S. A. Kukushkin

Synthesis of epitaxial silicon carbide films through the substitution of atoms in the silicon crystal lattice: A review

A review of recent advances in the field of epitaxial growth of SiC films on Si by means of a new method of epitaxial substitution of film atoms for substrate atoms has been presented. The basic statements of the theory of the new method used for synthesizing SiC on Si have been considered and extensive experimental data have been reported. The elastic energy relaxation mechanism implemented during the growth of epitaxial SiC films on Si by means of the new method of substitution of atoms has been described. This method consists in substituting a part of carbon atoms for silicon matrix atoms with the formation of silicon carbide molecules. It has been found experimentally that the substitution for matrix atoms occurs gradually without destroying the crystalline structure of the matrix. The orientation of the film is determined by the “old” crystalline structure of the initial silicon matrix rather than by the silicon substrate surface only, as is the case where conventional methods are used for growing the films. The new growth method has been compared with the classical mechanisms of thin film growth. The structure and composition of the grown SiC layers have been described in detail. A new mechanism of first-order phase transformations in solids with a chemical reaction through an intermediate state promoting the formation of a new-phase nuclei has been discussed. The mechanism providing the occurrence of a wide class of heterogeneous chemical reactions between the gas phase and a solid has been elucidated using the example of the chemical interaction of the CO gas with the single-crystal Si matrix. It has been shown that this mechanism makes it possible to grow a new type of templates, i.e., substrates with buffer transition layers for growing wide-band-gap semiconductor films on silicon. A number of heteroepitaxial films of wide-band-gap semiconductors, such as SiC, AlN, GaN, and AlGaN on silicon, whose quality is sufficient for the fabrication of a wide class of micro- and optoelectronic devices, have been grown on the SiC/Si substrate grown by solid-phase epitaxy.

New method for growing silicon carbide on silicon by solid-phase epitaxy: Model and experiment

A new method of solid-state epitaxy of silicon carbide (SiC) on silicon (Si) is proposed theoretically and realized experimentally. Films of various polytypes of SiC on Si(111) grow through a chemical reaction (at T = 1100–1400°C) between single-crystal silicon and gaseous carbon oxide CO (at p = 10–300 Pa). Some silicon atoms transform into gaseous silicon oxide SiO and escape from the system, which brings about the formation of vacancies and pores in the silicon near the interface between the silicon and the silicon carbide. These pores provide significant relaxation of the elastic stresses caused by the lattice misfit between Si and SiC. X-ray diffraction, electron diffraction, and electron microscopy studies and luminescence analysis showed that the silicon carbide layers are epitaxial, homogeneous over the thickness, and can contain various polytypes and a mixture of them, depending on the growth conditions. The typical pore size is 1 to 5 μm at film thicknesses of ∼20 to 100 nm. Thermodynamic nucleation theory is generalized to the case where a chemical reaction occurs. Kinetic and thermodynamic theories of this growth mechanism are constructed, and the time dependences of the number of new-phase nuclei, the concentrations of chemical components, and the film thickness are calculated. A model is proposed for relaxation of elastic stresses in a film favored by vacancies and pores in the substrate.

Raman Investigation of Different Polytypes in SiC Thin Films Grown by Solid-Gas Phase Epitaxy on Si (111) and 6H-SiC Substrates

Raman spectroscopy was applied to investigate a series of SiC films grown on Si and 6H-SiC substrates by a new method of solid gas phase epitaxy. During the growth characteristic voids are formed in Si at the SiC/Si interface. Raman peak position, intensity and linewidth were used to characterize the quality and the polytype structure of the SiC layers. A large enhancement in the peak intensity of the transverse optical and longitudinal optical phonon modes of SiC is observed for the Raman signal measured at the voids. In addition, scanning electron microscopy and atomic force microscopy were used to investigate the surface morphology of SiC layers.

Crystallization of thin polycrystalline PZT films on Si/SiO2/Pt substrates

This paper reports on a study of crystallization of thin lead zirconate-titanate films deposited on Si/SiO2/Pt substrates by RF magnetron sputtering at a low temperature and annealed at 540–580°C. In this temperature interval, one observes successively two first-order phase transitions: the low-temperature pyrochlore phase—perovskite-I phase and perovskite-I phase-perovskite-II phase transitions, which are accompanied by film volume shrinkage. The phase transformations have been studied by atomic force microscopy, scanning electron microscopy, X-ray diffraction and visual (optical) observation of the growth of islands of a new phase. It has been found that the dielectric parameters undergo substantial changes upon the transition from phase I to phase II. The origin of the observed effects has been discussed.

