In situ growth of nano-structures by metal-organic vapour phase epitaxy

Using spontaneous self-organization effects is an efficient way to produce nano-structures, as for instance quantum wires and quantum dots. This article is focused on the strain-induced self-organization, or “self-assembling” effect, producing quantum dots. Particularly the following aspects will be addressed: (i) the phenomenology of the 2D–3d morphology transition, (ii) the effects of materials choices and growth conditions on density, size and homogeneity of dots, and (iii) manipulations to get laterally aligned and vertically stacked dot structures.     

InGaN growth with various InN mole fractions on m-plane ZnO substrate by metalorganic vapor phase epitaxy

We have demonstrated In_xGa_1−xN epitaxial growth with InN mole fractions of x=0.07 to 0.17 on an m-plane ZnO substrate by metalorganic vapor phase epitaxy for the first time. The crystalline quality of the epilayers was found to be much higher than that of epilayers grown on a GaN template on an m-plane SiC substrate.     

Dependence of InP and GaAs chemical beam epitaxy growth rate on substrate orientations; applications to selective area epitaxy

In order to optimize the shape of chemical beam epitaxy (CBE) selective area growth, growth rates on (100), (111)B, (111)A and (110) substrate orientations have been examined for GaAs and InP materials. (111)B GaAs growth rate appears to be drastically enhanced at low V/III ratio, which has been applied to grow selective GaAs patterns limited by vertical sidewalls. Concerning InP, high growth rates were obtained on all orientations. This was used to perfectly fill a rectangular groove by selective embedded InP growth.     

Thermal decomposition of di-tertiarybutyl selenide and dimethylzinc in a metalorganic vapour phase epitaxy reactor

The thermal decomposition of di-tertiarybutyl selenide (DtBSe), both alone and in the presence of dimethylzinc (DMZn), was investigated using “ex-situ” Fourier transform infrared (FTIR) absorption spectroscopy in a low-pressure metalorganic vapour phase epitaxy (LP-MOVPE) reactor. The decomposition of DtBSe alone, yields isobutene as the major product, with a much smaller proportion of isobutane detected. Pyrolysis of DMZn in dihydrogen in the presence of DtBSe is very similar to pyrolysis of DMZn alone in dihydrogen with methane the exclusive product. This indicates that co-pyrolysis of the DMZn/DtBSe mixture occurs via radical attack by H on DMZn and largely independent pyrolysis of DtBSe via a β-hydrogen elimination reaction. Traces of the intermediate tertiarybutyl selenol (^tBuSeH) were also detected. The small difference observed in the decomposition behaviour of the DtBSe-DMZn mixture in a dihydrogen compared to a helium ambient further indicate that the pyrolysis processes are independent. These conclusions are supported by PM3 semi-empirical molecular orbital calculations, which indicate that the most likely pathway for unimolecular dissociation of DtBSe is via β-hydrogen elimination with C---Se bond homolysis only likely to be an effective competing mechanism at higher growth temperatures and reactor pressures.     

Growth of ZnTe layers on (111) GaAs substrates by metalorganic vapor phase epitaxy

ZnTe layers were grown on (111) GaAs substrates by metalorganic vapor phase epitaxy using dimethylzinc and diethyltelluride as the source materials. X-ray diffraction analysis revealed that epitaxial ZnTe layers can be obtained on (111) GaAs substrates. X-ray rocking curves, Raman spectroscopy, and photoluminescence measurements showed that the crystal quality of ZnTe layers depends on the substrate temperature during the growth. A high-crystalline quality (111) ZnTe heteroepitaxial layer with strong near-band-edge emission at 550 nm was obtained at a substrate temperature of 440 °C.     

Platinum-catalyst-assisted metalorganic vapor phase epitaxy of InN

This paper reports the first attempt of the Pt-catalyst-assisted MOVPE growth of InN. In order to enhance NH₃ decomposition at a relatively low growth temperature (～550 °C), Pt is used as a catalyst. The catalyst is installed in the NH₃ introduction tube in the MOVPE reactor and the tube is located just above the susceptor to be heated. Compared with InN films grown without the catalyst, the samples grown with Pt catalyst show improved electrical properties; a carrier concentration in the order of 10¹⁸ cm^?3 and a Hall mobility as high as 1350 cm²/Vs are obtained. The crystalline quality is also improved by employing the catalyst and a tilt fluctuation as low as 8.6 arcmin is obtained for a sample grown on a GaN/sapphire template. It is confirmed that for InN films grown at 550 °C with Pt catalyst, the electrical and crystallographic properties are also improved with increase in thickness. These results indicate that the growth at around 550 °C with the Pt catalyst is performed under the circumstances where NH₃ is effectively decomposed, whereas the deterioration of InN during growth is significantly suppressed.     

Metalorganic vapour phase epitaxy growth of InGaAs/GaAs strained layer quantum wells beyond the pseudomorphic limit

Low pressure metalorganic vapour phase epitaxy growth and characterization of strained InGaAs/GaAs quantum well structures beyond the pseudomorphic limit are reported. Photoluminescence and X-ray diffraction measurements of these structures show considerable gallium/indium interdiffusion at the interfaces and partial strain relaxation in the layers.     

