Atomic Substitution Method Research Articles

Structural and elastoplastic properties of $$\upbeta $$ β - $$\hbox {Ga}_{2}\hbox {O}_{3}$$ Ga 2 O 3 films grown on hybrid SiC/Si substrates

Structural and mechanical properties of gallium oxide films grown on (001), (011) and (111) silicon substrates with a buffer layer of silicon carbide are studied. The buffer layer was fabricated by the atom substitution method, i.e., one silicon atom per unit cell in the substrate was substituted by a carbon atom by chemical reaction with carbon monoxide. The surface and bulk structure properties of gallium oxide films have been studied by atomic-force microscopy and scanning electron microscopy. The nanoindentation method was used to investigate the elastoplastic characteristics of gallium oxide, and also to determine the elastic recovery parameter of the films under study. The ultimate tensile strength, hardness, elastic stiffness constants, elastic compliance constants, Young’s modulus, linear compressibility, shear modulus, Poisson’s ratio and other characteristics of gallium oxide have been calculated by quantum chemistry methods based on the PBESOL functional. It is shown that all these properties of gallium oxide are essentially anisotropic. The calculated values are compared with experimental data. We conclude that a change in the silicon orientation leads to a significant reorientation of gallium oxide.

IR spectra of carbon-vacancy clusters in the topochemical transformation of silicon into silicon carbide

Using infrared (IR) spectroscopy and spectral ellipsometry, we experimentally confirmed the previously predicted mechanochemical effect of the stoichiometric composition disorder leading to the formation of carbon-vacancy structures in silicon carbide (SiC) films grown on silicon substrates by the atom substitution method. It was found that a band at 960 cm–1 in the IR spectra of SiC films on silicon, corresponding to “carbon-vacancy clusters” is always present in SiC films grown under pure carbon monoxide (CO) or in a mixture of CO with silane (SiH4) on Si substrates of different orientation and doping level and type. There is no absorption band in the region of 960 cm–1 in the IR spectra of SiC films synthesized at the optimum ratio of the CO and trichlorosilane (SiHCl3) gas pressures. The previously predicted mechanism of the chemical reaction of substitution of Si atoms for carbon by the interaction of gases CO and SiHCl3 on the surface of the silicon substrate, which leads to the formation of epitaxial layers of single-crystal SiC, is experimentally confirmed.

Structural properties and parameters of epitaxial silicon carbide films, grown by atomic substitution on the high-resistance (111) oriented silicon

The structure, composition and physical parameters of multilayer silicon carbide system synthesized by atom substitution method on the surface of low-dislocation single-crystal (111) oriented silicon were studied by Raman spectroscopy, ellipsometry, X-ray reflectometry, electron diffraction, IR spectroscopy, X-ray diffraction, AFM and profilometry. It was revealed that SiC films consist of layers, differing in SiyC composition, structure and thickness. The upper layers is a single-crystal 3C-SiC and the lower layers lying in depth of the substrate contain silicon carbide nanocrystals with a high degree of structure perfection and average size of 3–7 nm capable of preferential orientation (311), as well as large crystals (60–260 μm). The presence of cubic (3C-SiC) and hexagonal (mainly, 2H-SiC) polytypes with largest content of crystalline SiC phases in films with the composition closest to stoichiometric was established. In all samples there is carbon in super stoichiometric state, and its structure depends on the synthesis conditions.

Photoelectric characteristics of silicon carbide–silicon structures grown by the atomic substitution method in a silicon crystal lattice

Data obtained in an experimental study of the photoelectric characteristics of silicon–silicon carbide structures grown by the atomic substitution method on silicon (100) and (111) substrates are presented. It is found that the maximum sunlight conversion efficiency of a silicon–silicon carbide (silicon carbide–silicon) heterojunction is 5.4%. The theory of dilatation dipole formation upon synthesis by the atomic substitution method is used to account for the mechanism of electrical barrier formation at the silicon–silicon carbide interface.

X-ray reflectometry and simulation of the parameters of SiC epitaxial films on Si(111), grown by the atomic substitution method

The structure and composition of SiC nanolayers are comprehensively studied by X-ray reflectometry, IR-spectroscopy, and atomic-force microscopy (AFM) methods for the first time. SiC films were synthesized by the new method of topochemical substitution of substrate atoms at various temperatures and pressure of CO active gas on the surface of high-resistivity low-dislocation single-crystal n-type silicon (111). Based on an analysis and generalization of experimental data obtained using X-ray reflectometry, IR spectroscopy, and AFM methods, a structural model of SiC films on Si was proposed. According to this model, silicon carbide film consists of a number of layers parallel to the substrate, reminiscent of a layer cake. The composition and thickness of each layer entering the film structure is experimentally determined. It was found that all samples contain superstoichiometric carbon; however, its structure is significantly different for the samples synthesized at temperatures of 1250 and 1330°C, respectively. In the former case, the film surface is saturated with silicon vacancies and carbon in the structurally loose form reminiscent of HOPG carbon. In the films grown at 1330°C, carbon is in a dense structure with a close-to-diamond density.

