I review advanced applications of boron nitride in the fields of optoelectronic and Infrared photonics and correlate them to electronic and phonon properties

AlyGa1−yN quantum dots (QDs) have been grown by molecular beam epitaxy on AlxGa1−xN (0001) using a 2-dimensional–3-dimensional growth mode transition that leads to the formation of QDs. QDs have been grown for Al compositions y varying between 10% and 40%. The influence of the active region design [composition y, QD height, and bandgap difference (ΔEg) between the AlxGa1−xN cladding layer and the AlyGa1−yN QDs] is discussed based on microscopy, continuous wave photoluminescence (PL), and time-resolved PL (TRPL) mea- surements. In particular, increasing y leads to a shift of the QD emission toward shorter wavelengths, allowing covering a spectral range in the UV from 332 nm (UVA) to 276 nm (UVC) at room temperature (RT). The low-temperature (LT) internal quantum efficiency of the QD ensembles was estimated from TRPL experiments at 8 K and values between 11% and 66% were deduced. The highest internal quantum efficiency (IQE)-LT is found for the QDs with higher Al content y. Then, the PL spectrally integrated intensity ratios between RT and LT were measured to estimate the IQE of the samples at RT. The PL ratio is higher for larger ΔEg, for QDs with y of 0.1 or 0.2, and high PL intensity ratios up to 30% were also measured for QDs with larger y of 0.3 and 0.4. RT IQE values between 5% and 20% are deduced for AlyGa1−yN QDs emitting in the 276–308 nm range.

We study shallow and deep levels in carbon-doped hexagonal boron nitride crystals precipitated from a molten metal solution in a high-temperature furnace. Reflectance and photoluminescence under deep ultraviolet excitation are complemented by spatially resolved experiments by means of a scanning confocal micro-photoluminescence setup operating in the ultraviolet. Isotopically controlled carbon doping does not induce any energy shift of the well-known deep-level emission at 4.1 eV. Our detailed characterization in a series of carbon-doped crystals reveals that the incorporation of carbon during the growth process results in a distinct class of shallow and deep levels in hexagonal boron nitride, calling into question the exact role of carbon in the growth of hexagonal boron nitride and its direct or indirect influence on the formation of the crystal defects.

We present an infrared reflectance and transmission study of a pressure-induced phase transition of boron nitride from the hexagonal layered structure to the wurtzitic phase. The transition is completed at about 13 GPa. The phase transition is nonreversible and the optical features of the metastable wurtzitic phase are retained after a pressure cycle from 20.5 GPa down to ambient pressure. This allows the infrared-active optical phonons and the dielectric properties of the cold-pressed wurtzitic boron nitride sample to be studied over the whole range of pressures. Experimental permittivity values of ε0 = 6.65 ± 0.03 and ε∞ = 4.50 ± 0.05 are determined from fits to the reflectance spectra at ambient pressure. Accurate values of the refractive index in the mid-infrared and visible–ultraviolet regions are evaluated from the interference patterns. Contrary to the h-BN case, the refractive index of w-BN decreases slightly with pressure, on account of the much lower compressibility of the close-packed structure. The pressure coefficients for the longitudinal optical and transverse optical modes are determined, and an overall good agreement with ab initio calculations is found.

The recent availability of isotopically pure samples of hexagonal boron nitride (h-BN) has allowed the isotopic substitution effects to be studied in this highly interesting layered crystal. Here, we review the application of Raman scattering to investigate phonon anharmonic decay and its particularities in layered crystals, exemplified by h-BN. The modification of the phonon spectrum and anharmonic phonon decay paths in isotopically pure samples is specifically addressed. Detailed information about phonon lifetimes and decay channels is obtained for h-BN from a thorough analysis of temperature-dependent Raman scattering measurements in the light of density functional theory and perturbation theory calculations. The phonon lifetime is substantially increased in isotopically pure crystals, which may have important implications for the development of low-loss h-BN based phonon-polariton devices. On account of the low cation mass, isotopic substitution substantially alters the dominant phonon decay pathways and changes the strength of phonon anharmonic interactions.

InSe is a promising material in many aspects where the role of excitons is decisive. Here we report the sequential appearance in its luminescence of the exciton, the biexciton, and the P-band of the exciton-exciton scattering while the excitation power increases. The strict energy and momentum conservation rules of the P-band are used to reexamine the exciton binding energy. The new value >= 20 meV is markedly higher than the currently accepted one (14 meV), being however well consistent with the robustness of the excitons up to room temperature. A peak controlled by the Sommerfeld factor is found near the bandgap (similar to 1.36 eV). Our findings supported by theoretical calculations taking into account the anisotropic material parameters question the pure three-dimensional character of the exciton in InSe, assumed up to now. The refined character and parameters of the exciton are of paramount importance for the successful application of InSe in nanophotonics.

We investigate the highly anisotropic behavior of the in-plane and out-of-plane infrared-active phonons of hexagonal boron nitride by means of infrared reflectivity and absorption measurements under high pressure. Infrared reflectivity spectra at normal incidence on high-quality single crystals show strict fulfillment of selection rules and an unusually long E1u[transverse-optic (TO)] phonon lifetime. Accurate values of the dielectric constants at ambient pressure ε⊥0 = 6.96, ε⊥∞ = 4.95, ε∥0 = 3.37, and ε∥∞ = 2.84 have been determined from fits to the reflectivity spectra. The out-of-plane A2u phonon reflectivity band is revealed in measurements on an inclined facet, and absorption measurements at an incidence angle of 30° allow us to observe both the transverse- and longitudinal-optic A2u modes. Pressure coefficients and Grüneisen parameters for all infrared-active modes are determined and compared with ab initio calculations. While Grüneisen parameters are generally small in this layered crystal, the A2u(TO) displays an exceptionally large and negative Grüneisen parameter that results in widening of the type I hyperbolic region with increasing pressure. Softening of the A2u(TO) mode is induced by dynamical buckling of the flat honeycomb layers.