperature solid-phase epitaxy of the regrowing layer, when the starting concentration level exceeds about 3.5×10²⁰ atoms/cm³. The presence, at the beginning of the annealing process, of inactive atoms in the form of small aggregates which behave as nucleation centers, markedly affects the precipitation kinetics during the thermal treatments. In these conditions the experimental data follow the Ham's theory of precipitation. On the contrary, if all the dopant is incorporated in the lattice side, nucleation is the limiting factor for boron deactivation.     

Luminescence centers in porous silicon

Photoluminescence studies on porous silicon show that there are luminescence centers present in the surface states. By taking photoluminescence spectra of porous silicon with respect to temperature, a distinct peak can be observed in the temperature range 100–150 K. Both linear and nonlinear relationships were observed between excitation laser power and the photoluminescence intensity within this temperature range. In addition, there was a tendency for the photoluminescence peak to red shift at low temperature as well as at low excitation power. This is interpreted as indicating that the lower energy transition becomes dominant at low temperature and excitation power. The presence of these luminescence centers can be explained in terms of porous silicon as a mixture of silicon clusters and wires in which quantum confinement along with surface passivation would cause a mixing of andX band structure between the surface states and the bulk. This mixing would allow the formation of luminescence centers.     

场发射栅孔阵列的制备

 采用硅的局部氧化技术以及湿法刻蚀技术,利用2.6 μm的光刻掩模板在n型硅片上形成了栅极孔径为1 μm的场发射阴极的栅极空腔阵列,实现了用大阵点尺寸的栅极掩模板制备较小尺寸栅孔阵列。硅的湿法刻蚀溶液采用各向同性的硝酸和氢氟酸混合溶液,刻蚀后空腔的深度和宽度均随刻蚀时间线性增加。同时,由于刻蚀溶液具有较高的Si/SiO₂ 刻蚀选择比,栅极孔径随刻蚀时间增大的速度远低于深度和宽度增大的速度,栅极孔径主要取决于掩模的尺寸和氧化层的厚度。通过选择掩模板的尺寸以及氧化层的厚度,采用局部氧化技术和湿法刻蚀技术能够制备出微米或亚微米的场发射阴极的栅极空腔阵列。     

Room temperature facile synthesis of CuO nanostructures by resistive heating

CuO porous layer and nanowires were in situ grown on Cu wires by a very simple catalyst-free thermal oxidation process based on resistive heating of pure metal wires at ambient conditions. The morphological, compositional and structural characterization of the obtained samples revealed that the nanowires are monoclinic single and bi-crystalline structures with mean diameters of 90–300 nm and typical length in the range 1–5 μm. The effects of the applied voltage values and treatment time on the morphology of the metal substrate and on the size of the nanowires were investigated. Different from the vapor–solid (V–S) mechanism, the growth of nanowires is found to be based on the Cu ion diffusion.