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.

Cylindrically shaped zinc-blende semiconductor quantum dots do not have cylindrical symmetry: Atomistic symmetry, atomic relaxation, and piezoelectric effects

Abstract: Self-assembled quantum dots are often modeled by continuum models (effective mass or $\mathbf{k}∙\mathbf{p}$) that assume the symmetry of the dot to be that of its overall geometric shape. Lens-shaped or conical dots are thus assumed to have continuous cylindrical symmetry ${C}_{\mathrm{\ensuremath{\infty}}v}$, whereas pyramidal dots are assumed to have ${C}_{4v}$ symmetry. However, considering that the III--V dots are made of atoms arranged on the (relaxed) positions of a zinc-blende lattice, one would expect the highest possible symmetry in these structures to be ${C}_{2v}$. In this symmetry group all states are singly degenerate and there are no a priori reason to expect, e.g., the electron $P$ states (usually the second and third electron levels of dominant orbital $P$ character) to be degenerate. Continuum models, however, predict these states to be energetically degenerate unless an irregular shape is postulated. We show that, in fact, the true (atomistic) symmetry of the dots is revealed when the effects of (i) interfacial symmetry, (ii) atomistic strain, and (iii) piezoelectricity are taken into account. We quantify the contributions of each of these effects separately by calculating the splitting of electron $P$ levels for different dot shapes at different levels of theory. We find that for an ideal square-based pyramidal InAs/GaAs dot the interfacial symmetry of the unrelaxed dot splits the $P$ level by 3.9 meV, atomistic relaxation adds a splitting of 18.3 meV (zero if continuum elasticity is used to calculate strain) and piezoelectricity reduces the splitting by \ensuremath{-}8.4 meV, for a total splitting of 13.8 meV. We further show that the atomistic effects (i) and (ii) favor an orientation of the electron wave functions along the $[1\overline{1}0]$ direction while effect (iii) favors the [110] direction. Whereas effects (i) + (ii) prevail for a pyramidal dot, for a lens shaped dot, effect (iii) is dominant. We show that the 8--band $\mathbf{k}∙\mathbf{p}$ method, applied to pyramidal InAs/GaAs dots describes incorrectly the splitting and order of $P$ levels (--9 meV instead of 14 meV splitting) and yields the orientation [110] instead of $[1\overline{1}0]$.

Electronic Structure of 3d Transition-Atom Impurities in Semiconductors

Abstract: Publisher Summary The chapter presents a discussion on electronic structure of three-dimensional (3d) transition-atom impurities in semiconductors. The effects of 3d impurities in semiconductors have preoccupied the field since the invention of the transistor. Reliable experimental data for germanium and silicon became available quite early. The chapter presents an in-depth review of the present status of the field. This review contains a most careful and detailed exposition of various aspects of the subject, presented, as the author states using “the combined points of view of theoretical solid-state physics, semiconductor physics, and classical inorganic chemistry.” The chapter discusses the great progress that has been made. The chapter presents a review on the recent developments vis a vis the new experimental methodologies and the classical phenomenological approaches used earlier to understand deep 3d impurities. The author attempts to present a coherent picture of the understanding of isolated 3d impurities in cubic semiconductors from the combined points of view of theoretical solid-state physics, semiconductor physics, and classical inorganic chemistry.

Cu-Au, Ag-Au, Cu-Ag and Ni-Au intermetallics: First-principles study of phase diagrams and structures

Abstract: The classic metallurgical systems -- noble metal alloys -- that have formed the benchmark for various alloy theories, are revisited. First-principles fully relaxed general potential LAPW total energies of a few ordered structures are used as input to a mixed-space cluster expansion calculation to study the phase stability, thermodynamic properties and bond lengths in Cu-Au, Ag-Au, Cu-Ag and Ni-Au alloys. (i) Our theoretical calculations correctly reproduce the tendencies of Ag-Au and Cu-Au to form compounds and Ni-Au and Cu-Ag to phase separate at T=0 K. (ii) Of all possible structures, Cu/sub 3/Au (L1/sub 2/) and CuAu (L1/sub 0/) are found to be the most stable low-temperature phases of Cu/sub 1-x/Au/sub x/ with transition temperatures of 530 K and 660 K, respectively, compared to the experimental values 663 K and 670 K. The significant improvement over previous first-principles studies is attributed to the more accurate treatment of atomic relaxations in the present work. (iii) LAPW formation enthalpies demonstrate that L1/sub 2/, the commonly assumed stable phase of CuAu/sub 3/, is not the ground state for Au-rich alloys, but rather that ordered superlattices are stabilized. (iv) We extract the non-configurational (e.g., vibrational) entropies of formation and obtain large values for the size mismatched systems: 0.48 k/sub B//atom in Ni/sub 0.5/Au/sub 0.5/ (T=1100 K), 0.37 k/sub B//atom in Cu/sub 0.14/Ag/sub 0.86/ (T=1052 K), and 0.16 k/sub B//atom in Cu/sub 0.5/Au/sub 0.5/ (T=800 K). (v) Using 8 atom/cell special quasirandom structures we study the bond lengths in disordered Cu-Au and Ni-Au alloys and obtain good qualitative agreement with recent EXAFS measurements.

Band‐gap narrowing in ordered and disordered semiconductor alloys

Abstract: Either spontaneous or artificial ordering of semiconductor alloys into CuAu‐like, chalcopyrite, or CuPt‐like structures is predicted to be accompanied by a reduction in the direct band gaps relative to the average over the binaries. In this letter calculated results are presented for seven III‐V and II‐VI alloys. We identify the mechanism for this band‐gap narrowing as band folding followed by repulsion between the folded states. The latter is coupled by the non‐zinc‐blende component of the superlattice potential. The same physical mechanism (but to a different extent) is responsible for gap bowing in disordered alloys.

Temperature dependence of excitonic radiative decay in CdSe quantum dots: the role of surface hole traps.

Abstract: Using atomistic, semiempirical pseudopotential calculations, we show that if one assumes the simplest form of a surface state in a CdSe nanocrystal--an unpassivated surface anion site--one can explain theoretically several puzzling aspects regarding the observed temperature dependence of the radiative decay of excitons. In particular, our calculations show that the presence of surface states leads to a mixing of the dark and bright exciton states, resulting in a decrease of 3 orders of magnitude of the dark-exciton radiative lifetime. This result explains the persistence of the zero-phonon emission line at low temperature, for which thermal population of higher-energy bright-exciton states is negligible. Thus, we suggest that surface states are the controlling factor of dark-exciton radiative recombination in currently synthesized colloidal CdSe nanocrystals.

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. ...