We report heteroepitaxial growth of (101 2) oriented (r-plane) ZnO films on Si(100) substrates. The films were grown by pulsed laser deposition and integration of ZnO with silicon was achieved using a tetragonal yttria stabilized zirconia (YSZ) buffer layer. It was observed that ZnO films grown at temperatures in the range of 700-750 degrees C with relatively high oxygen pressure ( approximately 70 mTorr) were (101 2) oriented. ZnO films deposited with lower oxygen pressures were found to be purely (0002) orientated. Experiments carried out to elucidate the role of oxygen pressure indicated that the crystallographic orientation of ZnO depends on the nature of atomic termination of YSZ layer. It has been proposed that crystallographic orientation of ZnO is controlled by chemical free energy associated with ZnO-YSZ interface. Detailed x-ray diffraction and transmission electron microscopy studies showed existence of four types of in-plane domains in r-plane ZnO films. Optical characterization demonstrated that photoluminescence of r-plane ZnO films was superior to that of c-plane ZnO films grown under similar conditions.