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Boron nitride (BN) layers with sp2 bonding have been grown by metal organic chemical vapor deposition on AlN underlayers, which are deposited on c-plane sapphire substrates. Two different boron precursors were employed—trimethylboron and triethylboron—while ammonia was used as the nitrogen precursor. The BN obtained epitaxial BN films contain ordered rhombohedral (rBN) and partially ordered turbostratic (tBN) stackings as evidenced by x-ray diffraction analysis. We discriminatively identify the PL signatures of the rBN and tBN from those typical of the hexagonal (hBN) and Bernal stackings (bBN). The optical signature of tBN appears at 5.45 eV, and it intercalates between the two recombination bands typical of rBN at 5.35 eV (strong intensity) and 5.55 eV(weaker intensity). The analogs of the high intensity band at 5.35 eV in rBN sit at 5.47 eV for hBN and at 5.54 eV for bBN. [ABSTRACT FROM AUTHOR]