Numerical study for diffusion processes in dissolution and growth of heterostructures formed by LPE. Part I. Isothermal conditions

The paper deals with computer simulation for growth and dissolution of ternary CdHgTe compounds in liquid-phase epitaxy (LPE) systems. The mathematical model accounts for the matter transport in both solid and liquid phases and the equilibrium phase diagram. The study displays the effect of solid-state diffusion on compositional grading at the substrate-layer boundary, on the formation of concentration distribution in both phases and on interface motion. The simulation has been done for isothermal conditions.     

Study of Ge epitaxial growth on Si substrates by cluster beam deposition

Ge epitaxial layers with reasonable quality were grown on Si (1 1 1) substrates by cluster beam deposition (CBD) process. Molecular dynamics study of the low energy Ge clusters deposition process utilizing the Stillinger–Weber two- and three-body interaction potentials was carried out to compare the experimental results. Both experimental and simulation results prove that the substrate temperature plays a dominant role in the epitaxial growth of Ge films in CBD process. The influence mechanisms of temperature are discussed.     

The influences of supersaturation on LPE growth of GaN single crystals using the Na flux method

The dependency of LPE growth rate and dislocation density on supersaturation in the growth of GaN single crystals in the Na flux was investigated. When the growth rate was low during the growth of GaN at a small value of supersaturation, the dislocation density was much lower compared with that of a substrate grown by the Metal Organic Chemical Vapor Deposition method (MOCVD). In contrast, when the growth rate of GaN was high at a large value of supersaturation, the crystal was hopper including a large number of dislocations. The relationship between the growth conditions and the crystal color in GaN single crystals grown in Na flux was also investigated. When at 800 °C the nitrogen concentration in Na–Ga melt was low, the grown crystals were always tinted black. When the nitrogen concentration at 850 °C was high, transparent crystals could be grown.     

Enhanced growth rates and reduced parasitic deposition by the substitution of Cl2 for HCl in GaN HVPE

The main limitation in the application of hydride vapor phase epitaxy for the large scale production of thick free-standing GaN substrates is the so-called parasitic deposition, which limits the growth time and wafer thickness by blocking the gallium precursor inlet. By utilizing Cl₂ instead of the usual HCl gas for the production of the gallium chlorine precursor, we found a rapid increase in growth rate from ∼80 to ∼400 μm/h for an equally large flow of 25 sccm. This allowed us to grow, without any additional optimization, 1.2 mm thick high quality GaN wafers, which spontaneously lifted off from their 0.3° mis-oriented GaN on sapphire HCl-based HVPE templates. These layers exhibited clear transparencies, indicating a high purity, dislocation densities in the order of 10⁶ cm⁻², and narrow rocking curve XRD FWHMs of 54 and 166 arcsec in for the 0002 and 101−5 directions, respectively.     

The incorporation behavior of arsenic and antimony in GaAsSb/GaAs grown by solid source molecular beam epitaxy

GaAsSb ternary epitaxial layers were grown on GaAs (0 0 1) substrate in various Sb₄/As₂ flux ratios by solid source molecular beam epitaxy. The alloy compositions of GaAs_1−ySb_y were inferred using high-resolution X-ray symmetric (0 0 4) and asymmetric (2 2 4) glance exit diffraction. The non-equilibrium thermodynamic model is used to explain the different incorporation behavior between the Sb₄ and As₂ under the assumption that one incident Sb₄ molecule produces one active Sb₂ molecule. It is inferred that the activation energy of Sb₄ dissociation is about 0.46 eV. The calculated results for the incorporation efficiency of group V are in good agreement with the experimental data.     

Method for HVPE growth of thick crack-free GaN layers

Twenty-five micrometer thick GaN was grown with hydride vapor phase epitaxy (HVPE) on metal-organic chemical vapor deposition (MOCVD) grown templates on sapphire substrates with the gallium treatment step (GTS) technique with varying buffer layer thickness. The samples are studied with atomic force microscopy (AFM), etching and scanning electron microscopy (SEM), photo-luminescence (PL), X-ray diffraction (XRD) and optical microscopy. The results show that the thickness of the buffer layer is not important for the layer quality once the growth in MOCVD starts to make the transition from 3D growth to 2D growth and HVPE continues in the same growth mode. We show that the MOCVD templates with GTS technique make excellent templates for HVPE growth, allowing growth of GaN without cracks in either sapphire or GaN.     

High-temperature conductivity in chemical bath deposited copper selenide thin films

This paper reports high-temperature (305–523 K) electrical studies of chemical bath deposited copper (I) selenide (Cu_2−xSe) and copper (II) selenide (Cu₃Se₂) thin films. Cu_2−xSe and Cu₃Se₂ have been prepared on glass substrates from the same chemical bath at room temperature by controlling the pH. From X-ray diffraction (XRD) profiles, it has been found that Cu_2−xSe and Cu₃Se₂ have cubic and tetragonal structures, respectively. The composition of the chemical constituent in the films has been confirmed from XRD data and energy-dispersive X-ray analysis (EDAX). It has been found that both phases of copper selenide thin films have thermally activated conduction in the high-temperature range. In this paper we also report the variation of electrical parameters with film thickness and the applied voltage.     