Photo-assisted growth of ZnTe by metalorganic chemical vapour deposition

The metalorganic chemical vapour deposition (MOCVD) photo-assisted growth of ZnTe using a xenon lamp has been performed at atmospheric pressure under hydrogen as a carrier gas. Epitaxial growth was achieved on (100) GaAs, (100) GaSb and (100) ZnTe substrates with diethylzinc (DEZn) and diethyltellurium (DETe) as precursors. We have studied the growth rate as a function of the growth temperature, the partial pressure of precursors, the inlet partial pressure ratio R = VI/II, the light intensity and the energy of the irradiating photons. A growth rate enhancement has been observed for illuminated layers grown on GaAs and ZnTe substrates in comparison with those grown without illumination. We have not observed any measurable enhancement for layers grown onto (100) GaSb. The growth rate as a function of the light intensity increases for intensities higher than 20 mW / cm² and saturates for P > 120 mW / cm². We relate the growth rate enhancement to irradiating photons with an energy higher than the band gap of ZnTe at the growth temperature.     

Stability of GaAs oxide under metalorganic molecular beam epitaxy process

Well-defined oxide of GaAs can be used as a mask material for selective-area metalorganic molecular beam epitaxy (MOMBE) of GaAs. In this study, the reaction between triethylgallium (TEG) and the GaAs oxide layer was studied using a quadrupole mass spectrometer (QMS) and an atomic force microscope (AFM). Results of the QMS observation showed that TEG was reflected on the GaAs oxide surface until the start of desorption of the GaAs oxide, and the GaAs oxide layer was desorbed from the wafer after a large time delay from the start of TEG supply. AFM images showed that many holes appeared on the GaAs oxide surface during the desorption of the GaAs oxide. The effect of incident TEG upon the stability of the GaAs oxide mask is discussed.     

Surface diffusion kinetics of GaAs and AlAs metalorganic vapor-phase epitaxy

We have investigated the surface kinetics during metalorganic vapor-phase epitaxy (MOVPE), using high-vacuum scanning tunneling microscopy (STM) observation of two-dimensional (2D) nuclei and denuded zones. Using Monte Carlo simulations based on the solid-on-solid model, from 2D nucleus densities we estimated the surface diffusion coefficients of GaAs and AlAs to be 2 × 10⁻⁶ and 1.5 × 10⁻⁷ cm²/s at 530°C, and the energy barriers for migration to be 0.62 and 0.8 eV, respectively. The 2D nucleus size in the [110] direction was about two times larger than that in the [ 10] direction. The size anisotropy is caused primarily by a difference in the lateral sticking probability (P_s) between steps along the [ 10] direction (A steps) and steps along the [110] direction (B steps). The P_s ratio was estimated to be more than 3:1. Denuded zone widths on upper terraces were 2 ± 0.5 times wider than those on lower terraces. This showed that P_s at descending steps was 10 to 3 × 10² times larger than P_s at ascending steps.     

GaN/GaAs(1 0 0) superlattices grown by metalorganic vapor phase epitaxy using dimethylhydrazine precursor

Superlattices of cubic gallium nitride (GaN) and gallium arsenide (GaAs) were grown on GaAs(1 0 0) substrates using metalorganic vapor phase epitaxy (MOVPE) with dimethylhydrazine (DMHy) as nitrogen source. Structures grown at low temperatures with varying layer thicknesses were characterized using high resolution X-ray diffraction and atomic force microscopy. Several growth modes of GaAs on GaN were observed: step-edge, layer-by-layer 2D, and 3D island growth. A two-temperature growth process was found to yield good crystal quality and atomically flat surfaces. The results suggest that MOVPE-grown thin GaN layers may be applicable to novel GaAs heterostructure devices.     

Controlled formation of GaAs pn junctions during hydride vapor phase epitaxy of GaAs

Interface formation in HVPE GaAs was investigated through the growth of multilayer test structures with alternately doped and undoped layers and subsequently, pn diode devices. Two growth procedures were used in device formation: continuous growth of all layers, and a growth interruption with simultaneous equilibration of new gas flows for subsequent layers. These junctions were probed using SIMS to determine the doping profiles and impurity incorporation near the interfaces and throughout the bulk of the layers. The junction I–V characteristics were measured with and without illumination to correlate the junction properties with the measured photovoltaic performance. It was discovered that the use of a growth interruption leads to doping transitions up to 6x narrower than samples grown without interruption. The growth interruption leads to an interfacial Si spike that is not observed in the uninterrupted samples during growth of GaAs doped with silane. This spike does not appear to degrade either the material quality or pn junction quality, and pn diodes grown with interruption have exhibited enhanced device efficiencies under solar simulation compared with devices grown without interruption, reaching efficiencies of up to 9.2% without the use of antireflective coatings.     

