We develop an atomistic, nearest-neighbor sp3s* tight-binding Hamiltonian to investigate the electronic structure of dilute bismide alloys of GaP and GaAs. Using this model we calculate that the incorporation of dilute concentrations of Bi in GaP introduces Bi-related defect states in the band gap, which interact with the host matrix valence band edge via a Bi composition dependent band anti-crossing (BAC) interaction. By extending this analysis to GaBiAs we demonstrate that the observed strong variation of the band gap Eg and spin-orbit-splitting (SO) energy with Bi composition can be well explained in terms of a BAC interaction between the extended states of the GaAs valence band edge and highly localized Bi-related defect states lying in the valence band, with the change in Eg also having a significant contribution from a conventional alloy reduction in the conduction band edge energy. Our calculated values of Eg and SO are in good agreement with experiment throughout the investigated composition range x less than 13%. In particular, our calculations reproduce the experimentally observed crossover to an Eg < SO regime at approximately 10.5% Bi composition in bulk GaBiAs. Recent x-ray spectroscopy measurements have indicated the presence of Bi pairs and clusters even for Bi compositions as low as 2%. We include a systematic study of different Bi nearest-neighbor environments in the alloy to achieve a quantitative understanding of the effect of Bi pairing and clustering on the GaBiAs electronic structure.
The addition of dilute concentrations of bismuth (Bi) into GaAs to form GaBiAs alloys results in a large reduction of the band gap energy Eg accompanied by a significant increase of the spin-orbit-splitting energy (delta_SO), leading to an Eg < delta_SO regime for ~10% Bi composition which is technologically relevant for the design of highly efficient photonic devices. The quaternary alloy GaBiNAs offers further flexibility for band gap tuning, because both nitrogen and bismuth can independently induce band gap reduction. This work reports sp3s* tight binding and 14-band k.p models for the stu…
Highly mismatched semiconductor alloys such as GaNAs and GaBiAs have several novel electronic properties, including a rapid reduction in energy gap with increasing x and also, for GaBiAs, a strong increase in spin orbit- splitting energy with increasing Bi composition. We review here the electronic structure of such alloys and their consequences for ideal lasers. We then describe the substantial progress made in the demonstration of actual GaInNAs telecomm lasers. These have characteristics comparable to conventional InP-based devices. This includes a strong Auger contribution to the threshold…
Incorporation of bismuth (Bi) in dilute quantities in (In)GaAs has been shown to lead to unique electronic properties that can in principle be exploited for the design of high efficiency telecomm lasers. This motivates the development of simple models of the electronic structure of these dilute bismide alloys, which can be used to evaluate their potential as a candidate material system for optical applications. Here, we begin by using detailed calculations based on an $sp^{3}s^{*}$ tight-binding model of (In)GaBi$_{x}$As$_{1-x}$ to verify the presence of a valence band-anticrossing interaction…
The electronic structure of bulk GaAs$_{1-x}$Bi$_x$ systems for different atomic configurations and Bi concentrations is calculated using density functional theory. The results show a Bi-induced splitting between the light-hole and heavy-hole bands at the $Γ$-point. We find a good agreement between our calculated splittings and experimental data. The magnitude of the splitting strongly depends on the local arrangement of the Bi atoms but not on the uni-directional lattice constant of the supercell. The additional influence of external strain due to epitaxial growth on GaAs substrates is studie…
Using an $sp^{3}s^{*}$ tight-binding model we demonstrate how the observed strong bowing of the band gap and spin-orbit-splitting with increasing Bi composition in the dilute bismide alloy GaBi$_{x}$As$_{1-x}$ can be described in terms of a band-anticrossing interaction between the extended states of the GaAs valence band edge and highly localised Bi-related resonant states lying below the GaAs valence band edge. We derive a 12-band $\textbf{k}\cdot\textbf{p}$ Hamiltonian to describe the band structure of GaBi$_{x}$As$_{1-x}$ and show that this model is in excellent agreement with full tight-b…
