Phase equilibria in III–V quaternary systems—application to Al-Ga-P-As

A method is given to calculate liquidus-solidus phase diagrams involving quaternary III–V solid solutions of the type A_xB_{1 ? x}C_yD_{1 ? y}. The calculation treats the mixture of A and B atoms on the group III sublattice and C and D atoms on the group V sublattice as strictly regular and the quaternary liquid solution as simple. The input parameters for the calculation are obtained from existing analyses of the binary and ternary boundaries of the phase diagram.Experimental liquidus and solidus data along several Al isoconcentration curves on the 900 ° and 1000 °C isotherm surface are presented for the Al-Ga-P-As system. The liquidus data are obtained by liquid observation and saturation techniques and solidus compositions determined on self-nucleated cyrstals and on mixed crystal layers grown on GaP substrates. The experimental results are consistent with the calculated phase diagram for this system.     

Thermodynamics of III–V solutions with n components

A method has been developed for the calculation of phase diagrams of III–V mixtures with more than three components. The equations for the chemical potentials, activity coefficients and the free energy of the mixture and for the liquidus- and iso-solidus-concentration lines are given. The parameters, needed for the calculation, are the temperature of fusion, heats of fusion, and the interaction parameters. The interaction parameters can be fitted to datas of the binary or quasi-binary phase diagrams, or can be calculated using the electronegativities, energies of sublimation and molar volumes of the constituent elements.Two approaches for a mixture with n components are given, which give in the ternary and binary case the known equations. The two possible cases of quaternary III–V solutions are discussed explicitly.     

III-V compound semiconductor (001) surfaces

There has been renewed interest in the structure of III-V compound semiconductor (001) surfaces caused by recent experimental and theoretical findings, which indicate that geometries different from the seemingly well-established dimer models describe the surface ground state for specific preparation conditions. I review briefly the structure information available on the (001) surfaces of GaP, InP, GaAs and InAs. These data are complemented with first-principles total-energy calculations. The calculated surface phase diagrams are used to explain the experimental data and reveal that the stability of specific surface structures depends largely on the relative size of the surface constituents. Several structural models for the Ga-rich GaAs (001)(4×6) surface are discussed, but dismissed on energetic grounds. I discuss in some detail the electronic properties of the recently proposed cation-rich GaAs (001)ζ(4×2) geometry. Received: 18 May 2001 / Revised version: 23 July 2001 / Published online: 3 April 2002     

Confirmation of bulk modulus model of III–V compounds under pressure effect using tight-binding method

The electronic band structure for GaAs, GaSb and GaP is studied using semi-empirical tight-binding sp³s* method for tetrahedrally coordinated cubic materials. By means of our empirical model, the structural property of bulk modulus at critical transition pressure is calculated. Also, the GaAs, GaSb and GaP compounds are found to be indirect-gap semiconductors under pressure effect. The noticed behaviour of the bonding character reflects the structural phase transition. These results are in good agreement with experimental and theoretical data.     

Laser technology for submicron-doped layers formation in semiconductors

A p–n junctions formed by means of laser stimulated diffusion of dopants into semiconductors (Si, GaAs, GaP, InP) were investigated. SIMS and AES spectroscopy methods were used to measure the depth profiles of the incorporated impurities: B into Si, Zn into GaAs, GaP and InP. The volt-capacity method using an electrochemical profilometer was used for the charge carrier concentration distribution in the doped layer. Spectroscopy investigations have shown that during solid phase diffusion locally doped regions almost exactly reproduce the shape and size of the windows in the dielectrics. The lateral diffusion of the dopant is about 0.01μm. The concentration profiles of charge carrier distribution in the doped layers clearly show the specific processes of dopant diffusion and evaporation at laser solid-phase doping of semiconductors. The comparative analysis of parameters of formed semiconductor structures shows that the procedure of laser solid-phase doping can stand the comparison with technology of implantation and conventional diffusion technology. Since the laser solid-phase doping ensures also a high degree of reproducibility of p–n junction parameters, it can be effectively used for electronic devices fabrication.     

Electronic surface properties of uhv-cleaved III–V compounds

Combined CPD and photoemission measurements were performed on uhv-cleaved surfaces of the III–V compounds InAs, GaSb, GaAs and GaP with moderate p-type and n-type dopings. Except for n-type GaP these materials show practically no band bending. N-type GaP exhibits surface Fermi level stabilization at 0.55 eV below the conduction band edge. This is ascribed to an intrinsic empty surface state band in the forbidden zone. On the basis of our experiments together with available data from literature we propose an empirical model for the (110) plane of III–V compounds containing In or Ga as metal and Sb, As or P as non-metal atoms from which the lower edge of the empty surface state band can be predicted. The model indicates that for any of these compounds except for GaP no empty surface state band exist in the band gap on the (110) surface.     

