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The electronic structure of few-layer(FL) black phosphorus(BP) sensitivelydepends on the sample thickness, strain and doping. In this paper, we show thatit is also vulnerable to air-exposure. The oxidation of BP caused byair-exposure gives several optical signatures, including the broadening ofresonance peaks and increased Stokes shift between infrared (IR) absorption andphotoluminescence (PL) peaks. More importantly, air exposure causes blue shiftsof all resonance peaks in IR absorption and PL spectra, with more prominenteffects for thinner samples and higher order subband transitions. Our studyalludes a convenient and exotic way for band-structure engineering of FL-BPthrough controllable air-exposure or defect creation.

Electronic structures of air-exposed few-layer black phosphorus by optical spectroscopy