The orientation dependence of the energy band discontinuities at an abrupt heterojunction between lattice‐matched zincblende semiconductors is studied by modeling the microscopic charge distribuion near the heterojunction. The model includes both ionic and bond charges, and assumes that each chemical bond contributes independently to the total charge distribution. The energy band lineups are derived by calculating the interface dipole. The results indicate that there should be no difference in the band lineups for heterojuncions on (100) and (111) faces of similar polarity, and that the (110) lineup should be equal to the mean of the lineups for the A and B polar faces. The lineup should be completely independent of orientation for heterojunctions which have an element common to both semiconductors, such as GaAs–AlAs. Any difference in band lineup between heterojunctions on nonpolar (110) planes and those on the (100) or (111) planes is related to deviations of the bond parameters from chemically systematic behavior, and thus is expected to be small.

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