We use real-time spectroscopic polarimetric observations of growth and a chemical model derived therefrom, to develop a method of growing dense, two-dimensional zinc oxide epitaxially on sapphire by metalorganic chemical vapor deposition. Particulate zinc oxide formed in the gas phase is used to advantage as the deposition source. Our real-time data provide unequivocal evidence that: a seed layer is required; unwanted fractions of ZnO are deposited; but these fractions can be removed by cycling between brief periods of net deposition and etching. The transition between deposition and etching occurs with zinc precursor concentrations that only differ by 13%. These processes are understood by considering the chemistry involved.
BaZn2As2 is expected for a good p-type semiconductor and has two crystalline phases of an orthorhombic alpha phase and a higher-symmetry tetragonal beta phase. Here, we report high-quality epitaxial films of the tetragonal beta-BaZn2As2 were grown on single-crystal MgO (001) substrates by a reactive solid-phase epitaxy technique. Out-of-plane and in-plane epitaxial relationships between the film and the substrate were BaZn2As2 (00l)//MgO (001) and BaZn2As2 [200]//MgO [200], respectively. The full-widths at half maximum were 0.082o for a 008 out-of-plane rocking curve and 0.342o for a 200 in-pl…
Variable resistors were constructed from epitaxial SrRuO3 (SRO), La0.67Sr0.33MnO3 (LSMO) and SrTiO3 layers with perovskite crystal structure. Each layer was patterned separately by lithographic methods. Optimized wet chemical etchants and several polishing steps in organic solvents allowed good epitaxy of subsequent layers, comparable to epitaxy on pristine substrates. Periodate as the oxidizing agent for SRO and iodide with ascorbic acid as the reducing agents for LSMO were used to attack these chemically resistant oxides. The final devices changed their conductance in a similar manner to pre…
We present an innovative method of selective epitaxial growth of few layers graphene (FLG) on a pre-patterned SiC substrate. The methods involves, successively, the sputtering of a thin AlN layer on top of a mono-crystalline SiC substrate and, then, patterning it with e-beam lithography (EBL) and wet etching. The sublimation of few atomic layers of Si from the SiC substrate occurs only through the selectively etched AlN layer. The presence of the Raman G-band at ~1582 cm-1 in the AlN-free areas is used to validate the concept, it gives absolute evidence of the selective FLG growth.
The exploration of new catalysts for the vapor-liquid-solid (VLS) synthesis of one-dimensional (1-D) materials promises to yield new morphologies and functionality. Here, we show, for the model ZnO system, that this possible using a semiconductor (Ge) catalyst. In particular, two unusual morphologies are described: twisted nanowires and twisted nanotubes, in addition to the usual straight nanowires. The twisted nanotubes show large hollow cores and surprisingly high twisting rates (up to 9o/μm), which cannot be easily explained through the Eshelby twist model. A combination of ex situ and in s…
We demonstrate hydrogen assisted growth of high quality epitaxial graphene on the C-face of 4H-SiC. Compared with the conventional thermal decomposition technique, the size of the growth domain by this method is substantially increased and the thickness variation is reduced. Based on the morphology of epitaxial graphene, the role of hydrogen is revealed. It is found that hydrogen acts as a carbon etchant. It suppresses the defect formation and nucleation of graphene. It also improves the kinetics of carbon atoms via hydrocarbon species. These effects lead to increase of the domain size and the…
The direct liquid injection chemical vapor deposition (DLI-CVD) technique has been used for the growth of cobalt ferrite (CFO) films on (100)-oriented MgAl$_2$O$_4$ (MAO) substrates. Smooth and highly epitaxial cobalt ferrite thin films, with the epitaxial relationship $\mathrm{MAO} (100)\:[001] \parallel \mathrm{CFO} (100)\:[001]$, are obtained under optimized deposition conditions. The films exhibit bulk-like structural and magnetic properties with an out-of-plane lattice constant of $8.370\;\mathrmÅ$ and a saturation magnetization of $420\;\mathrm{kA/m}$ at room temperature. The Raman spect…
Positively charged zinc oxide clusters ZnnOm (up to n = 16, m <= n) of various stoichiometry were synthesized in the gas phase by excimer ArF laser ablation of a ZnO target and investigated using time-of-flight mass spectrometry. Depending on ablation conditions, either metal rich or stoichiometric clusters dominate in the mass spectrum. When the irradiated target surface is fairly fresh, the most abundant clusters are metal rich with Zn(n+1)On and Zn(n+3)On being the major series. The stoichiometric clusters are observed with an etched ablated surface. The magic numbers at n = 9, 11 and 15 in…
Mathematical model that allows for direct tracking of the homoepitaxial crystal growth out of the window etched in the solid, pre-deposited layer on the substrate is described. The growth is governed by the normal (to the crystal-vapor interface) flux from the vapor phase and by the interface diffusion. The model accounts for possibly inhomogeneous energy of the mask surface and for strong anisotropies of crystal-vapor interfacial energy and kinetic mobility. Results demonstrate that the motion of the crystal-mask contact line slows down abruptly as radius of curvature of the mask edge approac…
Thick, high quality 4H-SiC epilayers have been grown in a vertical hot-wall chemical vapor deposition system at a high growth rate on (0001) 80 off-axis substrates. We discuss the use of dichlorosilane as the Si-precursor for 4H-SiC epitaxial growth as it provides the most direct decomposition route into SiCl2, which is the predominant growth species in chlorinated chemistries. A specular surface morphology was attained by limiting the hydrogen etch rate until the system was equilibrated at the desired growth temperature. The RMS roughness of the grown films ranged from 0.5-2.0 nm with very fe…
