On the kinetics of nitrogen incorporation in GaP LPE layers using NH3 vapour doping

The partial substitution of N for P in GaP has a considerable effect on the luminescence quantum efficiency of GaP epitactic layers. The incorporation of N in GaP liquid phase epitactic layers using NH₃ vapour doping has been studied at different H₂ partial pressures in argon gas. It is shown that the incorporation of N in different ambients is conveniently described by just one parameter. The reaction of NH₃ with Ga is found to be an equilibrium process. The N concentration in the layer is directly proportional to the GaN concentration in the melt. From the correlation of the dissociation of NH₃ with the formation of GaN it is concluded that the NH₃ pressure, as measured in the exit gas, is not representative of the NH₃ pressure at the melt. The dissociation of NH₃ is found to be strongly retarded by H₂ owing to adsorption of H₂ on the surface of reactor materials which catalyse the dissociation.     

Synthesis of gallium nitride by ammonia injection into gallium melt

Gallium nitride (GaN) was synthesized by injecting ammonia gas into molten gallium at 900–980°C under atmospheric pressure. A large amount of GaN powder was reproducibly obtained using a simple apparatus. The synthesized powder was characterized by scanning electron microscopy, X-ray diffraction, photoluminescence and energy dispersive X-ray spectroscopy, and was found to consist of fine crystals of hexagonal GaN of good quality. The total of GaN obtained was far more than the amount calculated from expected saturation solubility in the Ga melt at that temperature. We speculate that the GaN crystals were largely formed by direct reaction between Ga and the gaseous N source at the surface of the NH₃ bubbles in the melt. GaN synthesized by this method may be useful as a starting material for bulk growth.     

Study of InxGa1–xP/GaAs Films Formation on the Basis of In–Ga–P Liquidus Precised Investigation

It is shown that the In–Ga–P melt which is prepared by contacting with the GaP seed becomes supersaturated in reality. Some peculiarities of In_xGa_1–xP/GaAs films formation at quasi-equilibrium conditions are described. It is observed that the saturated In–Ga–P melt dissolves the GaAs substrate when isothermally contacting if the In_xGa_1–xP equilibrium solid has the lattice parameter less than that of GaAs. As a result some InGaAsp deposit arises on the substrate. This phenomenon takes place if the In–Ga–P melt is just supercooled. This instability of the liquid-solid interface is explained on the basis of the relaxation theory of non-equilibrium liquid-solid contact which has been created by the author in previous papers.     

Preparation of GaN crystals by heating a Li3N‐added Ga melt in Na vapor and their photoluminescence

GaN crystals were prepared by heating a Ga melt with 1 at% Li₃N against Ga at 750 °C in Na vapor under N₂ pressures of 0.4–1.0 MPa. The GaN crystals grown at 1.0 MPa of N₂ were colorless and transparent prismatic, having a size of approximately 0.7 mm in length. A secondary ion mass spectrometry (SIMS) showed the contaminant of lithium in the obtained crystals. A large broad yellow band emission peak of 2.28 eV was observed at room temperature in the photoluminescence spectrum in addition to the near band emission peak of GaN at 3.39 eV and a small broad satellite emission at 3.24 eV. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A difference between initial growth stages of the AlGaAs/GaAs and GaAs/AlGaAs heterostructures produced by contact replacement of solutions

The method of liquid epitaxial growth of GaAs/AlGaAs/GaAs heterostructures when the change of solutions occurs due to pushing off one melt by another is discussed. It has been shown theoretically and experimentally that the initial stages of film growth after the change of the binary Ga As melt on the ternary Al Ga As melt differ from that when the Ga As solution pushes off the Al Ga As liquid. The difference is caused by the inequality of the diffusion coefficients of As and Al in a multicomponent Al Ga As liquid (D_Al > D_As). As a result, the growth of an AlGaAs film begins immediately in the case when the Al Ga As solution pushes off the Ga As liquid but in the opposite case the dissolution of an underlying AlGaAs solid is unavoidable and depends little on degree of a saturation of the Ga As washing solution. These peculiarities must be taken into account in discussions of abruptness and other properties of LPE-grown AlGaAs/GaAs and GaAs/AlGaAs heterojunctions.     