Structural and optical properties of CuGaSe2 layers grown by the hot wall epitaxy method

Copper gallium selenide (CuGaSe₂, CGS) layers were grown by the hot wall epitaxy method. The optimum temperatures of the substrate and source for growth turned out to be 450 and 610 °C, respectively. The CGS layers were epitaxially grown along the 1 1 0 direction and consisted of Ga-rich components indicating the slight stoichiometric deviations. Based on the absorption measurement, the band-gap variation of CGS was well interpreted by the Varshni's equation. The band-gap energies at low temperatures, however, had a higher value than those of other CGS. It suggests that the band-gap increase is influenced by the slightly Ga-rich composition. From the low-temperature photoluminescence experiment, sharp and intensive free- and bound-exciton peaks were observed. By analyzing these emissions, a band diagram of the observed optical transitions was obtained. From the solar cell measurement, an 11.17% efficiency on the n-CdS/p-CGS junction was achieved.     

Enlarged ferromagnetic hysteresis in InMnP:Be epilayers formed by thermal diffusion using MBE-grown Mn/InP:Be bilayers

The p-type InMnP:Be epilayers, which were prepared by thermal diffusion of Mn through in-situ deposition of Mn layer using molecular beam epitaxy (MBE) onto MBE-grown InP:Be epilayers and subsequent in-situ annealing at 300–350 °C, were investigated. InMnP:Be epilayers prepared by the above sequence clearly showed the Mn-related emission band at 1.1–1.2 eV, which indicates the effective incorporation of Mn²⁺ ions into the host layer InP:Be. The samples demonstrated very large ferromagnetic hysteresis loops with enhanced coercivity, and the ferromagnetic-to-paramagnetic transition of the samples was observed to occur at ∼85 K. These results suggest that InP-based ferromagnetic semiconductor layers having enhanced ferromagnetism can be effectively formed by the above-mentioned sequential in-situ processes.     

Solvothermal growth of ZnO

The growth of ZnO single crystals and crystalline films by solvothermal techniques is reviewed. Largest ZnO crystals of 3 inch in diameter are grown by a high-pressure medium-temperature hydrothermal process employing alkaline-metal mineralizer for solubility enhancement. Structural, thermal, optical and electrical properties, impurities and annealing effects as well as machining are discussed. Poly- and single-crystalline ZnO films are fabricated from aqueous and non-aqueous solutions on a variety of substrates like glass, (100) silicon, -Al₂O₃, Mg₂AlO₄, ScAlMgO₄, ZnO and even some plastics at temperatures as low as 50 °C and ambient air conditions. Film thickness from a few nanometers up to some tens of micrometers is achieved. Lateral epitaxial overgrowth of thick ZnO films on Mg₂AlO₄ from aqueous solution at 90 °C was recently developed. The best crystallinity with a full-width half-maximum from the (0002) reflection of 26 arcsec has been obtained by liquid phase epitaxy employing alkaline-metal chlorides as solvent. Doping behavior (Cu, Ga, In, Ge) and the formation of solid solutions with MgO and CdO are reported. Photoluminescence and radioluminescence are discussed.     

Polarization induced 2D hole gas in GaN/AlGaN heterostructures

The generation of high density 2D hole gases is crucial for further progress in the electronic and optoelectronic nitride devices. In this paper, we present systematic theoretical studies of Mg-doped GaN/AlGaN gated heterostructures and superlattices. Our calculations are based on a self-consistent solution of the multiband k.p Schrödinger and Poisson equation and reveal that the hole 2D sheet density is mainly determined by the polarization induced interface charges. For an aluminium concentration of 30%, the induced hole density in the heterostructure can reach values up to 1.5×10¹³ cm⁻². In the GaN/AlGaN superlattices, the hole sheet density increases with the superlattice period and saturates for a period of 40 nm at a value of 1.5×10¹³ cm⁻².     

Understanding the cubic AlN growth plane from first principles

The structure of clean and reconstructed cubic AlN (0 0 1) surfaces has been investigated from first principles. In the nitrogen rich part of the phase diagram, a nitrogen termination has been found to be favored. Under aluminum-rich conditions, a contracted adlayer of Al-atoms on top of an Al-termination is favored.     

