Raman spectroscopy studies of black phosphorus

•The intrinsic properties and applications of black phosphorus are fully and systematically characterized by various Raman spectra.•The crystal orientations of anisotropic black phosphorus was successfully judged only by the angular polarization Raman spectroscopy of the Ag modes under the rarely studied orthogonal polarization configuration.•Temperature dependent Raman spectroscopy reveals the excellent thermal properties of few-layer black phosphorus.•The prepared black phosphorous sheets as surface-enhanced Raman spectroscopy substrates have strong enhancement effect and good uniformity.