Using spectroscopic ellipsometry measurements on GaP$_{1-x}$Bi$_{x}$/GaP epitaxial layers up to $x = 3.7$% we observe a giant bowing of the direct band gap ($E_{g}^Γ$) and valence band spin-orbit splitting energy ($Δ_{\textrm{SO}}$). $E_{g}^Γ$ ($Δ_{\textrm{SO}}$) is measured to decrease (increase) by approximately 200 meV (240 meV) with the incorporation of 1% Bi, corresponding to a greater than fourfold increase in $Δ_{\textrm{SO}}$ in going from GaP to GaP$_{0.99}$Bi$_{0.01}$. The evolution of $E_{g}^Γ$ and $Δ_{\textrm{SO}}$ with $x$ is characterised by strong, composition-dependent bowing. …
Bismide semiconductor materials and heterostructures are considered a promising candidate for the design and implementation of photonic, thermoelectric, photovoltaic, and spintronic devices. This work presents a detailed theoretical study of the electronic and optical properties of strongly-coupled GaBi$_x$As$_{1-x}$/GaAs multiple quantum well (MQW) structures. Based on a systematic set of large-scale atomistic tight-binding calculations, our results reveal that the impact of atomic-scale fluctuations in alloy composition is stronger than the inter-well coupling effect, and plays an important …
The LDA-1/2 method is employed in density functional theory calculations for the electronic structure of III-V dilute bismide systems. For the representative example of Ga(SbBi) with Bi concentrations below $10 \%$, it is shown that this method works very efficiently, especially due to its reasonably low demand on computer memory. The resulting bandstructure and wavefunctions are used to compute the interaction matrix elements that serve as input to microscopic calculations of the optical properties and intrinsic losses relevant for optoelectronic applications of dilute bismides.
The magnetic-field dependence of the energy spectrum of GaAs doped with nitrogen impurities is investigated. Our theoretical model is based on the phenomenological Band Anticrossing Model (BAC) which we extended in order to include magnetic field and electron - phonon interaction. Due to the highly localized nature of the nitrogen state, we find that the energy levels are very different from those of pure GaAs. The polaron correction results in a lower cyclotron resonance energy as compared to pure GaAs. The magneto-absorption spectrum exhibits series of asymmetric peaks close to the cyclotron…
Recently, there has been tremendous research interest in novel bismide semiconductor materials (such as GaBi$_x$As$_{1-x}$) for wavelength-engineered, low-loss optoelectronic devices. We report a first study of the quantum confined Stark effect (QCSE) computed for GaBi$_x$As$_{1-x}$/GaAs quantum well (QW) structures based on large-scale atomistic tight-binding calculations. A comprehensive investigation of the QCSE as a function of the applied electric field orientations and the QW Bi fractions reveals unconventional character of the Stark shift at low Bi compositions ($x$=3.125\%). This atypi…
While isovalent doping of GaAs (e.g. by In) leads to a repulsion between the solute atoms, two Cr, Mn, or Fe atoms in GaAs are found to have lower energy than the well-separated pair, and hence attract each other. The strong bonding interaction between levels with t2 symmetry on the transition metal (TM) atoms results in these atoms exhibiting a strong tendency to cluster. Using first-principles calculations, we show that this attraction is maximal for Cr, Mn and Fe while it is minimal for V. The difference is attributed to the symmetry of the highest occupied levels. While the intention is to…
Dilute bismuth (Bi) III-V alloys have recently attracted great attention, due to their properties of band-gap reduction and spin-orbit splitting. The incorporation of Bi into antimonide based III-V semiconductors is very attractive for the development of new optoelectronic devices working in the mid-infrared range (2-5 $μ$m). However, due to its large size, Bi does not readily incorporate into III-V alloys and the epitaxy of III-V dilute bismides is thus very challenging. This book chapter presents the most recent developments in the epitaxy and characterization of GaSbBi alloys and heterostru…
Based on ab initio calculations of Ga_{1-x}Mn_xN_yAs_{1-y} and Ga_{1-x}Mn_xC_yAs_{1-y}, we propose a new codoping method to enhance the Curie temperature T_c of diluted magnetic semiconductors. The solubility of Mn can be increased up to high concentration by the codoping of N or C to reduce the lattice and volume expansion caused by Mn doping. It is found that the impurity band of the majority spin is strongly broadened and pushed up into the higher energy region due to the strong p-d hybridization caused by the codoping, and the T_c becomes higher than the room temperature at x>0.06.