Liquid phase epitaxy (LPE) of GaN on c- and r-faces of AlN substrates

We present the optical properties of MBE-grown GaAs–AlGaAs core–shell nanowires (NWs) grown on anodized-aluminum-oxide (AAO) patterned-Si (1 1 1) substrate using photoluminescence and Raman scattering spectroscopy. The GaAs NWs were grown via the vapor–liquid–solid method with Au-nanoparticles as catalysts. Enhancement in emission of at least an order of magnitude was observed from the GaAs–AlGaAs core–shell NWs as compared to the bare GaAs NWs grown under similar conditions, which is an indication of improved radiative efficiency. The improvement in radiative efficiency is due to the passivating effect of the AlGaAs shell. Variation in bandgap emission energy as a function of temperature was analyzed using the semi-empirical Bose–Einstein model. Results show that the free exciton energy of the GaAs core–shell agrees well with the known emission energy of zinc blende (ZB) bulk GaAs. Further analysis on the linear slope of the temperature dependence curve of photoluminescence emission energy at low temperatures shows that there is no difference between core–shell nanowires and bulk GaAs, strongly indicating that the grown NWs are indeed predominantly ZB in structure. The Raman modes show downshift and asymmetrical broadening, which are characteristic features of NWs. The downshift is attributed to lattice defects rather than the confinement or shape effect.     

Growth of AlN films on SiC substrates by RF-MBE and RF-MEE

Epitaxial AlN films have been grown on SiC substrate by molecular beam epitaxy (MBE) and migration-enhanced epitaxy (MEE) using radio frequency (RF) plasma-excited nitrogen. In the RF-MBE growth, the growth rates have been found to be almost constant and the crystal quality improved with increasing the substrate temperature up to 850°C. Further increases of substrate temperature decreased the growth rate and degraded the crystal quality. Using the optimum substrate temperature of 850°C and optimizing the shutter open time, smooth AlN films with atomic force microscope roughness as low as 0.2 nm have been grown by RF-MEE growth.     

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.     

Low temperature II–VI nanowire growth using Au–Sn catalysts

Epitaxial lateral overgrowth is reported for semi-polar (Al,Ga)N(1 1 .2) layers. The mask pattern consisted of periodic stripes of SiO₂ oriented parallel to either the GaN[1 1 .0] or the GaN[1 1 .1] direction. Lateral growth occurred either along GaN[1 1 .1] or along GaN[1 1 .0]. For growth along the [1 1 .0] direction, coalescence was achieved for layer thicknesses >4 μm. However, planarization was not observed yielding extremely corrugated surfaces. For growth in [1 1 .1] direction, coalescence was delayed by a diminishing lateral growth rate. Growth of AlGaN during ELOG resulted in coalescence. Improvement in crystal quality of such buffer layers for the growth of InGaN/GaN quantum wells was confirmed by X-ray diffraction and photoluminescence spectroscopy.     

Effect of Mn concentration and growth temperature on nanostructures and magnetic properties of Ge1−xMnx grown on Si

The nanostructures and magnetic properties of Ge_1−xMn_x thin films grown on Si substrates by molecular beam epitaxy, with different nominal Mn concentrations (1−4%) and different growth temperatures, have been systematically investigated by transmission electron microscopy and superconducting quantum interference device. It was discovered that when Ge_1−xMn_x thin films were grown at 70 °C, with increase in Mn concentration, Mn-rich tadpole shaped clusters started to nucleate at 1% Mn and become dominate in the entire film at 4% Mn. While for the thin films grown at 150 °C, tadpoles was firstly seen in the film with 1% Mn and subsequently Mn-rich secondary precipitates became dominant. The magnetic properties show specific features, which are mainly related to the nature and amount of Mn-rich clusters/precipitates within these thin films.     

Synthesis of AlGaAs-based strained separately confined heterostructure laser diodes by low temperature liquid-phase epitaxy

AlGaAs-based strained separately confined heterostructure laser diodes operating in the 800–900 nm wavelength range have been fabricated from the structures grown using low temperature liquid-phase epitaxy (LPE). Addition of P/Sb to the active region introduces tensile/compressive strain in the structure and is found useful in tuning the emission wavelength. Details of the growth experiments, strain measurements, fabrication and characterization of the laser diodes are described.     

Investigation of void formation beneath thin AlN layers by decomposition of sapphire substrates for self-separation of thick AlN layers grown by HVPE

Void formation at the interface between thick AlN layers and (0 0 0 1) sapphire substrates was investigated to form a predefined separation point of the thick AlN layers for the preparation of freestanding AlN substrates by hydride vapor phase epitaxy (HVPE). By heating 50–200 nm thick intermediate AlN layers above 1400 °C in a gas flow containing H₂ and NH₃, voids were formed beneath the AlN layers by the decomposition reaction of sapphire with hydrogen diffusing to the interface. The volume of the sapphire decomposed at the interface increased as the temperature and time of the heat treatment was increased and as the thickness of the AlN layer decreased. Thick AlN layers subsequently grown at 1450 °C after the formation of voids beneath the intermediate AlN layer with a thickness of 100 nm or above self-separated from the sapphire substrates during post-growth cooling with the aid of voids. The 79 μm thick freestanding AlN substrate obtained using a 200 nm thick intermediate AlN layer had a flat surface with no pits, high optical transparency at wavelengths above 208.1 nm, and a dislocation density of 1.5×10⁸ cm⁻².