Alex Zunger

Calculated natural band offsets of all II–VI and III–V semiconductors: Chemical trends and the role of cation d orbitals

Using first-principles all-electron band structure method, we have systematically calculated the natural band offsets ΔEv between all II–VI and separately between III–V semiconductor compounds. Fundamental regularities are uncovered: for common-cation systems ΔEv decreases when the cation atomic number increases, while for common-anion systems ΔEv decreases when the anion atomic number increases. We find that coupling between anion p and cation d states plays a decisive role in determining the absolute position of the valence band maximum and thus the observed chemical trends.

Effects of Ga addition to CuInSe2 on its electronic, structural, and defect properties

Using a first-principles band structure method we have theoretically studied the effects of Ga additions on the electronic and structural properties of CuInSe2. We find that (i) with increasing xGa, the valence band maximum of CuIn1−xGaxSe2 (CIGS) decreases slightly, while the conduction band minimum (and the band gap) of CIGS increases significantly, (ii) the acceptor formation energies are similar in both CuInSe2 (CIS) and CuGaSe2 (CGS), but the donor formation energy is larger in CGS than in CIS, (iii) the acceptor transition levels are shallower in CGS than in CIS, but the GaCu donor level in CGS is much deeper than the InCu donor level in CIS, and (iv) the stability domain of the chalcopyrite phase increases with respect to ordered defect compounds. Our results are compared with available experimental observations.

A phenomenological model for systematization and prediction of doping limits in II–VI and I–III–VI2 compounds

Semiconductors differ widely in their ability to be doped. As their band gap increases, it is usually possible to dope them either n or p type, but not both. This asymmetry is documented here, and explained phenomenologically in terms of the “doping pinning rule.”

Band offsets and optical bowings of chalcopyrites and Zn‐based II‐VI alloys

Using first‐principles band‐structure theory we have systematically calculated the (i) alloy bowing coefficients, (ii) alloy mixing enthalpies, and (iii) interfacial valence‐ and conduction‐band offsets for three mixed‐anion (CuInX2, X=S, Se, Te) and three mixed‐cation (CuMSe2, M=Al, Ga, In) chalcopyrite systems. The random chalcopyrite alloys are represented by special quasirandom structures (SQS). The calculated bowing coefficients are in good agreement with the most recent experimental data for stoichiometric alloys. Results for the mixing enthalpies and the band offsets are provided as predictions to be tested experimentally. Comparing our calculated bowing and band offsets for the mixed‐anion chalcopyrite alloys with those of the corresponding Zn chalcogenide alloys (ZnX, X=S, Se, Te), we find that the larger p−d coupling in chalcopyrite alloys reduces their band offsets and optical bowing. Bowing parameters for ordered, Zn‐based II‐VI alloys in the CuAu, CuPt, and chalcopyrite structures are present...

Comparison of two methods for describing the strain profiles in quantum dots

The electronic structure of interfaces between lattice-mismatched semiconductors is sensitive to the strain. We compare two approaches for calculating such inhomogeneous strain—continuum elasticity [(CE), treated as a finite difference problem] and atomistic elasticity. While for small strain the two methods must agree, for the large strains that exist between lattice-mismatched III-V semiconductors (e.g., 7% for InAs/GaAs outside the linearity regime of CE) there are discrepancies. We compare the strain profile obtained by both approaches (including the approximation of the correct C2 symmetry by the C4 symmetry in the CE method) when applied to C2-symmetric InAs pyramidal dots capped by GaAs.

First-principles calculation of band offsets, optical bowings, and defects in CdS, CdSe, CdTe, and their alloys

Using first principles band structure theory we have calculated (i) the alloy bowing coefficients, (ii) the alloy mixing enthalpies, and (iii) the interfacial valence band offsets for three Cd-based (CdS, CdSe, CdTe) compounds. We have also calculated defect formation energies and defect transition energy levels of Cd vacancy VCd and CuCd substitutional defect in CdS and CdTe, as well as the isovalent defect TeS in CdS. The calculated results are compared with available experimental data.

Effects of Na on the electrical and structural properties of CuInSe2

We found theoretically that Na has three effects on CuInSe2: (1) If available in stoichiometric quantities, Na will replace Cu, forming a more stable NaInSe2 compound having a larger band gap (higher open-circuit voltage) and a (112)tetra morphology. The ensuing alloy NaxCu1−xInSe2 has, however, a positive mixing enthalpy, so NaInSe2 will phase separate, forming precipitates. (2) When available in small quantities, Na will form defect on Cu site and In site. Na on Cu site does not create electric levels in the band gap, while Na on In site creates acceptor levels that are shallower than CuIn. The formation energy of Na(InCu) is very exothermic, therefore, the major effect of Na is the elimination of the InCu defects and the resulting increase of the effective hole densities. The quenching of InCu as well as VCu by Na reduces the stability of the (2VCu−+InCu2+), thus suppressing the formation of the “Ordered Defect Compounds.” (3) Na on the surface of CuInSe2 is known to catalyze the dissociation of O2 int...

n -type doping of CuIn Se 2 and CuGa Se 2

The efficiency of

Valence band splittings and band offsets of AlN, GaN, and InN

\mathrm{CuIn}{\mathrm{Se}}_{2}

Practical doping principles

based solar cell devices could improve significantly if