Anion substitution with bismuth (Bi) in III-V semiconductors is an effective method for experimental engineering of the band gap Eg at low Bi concentrations, in particular in gallium arsenide (GaAs). The inverse Bi-concentration dependence of Eg has been found to be linear at low concentrations x and dominated by a valence band-defect level anticrossing between As and Bi occupied p levels. This dependence breaks down at high concentrations where empirical models accounting only for the As-Bi interaction are not applicable. Predictive models for the valence band hybridization require a first-pr…
Using first-principles total-energy methods, we investigate Jahn-Teller distortions in III-V dilute magnetic semiconductors, GaAs:Mn and GaN:Mn in the cubic zinc blende structure. The results for an isolated Mn impurity on a Ga site show that there is no appreciable effect in GaAs, whereas, in GaN there is a Jahn-Teller effect in which the symmetry around the impurity changes from T$_{d}$ to D$_{2d}$ or to C$_{2v}$. The large effect in GaN occurs because of the localized d$^4$ character, which is further enhanced by the distortion. The lower symmetry should be detectable experimentally in cubi…
Dilute-N GaPAsN alloys have great potential for optoelectronics lattice-matched to Si. However, there is a lack of systematic calculation of the optical response of these alloys. The present paper uses the sp^3d^5s^*s_N tight-binding model to calculate the fullband electronic structure of dilute-N GaPAsN, and then calculate the optical response functions considering direct transitions within the electric dipole approximation. Good agreement is obtained for the dielectric function in comparison to available optical data for dilute nitrides. To achieve this, the sp^3d^5s^* parameters for GaP and…
A self-consistent electronic structure calculation based on the Luttinger-Kohn model is performed on GaMnAs/GaAs multilayers. The Diluted Magnetic Semiconductor layers are assumed to be metallic and ferromagnetic. The high Mn concentration (considered as 5% in our calculation) makes it possible to assume the density of magnetic moments as a continuous distribution, when treating the magnetic interaction between holes and the localized moment on the Mn(++) sites. Our calculation shows the distribution of heavy holes and light holes in the structure. A strong spin-polarization is observed, and t…
It is demonstrated that the nearest neighbor Mn pair on the GaAs (001) surface has a lower energy for the [-110] direction comparing to the [110] case. According to the group theory and the Luttinger's method of invariants, this specific Mn distribution results in bulk uniaxial in-plane and out-of-plane anisotropies. The sign and magnitude of the corresponding anisotropy energies determined by a perturbation method and ab initio computations are consistent with experimental results.
We study energetic, magnetic, and electronic properties of diluted substitutional Mn-pairs on the reconstructed $(001)$ GaAs surfaces. The studies are based on first-principles calculations in the framework of the density functional theory. We demonstrate that the stability of the systems strongly depends on the position, orientation, and the distance between the Mn-atoms constituting the pair. Independently of the considered surface reconstruction pattern, the Mn-pairs with Mn-atoms being the nearest neighbors (NN) on cationic sublattice turn out to be energetically more favorable than the pa…
The local electronic structure of N atoms in a diluted GaAs1-xNx (x=3%) alloy, in view of applications in optoelectronics, is determined for the first time using soft-X-ray absorption (SXA) and emission (SXE). Deviations from crystalline GaN, in particular in the conduction band, are dramatic. Employing the orbital character and elemental specificity of the SXE/SXA spectroscopies, we identify a charge transfer from the N atoms at the valence band maximum, reducing the overlap with the wavefunction in conduction band minimum, as the main factor limiting the optical efficiency of GaAs1-xNx alloy…
We present a comparison of the band alignment of the Ga1-xInxNyAs1-y active layers on GaAs and InP substrates in the case of conventionally strained and strained-compensated quantum wells. Our calculated results present that the band alignment of the tensiley strained Ga1-xInxNyAs1-y quantum wells on InP substrates is better than than that of the compressively strained Ga1-xInxNyAs1-y quantum wells on GaAs substrates and both substrates provide deeper conduction wells. Therefore, tensiley strained Ga1-xInxNyAs1-y quantum wells with In concentrations of x<=0.53 on InP substrates can be used saf…