Preparation and characterization of electrodeposited indium selenide thin films

Indium Selenide (InSe) thin films were deposited from a mixture of Indium chloride and selenium dioxide in aqueous solution by electrodeposition technique on Indium Tin oxide coated glass substrates. The effects of the parameters during deposition such as current density, deposition potential versus saturated calomel electrode, pH value and concentration of source material were studied. X‐ray diffraction studies were carried out on the films to analyze the microstructure using an x‐ray diffractometer and were examined by RAMAN spectroscopy. The Raman peak position did not change much with chemical concentrations. Raman scattering due to the (LO) phonon was observed at 211 cm^–1. Optical absorption studies were performed with a double beam ultra violet‐visible –NIR spectrophotometer in the wavelength 300–1100 nm. The surface morphology of the layer was examined using a scanning electron micrograph. The composition of the films was studied using an Energy Dispersive Analysis by X‐Rays (EDAX).     

Untersuchungen zur heteroepitaktischen Abscheidung von GaP auf GaAs aus der Sn-Lösung

The used liquid-phase epitaxy apparates are described and the experimental conditions of growth on GaP and Ga(AsP) onto GaAs-substrates are reported. The influence of growing conditions (temperature, cooling rate, composition of melt) on the quality of interface and on the inlusion of solvent are discussed. The consequence of varying degrees of substrat-misorientation on the surface morphology has been studied.     

Characterization of large‐sized Nd:YAG single crystals grown by horizontal directional solidification

Nd³⁺‐doped Y₃Al₅O₁₂ single crystals have been grown by the horizontal directional solidification (HDS) method in different thermal zone. The Grashof (G_r), Prandtl (P_r), Marangoni (M_a) and Rayleigh (R_a) numbers of melt in HDS system have been discussed for our experimental system to understand the mechanism of melt flow patterns and concentration gradient of dopant. The concentration gradient of Nd³⁺ ions was explained with melt flow processes during crystal growth in different thermal zone, and results indicated that high growth temperature will be helpful for uniformity of dopant in HDS‐grown single crystal. The main microscopic growth defects such as bubbles and irregular inclusions in HDS‐grown Nd:YAG crystals were observed, and the causes were discussed as well. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A thermodynamic factor influencing the growth rate and purity of epitaxial layers in the Ga-AsCl3-H2 system

Thermodynamic calculations of the Ga-AsCl₃-H₂ VPE system were expanded to incorporate the incompleteness of the reaction between the source Ga and gas phase. As a result, a saturation temperature was obtained, at which the gas phase reaches equilibrium with the substrate GaAs. The effect of incomplete contact between the gas and the source Ga was taken into account in the calculation by a flow efficiency which defined the hypothetical fraction of the gas which made complete contact with the source Ga. The limitation of the kinetics was described by a reaction efficiency which was incorporated into the reaction constant. The saturation temperature was measured experimentally for two reactors with different geometry. Values of the two efficiencies were derived and their dependence on growth conditions were also examined. The growth rate and undoped impurity level were found to be related in a simpler and perhaps more fundamental way to the saturation temperature than to other growth parameters.     

Axial macrosegregation in Ga‐doped germanium grown by the vertical gradient freeze technique with a rotating magnetic field

The impact of a rotating magnetic field (RMF) on the axial segregation in Vertical Gradient Freeze (VGF) grown, Ga doped germanium is investigated. Growth experiments were performed using the VGF‐RMF as well as the conventional VGF technique. Carrier concentration profiles characterising the Ga segregation were measured by the Spreading Resistance method and calibrated using Hall values of carrier concentration and mobility. The Ga concentration rises more gradually under RMF action, i.e., the dopant segregation is significantly reduced by the rotating field. This effect is attributed to a better mixing of the melt. Numerical results on the flow velocity confirm this explanation. The RMF induced flow is much more intense than the natural buoyant convection due to the radial temperature gradient and leads to a pronounced decrease of the effective partition coefficient k_eff. In the early stages of growth a k_eff value close to k₀ was obtained, i.e., the gallium was almost homogeneously distributed within the melt. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ga and In incorporation rates in Ga1−xInxAs growth by chemical beam epitaxy

