Temperature dependence of the energy bandgap of two-dimensional hexagonal boron nitride probed by excitonic photoluminescence

Hexagonal boron nitride (hBN) is an emerging material for the exploration of new physics in two-dimensional (2D) systems that are complementary to graphene. Nanotubes with a diameter (∼60 nm) that is much larger than the exciton binding energy in hBN have been synthesized and utilized to probe the fundamental optical transitions and the temperature dependence of the energy bandgap of the corresponding 2D hBN sheets. An excitonic transition at 5.901 eV and its longitudinal optical phonon replica at 5.735 eV were observed. The excitonic emission line is blue shifted by about 130 meV with respect to that in hBN bulk crystals due to the effects of reduced dimensionality. The temperature evolution of the excitonic emission line measured from 300 to 800 K revealed that the temperature coefficient of the energy bandgap of hBN nanotubes with large diameters (or equivalently hBN sheets) is about 0.43 meV/0K, which is a factor of about 5 times smaller than the theoretically predicted value for the transitions between the π and π* bands in hBN bulk crystals and 6 times smaller than the measured value in AlN epilayers with a comparable energy bandgap. The observed weaker temperature dependence of the bandgap than those in 3D hBN and AlN is a consequence of the effects of reduced dimensionality in layer-structured hBN