GaSb:N displays promise towards realization of optoelectronic devices accessing the mid-infrared wavelength regime. Theoretical and experimental results on its electronic and optical properties are however few. To address this, we present a first principles, density functional theory study using the hybrid HSE06 exchange-correlation functional of GaSb doped with 1.6$\%$ nitrogen. To study dilute-nitrides with small band gaps, the local density approximation (LDA) is insufficient and more accurate techniques such as HSE06 are needed. We conduct a comparative study on GaAs:N, also with 1.6$\%$ n…
We study light-induced nuclear spin-polarization in a thin film of Ga1-xMnxAs (x 0.04), a dilute ferromagnetic semiconductor, grown on a GaAs substrate. High-field inductively-detected Ga-71 NMR was performed with samples immersed in superfluid He to investigate the effects of continuous-wave near band-edge optical illumination on lattice nuclear spins in the ferromagnetic phase. The photon energy dependence of the light-induced NMR signals for GaAs and the GaMnAs film samples were recorded using circularly polarized light. Interpretation of the data was guided by electronic band structure cal…
We use density-functional theory to describe the initial stages of Fe film growth on GaAs(001), focusing on the interplay between chemistry and magnetism at the interface. Four features appear to be generic: (1) At submonolayer coverages, a strong chemical interaction between Fe and substrate atoms leads to substitutional adsorption and intermixing. (2) For films of several monolayers and more, atomically abrupt interfaces are energetically favored. (3) For Fe films over a range of thicknesses, both Ga- and As-adlayers dramatically reduce the formation energies of the films, suggesting a surfa…
The electronic structures of substitutional rare-earth (RE) impurities in GaAs and cubic GaN are calculated. The total energy is evaluated with the self-interaction corrected local spin density approximation, by which several configurations of the open 4f shell of the rare-earth ion may be investigated. The defects are modelled by supercells of type REGa$_{n-1}$As$_n$, for n=4, 8 and 16. The preferred defect is the rare-earth substituting Ga, for which case the rare-earth valency in intrinsic material is found to be trivalent in all cases except Ce and Pr in GaN. The 3+ --> 2+ f-level is found…
We theoretically analyse band-to-band tunneling (BTBT) in highly-mismatched, narrow-gap dilute nitride and bismide alloys, and quantify the impact of the N- or Bi-induced perturbation of the band structure -- due to band-anticrossing (BAC) with localised impurity states -- on the electric field-dependent BTBT generation rate. For this class of semiconductors the assumptions underpinning the widely-employed Kane model of direct BTBT break down, due to the strong band edge nonparabolicity resulting from BAC interactions. Via numerical calculations based on the Wentzel-Kramers-Brillouin approxima…
We have investigated the electronic structure of the dilute magnetic semiconductor (DMS) $Ga_{0.98}Mn_{0.02}P$ and compared it to that of an undoped $GaP$ reference sample, using hard X-ray photoelectron spectroscopy (HXPS) and hard X-ray angle-resolved photoemission spectroscopy (HARPES) at energies of about 3 keV. We present experimental data, as well as theoretical calculations, in order to understand the role of the Mn dopant in the emergence of ferromagnetism in this material. Both core-level spectra and angle-resolved or angle-integrated valence spectra are discussed. In particular, the …
We report on design, fabrication, and magnetooptical studies of a III-V/II-VI hybrid structure containing a GaAs/AlGaAs/ZnSe/ZnCdMnSe double quantum well (QW). The structure design allows one to tune the QW levels into the resonance, thus facilitating penetration of the electron wave function from the diluted magnetic semiconductor ZnCdMnSe QW into the nonmagnetic GaAs QW and vice versa. Magneto-photoluminescence studies demonstrate level anticrossing and strong intermixing resulting in a drastic renormalization of the electron effective g factor, in perfect agreement with the energy level cal…
