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For the implementation of optoelectronic devices on silicon, which could be realized by a combination of Si and direct-bandgap III/V semiconductors, a defect free nucleation layer of GaP on Si is essential. This paper summarizes the results of structural investigations carried out by transmission electron microscopy on defects, which can be observed in GaP films grown by metal organic vapor phase epitaxy on exactly oriented (001) Si substrates. Under optimized growth conditions the anti phase domains (APDs), which arise in the III/V semiconductor at the monoatomic steps on the silicon surface, show a specific typical shape. They self-annihilate on {112} planes in the GaP and can be observed in [110] cross-section, looking perpendicular to the steps on the Si surface. In contrast to that, the anti phase boundaries (APBs) lie on {110} GaP planes in the [−110] direction, parallel to the steps on the Si surface. From convergent beam electron diffraction one can show, that the GaP has Ga-polarity in the [110] direction, viewing perpendicular to the steps on the Si-surface. With the knowledge of the polarity and the shape of the APDs, we suggest a model for chemical composition of their boundaries. According to this model the APBs, which lie on {110} and {112} planes, consist of an equal amount of Ga-Ga and P-P bonds. Furthermore, when stacking faults and twins are observed, they only occur in the Ga-polar [110] GaP direction, and consequently lie on {111}A planes. With the knowledge of the structure of the defects that arise at the GaP/Si interface we suggest growth conditions and an optimum Si surface structure, which guarantee a defect-free GaP overgrowth layer after several 10 nms of III/V material, even on exact Si substrates.

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