GaAs, InAs and Ga_1?xIn_xAs layers were grown by chemical beam epitaxy (CBE) using triethylgallium, trimethylindium and tertiarybutylarsine as precursors for Ga, In and As, respectively. The growth rate during the homoepitaxial growth of GaAs and InAs, deduced from the frequency of reflection high-energy electron diffraction intensity oscillations, was used to calibrate the incorporation rates for the III elements. The In content of the Ga_1?xIn_xAs layers was measured by Rutherford backscattering spectrometry and compared with the value predicted from the above calibration data; while the measured In mole fraction is close to the predicted value for the samples grown for low In to Ga flux ratios (x<0.2), the In incorporation is enhanced for larger values of this ratio. The results obtained on layers grown at different substrate temperatures show that In mole fraction is almost constant at growth temperatures in the range 400–500 °C, but a strong dependence on the substrate temperature has been found outside this range. The above results, not observed for samples grown by solid source molecular beam epitaxy, indicate that some interaction between Ga and In precursors at the sample surface could take place during the growth by CBE.     

Das quaternäre Schmelzdiagramm Ga?As-P Sn

The pseudoternary cut Sn GaAs GaP of the quarternary system Ga As P Sn has been investigated in a temperature range from 860 to 1200°C. The calculation based on Vieland's method by use of Darken's quadratic formalism. A comparision between the solvents tin and gallium shows a higher solubility in tin for the mixed crystal Ga_xPAs_1−x and a stronger variation of the composition along the growth direction.     

Growth of low defect density GaP layers on Si substrates within the critical thickness by optimized shutter sequence and post-growth annealing

We have developed a growth procedure for realizing a low defect density GaP layer on an Si substrate. The growth procedure consists of two parts. One is the post-growth annealing for the annihilation of stacking faults (SFs). We have investigated an annihilation mechanism with molecular beam epitaxy grown GaP layers. 1-monolayer-thick SFs typically generate from the GaP/Si interface in a non-annealed GaP layer. In a 700 °C annealed GaP layer, generation points of these SFs tend to shift toward the GaP surface. In a 730 °C annealed GaP layer, SFs density is effectively decreased. These results suggest that SFs are annihilated through the climb motion of two partial dislocations during the post-growth annealing. Another one is the optimized shutter sequence for migration enhanced epitaxy. We have revealed that it is effective for the suppression of both three-dimensional growth and melt-back etching to increase in a stepwise manner the number of supplied Ga atoms per cycle. As a result, the generation of threading dislocations and pits is remarkably suppressed. A root mean square surface roughness of 0.13 nm is obtained within the critical thickness. We have estimated etch pit density (EPD) to be ∼7×10⁵ cm⁻² with a GaPN/GaP/Si structure. To the best of our knowledge, this value is same as that of commercially available GaP substrates and is the lowest one in the EPD of GaP/Si heteroepitaxy.     

Numerical modeling of frequency influence on the electromagnetic stirring of semiconductor melts

Alternating magnetic fields can be used in order to increase the level of convection and to mix the doped semiconductor alloys. A numerical analysis of the electromagnetic induced convection in GaInSb semiconductor melts is performed by using the software package CrysVUn. The magnetic field parameters are varied in order to obtain a maximum efficiency of the induced convection with a minimum quantity of the heat released in the melt. The influence of the electrical current frequency on the convection intensity is analyzed for samples with various radii (R = 0.5 – 3cm). Numerical procedure is validated by comparing the numerical results obtained in mercury samples with the experimental data given from the literature, which show a maximum stirring for a magnetic skin depth δ = 0.2R , in the case of a mercury sample with the radius R = 10 cm. This maximum corresponds to a shielding parameter R _ω = 40. Our numerical results show that the value of the shielding parameter for which the convection intensity reaches the maximum depends on the sample radius and increases when the sample radius increases. The results of this analysis are important in the case of samples with small radius, when a good mixing of the melt can be obtained for frequencies much lower than those corresponding to a shielding parameter R_ω = 40. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chemical Segregation in Vertical Bridgman Growth of GaInSb Alloys