用赝势微扰法计算某些半导体的能带结构(用于GaAs,GaP和Ga[As1-xPx]合金)

用赝势微扰法计算了GaAs,GaP和Ga[As_1-xP_x]合金的能带。赝势选择的原则是使计算所得直接能隙和间接能隙与实验值相符合。计算结果表明,不但能带次序准确,而且与室温下的实验值符合得很好。基于由GaAs到GaP晶格常数和赝势是线性变化的假设,计算了GaP含量为20％,50％和80％时Ga[As_1-xP_x]合金的能带。当GaP含量为41％时,直接能隙和间接能隙相等,这一数值刚好是Spitzer和Fenner的实验值的平均值。此时,由于很好满足光激射器p-n结所要求的条件,因此可望在光激射器中得到应用,它们的能带也就有一定的参考价值。     

GaAs,GaP和GaAsxP1-x合金能带的计算

使用分区变分法计算了GaAs,GaP和GaAs_xP_1-x合金的能带。鉴于原胞内包含不同的原子,依据实际原子的大小,对不同原子球选用了不同的半径。晶体势用相应原子势的迭加势来计算。考虑到组成晶体时原子势场由于电子成键而产生畸变,因而在球外成键区选用了一些调整参数来调整势场,然后再用解析表式来逼近这种调整原子势。适当地选择调整参数使算得的能带同已知的实验值接近。对GaAs和GaP已算得了同实验结果符合的能带结构。使用所得的调整原子势进一步计算了GaAs_xP_1-x合金的能带。 关键词：     

Implantation and diffusion of 73As in GaAs and GaP

Self-diffusion on the As sublattice in intrinsic GaAs and foreign-atom diffusion on the P sublattice in intrinsic GaP were investigated in a direct way by As tracer diffusion measurements using the radioisotope ⁷³As. For this purpose ⁷³As was implanted in both materials at the ISOLDE facility of CERN. Then diffusion annealings were performed followed by serial sectioning and counting of the radioactivity in each section. The resulting profiles were simulated within a computer model which accounts for the observed loss of tracer to the diffusion ambient. The so-obtained diffusion coefficients for As in GaAs and GaP are compared with existing diffusivities in these compounds. This revised version was published online in July 2006 with corrections to the Cover Date.     

An upgraded TOF-SIMS VG Ionex IX23LS: Study on the negative secondary ion emission of III-V compound semiconductors with prior neutral cesium deposition

A TOF-SIMS VG Ionex IX23LS with upgraded data acquisition and control system was used to study the secondary emission of negative atomic and cluster ions of non-metallic elements (P, As and Sb) upon a 19 keV Ga⁺ bombardment of non-degenerated III-V semiconductors (GaP, GaAs, GaSb, InP, InAs and InSb) with prior neutral Cs deposition from a getter dispenser. It was found that surface cesiation enhances the peak intensity of all negative ion species; in the case of atomic ions, the greatest increase (360) was observed for P⁻ emitted from InP. Such an enhancement was larger for In-based than for Ga-based compounds. We explained that in terms of an electronegativity difference between the composing atoms of III-V semiconductors. The greater electronegativity difference (bond ionicity) of In-based compounds resulted in the greater Cs-induced work function decrease leading to a higher increase in the ionization probability of secondary ions.     

Advances in the optical analysis of semiconductor materials

Recent progress is reviewed for optical techniques of semiconductor materials characterization. Luminescence is emphasized because of its inherently high sensitivity to detect impurities and imperfections, especially in the presently best understood compounds GaAs and GaP. Examples are discussed for optical determination of mechanical stresses, the effect of dislocations, dopant inhomogeneities and compensation ratio, carrier relaxation and electron drift mobilities, as well as energy transfer processes. Adaptation of an invited paper presented at the Solid State Device Conference, Tokyo, September 1975.     

A calculation of defect gap states on the clean (110) surfaces of some III-V semiconductors

The gap electronic structure of various defects on the (110) faces of GaSb, GaAs, GaP, InAs and InP is studied. States associated with defects having one or two dangling bonds on either metallic and non-metallic atoms are considered. For interacting defects the barycenter of the states is calculated and their splitting is estimated. It is found that for GaSb, GaAs, GaP and InAs only two clearly distinct groups of levels can be identified. The upper one always corresponds to centers with one dangling bond on a metallic atom, while the lower one contains the levels associated to all the other possibilities we have investigated. For InP, levels associated with two dangling bonds on a metallic atom are raised from the lower group. This is in agreement with the other available theoretical results. A discussion of the experimental data in the light of our results is presented.     

Raman tensor of germanium and zincblende-type semiconductors

It is shown that the one-phonon Raman tensor of germanium and zincblende-type materials can be calculated from a model density of states consisting only of the E₀ and the E₀ + Δ₀ parabolic critical points. The calculated Raman tensors and their spectral dependence are compared with experimental results for GaP, GaAs, and ZnSe and with a recent calculation for Ge based on the complete band structure.     