Semipolar AlN on Si(100): Technology and properties

Initial stages of the semipolar AlN layer formation by chloride-hydride vapor phase epitaxy on a misoriented Si(100) substrate with a thin intermediate nano-SiC layer grown by atomic substitution method are investigated. It is found that once the growth rate of AlN layer on a nano-SiC/Si(100) substrate is about 0.02μm/h, the layer is formed in a polar direction. On the other hand, at the growth rate of 1μm/h the layer is formed in a semipolar direction. We propose the model of the semipolar AlN layer growth based on the formation of the special structure on the SiC layer synthesized by atomic substitution and on the possibility of the matching of the quasi-lattices of Al(20−23) and 3CSiC(100) planes assuming bonding of four atoms from the layer to four atoms of the 3CSiC quasi-lattice consisting of three lattice unit cells in one of the directions.

Photoemission studies of the vicinal SiC(100) 4° surface and the Cs/SiC(100) 4° interface

Photoemission studies of the electronic structure of the vicinal SiC(100) 4° surface, which was grown using a new substrate atom substitution method, and the Cs/SiC(100) 4° interface have been performed for the first time. The modification of spectra of the valence band and C 1s and Si 2p core levels in the process of formation of the Cs/SiC(100) 4° interface was analyzed. The suppression of the surface SiC state with a binding energy of 2.8 eV and the formation of a cesium-induced state with a binding energy of 10.5 eV were observed. The modification of the complex component structure in the spectrum of C 1s core level has been detected and examined for the first time. It was found that Cs adsorption on the vicinal SiC(100) 4° surface results in intercalation of graphene islands on SiC(100) 4° with Cs atoms.

Pyroelectric and piezoelectric responses of thin AlN films epitaxy-grown on a SiC/Si substrate

This paper presents the results of pyroelectric and piezoelectric studies of AlN films formed by chloride–hydride epitaxy (CHE) and molecular beam epitaxy (MBE) on epitaxial SiC nanolayers grown on Si by the atom substitution method. The surface topography and piezoelectric and pyroelecrtric responses of AlN films have been analyzed. The results of the study have shown that the vertical component of the piezoresponse in CHE-grown AlN films is more homogeneous over the film area than that in MBE-grown AlN films. However, the signal from the MBE-synthesized AlN films proved to be stronger. The inversion of the polar axis (polarization vector) on passage from MBE-grown AlN films to CHE-grown AlN films has been found experimentally. It has been shown that the polar axis in MBE-grown films is directed from the free surface of the film toward the Si substrate while, in CHE-grown films, the polarization vector is directed toward the free surface.

Determining polytype composition of silicon carbide films by UV ellipsometry

A universal ellipsometric model is proposed that describes the optical properties of silicon carbide (SiC) films grown on Si substrates by the method of atomic substitution due to a chemical reaction between the substrate and gaseous carbon monoxide. According to the proposed three-layer model, Si concentration decreases in a stepwise manner from the substrate to SiC film surface. The ellipsometric curves of SiC/Si(111), SiC/Si(100), and SiC/Si(110) samples grown under otherwise identical conditions have been measured in a 1.35–9.25 eV range using a VUV-VASE (J.A. Woollam Co.) ellipsometer with a rotating analyzer. Processing of the obtained spectra in the framework of the proposed model allowed the polytype composition of SiC films to be determined for the first time. It is established that SiC grown on Si(111) is predominantly cubic, while SiC on Si(110) is predominantly hexagonal (with cubic polytype admixture) and SiC on Si(100) has a mixed polytype composition.

The equilibrium state in the Si-O-C ternary system during SiC growth by chemical substitution of atoms

The equilibrium state in the silicon-carbon-oxygen (Si-O-C) ternary system has been calculated in the framework of the thermodynamics of chemical reactions. It is established that, in the practically important temperature interval of 1000°C < T < 1400°C, the system initially consisting of crystalline Si and gaseous CO tends toward an equilibrium state comprising a mixture of four solid phases (Si, C, SiC, and SiO2) and vapor mixture (predominantly of SiO, CO, Si, and CO2). Equilibrium partial pressures of all gases in the mixture have been calculated. An optimum regime of SiC film growth from Si by the method of atomic substitution is proposed, whereby only SiC phase is growing while SiO2 and C phases are not formed.

Nanoindentation and deformation properties of nanoscale silicon carbide films on silicon substrate

We propose a model to describe the microhardness of a nanoscale film-substrate system as a function of the depth of indenter penetration. The proposed model has been used to study the deformation characteristics of a nanometer-thick silicon carbide (SiC) grown on a silicon substrate by the method of atomic substitution. The microhardness of as-grown SiC film and a modified silicon layer has been determined. The SiC film thickness has been determined using the nanoindentation technique. The data of nanoindentation are in good agreement with the results of ellipsometric measurements.

CdS thin films on LiNbO 3 (1 0 4) and silicon (1 1 1) substrates prepared through an atom substitution method

CdS thin films on LiNbO 3 (1 0 4) and silicon (1 1 1) substrates were prepared through an atom substitution technique using cadmium nitrate as a reactant in an H 2S atmosphere at 230 °C. X−ray diffraction, scanning electron microscopy and transmission microscopy results indicate that the CdS film grows on LiNbO 3 oriented along the [0 0 1] axis in form of crystallized nanoplates, while that deposited on silicon forms randomly oriented nanoparticles. Investigation of the precursor thin film suggests that CdS forms from the O in the CdO precursor thin film being substituted by S from H 2S in the surrounding environment, which is designated as an atom substitution process. This novel method involving an atom substitution reaction between the CdO precursor thin film and its environment can provide a new low cost approach to the preparation of chalcogenide or other compound thin films. A schematic illustration and corresponding mechanism describing the details of this method are proposed.