Epitaxy: the motion picture

The engineering of many modern electronic devices demands control over a crystal down to the thickness of a single layer of atoms—and future demands will be even more challenging. Such control is achieved by the method of crystal growth known as epitaxy, and that makes this method the subject of intense study. More than that, recent advances are revolutionizing our knowledge of how surfaces grow. In fact, growing surfaces show a beautifully rich variety of phenomena, many of which are only now beginning to be uncovered. In the past few years many surface imaging techniques have been used to give us a close look at how crystals grow—while they are growing. The purpose of this article will be to illustrate some of the ways real surfaces grow and change as revealed by some of the latest in situ microscopic imaging technologies.

It is often said that crystal growth is more of an art than a science. Here we will show that it is emphatically both.     

Biomorphous SiC ceramics prepared from cork oak as precursor

Porous ceramic materials of SiC were synthesized from carbon matrices obtained via pyrolysis of natural cork as precursor. We propose a method for the fabrication of complex-shaped porous ceramic hardware consisting of separate parts prepared from natural cork. It is demonstrated that the thickness of the carbon-matrix walls can be increased through their impregnation with Bakelite phenolic glue solution followed by pyrolysis. This decreases the material’s porosity and can be used as a way to modify its mechanical and thermal characteristics. Both the carbon matrices (resulted from the pyrolysis step) and the resultant SiC ceramics are shown to be pseudomorphous to the structure of initial cork. Depending on the synthesis temperature, 3C-SiC, 6H-SiC, or a mixture of these polytypes, could be obtained. By varying the mass ratio of initial carbon and silicon components, stoichiometric SiC or SiC:С:Si, SiC:С, and SiC:Si ceramics could be produced. The structure, as well as chemical and phase composition of the prepared materials were studied by means of Raman spectroscopy and scanning electron microscopy.     

Real time ellipsometry for monitoring plasma-assisted epitaxial growth of GaN

GaN is grown on Si-face 4H-SiC(0 0 0 1) substrates using remote plasma-assisted methods including metalorganic chemical vapour deposition (RP-MOCVD) and molecular beam epitaxy (MBE). Real time spectroscopic ellipsometry is used for monitoring all the steps of substrate pre-treatments and the heteroepitaxial growth of GaN on SiC. Our characterization emphasis is on understanding the nucleation mechanism and the GaN growth mode, which depend on the SiC surface preparation.     

Shape variation in epitaxial microstructures of gold silicide grown on Br-passivated Si(1 1 1) surfaces

Kinetic Monte Carlo simulations for growth on substrates of three-fold symmetry predict the growth of islands of various shapes depending on the growth temperature [Phys. Rev. Lett. 71 (1993) 2967]. On Br-Si(1 1 1) substrates growth of epitaxial gold silicide islands of equilateral triangular and trapezoidal shapes have earlier been observed by annealing at the Au-Si eutectic temperature, 363 °C [Phys. Rev. B 51 (1995) 14330]. We carried out annealing with temperature variation within a small window--(363 ± 30) °C. This has led to island growth of additional shapes like regular hexagon, elongated hexagon, walled hexagon and dendrite. Some of the observed island shapes have not been predicted.     

Synthesis of salicylaldehyde Schiff base modified Cu nanocrystals by thermal treatment in liquid paraffin

Cuboid copper nanocrystals were synthesized by thermal treatment in liquid paraffin without any inert gas protection with salicylaldehyde Schiff base copper (II) (Cu (II)-Salen) complex as precursor. Liquid paraffin was used as solvent and reductant. The obtained copper nanocrystals are morphology-controlled and stable when exposed to air for one year. The nanocrystals were characterized by X-ray diffraction measurements (XRD), UV-visible spectroscopy (UV-vis), transmission electron microscope (TEM), and Fourier transform infrared spectroscopy (FT-IR). The results showed that the stable cuboid copper nanocrystals are synthesized by using Salen as capping agents.     

SiC材料及器件研制的进展

作为第三代的半导体材料－ＳｉＣ具有禁带宽度大、热导率高、电子的饱和漂移速度大、临界击穿电场高和介电常数低等特点,在高频、大功率、耐高温、抗辐照的半民体器件及紫外探测器和短波发光二级管等方面具有广泛的应用前景,文章综述了半导体ＳｉＣ材料生长及其器件研制的概况。     

Characterization of a SiC/SiC composite by X-ray diffraction, atomic force microscopy and positron spectroscopies

A SiC/SiC composite is characterized by X-ray diffraction, atomic force microscopy and various positron spectroscopies (slow positron implantation, positron lifetime and re-emission). It is found that besides its main constituent 3C-SiC the composite still must contain some graphite. In order to better interpret the experimental findings of the composite, a pyrolytic graphite sample was also investigated by slow positron implantation and positron lifetime spectroscopies. In addition, theoretical calculations of positron properties of graphite are presented.     