The detailed nature of electronic states mediating ferromagnetic coupling in dilute magnetic semiconductors, specifically (Ga,Mn)As, has been an issue of long debate. Two confronting models have been discussed emphasizing host band vs. impurity band carriers. Using angle resolved photoemission we are for the first time able to identify a highly dispersive Mn-induced energy band in (Ga,Mn)As. Our results show that the electronic structure of the (Ga,Mn)As system is significantly modified from that of GaAs throughout the valence band. Close to the Fermi energy, the presence of Mn induces a stron…
Diluted magnetic semiconductors (DMS) like Ga$_{1-x}$Mn$_{x}$As are described by a realistic tight-binding model (TBM) for the (valence) bands of GaAs, by a Zener (J-)term modeling the coupling of the localized Mn-spins to the spins of the valence band electrons, and by an additional potential scattering (V-) term due to the Mn-impurities. We calculate the effective (Heisenberg) exchange interaction between two Mn-moments mediated by the valence electrons. The influence of the number of bands taken into account (6-band or 8-band TBM) and of the potential (impurity) scattering V-term is investi…
The diluted (Ga,Mn)As became a model ferromagnetic semiconductor, however there is still a disagreement on the source of its magnetism. The divergences arise from the results indicating that the holes mediated ferromagnetism reside in the valence band or the impurity band. Full understanding of character of the Mn states in GaAs can bring the increase of (Ga,Mn)As Curie temperature. In this paper we verify the ellipsometric results and compare with more precise photoreflectance method which gives a new insight into the interactions of Mn impurity states with GaAs valence band. Indeed, $E_{1}$ …
We present a theoretical analysis and optimisation of the properties and performance of mid-infrared semiconductor lasers based on the dilute bismide alloy In$_{x}$Ga$_{1-x}$As$_{1-y}$Bi$_{y}$, grown on conventional (001) InP substrates. The ability to independently vary the epitaxial strain and emission wavelength in this quaternary alloy provides significant scope for band structure engineering. Our calculations demonstrate that structures based on compressively strained In$_{x}$Ga$_{1-x}$As$_{1-y}$Bi$_{y}$ quantum wells (QWs) can readily achieve emission wavelengths in the 3 -- 5 $μ$m range…
The crossover between an impurity band (IB) and a valence band (VB) regime as a function of the magnetic impurity concentration in models for diluted magnetic semiconductors (DMS) is studied systematically by taking into consideration the Coulomb attraction between the carriers and the magnetic impurities. The density of states and the ferromagnetic transition temperature of a Spin-Fermion model applied to DMS are evaluated using Dynamical Mean-Field Theory (DMFT) and Monte Carlo (MC) calculations. It is shown that the addition of a square-well-like attractive potential can generate an IB at s…
We report ultrafast transient-grating measurements, above and below the Curie temperature, of the dilute ferromagnetic semiconductor (Ga,Mn)As containing 6% Mn. At 80 K (15 K), we observe that photoexcited electrons in the conduction band have a lifetime of 8 ps (5 ps) and diffuse at about 70 cm2/s (60 cm2/s). Such rapid diffusion requires either an electronic mobility exceeding 7,700 cm2/Vs or a conduction-band effective mass less than half the GaAs value. Our data suggest that neither the scattering rate nor the effective mass of the (Ga,Mn)As conduction band differs significantly from that …
Fundamental optical properties of thin films of (Ga,Mn)As diluted ferromagnetic semiconductor with a low (1%) and high (6%) Mn content and of a reference GaAs film, grown by low-temperature molecular-beam epitaxy, have been investigated by photoreflectance (PR) spectroscopy. In addition, the films were subjected to complementary characterization by means of superconducting quantum interference device (SQUID) magnetometry, Raman spectroscopy, and high resolution X-ray diffractometry. Thorough full-line-shape analysis of the PR spectra, which enabled determination of the E0 electronic transition…
Supercells are often used in ab initio calculations to model compound alloys, surfaces and defects. One of the main challenges of supercell electronic structure calculations is to recover the Bloch character of electronic eigenstates perturbed by disorder. Here we apply the spectral weight approach to unfolding the electronic structure of group III-V and II-VI semiconductor solid solutions. The illustrative examples include: formation of donor-like states in dilute Ga(PN) and associated enhancement of its optical activity, direct observation of the valence band anticrossing in dilute GaAs:Bi, …