We report the growth of high-quality triangular GaN nanomesas, 30-nm thick, on the C-face of 4H-SiC using nano selective area growth (NSAG) with patterned epitaxial graphene grown on SiC as an embedded mask. NSAG alleviates the problems of defective crystals in the heteroepitaxial growth of nitrides, and the high mobility graphene film can readily provide the back low-dissipative electrode in GaN-based optoelectronic devices. The process consists in first growing a 5-8 graphene layers film on the C-face of 4H- SiC by confinement-controlled sublimation of silicon carbide. The graphene film is t…
SiC epitaxial films grown in an inverted chimney CVD reactor are analyzed and compared for growth rates, doping concentration and surface morphology using silane-propane-hydrogen and dichlorosilane (DCS)-propane-hydrogen chemistry systems. A general 1-D analytical model is presented to estimate the diffusivity of precursor gases, boundary layer thickness and growth rates for both gas systems. Decomposition of precursor gases into Si growth species is investigated by a commercial simulation tool, Virtual Reactor (VR). DCS suppresses the formation of elemental Si at lower pressures, reduces prec…
A major challenge for ferroelectric devices is the depolarization field, which competes with and often destroys long-range polar order in the limit of ultrathin films. Recent theoretical predictions suggest a new class of materials, termed hyperferroelectics, that should be robust against the depolarization field and enable ferroelectricity down to the monolayer limit. Here we demonstrate the epitaxial growth of hexagonal LiZnSb, one of the hyperferroelectric candidate materials, by molecular-beam epitaxy on GaSb (111)B substrates. Due to the high volatility of all three atomic species, we fin…
Etching of elemental layers in oxide molecular beam epitaxy by O2-assisted formation and evaporation of their volatile suboxide: The examples of Ga and Ge
A major issue in the development of the technology of nitride based materials is the choice of substrate. The structural and optical properties of the layers are intimately connected to the substrate material used in the epitaxial growth. Key issues include lattice matching of substrate and epitaxial layer and the difference in the thermal expansion between the substrate and epitaxial layer. Due to the extremely high vapor pressure of nitrogen over Gallium Nitride (GaN), pure GaN substrate are very difficult to produce and currently almost all nitride-based device are fabricated by hetero-epit…
We discuss unreported transitions of oxidized GaAs surfaces between (super)hydrophilic and hydrophobic states when stored in ambient conditions. Contact angles higher than 90deg and high adhesive force were observed for several air-aged epitaxial samples grown under different conditions as well as on epi-ready wafers. Regardless of the morphologies of the surface, superhydrophilicity of oxygen-plasma treated samples was observed, an effect disappearing with storage time. Reproducible hydrophobicity was likewise observed, as expected, after standard HCl surface etching. The relation between sur…
Nanoporous materials represent a versatile solution for a number of applications ranging from sensing, energy applications, catalysis, drug delivery, and many others. The synergy between the outstanding properties of graphene with a three-dimensional porous structure, circumventing the limits of its 2D nature, constitutes therefore a breakthrough for many fields. We report the first three-dimensional growth of epitaxial graphene on a porousified crystalline 4H-SiC(0001). The wafer porosification is performed via a sequence of metal-assisted photochemical and photoelectrochemical etching in hyd…
Micro-solid oxide fuel cells based on thin films have strong potential for use in portable power devices. However, devices based on silicon substrates typically involve thin-film metallic electrodes which are unstable at high temperatures. Devices based on bulk metal substrates overcome these limitations, though performance is hindered by the challenge of growing state-of-the-art epitaxial materials on metals. Here, we demonstrate for the first time the growth of epitaxial cathode materials on metal substrates (stainless steel) commercially supplied with epitaxial electrolyte layers (1.5 {um (…
We have investigated the growth of BaTiO3 thin films deposited on pure and 1% Nb-doped SrTiO3(001) single crystals using atomic oxygen assisted molecular beam epitaxy (AO-MBE) and dedicated Ba and Ti Knudsen cells. Thicknesses up to 30 nm were investigated for various layer compositions. We demonstrate 2D growth and epitaxial single crystalline BaTiO3 layers up to 10 nm before additional 3D features appear; lattice parameter relaxation occurs during the first few nanometers and is completed at »10 nm. The presence of a Ba oxide rich top layer that probably favors 2D growth is evidenced for wel…
Pulsed laser deposition, a non-equilibrium thin-film growth technique, was used to stabilize metastable tetragonal iron sulfide (FeS), the bulk state of which is known as a superconductor with a critical temperature of 4 K. Comprehensive experiments revealed four important factors to stabilize tetragonal FeS epitaxial thin films: (i) an optimum growth temperature of 300 °C followed by thermal quenching, (ii) an optimum growth rate of ~7 nm/min, (iii) use of a high-purity bulk target, and (iv) use of a single-crystal substrate with small in-plane lattice mismatch (CaF2). Electrical resistivity …
In order to improve the performance of existing technologies based on single crystal diamond grown by chemical vapour deposition (CVD), and to open up new technologies in fields such as quantum computing or solid state and semiconductor disc lasers, control over surface and bulk crystalline quality is of great importance. Inductively coupled plasma (ICP) etching using an Ar/Cl gas mixture is demonstrated to remove sub-surface damage of mechanically processed surfaces, whilst maintaining macroscopic planarity and low roughness on a microscopic scale. Dislocations in high quality single crystal …