First-order phase transition through an intermediate state

The theory of first-order phase transitions in systems where the direct formation of nuclei of a new phase is inhibited for any reason, for example, because of the extremely high elastic energy, has been constructed using the example of the silicon-silicon carbide phase transition due to the chemical reaction with carbon monoxide. It has been shown that, in this case, the phase transition occurs through an intermediate state, which significantly promotes the formation of new-phase nuclei. For the silicon-silicon carbide phase transition, such an intermediate state is the “pre-carbide” state of silicon saturated with dilatation dipoles, i.e., pairs formed by a carbon atom and a silicon vacancy that are strongly attracted to each other. The model dependence of the potential energy of systems with an intermediate phase on the reaction coordinates has been investigated. The kinetics of transformation of the intermediate state into a new phase has been described.

Micro-Raman Mapping of 3C-SiC Thin Films Grown by Solid-Gas Phase Epitaxy on Si (111).

A series of 3C-SiC films have been grown by a novel method of solid–gas phase epitaxy and studied by Raman scattering and scanning electron microscopy (SEM). It is shown that during the epitaxial growth in an atmosphere of CO, 3C-SiC films of high crystalline quality, with a thickness of 20 nm up to few hundreds nanometers can be formed on a (111) Si wafer, with a simultaneous growth of voids in the silicon substrate under the SiC film. The presence of these voids has been confirmed by SEM and micro-Raman line-mapping experiments. A significant enhancement of the Raman signal was observed in SiC films grown above the voids, and the mechanisms responsible for this enhancement are discussed.

Electron-microscopic investigation of a SiC/Si(111) structure obtained by solid phase epitaxy

First results of the electron-microscopic investigation of thin silicon carbide (SiC) layers grown on silicon using a new method of solid phase epitaxy are presented. It is shown that, at the initial stage of epitaxial growth, a transition layer is formed which consists of various SiC polytypes. This layer occurs at the interface between the substrate and a single-crystalline SiC layer possessing predominantly a 3C polytype structure. It is established that pores with dimensions ranging from a fraction of micron to several dozen nanometers are formed in a near-surface layer of the silicon substrate, which favor the growth of epitaxial, weakly strained single-crystalline SiC layers.

Perturbation theory in the kinetics of first-order phase transitions

Perturbation theory is applied to the description of the kinetics of a first-order phase transition illustrated by thin film growth. A small parameter was chosen as the quantity 1/ic, where ic is the number of particles in a critical nucleus under maximum supersaturation in the course of the phase transition. Uniform convergence of the expansions obtained is reached through time renormalization. The cases of single- and multi-component condensation have been studied.

Self-organization in the formation of a nanoporous carbon material

A new mechanism of nanopore formation in carbon materials produced by the interaction of car-bides with chlorine is proposed. In essence, this method is the following. A series of nonlinear chemical reactions proceed in the course of a chemical interaction between chlorine and a carbide. If the external parameters, the component fluxes, and the diffusion rates satisfy certain relations, the self-organization process can occur. This process results in the creation of a periodic nanoporous structure in the carbon material formed. A mathematical model is proposed, the main characteristics of the process are calculated, and the restrictions on the parameters at which the formation of the porous structure becomes possible are found.

Structural characterization of GaN epilayers on silicon: Effect of buffer layers

Cross-sections of GaN/AlN/3C-SiC/Si(111) system have been studied by electron microscopy techniques. A nanometer thick buffer layer of silicon carbide on Si(111) substrate was formed using an original solid-phase epitaxy method. The subsequent layers of gallium nitride and aluminum nitride were grown by the method hydride-chloride vapor phase epitaxy. The resulting GaN layers display neither threading dislocations nor cracks on any scale. The main fraction of defects in GaN layers have the form of dislocation pileups that are localized at and oriented parallel to the GaN/AlN interface. The dislocation density in the obtained GaN layers is (1–2) × 109 cm−2, which corresponds to a minimum level reported in the available literature. The buffer AlN layer contains nanopores, which reduce the level of stresses at the GaN/AlN interface and thus almost completely inhibit the formation of threading dislocations.