A pole figure of the {101 ̅ 4} planes (2θ = 35.08°) of a r-BxC film deposited at 1400 °C and 0.1 s residence time is shown in Figure . This film is polycrystalline, mainly orientated along the [101 ̅ 4] direction, and graphite-contaminated, as seen in Figure . The pole figure shows three concentric patterns. The outer most pattern, consists in 6 poles at ψ ≈ 75°, which as for Fig. , originates from the substrate and are the tails of 4H-SiC{101 ̅ 1}. The second pattern at ψ ≈ 60° appears to be five-fold. This may seem counterintuitive considering two aspects: 1) the crystal structure of r-BxC which is rhombohedral and 2) the polycrystalline nature of the textured films, which would usually exhibit a fiber texture without symmetry. The five-fold symmetry originates from the tendency of r-BxC to form five-fold twinning (Fig. ). However, upon closer inspection of the five broad poles at ψ ≈ 60°, reveals the further division into three distinct peaks within each of these five broad poles. This is consistent with the fact that five and six are non-divisible: for a given family of the directions of a five-fold crystal, can only be aligned with one of the 〈112 ̅ 0〉 directions of 4H-SiC. As such, an alignment along [112 ̅ 0], [12 ̅ 10] and [2 ̅ 110], will result in three adjacent 5-fold patterns as can be seen in Fig. . Furthermore, due to the lack of axial symmetry of five-fold objects (e.g., a pentagon) there are two ways two align a five-fold crystal along a given direction (e.g., the apex of a pentagon pointing towards either 4H-SiC[112 ̅ 0] or 4H-SiC [11 ̅̅̅̅ 20]), so that one pole pattern is centrosymmetric with respect to the other. In our case, this observed in Fig. where poles of much fainter intensity can be found between the more intense poles of the five-fold patterns. As a result, the ring pattern comprises 5 (r-BxC twinning) x 3 (4H-SiC symmetry axes) x 2 (lack of axial symmetry of 5-fold objects) = 30 poles (Fig. ). The fortuitous varying intensity of the pattern brings to light that these five-fold twinned crystals or domains grow along each 〈112 ̅ 0〉 axes of the 4H-SiC surface in a heteroepitaxial fashion. The third pattern at the center of the pole figure is the superpositions of the last of the three BxC{101 ̅ 4} poles (ψ ≈ 7°) but are shadowed by the strong 4H-SiC(0001) pole (ψ ≈ 0°). From top-view scanning electron microscopy (Figure ), the films deposited at 1100 °C appear to comprise nodular grains (Fig. ). The films deposited between 1200 and 1400 °C (Figs. ) show highly twinned grains with a more pronounced faceting with increasing temperature. The grain size is around 1 µm. The surface morphology of these films deposited is consistent with the texture evolution of the film. The crystallites of the films deposited at 1200 °C (Fig. ) and 1300 °C (Fig. ) appear as square-based pyramids. This is associated with films with a strong [022 ̅ 1] texture. At 1400 °C (Fig. ), the films appear porous and some of the grains with 5-fold twinning are visible, as expected from the pole figure of the [101 ̅ 4] orientated films. At 1500 °C (Fig. ), the boron carbide grains do not show preferred orientation. Finally for comparison, the elemental composition of the film on the Si-face at 1300 °C determined using ToF-ERDA also yielded a ratio of 4:1 (B -79.4% ± 0.7%, C -20.5% ± 0.3%) with around 0.1% of O incorporation and the absence of H as it is below the detection limit of the instrument.