Thermodynamically ZnO is a prototype material which stabilizes with stable and metastable wurtzite and zincblende phases. In principle, the phase stability of ZnO depends on many parameters; however, heterointerface plays a significant role in controlling the ZnO crystalline structures. ZnO/SiC and ZnO/ZnS heterointerfaces have been studied where ZnO layers grow along the out-of-plane with an epitaxial relationship of (0 0 0 1)(ZnO)parallel to|(0 0 0 1)(SiC), [1 1 (2) over bar 0](ZnO)parallel to|[1 1 (2) over bar 0](SiC) and [1 1 0](ZnO)parallel to|[1 1 0](GaAs), [1 (1) over bar 0](ZnO)[1 (1) over bar 0](GaAs), respectively. Although both the ZnO phases grew uniaxially with the substrates, thin-interlayer and imbalanced charge distribution were observed in the ZnO/SiC heterointerfaces, while the ZnO/GaAs heterointerface was dominant with stacking faults and phase coexistence in lattice matrix, together with the common misfit-dislocations. Photoluminescence showed a significant bandgap energy difference in ZnO phases by similar to 60 meV, and higher electron mobility in the zincblende ZnO material. (C) 2008 Elsevier B. V. All rights reserved.