Boron nitride (BN) thin films have been grown on the (100) surfaces of Si, diamond, Ni and Cu via ion beam assisted deposition (IBAD) using electron beam evaporation of B in tandem with N and Ar ion bombardment within the ranges of substrate temperature and ion flux of 200–700°C and 0.20–0.30 mA/Cm2, respectively, Fourier-transform infrared spectroscopy (FTIR) and high resolution transmission electron microscopy (HRTEM) revealed a growth sequence of amorphous (a-BN), hexagonal (h-BN) and cubic (c-BN) layers on Si and diamond under most conditions. This sequence is attributed primarily to increasing biaxial compressive stress with film thickness due to interstitial Ar incorporation observed via Rutherford backscattering spectroscopy (RBS). The effect of deposition conditions, specifically substrate temperature and bombardment intensity, on the film growth was studied. Increasing the substrate temperature above 400°C led to the onset of the cubic phase at a greater film thickness, while increased ion flux led to earlier growth of this phase. These results may be explained by the relaxation of intrinsic stress in the films at higher temperatures due to increased adatom mobility and to increased intrinsic stress in the films resulting from increased ion bombardment, respectively. Lower temperatures led to mixed phase growth. A minimum substrate temperature (200–300°C) is required for nucleation and growth of single phase c-BN by this technique. A combination of h-BN and c-BN was deposited on Ni; only h-BN was obtained on Cu substrates.