A set of experiments on the solidification of Ga _1-x In _x Sb alloys with a large variation of the sample diameter (from 1mm to 10mm), of the growth rate (from 0.7 to 7 μm/s) and of the concentration (from x=0.01 to x= 0.1) is described. The associated radial and longitudinal segregation of the In have been analysed by SIMS or electron microprobe. Numerical simulation of the experiments, taking into account thermal, hydrodynamic and chemical behaviour has been carried out with the help of FIDAP. It is shown from these numerical results that a plateau of concentration can be reached even if a convective loop is present close to the interface, provided that the convection does not extend into the bulk of the liquid. This is in full agreement with the experimental results obtained. Supporting this analysis, in some experiments, a defect in term of verticality of the crucible led to complex 3-D convection involving the whole liquid, and in that case no plateau was obtained. For the radial segregation ΔC_R, three regimes of transport are found, characterised by the convective level: - A diffusive one, with a low, constant, ΔC_R related to the interface curvature. - A quasi-diffusive one (weak convection) in which ΔC_R increases with convection. - A convective one in which it decreases. Measured radial segregations are in good agreement with predictions from the numerical simulations.     

Studies on fabrication of urchin‐like WO3·H2O hollow spheres and their photocatalytic properties

Urchin‐like tungsten oxide hydrate (WO₃ · H₂O) hollow spheres were successfully synthesized via a self‐sacrifice template method at low temperature. The effects of reaction parameters on the preparation were studied in solution. The growth mechanism was also proposed on the basis of experimental results. In addition, the acid amount and temperature have important effects on size control of the as‐obtained samples. The achieved nanoarchitectures have typical diameters of 4–6 μm with nanoflakes of several nanometers at surface. Crystal structure, morphology, and composition of final nanostructures were characterized by X–ray diffraction (XRD) and scanning electron microscopy (SEM). Degradation experiments of organic contaminant were also performed on samples of hollow spheres and walnut‐like structures under visible‐light illumination. Hollow sphere sample exhibited better photocatalytic capability than walnut‐like sample. Possible mechanism was studied for WO₃ · H₂O assisted photocatalytic degradation of organic contaminant under visible light.     

Effect of growth parameters on the properties of GaN : Zn epilayers

The vapor-phase HCl/Ga/NH₃ method for deposition of GaN : Zn epilayers on sapphire substrates has been investigated to determine the dependence of epilayer resistivity, cathodoluminescence, and surface quality on the growth parameters. Both nucleation and control of the epilayer properties have been significantly improved by introducing HCl directly into the deposition zone in addition to the HCl that passes over the Ga source to produce GaCl. The effect of annealing on the stability of undoped layers and on the cathololuminescence of Zn-doped layers has also been investigated. Electroluminescent devices with reproducible properties have been obtained by growing structures consisting of an undoped n⁺ layer, a Zn-doped n-type layer, and a very thin, Zn-doped, high-resistivity layer whose growth parameters determine the emission wavelength and electroluminescence efficiency.     

Thermodynamic feasibility study for chemical vapour deposition of some ternary crystals using iodine and hydrogen iodide

Thermodynamic feasibility of transition metal dichalcogenide (TMDC) single crystals of Cu Al S₂, Cu Al Se₂, Cu Al Te₂, Cu Ga S₂, Cu Ga Se₂, Cu Ga Te₂, Cu In S₂, Cu In Se₂, Cu In Te₂, Ag Ga S₂, Ag Ga Se₂, Ag Ga Te₂, Ag In Se₂, Ag In Te₂, using iodine and hydrogen iodide as transporting agents has been reported in this paper. Results give range of temperature for the iodide transport and prevention of starting material formation (elemental transport) in the growth zone. From the range of temperature for the growth of crystals, selected source zone and growth zone temperatures with a differential of 100 °C are also listed. Referring the data listed in the tables can grow good quality crystals. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Vacancy defects in as-grown and nº-irradiated GaP and GaAs1−xPx Studied by Positrons

Measurements of positron lifetime τ and of the shape parameter S of the Doppler-broadened annihilation line are used to study bulk and defect properties in GaP and GaAs_1−xP_x. τ and S decrease linearly with the composition x of GaAs_1−xP_x layers. A second lifetime component (τ₂ = 290 ps) observed in as-grown GaP is attributed to stoichiometric P vacancies. After neutron irradiation of GaP and GaAs_0.13P_0.87 positrons are trapped by Ga vacancies (τ₂ = 250 ps). These vacancies anneal out in two stages at 200–550 °C and 550–800 °C.