Elastic energy mapping of epitaxial nanocrystals

Self-assembled nanocrystals grown by epitaxy represent a viable way to mass produce quantum structures exhibiting novel electronic properties. In order to infer the electronic properties of such systems, knowledge of both composition and strain is necessary. Here, detailed maps of these quantities were obtained by anomalous X-ray diffraction for samples grown at 600 °C and 700 °C by chemical vapor deposition and molecular beam epitaxy, respectively – two different temperatures and growth techniques. From these maps, the elastic energies stored in the islands were evaluated. It was found that the elastic energy is concentrated at the island borders, regardless of the growth temperature or method. In contrast, the regions with the lowest elastic energy were the island core and top. These results provide insight into the mechanisms that govern the growth and evolution of strained nanocrystals. PACS 71.35.Ji; 78.67.Hc; 73.22.Dj     

SiC/SiC复合材料第一壁热工设计

以日本原子力研究所那珂研究所聚变堆设计室进行的先进稳态托卡马克聚变堆2（A－SSTR2）概念设计为基础,对SiC/SiC复合材料包层／第一壁热工设计进行了分析计算。通过选取各种几何位形和材料敏感特性参数,用有限元法进行了大量的热工计算,以最高温度、最大热应力为基础建立了包层／第一壁设计窗口,选取了满足热工要求的最佳设计方案,对今后的工程设计具有指导作用和重要的参考价值。     

Gadolinium doped Ceria nanocrystals synthesized from mesoporous silica

Highly crystalline and thermally stable gadolinium doped ceria (GDC) particles have been synthesized by hard template route for the first time. This oxide is being recognized as an intermediate temperature (500–700 °C) electrolyte material for applications in solid-oxide fuel cells. The GDC particles show high crystallinity and nanometric size (2.83 ± 0.05 nm in diameter) and Raman analyses confirm the formation of the solid solution instead of a CeO₂ and Gd₂O₃ mixture. EDX and EELS studies indicate a stoichiometry coherent with the Gd_0.2Ce_0.8O_1.9 phase. The synthesized nanometric powder is expected to be used in solid oxide fuel cells as well as in the catalytic treatment of automobile exhaust fumes.

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Graphical abstract

     

Influence of silicon and carbon excesses on the aqueous dispersion of SiC nanocrystals for optical application

The dispersion behaviour of laser-synthesized silicon carbide nanoparticles (npSiC) in water is investigated by photon correlation spectroscopy (PCS). With regard to previous studies and due to an application in the processing of optical materials, this paper concerns low npSiC contents (from 0.05 to 10 wt.%). The role played by the particle surface state is be pointed out through the consideration of stochiometric (C/Si = 1), carbon-rich (C/Si > 1) and silicon-rich (C/Si < 1) nanopowders. Suspensions made from stoichiometric and silicon-rich nanopowders are easily dispersed and stable with time. The PCS measurements reveal in this case more than 95% of isolated nanoparticles, pointing out the key role of the oxidized layer covering the grain of silicon-rich samples. At the opposite, the carbon-rich powders are hardly dispersed in pure water, correlated with the presence of a relatively inert graphitic carbon layer at the grain surface. However, by addition of a commercial polymeric dispersant, all nanopowders induce high quality suspensions. In particular, the carbon-rich samples are easily dispersed, and possible dispersion mechanisms of npSiC in presence of a polymeric surfactant are discussed. The influence of the npSiC loading and the time evolution of the suspension are also presented. By considering stoichiometric, as well as carbon- and silicon-rich samples, this paper demonstrates the possibility to achieve high quality dispersions of SiC nanoparticles, whatever the chemical composition of the powder, as an easy step for optical material processing.This revised version was published online in August 2005 with a corrected issue number.     

Spinodal-like decomposition of InGaP epitaxial layers grown on GaP substrates

The spinodal-like decomposition of In_xGa_1−xP epitaxial layer prepared by low-pressure metallorganic vapour phase epitaxy was studied by means of photoluminescence and transmission electron microscopy. Epitaxial layers were grown on GaP substrates at T_g = 740 °C and reactor pressure of 20 mbar. We show that presence of spinodal-like decomposition occur at samples with InP mole fraction higher as x = 0.2 and V/III ratio of 75. The low-temperature photoluminescence spectra shows that in partially decomposed samples a characteristic broad band occurred close to 1.985 eV. An increase in the V/III ratio up to a value of 350 suppressed the decomposition, and PL signal with only one narrow transition was obtained.     

Formation of one-dimensional crystalline silica on a metal substrate

We have observed formation of one-dimensional silica structures of 0.5 nm in width on Mo(1 1 2) single crystal surface. Combination of high-resolution scanning tunneling microscopy, photoelectron and infrared spectroscopy, and density functional theory provides strong evidence for formation of paired rows of corner sharing [SiO₄] tetrahedra chemisorbed on a metal substrate.     

