Alex Zunger

Bio: Alex Zunger is an academic researcher from University of Colorado Boulder. The author has contributed to research in topics: Band gap & Quantum dot. The author has an hindex of 128, co-authored 826 publications receiving 78798 citations. Previous affiliations of Alex Zunger include Tel Aviv University & University of Wisconsin-Madison.

A universal trend in the binding energies of deep impurities in semiconductors

Abstract: Whereas the conventional practice of referring binding energies of deep donors and acceptors to the band edges of the host semiconductor does not produce transparent chemical trends when the same impurity is compared in different crystals, referring them to the vacuum level through the use of the photothreshold reveals a remarkable material invariance of the levels in III-V and II-VI semiconductors. It is shown that this is a consequence of the antibonding nature of the deep gap level with respect to the impurity atom-host orbital combinations.

Origins of the doping asymmetry in oxides : hole doping in NiO versus electron doping in ZnO

Abstract: The doping response of the prototypical transparent oxides NiO ($p$-type), ZnO ($n$-type), and MgO (insulating) is caused by spontaneous formation of compensating centers, leading to Fermi-level pinning at critical Fermi energies. We study the doping principles in these oxides by first-principles calculations of carrier-producing or -compensating defects and of the natural band offsets, and identify the dopability trends with the ionization potentials and electron affinities of the oxides. We find that the room-temperature free-hole density of cation-deficient NiO is limited by a too large ionization energy of the Ni vacancy, but it can be strongly increased by extrinsic dopants with shallower acceptor levels.

Many-electron multiplet effects in the spectra of 3 d impurities in heteropolar semiconductors

Abstract: The excitation energies of impurities in semiconductors, as well as their donor and acceptor ionization energies, represent a combination of one-electron and many-electron multiplet effects, where the latter contribution becomes increasingly significant as localized states are formed. Analysis of the absorption and ionization data for 3d impurities is often obscured by the inability of contemporary multiplet theories (e.g., the Tanabe-Sugano approach) to separate these two contributions and by the inadequacy of mean-field, one-electron theories that neglect multiplet effects altogether. We present a novel theory of the multiplet structure of localized impurities in semiconductors that circumvents the major shortcomings of the classical Tanabe-Sugano approach and at the same time separates many-electron from mean-field effects. Excitation and ionization energies are given as a sum of mean-field (MF) and multiplet corrections (MC): AE =hEMF +AEMc. We determine EEMc from the analysis of the experimental data. This provides a way to compare experimentally deduced mean-field excitation and ionization energies AEMF —AE —AEMc with the results of electronicstructure calculations. The three central quantities of the theory —the eand t2-orbital deformation parameters and the effective crystal-field splitting —can be obtained from mean-field electronicstructure calculations, or, alternatively, can be deduced from experiment. In this paper, we analyze the absorption spectra of 3d impurities in ZnO, ZnS, ZnSe, and GaP, as well as those of the bulk Mott insulators NiO, CoO, and MnO, in light of the new approach to multiplet effects. These mean-field parameters are shown to display simple chemical regularities with the impurity atomic number and the covalency of the host crystal; they combine, however, to produce interesting nonmonotonic trends in the many-electron correction terms AEMC. These trends explain many of the hitherto puzzling discrepancies between one-electron (AEMF ) theory and experiment (hE). This approach unravels the chemical trends underlying the excitation and donor or acceptor spectra, pro-

Effective Band Structure of Random Alloys

Abstract: Random substitutional A(x)B(1-x) alloys lack formal translational symmetry and thus cannot be described by the language of band-structure dispersion E(k(→)) Yet, many alloy experiments are interpreted phenomenologically precisely by constructs derived from wave vector k(→), eg, effective masses or van Hove singularities Here we use large supercells with randomly distributed A and B atoms, whereby many different local environments are allowed to coexist, and transform the eigenstates into an effective band structure (EBS) in the primitive cell using a spectral decomposition The resulting EBS reveals the extent to which band characteristics are preserved or lost at different compositions, band indices, and k(→) points, showing in (In,Ga)N the rapid disintegration of the valence band Bloch character and in Ga(N,P) the appearance of a pinned impurity band

First-principles statistical mechanics of structural stability of intermetallic compounds.

