A study of phase equilibria and heterojunctions in Ga–In–As–Sb quaternary system

The phase diagram of the Ga–In–As–Sb quaternary system has been determined experimentally and also has been treated on the base of thermodynamic calculations. The liquidus data were obtained by DTA and solidus data were determined using electron microprobe analysis on LPE-layers of Ga_xIn_1–xAs_ySb_1–y on GaSb and InAs substrates. Isolattice-parameter heterostructures prepared on these substrates were free of mismatch dislocations and suitable for application to light-emitting diodes and semiconductor lasers.     

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.     

Phase equilibria in the Ga–P system. Calculation of activities and vapour pressures using a simple asymmetrical solution model

KRUPKOWSKI'S expression of activity coefficients has been applied to the liquid binary mixed phase of Ga–P. An interaction parameter of α = 1909 – 4.107 T and an asymmetry coefficient of m = 1.448 were determined from liquidus data and an entropy of fusion of GaP of 16.8 e.u. per mole at 1743 K. The activity coefficient of phosphorus along the liquidus curve shows a minimum at x_P = 0.032. There is an excellent agreement between calculated and experimental activities and vapour pressures over the whole controllable range of concentrations of the liquid phase. A total phosphorus pressure of 30.8 atms was calculated for the melting point of GaP.     

Phase Equilibrium of the Ga–Al–Sb system

Employing the method of liquid-phase epitaxy (LPE) solid-solutions of Ga_1–xAl_xAl_xSb (0 ≦ x ≦ 0.8) have been obtained. The dependence of Sb solubility on Al concentration in the liquid phase at 403°C, 452°C, 500°C has been established. The dependence of AlSb concentration in the solid phase on the composition of the liquid phase has been investigated at 452°C. Using the chemical constants equilibrium method, the phase equilibrium of the Ga–Al–Sb system in the region of liquid phase composition near the Ga-rich corner of the phase diagram has been calculated. The comparison of experimental and calculated data for the liquid and solid phases shows their agreement within the limits of experimental error.     

Effect of bismuth on liquid-phase epitaxy (LPE) grown GaAs layer using Ga–As–Bi melt

GaAs epitaxial layers of high structural quality have been realised from Ga–As–Bi melt using liquid-phase epitaxy (LPE). LPE grown GaAs epitaxial layer using bismuth solvent on GaAs substrate has been found to be of good structural perfection as compared to layers using gallium solvent. The temperature-dependent PL spectra of GaAs layer, grown from Ga+Bi mixed solvent has shown that the use of bismuth does not change the band energy. ECV depth profile of heavily zinc-doped epitaxial layer shows uniform doping in the GaAs layer grown using gallium solvent as compared to the layer grown using bismuth solvent.     

Calculations of homogeneous region in Ga1−xAlxAs and GaAs1−xPx ternary solid solutions

Ternary solid solutions of A^IIIB^V compounds are considered as pseudobinary A(x)^IIIB(x)^v compounds, where the behaviour of A(x)^III and B(x)^v pseudoatoms is quite similar to A^III and B^v atoms in a binary A^IIIB^v crystal. Weak dependence of point defect contribution into Gibb's energy of A^IIIB^v crystal on its defect nature, random character of ternary solid solutions of A^IIIB^v compounds allow to use already for binary compounds developed formalism in the determination of component thermodynamic potentials of solid solution. Basing on literature data for the equilibrium solidus of AlAs the approximation for the temperature dependence of thermodynamic potential of an AB quasimolecule in A^IIIB^v crystal is revised. This result together with the well-known parameters for the equilibrium liquidus in Ga–P, Ga–As, and Al–As systems were used for calculations of the nonstoichiometric factor at the boundary of a homogeneous region in Ga_1−xAl_xAs and GaAs_1−xP_x ternary solid solutions. The results are compared with the known literature data.     