Electrical conductance at initial stage in epitaxial growth of Pb, Ag, Au and In on modified Si(1 1 1) surface

The electronic properties of thin metallic films of Pb, Ag, Au and In atoms deposited at 105 K on well defined metallic surface, i.e. Si(1 1 1)-(6 × 6)Au surface with 10 ML of annealed Pb, were investigated using four-point probe method in UHV condition. The structure of the substrate and deposited metals were monitored by the RHEED system. The electrical conductance, measured during the deposition of In and Pb atoms, shows the local minimum for the coverage equals about 0.3 ML whereas for Au and Ag atoms the conductance decreases during the first monolayer growth. For Au atoms the local maximum in the conductance was observed for the coverage about 0.55 ML, which can be connected with localized states. To describe theoretically the conductance behavior the tight-binding Hamiltonian and equation of motion for the Green’s function were used and good qualitative agreement was obtained.     

Reconstructions 3 × 3 and √3 × √3 on SiC(0 0 0 1) studied using RHEED

The 3 × 3 and √3 × √3 reconstructions on 6H-SiC(0 0 0 1) surface were obtained via depositing thin silicon layer and annealing it in ultrahigh vacuum (without Si flux). Rocking curves of reflection high energy electron diffraction (RHEED) were measured for integer and fractional order beams. They were fitted with results of many-beam calculation on the basis of dynamical theory of RHEED to determine structural parameters. For √3 × √3 superstructure, it was found that the occupancy of adatom states is 0.45 (incomplete coverage). In the sequence of Si-C double layers ABCACB, the lattice is terminated with the layer A. For 3 × 3 superstructure, the rocking curves support the model with twisted tetra-cluster. The best-fit twist is as half of that predicted in ab initio calculations; it is due to limited source of Si atoms to build up the superstructure. Larger twist correlates with higher occupancy of corner sites and with slower cooling rate of the sample after annealing.     

Correlation between structural and electrical properties of InN thin films prepared by molecular beam epitaxy

The strain-relaxation phenomena and the formation of a dislocation network in 2H-InN epilayers during molecular beam epitaxy are reported. The proposed growth model emphasizes the dominant role of the coalescence process in the formation of a dislocation network in 2H-InN. Edge type threading dislocations and dislocations of mixed character have been found to be the dominating defects in wurtzite InN layers. It is demonstrated that these dislocations are active suppliers of electrons and an exponential decay of their density with the thickness implies a corresponding decay in the carrier density. Room temperature mobility in excess of 1500 cm² V ⁻¹ s⁻¹ was obtained for 800 nm thick InN layers with dislocation densities of 3×10⁹ cm⁻².     

Numerical and experimental investigations of the size ordering of nanocrystals

The nucleation and growth of particles on the 1–100 nm length scale is a phenomenon of increasing interest in the areas of electronics and optoelectronics. Dealing with the preparation of nanoparticle distribution on a substrate by self-organization, we wish to determine whether conditions exist where the distributions approach an array structure which can be compared to so-called quantum dot organized structures. This means that it is fundamental to obtain particles of the same shape with a low dispersion in size and an isotropic distribution on the substrate. This work is devoted to the numerical investigation of growth phenomena on a plane substrate in the case where diffusion and coalescence are mainly taken into account. Experiments on a model system, i.e. Sn/SiO_x, are compared to simulations.     

SiC epitaxy growth using chloride-based CVD

The growth of thick epitaxial SiC layers needed for high-voltage, high-power devices is investigated with the chloride-based chemical vapor deposition. High growth rates exceeding 100 μm/h can be obtained, however to obtain device quality epilayers adjustments of the process parameters should be carried out appropriately for the chemistry used. Two different chemistry approaches are compared: addition of hydrogen chloride to the standard precursors or using methyltrichlorosilane, a molecule that contains silicon, carbon and chlorine. Optical and electrical techniques are used to characterize the layers.     

A tem study on polyoxymethylene rodlike crystals grown epitaxially on NaCl

Rodlike crystals of polyoxymethylene (POM) were isothermally grown onto the newly cleaved (001) face of NaCI from a 0.1 wt% solution in nitrobenzene and then were studied by transmission electron microscopy (TEM). Morphological observation in bright- and dark-field imaging modes and selected-area electron diffraction analysis directly evidenced that POM chain stems in the rodlike crystals are set parallel to the substrate surface and also perpendicular to the rod axis. That is, each of the rodlike crystals is an “edge-on” lamella of POM, the lateral face of which is in contact with the substrate surface. The contact plane of the edge-on lamella in question, namely, the crystallographic plane parallel to the substrate surface, is determined as the (100) plane of the hexagonal crystal lattice of POM.     

Nanoscratch studies of SiGe epitaxial layer damage on the Si substrate

The present study evaluates the wear performance of silicon-germanium (SiGe) epitaxial growth of thin films, in which the in situ scratch profile is followed by ex situ atomic force microscopy (AFM) examinations. The wear evaluation of SiGe films was carried out at different constant loads (2000, 4000, and 6000 μN) with the same sliding speeds. The microstructural morphology was observed by means of transmission electron microscopy (TEM)Findings show that annealing treatments of SiGe films exhibit the highest scratch resistance at 400 °C compared to that of the as-deposited sample. The main characteristic of SiGe film is its ability to withstand wear resistance; observations show that moderate compressive residual is beneficial to the film, since it can suppress crack initiation. The annealing treatments of SiGe films revealed the resultant adhesive and cohesive failure mechanism.