Mn doped semiconductors are extremely interesting systems due to their novel magnetic properties suitable for the spintronics applications. It has been shown recently by both theory and experiment that Mn doped GaN systems have a very high Curie temperature compared to that of Mn doped GaAs systems. To understand the electronic and magnetic properties, we have studied Mn doped GaN system in detail by a first principles plane wave method. We show here the effect of varying Mn concentration on the electronic and magnetic properties. For dilute Mn concentration, $d$ states of Mn form an impurity …
The band structure of a prototypical dilute ferromagnetic semiconductor, Ga$_{1-x}$Mn$_{x}$As, is studied across the phase diagram via optical spectroscopy. We prove that the Fermi energy ($E_{F}$) resides in a Mn induced impurity band (IB). This conclusion is based upon careful analysis of the frequency and temperature dependence of the optical conductivity ($σ_{1}(ω,T)$). From our analysis of $σ_{1}(ω,T)$ we infer a large effective mass ($m^*$) of the carriers, supporting the view that conduction occurs in an IB. Our results also provide useful insights into the transport properties of Mn-do…
For the prototype diluted ferromagnetic semiconductor (Ga,Mn)As, there is a fundamental concern about the electronic states near the Fermi level, i.e., whether the Fermi level resides in a well-separated impurity band derived from Mn doping (impurity-band model) or in the valence band that is already merged with the Mn-derived impurity band (valence-band model). We investigate this question by carefully shifting the Fermi level by means of carrier compensation. We use helium-ion implantation, a standard industry technology, to precisely compensate the hole doping of GaAs-based diluted ferromag…
We present a theoretical study of (Ga,Mn)(As,C) diluted magnetic semiconductors with high C acceptor density that combines insights from phenomenological model and microscopic approaches. A tight-binding coherent potential approximation is used to describe the electronic structure in the presence of Mn$_{\rm Ga}$ and C$_{\rm As}$ impurities. We find only a small effect of C on the distribution and coherence of electronic states close to the top of the valence band and on the coupling between Mn moments, even at doping levels of several per cent. These results justify applying the model of ferr…
Gallium oxide (Ga2O3) is a wide-band-gap semiconductor promising for UV sensors and high power transistor applications, with Baliga's figure of merit that far exceeds those of GaN and SiC, second only to diamond. Engineering its band structure through alloying will broaden its range of applications. Using hybrid density functional calculations we study the effects on adding Bi to Ga2O3. While in III-V semiconductors, such as GaAs and InAs, Bi tend to substitute on the pnictide site, we find that in Ga2O3, Bi prefers to substitute on the Ga site, resulting in dilute (Ga_{1-x}Bi_{x})2O3 alloys w…
(Ga,Mn)As is a paradigm diluted magnetic semiconductor which shows ferromagnetism induced by doped hole carriers. With a few controversial models emerged from numerous experimental and theoretical studies, the mechanism of the ferromagnetism in (Ga,Mn)As still remains a puzzling enigma. In this Letter, we use soft x-ray angle-resolved photoemission spectroscopy to positively identify the ferromagnetic Mn 3d-derived impurity band in (Ga,Mn)As. The band appears hybridized with the light-hole band of the host GaAs. These findings conclude the picture of the valence band structure of (Ga,Mn)As dis…
Modulation photoreflectance spectroscopy and Raman spectroscopy have been applied to study the electronic- and band-structure evolution in (Ga,Mn)As epitaxial layers with increasing Mn doping in the range of low Mn content, up to 1.2%. Structural and magnetic properties of the layers were characterized with high-resolution X-ray diffractometry and SQUID magnetometery, respectively. The revealed results of decrease in the band-gap transition energy with increasing Mn content in very low-doped (Ga,Mn)As layers with n-type conductivity are interpreted as a result of merging the Mn-related impurit…