Liquidphasen-Epitaxie von Si-dotiertem AlxGa1−xAs

The liquidus and solidus isotherms of the quaternary phase diagram Ga—Al—As–Si have been estimated at 850 °C and N_Si = 0.04 and 0.1. Epitaxial layers were grown and the influence of silicon on the growth rate was investigated. Hall-effect measurements give informations on the dependence of the carrier concentration on the silicon content in the melt. The donor ionization energies vary from 32 to 69 meV and are diminished proportional to N.     

Saturation Behaviour of In – Ga – As Melts and Growth of In.53Ga.47As Lattice-matched to (001) InP Substrates

This paper presents the saturation behaviour of In – Ga – As melts with monocrystalline GaAs. The coulometric As-analysis confirmed that the source-seed-technique produces In – Ga – As melts of defined compositions. The growth results of the step cooling technique applying both the source-seed technique and the single phase melts are compared.     

Optical properties of Ga1–xInxAs LPE-layers and p-n structures

The multiple layer structure nGaAs(n Ga_1–xIn_xAs) p Ga_1–xIn_xAs (0 ≦ × ≦ 0.18) was realized by liquid phase epitaxy from In–Ga–As-melts on (111)-oriented GaAs substrates. The InAs-content of the mixed crystal layers was found to be dominating for crystal perfection and growth rate. The cathodoluminescence spectra of p-and n-type Ga_1–xIn_xAs and spectral distribution of the electroluminescence from pn-junctions were measured at T = 77 K and 300 K. The external quantum efficiency wa found to have a maximum for diodes with x ≈ ≈ 0.006. This is caused by the decrease of the optical absorption with increasing x and increasing dislocation density on the other hand.     

Low-temperature Region of the In–Se System

A study of the low-temperature region of the In–Se system has been performed by means of isothermal annealing of diffusion couples as well as by X-ray, microscopic and microprobe analyses. Four binary compounds have been observed – In₄Se₃, InSe, In₆Se₇ and In₂Se₃. Original experimental results about the crystal structure and electrical conductivities of the binary compounds have been compared with available literature data or calculated values. A DSC study of the compound InSe has revealed that it melts peritecticly at about 618 °C. The diffusion controlled transition from one In-Se compound to another can be achieved without kinetic difficulties, following the phase arrangement from the equilibrium phase diagram. There are indications that small deviations from the exact stoichiometric ratios are possible.     

Die mittlere quadratische Auslenkung der Atome und der Nachweis eines statischen Verzerrungsanteils in Al1–xGaxAs mit Röntgenbeugungsmethoden

The mean square atomic displacement in Al_1–xGa_xAs solid solution (x = 0.16) has been determined by integrated intensity measurements of X-ray Bragg diffraction from a polycrystalline sample at room temperature. The X-ray Debye-temperature of the solid solution was determined. The mean square displacement of the Al-atoms is smaller than those resulting for the Ga/As-atoms.     

Local structural environment and intra-4f transition of rare-earth ion in chalcogenide glass: Comparison between Dy-doped Ge–As–S and Ge–Ga–S glasses

We have employed Dy L₃-edge extended X-ray absorption fine structure measurements to investigate the local structures of Dy doped in Ge–As–S and Ge–Ga–S glasses. It turned out that Dy–S distance on average is conspicuously longer in Ge–Ga–S glass despite the number of the nearest neighboring S atoms being nearly identical with each other. The enhanced rare-earth solubility of Ge–Ga–S glass is then explained in connection with decrease in covalence of Ga–S bonds compared with Ge–S or As–S bonds, and structural correlation between GaS₄ tetrahedra and Dy. The discrepancy in the local structural environments of trivalent Dy, however, results in no significant changes in the spectral lineshape and the mean energy of its intra-4f-configurational transitions.     

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)     

Thermodynamic restrictions of LPE of bismuth-containing А3В5 solid solutions

A heterophase equilibrium estimation procedure is proposed for systems InBiAsSb and GaInBiAsSb using the simple solution model and a ‘virtual’ GaBi compound. Thermodynamic characteristics and crystal-chemical parameters of the GaBi compound have been determined for the calculation with the linear interpolation method. Phase equilibrium in In–Bi–As–Sb and Ga–In–Bi–As–Sb systems has been analyzed for the 650–780 K temperature range. The existence limits for solid solutions have been set and the thermodynamic restrictions characterizing the capacity for synthesis have been ascertained. The data obtained may be useful in optimization of LPE methods.     