Fabrication of GaAs quantum wires by metalorganic molecular beam epitaxy and their optical properties

We have grown GaAs quantum wires having nominal cross-sectional dimensions of 20×20 nm² buried in AlGaAs layers, by lateral metalorganic molecular beam epitaxy on the terraced sidewalls of mesa-grooved ( ) substrates. In the photoluminescence spectrum of this sample at 77 K, a dominant emission has been observed at a peak wavelength of 780 nm which corresponds to a blue shift of 80 meV from the GaAs bulk transition. Emission spectroscopy from different positions and imaging by cathodoluminescence have demonstrated that this emission was generated from the sidewalls, indicating that it originates from the quantum wire.     

Kinetics of dopant incorporation in GaAs grown by organometallic vapor-phase epitaxy

A diffusive capture reaction of dopant atoms by relevant host atoms, via the Rideal–Eley mechanism, in GaAs grown by organometallic vapor-phase epitaxy is shown to result in the dopant concentration in the crystal acquiring a dependence on p_Ga (which is proportional to the growth rate) in agreement with data on S_As, Zn_Ga, and Si_Ga where p_Ga is the partial pressure of trimethylgallium in the input gas stream.     

Hydrogen and nitrogen ambient effects on epitaxial growth of GaN by hydride vapour phase epitaxy

This study presents the influence of the composition of the carrier gas on the growth of GaN by HVPE. Since no hydrogen is introduced in the vapour phase, the deposition is expected to be controlled by Cl desorption in the form of GaCl₃, as has been proposed for GaAs. However, our published model predicts much lower growth rates than those observed. We can account for both the observed parasitic deposition and GaN growth rate if we assume that GaCl₃ is not at its equilibrium pressure in the deposition zone and where nucleation takes place on the walls as well as on the substrate. This yields a high rate of parasitic nucleation even though the nominal supersaturation is vanishing small. Very little growth takes place on the substrate where the equilibrium pressure of GaCl₃ is reached. We describe similar experiments performed with a H₂/N₂ mixture as the carrier gas. In this case, we expect GaN deposition to be controlled by desorption of Cl as HCl, which is known as the H₂ mechanism. It is speculated that the results show the existence of a new growth mechanism.     

Metalorganic vapour phase epitaxy of mercury cadmium telluride

The present review covers the fundamental factors involved in the the metalorganic vapour phase epitaxy of mercury cadmium telluride. In addition recent significant developments which could have an important influence on the future of the technology are discussed. The topics covering these developments include growth techniques, photoepitaxy, in-situ monitoring, “new” precursors, substrates and layer quality. The review highlights the advanced nature of the technology, which inspite of currently-addressed limitations has an important future.     

Deep hole trap level of nitrogen-doped ZnSe grown by metalorganic vapor phase epitaxy

We investigated the hole trap level of nitrogen-doped ZnSe grown by a metalorganic vapor phase epitaxy method. The deep level transient spectroscopy (DLTS) signal and the C-V profile were measured to obtain the trap level, the capture cross section and the trap concentration. A deep hole trap level of about 1 eV from a valence band (labeled TLIS) was extracted from the tail of the DLTS peak. The distributions of the capture cross section and the trap level of the samples for different growth conditions were drawn in a figure to investigate the validity of the resolution of the DLTS signal. The origin of TLIS is thought to be in relation to the ionized acceptor or the charged acceptor-like localized defects.     

Electro-optical properties of InGaAs layers grown by hydride vapour phase epitaxy

A series of epitaxial layers of the InGaAs alloy were deposited on (001) oriented InP substrates by using hydride VPE technique. The layers were characterized by Double Crystal Diffractometry (DCD), Photoluminescence (PL), Hall effect and Capacitance-Voltage (C-V) measurements. The growth parameters and the quality of the grown layers are discussed on the basis of electrical and structural data analysis.     

A theoretical treatment of GaAs growth by vapour phase transport for {001} orientation

The normal growth rate of a {001} face has been theoretically studied; by considering either direct fixation of gallium arsenide molecules, or formation of intermediate surface compounds. From the theory of rate processes, it appears that experimental results can be interpreted by considering the reactions of desorption of the chlorine atoms adsorbed on surface as limiting the growth. A theoretical expression of the normal growth rate based on desorption by hydrogen has been performed. The descending portions of the curves with decreasing substrate temperature or increasing partial pressure of gallium monochloride, appear as due to an increasing coverage of surface with gallium monochloride molecules. Absolute theoretical values agree with experimental published measures, except for the weakest substrate temperatures. This disagreement may be due to the possibility of desorption of two chlorine atoms by gallium monochloride and formation of gallium trichloride molecules.     

Carbon reduction and antimony incorporation in InGaAsSb films grown by metalorganic molecular beam epitaxy using tris-dimethylaminoantimony

InGaAsSb layers nearly lattice-matched to InP were grown by metalorganic molecular beam epitaxy using tris-dimethylaminoantimony (TDMASb). Secondary-ion mass spectroscopy measurements revealed that TDMASb is useful not only as an Sb source but also as an additive that reduces the incorporation of C into the film from group-III metalorganic sources. In the room-temperature photoluminescence spectrum, the incorporation of Sb into InGaAs shifted the peak wavelength from 1.66 to 1.75 μm and, simultaneously, the peak intensity of InGaAsSb became more than twice that of InGaAs.