Abstract: While as elemental solids, Al, Ni, Cu, Rh, Pd, Pt, and Au crystallize in the face-centered-cubic (fcc) structure, at low temperatures, their 50%-50% compounds exhibit a range of structural symmetries: CuAu has the fcc-based L1o structure, CuPt has the rhombohedral L1& structure, and CuPd and A1Ni have the body-centered-cubic B2 structure, while CuRh does not exist (it phase separates into Cu and Rh). Phenomenological approaches attempt to rationalize this type of structural selectivity in terms of classical constructs such as atomic sizes, electronegativities, and electron/atom ratios. More recently, attempts have been made at explaining this type of selectivity in terms of the (quantum-mechanical) electronic structure, e.g. , by contrasting the self-consistently calculated total electron+ion energy of various ordered structures. Such calculations, however, normally select but a small, O(10) subset of "intuitive structures" out of the 2 possible configurations of two types of atoms on a fixed lattice with X sites, searching for the lowest energy. We use instead first-principles calculations of the total energies of O(10) structures to define a multispin Ising Hamiltonian, whose ground-state structures can be systematically searched by using methods of lattice theories. Extending our previous work on semiconductor alloys [S.-H. Wei, L. G. Ferreira, and A. Zunger, Phys. Rev. B 41, 8240 (1990)], this is illustrated here for the intermetallic compounds A1Ni, CuRh, CuPd, CuPt, and CuAu, for which the correct ground states are identified out of -65000 configurations, through the combined use of the densityfunctional formalism (to extract Ising-type interaction energies) with a simple configurational-search strategy (to find ground states). This establishes a direct and systematic link between the electronic structure and phase stability.

Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium.

Abstract: We present ab initio quantum-mechanical molecular-dynamics simulations of the liquid-metal--amorphous-semiconductor transition in Ge. Our simulations are based on (a) finite-temperature density-functional theory of the one-electron states, (b) exact energy minimization and hence calculation of the exact Hellmann-Feynman forces after each molecular-dynamics step using preconditioned conjugate-gradient techniques, (c) accurate nonlocal pseudopotentials, and (d) Nos\'e dynamics for generating a canonical ensemble. This method gives perfect control of the adiabaticity of the electron-ion ensemble and allows us to perform simulations over more than 30 ps. The computer-generated ensemble describes the structural, dynamic, and electronic properties of liquid and amorphous Ge in very good agreement with experiment. The simulation allows us to study in detail the changes in the structure-property relationship through the metal-semiconductor transition. We report a detailed analysis of the local structural properties and their changes induced by an annealing process. The geometrical, bonding, and spectral properties of defects in the disordered tetrahedral network are investigated and compared with experiment.

Self-interaction correction to density-functional approximations for many-electron systems

Abstract: The exact density functional for the ground-state energy is strictly self-interaction-free (i.e., orbitals demonstrably do not self-interact), but many approximations to it, including the local-spin-density (LSD) approximation for exchange and correlation, are not. We present two related methods for the self-interaction correction (SIC) of any density functional for the energy; correction of the self-consistent one-electron potenial follows naturally from the variational principle. Both methods are sanctioned by the Hohenberg-Kohn theorem. Although the first method introduces an orbital-dependent single-particle potential, the second involves a local potential as in the Kohn-Sham scheme. We apply the first method to LSD and show that it properly conserves the number content of the exchange-correlation hole, while substantially improving the description of its shape. We apply this method to a number of physical problems, where the uncorrected LSD approach produces systematic errors. We find systematic improvements, qualitative as well as quantitative, from this simple correction. Benefits of SIC in atomic calculations include (i) improved values for the total energy and for the separate exchange and correlation pieces of it, (ii) accurate binding energies of negative ions, which are wrongly unstable in LSD, (iii) more accurate electron densities, (iv) orbital eigenvalues that closely approximate physical removal energies, including relaxation, and (v) correct longrange behavior of the potential and density. It appears that SIC can also remedy the LSD underestimate of the band gaps in insulators (as shown by numerical calculations for the rare-gas solids and CuCl), and the LSD overestimate of the cohesive energies of transition metals. The LSD spin splitting in atomic Ni and $s\ensuremath{-}d$ interconfigurational energies of transition elements are almost unchanged by SIC. We also discuss the admissibility of fractional occupation numbers, and present a parametrization of the electron-gas correlation energy at any density, based on the recent results of Ceperley and Alder.

A comprehensive review of zno materials and devices

Abstract: The semiconductor ZnO has gained substantial interest in the research community in part because of its large exciton binding energy (60meV) which could lead to lasing action based on exciton recombination even above room temperature. Even though research focusing on ZnO goes back many decades, the renewed interest is fueled by availability of high-quality substrates and reports of p-type conduction and ferromagnetic behavior when doped with transitions metals, both of which remain controversial. It is this renewed interest in ZnO which forms the basis of this review. As mentioned already, ZnO is not new to the semiconductor field, with studies of its lattice parameter dating back to 1935 by Bunn [Proc. Phys. Soc. London 47, 836 (1935)], studies of its vibrational properties with Raman scattering in 1966 by Damen et al. [Phys. Rev. 142, 570 (1966)], detailed optical studies in 1954 by Mollwo [Z. Angew. Phys. 6, 257 (1954)], and its growth by chemical-vapor transport in 1970 by Galli and Coker [Appl. Phys. ...