Chemical trends of stability and band alignment of lattice-matched II-VI/III-V semiconductor interfaces

Using the first-principles density functional theory method, we systematically investigate the structural and electronic properties of heterovalent interfaces of the lattice-matched II-VI/III-V semiconductors, i.e., ZnTe/GaSb, ZnSe/GaAs, ZnS/GaP, andZnO/GaN. We find that, independent of the orientations, the heterovalent superlattices with period n = 6 are energetically more favorable to form nonpolar interfaces. For the [001] interface, the stable nonpolar interfaces are formed by mixing 50% group-III with 50% group-II atoms or by mixing 50% group-V with 50% group-VI atoms; for the [111] nonpolar interfaces, the mixings are 25% group-III (II) and 75% group-II (III) atoms or 25% group-V (VI) and 75% group-VI (V) atoms. For all the nonpolar interfaces, the [110] interface has the lowest interfacial energy because it has the minimum number of II-V or III-VI "wrong bonds" per unit interfacial area. The interfacial energy increases when the atomic number of the elements decreases, except for the ZnO/GaN system. The band alignments between the II-VI and III-V compounds are drastically different depending on whether they have mixed-cation or mixed-anion interfaces, but the averaged values are nearly independent of the orientations. Similarly, other than ZnO/GaN, the valence-band offsets also increase as the atomic number of the elements decreases. The abnormal trends in interfacial energy and band alignment for ZnO/GaN are primarily attributed to the very short bond lengths in this system. The underlying physics behind these trends are explained.