Energieverlustmessungen an III–V-Verbindungen

Energy loss measurements with 55 keV electrons were made on the III–V compounds GaP, GaAs, GaSb, InAs and InSb. Retardation effects become important, because for these substances the condition for Cerenkov radiation is fulfilled. These produce an additional peak in the energy loss spectrum; its angular distribution and its dependance on the foil thickness were measured. The experimental results are in good agreement with the energy loss probability calculated by Kröger taking into account the retardation. Retardation- and surface effects vanish for scattering anglesθ≧0.6; 0.6 mrad. Then it is possible to determine the energy loss function Im(1/?). By means of the KramersKronig analysis the optical constants? ₁ and? ₂ were computed. The values are in agreement with data obtained from optical measurements.     

Study of radiation-induced damage to type III–V semiconductor compounds irradiated with γ quanta and protons using positron annihilation spectroscopy

The effect of proton and ?? radiation on characteristics of the spectra for the angular distribution of annihilation photons (ADAP) have been studied in the case of positron annihilation in GaAs and GaP single crystals. Relative variations in defect accumulation and annealing under irradiation and subsequent isochronous annealing of the samples have been studied using variations in the basic parameters of the ADAP spectra. In both cases (GaAs and GaP), the variations in the ADAP spectral parameters as functions of the annealing temperature have a steplike character, which is interpreted as the formation of a certain type of defects with different annealing activation energies.     

Semiempirical tight-binding calculation of the Schottky barrier heights

Barrier heights of the interfaces between metal monolayers and the (110) surfaces of GaAs, GaP, ZnSe and ZnS were calculated in the tight-binding approach. The slopes of the calculated dependences of barrier height vs work function agree very well with experiment in all cases. In accordance with recent empirical conclusions the calculation indicates that covalent crystals have stronger chemical bonds with metal overlayers than do ionic crystals.     

Interstitial Mn as a new donor in GaP and GaAs: an EPR study

We report the observation of a new electron paramagnetic resonance centre in neutron-irradiated GaP and a similar new EPR centre in Mn-doped GaAs. Both centres have been identified as interstitial Mn and act as a donor. To our knowledge this is the first observation by EPR of an interstitial transition-metal impurity in a III-V compound. The implication of this new finding on the issue of Mn diffusion is discussed.     

Distribution of silicon over sublattices in semiconducting A3B5 compounds

The stable site of Si substitutional impurities in GaAs and AlAs at T=0 K is determined on the basis of an analysis of the energy of solution of silicon, and of the energies of formation of intrinsic defects and the reaction energies of their interaction obtained by calculating the total energy of the disordered compounds. These calculations indicate that amphotericity and vacancies have an effect on the distribution of Si. At low Si concentrations, Si in GaAs is located on the sublattice of the group III element, and in AlAs, on the sublattice of the group V element. Fiz. Tverd. Tela (St. Petersburg) 39, 264–266 (February 1997)     

Energy bands of atomic monolayers of various materials: Possibility of energy gap engineering

The mobility of graphene is very high because the quantum Hall effects can be observed even at room temperature. Graphene has the potential of the material for novel devices because of this high mobility. But the energy gap of graphene is zero, so graphene cannot be applied to semiconductor devices such as transistors, LEDs, etc. In order to control the energy gaps, we propose atomic monolayers which consist of various materials besides carbon atoms.To examine the energy dispersions of atomic monolayers of various materials, we calculated the electronic states of these atomic monolayers using density functional theory with structural optimizations. The quantum chemical calculation software Gaussian 03 was used under periodic boundary conditions. The calculation method is LSDA/6-311G(d,p), B3LYP/6-31G(d), or B3LYP/6-311G(d,p).The calculated materials are C (graphene), Si (silicene), Ge, SiC, GeC, GeSi, BN, BP, BAs, AlP, AlAs, GaP, and GaAs. These atomic monolayers can exist in the flat honeycomb shapes. The energy gaps of these atomic monolayers take various values. Ge is a semimetal; AlP, AlAs, GaP, and GaAs are indirect semiconductors; and others are direct semiconductors.We also calculated the change of energy dispersions accompanied by the substitution of the atoms. Our results suggest that the substitution of impurity atoms for monolayer materials can control the energy gaps of the atomic monolayers.We conclude that atomic monolayers of various materials have the potential for novel devices.     

Large-scale Monte Carlo study of a realistic lattice model for Ga(1-x)MnxAs

Mn-doped GaAs is studied with a real-space Hamiltonian on an fcc lattice that reproduces the valence bands of undoped GaAs. Large-scale Monte Carlo (MC) simulations on a Cray XT3, using up to a thousand nodes, were needed. Spin-orbit interaction and the random distribution of the Mn ions are considered. The hopping amplitudes are functions of the GaAs Luttinger parameters. At the realistic coupling J approximately 1.2 eV the MC Curie temperature and magnetization curves agree with experiments for x = 8.5% annealed samples. Mn-doped GaSb and GaP are also briefly discussed.