Magnetism without magnetic ions: percolation, exchange, and formation energies of magnetism-promoting intrinsic defects in CaO

We investigate theoretically the prospects of ferromagnetism being induced by cation vacancies in nonmagnetic oxides. A single Ca vacancy V(0)(Ca) has a magnetic moment due to its open-shell structure but the ferromagnetic interaction between two vacancies extends only to four neighbors or less. To achieve magnetic percolation on a fcc lattice with such an interaction range one needs a minimum of 4.9% vacancies, or a concentration 1.8 x 10(21) cm(-3). Total-energy calculations for CaO show, however, that due to the high vacancy formation energy even under the most favorable growth conditions one can not obtain more than 0.003% or 10(18) cm(-3) vacancies at equilibrium, showing that a nonequilibrium vacancy-enhancement factor of 10(3) is needed to achieve magnetism in such systems.     

Metal-dimer atomic reconstruction leading to deep donor states of the anion vacancy in II-VI and chalcopyrite semiconductors

First-principles total-energy calculations reveal a novel local atomic reconstruction mode around anion vacancies in II-VI and chalcopyrite compounds resulting from the formation of metal dimers. As a consequence, the neutral Se vacancy has an unexpected low symmetry in ZnSe and becomes a deep donor in both ZnSe and CuGaSe2, contrary to the common belief regarding chalcopyrites. The calculated optical transition energies explain the hitherto puzzling absorption bands observed in the classic experiments of the color center in ZnS.     

Density functional theory calculations establish the experimental evidence of the DX center atomic structure in CdTe

The In DX center and the DX-like configuration of the Cd host atom in CdTe are investigated using density functional theory. The simultaneous calculation of the atomic structure and the electric field gradient (EFG) allows one to correlate the theoretically predicted structure of the DX center with an experimental observable, namely, the EFG obtained from radioactive 111In/111Cd probe atoms in In doped CdTe. In this way, the experimental identification of the DX center structure is established.     

Impurity clustering and ferromagnetic interactions that are not carrier induced in dilute magnetic semiconductors: the case of Cu2O:Co

Current models for ferromagnetism in diluted magnetic semiconductors, such as "p-d exchange" or "double-exchange", rely on the presence of partially filled gap states. We point out a new mechanism, not requiring partially filled states, in which ferromagnetic coupling arises from the occupation of previously unoccupied levels when two transition metal impurities form a close pair. We find from first-principles calculations that this mechanism explains strong ferromagnetic coupling between Co impurities in Cu2O, and at the same time gives rise to Co clustering.     

Intrinsic DX centers in ternary chalcopyrite semiconductors

In III-V and II-VI semiconductors, certain nominally electron-donating impurities do not release electrons but instead form deep electron-traps known as "DX centers." While in these compounds, such traps occur only after the introduction of foreign impurity atoms, we find from first-principles calculations that in ternary I-III-VI2 chalcopyrites like CuInSe2 and CuGaSe2, DX-like centers can develop without the presence of any extrinsic impurities. These intrinsic DX centers are suggested as a cause of the difficulties to maintain high efficiencies in CuInSe2-based thin-film solar-cells when the band gap is increased by addition of Ga.     

Surface origin of high conductivities in undoped In2O3 thin films

The microscopic cause of conductivity in transparent conducting oxides like ZnO, In{2}O{3}, and SnO{2} is generally considered to be a point defect mechanism in the bulk, involving intrinsic lattice defects, extrinsic dopants, or unintentional impurities like hydrogen. We confirm here that the defect theory for O-vacancies can quantitatively account for the rather moderate conductivity and off-stoichiometry observed in bulk In{2}O{3} samples under high-temperature equilibrium conditions. However, nominally undoped thin-films of In{2}O{3} can exhibit surprisingly high conductivities exceeding by 4-5 orders of magnitude that of bulk samples under identical conditions (temperature and O{2} partial pressure). Employing surface calculations and thickness-dependent Hall measurements, we demonstrate that surface donors rather than bulk defects dominate the conductivity of In{2}O{3} thin films.     

Atomic control of conductivity versus ferromagnetism in wide-gap oxides via selective doping: V, Nb, Ta in anatase TiO2

We identify two general types of electronic behaviors for transition-metal impurities that introduce excess electrons in oxides. (i) The dopants introduce resonant states inside the host conduction band and produce free electrons; (ii) the dopants introduce a deep gap state that carries a magnetic moment. By combining electronic structure calculations, thermodynamic simulations, and percolation theory, we quantify these behaviors for the case of column V-B dopants in anatase TiO2. Showing behavior (i), Nb and Ta dopants can convert the insulator TiO2 into a transparent conductor. Showing behavior (ii), V dopants could convert nonmagnetic TiO2 into a ferromagnet. Whether a dopant shows behavior (i) or (ii) is encoded in its atomic d orbital energy.     

Dopability, intrinsic conductivity, and nonstoichiometry of transparent conducting oxides

Existing defect models for In(2)O(3) and ZnO are inconclusive about the origin of conductivity, nonstoichiometry, and coloration. We apply systematic corrections to first-principles calculated formation energies Delta H, and validate our theoretical defect model against measured defect and carrier densities. We find that (i) intrinsic acceptors ("electron killers") have a high Delta H explaining high n-dopability, (ii) intrinsic donors ("electron producers") have either a high Delta H or deep levels, and do not cause equilibrium-stable conductivity, (iii) the O vacancy V(O) has a low Delta H leading to O deficiency, and (iv) V(O) has a metastable shallow state, explaining the paradoxical coexistence of coloration and conductivity.     

Identification of Defects in Semiconductors via their Electric Field Gradients

Recent theoretical calculations show for defect complexes in semiconductors, characterized by electric field gradients (EFG), that their chemical compositions, electronic charge states and the induced lattice relaxations can be obtained by comparing the experimental and calculated EFG. The experimental data are obtained by perturbed γγ angular correlation experiments and the calculations are performed using ab initio full potential methods in the framework of density functional theory. This revised version was published online in September 2006 with corrections to the Cover Date.