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Despite its simple crystal structure, layered boron nitride features asurprisingly complex variety of phonon-assisted luminescence peaks. We presenta combined experimental and theoretical study on ultraviolet-light emission inhexagonal and rhombohedral bulk boron nitride crystals. Emission spectra ofhigh-quality samples are measured via cathodoluminescence spectroscopy,displaying characteristic differences between the two polytypes. Thesedifferences are explained using a fully first-principles computationaltechnique that takes into account radiative emission from ``indirect'',finite-momentum, excitons via coupling to finite-momentum phonons. We show thatthe differences in peak positions, number of peaks and relative intensities canbe qualitatively and quantitatively explained, once a full integration over allrelevant momenta of excitons and phonons is performed.

Distinguishing different stackings in layered materials via luminescence spectroscopy