The allotropes of boron nitride include two sp2-bonded phases with hexagonal and rhombohedral structures (hBN and rBN) and two sp3-bonded phases with cubic (zincblende) and hexagonal (wurtzitic) structures (cBN and wBN) (Fig. 1). Although cBN is synthesized in bulk form by conversion of hBN at high temperatures and pressures, low-pressure synthesis of cBN as a thin film is more difficult and succeeds only when the growing film is simultaneously irradiated with a high flux of ions. Only sp2-bonded material, which generally has a disordered, turbostratic microstructure (tBN), will form in the absence of ion-irradiation. The mechanistic role of the irradiation is not well understood, but recent work suggests that ion-induced compressive film stress may induce the transformation to cBN.Typically, BN films are deposited at temperatures less than 1000°C, a regime for which the structure of the sp2-bonded precursor material dictates the phase and microstructure of the material that forms from conventional (bulk) high pressure treatment.