We structurally, compositionally, and optically characterize vertically aligned AlAs/GaAs/GaP heterostructured nanowires (NWs) grown on a Si substrate used for the integration of an optically active material into Si-based technology and its band-gap engineering. The NWs were grown using Au colloidal nanoparticles as catalysts via the vapor–liquid–solid mode. By alternately changing the source material between Ga and Al, we grew GaAs/AlAs/GaAs/AlAs/GaAs NWs with a well-controlled periodic structure and composition on a GaP segment, which was epitaxially grown on a Si substrate. No dislocations induced by the lattice mismatch were found in the GaAs segment of the NWs grown on the GaP segment despite a lattice mismatch of as large as 4%. This is because the NWs have a particular columnar structure with nanoscale diameters and can therefore relax laterally and accommodate a high strain. Stacking faults exist in zinc-blende-structured GaP and GaAs segments, while the AlAs segment has a pure wurtzite crystal structure without any stacking faults. It is found that the stacking fault in III–V NWs is significantly dependent on the stacking fault energy and ionicity. With increasing ionicity, stacking faults can be more easily introduced, and these NWs tend to have a wurtzite crystal structure. In addition, owing to the high surface nonradiative recombination rate resulting from the surface states on the GaAs NW surface, the excitonic emission of photoluminescence from the bare GaAs NW segment has a decay time of as short as 30 ps. With the growth of an AlGaAs capping layer and GaAs outer shell layer, the decay time of the excitonic emission increased 46-fold, indicating an excellent passivation effect on the GaAs segment surface.
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