Self-standing highly crystallized hexagonal boron nitride (h-BN) mono-, bi- and few-layers have been obtained for the first time via the Polymer Derived Ceramics (PDCs) route by adding lithium nitride (Li₃N) micropowders to liquid-state polyborazylene (PBN). Incorporation of Li₃N as a crystallization promoter allows the onset of crystallization of h-BN at a lower temperature (1200 °C) than under classical conditions (1800 °C). The hexagonal structure was confirmed by both electron and X-ray diffraction.

BN-based coatings on metallic (titanium, aluminium and copper) substrates are prepared by infrared irradiation of a dip-coated polyborazylene. This innovative strategy creates an access towards the molecular design of hexagonal-boron nitride coatings as protective materials for low melting point metals.