Structural and optical properties of heterostructured GaAs/AlGaAs/GaAs core/inner shell/outer shell nanowires are studied. Transmission electron microscopy and Raman scattering measurements unambiguously identify the presence of segments crystallized in zincblende and wurtzite phases, which spread to the shells. Four observed photoluminescence lines are assigned to the radiative recombination of photoexcited electrons confined in the center of the GaAs core and at the heterointerface between the outer GaAs shell and the inner AlGaAs shell with the holes localized at the heterointerface between the core and the inner AlGaAs shell; both recombinations take place in zincblende and wurtzite phases. One additional photoluminescence line is attributed to the spatially indirect recombination between the electrons in zincblende and the holes in wurtzite phases. The bandgap of the wurtzite phase and the band offsets between the zincblende and wurtzite phases are determined.
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