Possibility of heterostructure band offsets as bulk properties: transitivity rule and orientation effects

New first-principles calculations of valence-band offsets at ZnTe/InAs, CuBr/Ge, CuBr/AlAs, and ZnSe/CuBr interfaces are reported. These are used, together with earlier theoretical values for other systems, to investigate the range of validity of the transitivity rule. For a wide class of systems this rule is found to hold with good precision, but a few compounds (e.g., CuBr) cause pronounced nontransitivity. For three common-anion systems, GaAs/AlAs, AlP/GaP, and AlSb/GaSb, we examine the dependence of the offset on growth direction. The differences between the (110) and (001) discontinuities for these systems are small, less than 0.07 eV.