Surface morphology of as-deposited and illuminated As–Se chalcogenide thin films

The role of the composition and of the related changes of the structure in the formation of the surface of amorphous As_xSe_1−x (0 < x < 0.5) layers before and after light treatment was investigated by direct measurements of the surface roughness at nanometer-scale and surface deformations at micrometer-scale under influence of illumination. It was established that the surface roughness of the films, deposited by vacuum thermal evaporation, decreased with increasing As content, especially in compositions 0.1  x  0.3, where the maximum light stimulated surface deformations (localized expansion) occurs. Both relate to the rigidity percolation range and the maximum photoplastic effects, which are not directly connected to the known photodarkening effect, since it is minimal for these compositions.     

Thermal stability and crystallization kinetics of new As–Ge–Se–Sb glasses

Thermal stability and crystallization kinetics of As₁₄Ge₁₄Se_72−xSb_x (where x = 3, 6, 9, 12 and 15 at.%) glasses are studied by the differential scanning calorimetry. The values of the glass transition temperature (T_g) and the peak temperature of crystallization (T_p) are found to be dependent on heating rate and antimony content. From the heating rate dependence of T_g and T_p the values of the activation energy for glass transition (E_t) and the activation energy for crystallization (E_c) are evaluated and their composition dependence discussed. Crystallization studies have been made under non-isothermal conditions with the samples heated at several uniform rates. Using a recent analysis developed for non-isothermal crystallization studies, information on some aspects of the crystallization process has been obtained. The stability calculations emphasized that the thermal stability decreases with increasing the Sb content.     

AlxGa1−xAs LPE growth

Al_xGa_1−xAs LPE growth was studied within the temperature range of 930–900°C with Al concentrations in solutions from 0.04 to 2.4 at.%. AlAs concentration in layers has been shown to grow with the cooling rate increase of solution. Interface and volume nucleation parameter dependence of K_i and K_v and formation time t_f on Al concentration in Ga solution have been found. Addition of Al to Ga solution increases critical values of As supersaturation (supercooling) and, as a result, increase in thickness of Al_xGa_1−xAs layers compared with GaAs layers have been determined in spite of As concentration lowering in Ga solution.     

Structural and optoelectrical properties of Ga‐doped ZnO semiconductor thin films grown by magnetron sputtering

Transparent conductive gallium‐doped zinc oxide (Ga‐doped ZnO) films were prepared on glass substrate by magnetron sputtering. The influence of substrate temperature on structural, optoelectrical and surface properties of the films were investigated by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), spectrophotometer, four‐point probe and goniometry, respectively. Experimental results show that all the films are found to be oriented along the c‐axis. The grain size and optical transmittance of the films increase with increasing substrate temperature. The average transmittance in the visible wavelength range is above 83% for all the samples. It is observed that the optoelectrical property is correlated with the film structure. The Ga‐doped ZnO film grown at the substrate temperature of 400 °C has the highest figure of merit of 1.25 × 10⁻² Ω⁻¹, the lowest resistivity of 1.56 × 10⁻³ Ω·cm and the highest surface energy of 32.3 mJ/m².     

Thermodynamic modeling of the system As–Fe combined with first-principles total energy calculations

A thermodynamic model has been developed for the system As–Fe by combining the Calphad approach and the first-principles total energy calculations. Our first-principles calculations are based on the projector augmented wave method within the generalized gradient approximation. We performed these calculations because the experimental values for the enthalpy of formation of the compounds As₂Fe, AsFe and AsFe₂ may have a large uncertainty. Our results indicate significantly more negative values for the enthalpy of formation of these compounds relative to the experimentally established values. We demonstrate that applying our first-principles results in a thermodynamic analysis based on the Calphad approach leads to a calculated phase diagram and thermodynamic properties which are not significantly different from experimental data.