Homoepitaxy of Boron Nitride on Exfoliated Hexagonal Boron Nitride Flakes.

Although large efforts have been made to improve the growth of hexagonal boron nitride (hBN) by heteroepitaxy, the non-native substrates remain a fundamental factor that limits the quality. This problem can be solved by homoepitaxy, which is the growth of hBN on hBN substrates. In this report, we demonstrate the homoepitaxial growth of triangular BN grains on exfoliated hBN flakes by Metal-Organic Vapor Phase Epitaxy and show by atomic force microscopy and photoluminescence that the stacking of these triangular islands can deviate from the AA' stacking of hBN. We show that the stacking order is enforced by the crystallographic direction of the edge of the exfoliated hBN flakes, with armchair edges allowing for centrosymmetric stacking, whereas zigzag edges lead to the growth of noncentrosymmetric BN polytypes. Our results indicate pathways to grow homoepitaxial BN with tunable layer stacking, which is required to induce piezoelectricity or ferroelectricity.

Monolayer Boron Nitride: Hyperspectral Imaging in the Deep Ultraviolet.

The optical response of 2D materials and their heterostructures is the subject of intense research with advanced investigation of the luminescence properties in devices made of exfoliated flakes of few- down to one-monolayer thickness. Despite its prevalence in 2D materials research, hexagonal boron nitride (hBN) remains unexplored in this ultimate regime because of its ultrawide bandgap of about 6 eV and the technical difficulties related to performing microscopy in the deep-ultraviolet domain. Here, we report hyperspectral imaging at wavelengths around 200 nm in exfoliated hBN at low temperature. In monolayer boron nitride, we observe direct-gap emission around 6.1 eV. In marked contrast to transition metal dichalcogenides, the photoluminescence signal is intense in few-layer hBN, a result of the near unity radiative efficiency in indirect-gap multilayer hBN.

Selective area growth of AlGaN nanopyramids by conventional and pulsed MOVPE.

Planar UV-C light emitting diodes still suffer from low efficiency, mainly due to substrate crystalline quality, p doped conductivity and extraction efficiency. One possible way to overcome partly these issues is to realize the whole UV structure on AlGaN pyramids by selective area growth in order to benefit from the advantages of such structures, i.e. the dislocation filtering and the semi polar planes. We present here a detailed study about the epitaxy of AlGaN nano-sized pyramids by metal organic vapor phase epitaxy on patterned templates presenting different holes apertures and pitches as 1.5 µm and 4 µm or 100 nm and 250 nm respectively. While increasing the Al content, their height decreases while the thickness of the deposition on the mask increases whatever the design of the mask. Those changes of the pyramid shapes and deposition are directly linked to the properties of Al adatoms, i.e. low Al diffusion length. Using the conventional growth mode for the epitaxy of those pyramids did not permit the incorporation of Al from the base of the pyramids to their truncated apex. Its presence was concentrated on the edges and top of the pyramids. On the contrary, a pulsed growth mode, coupled with a strongly reduced pitch, allowed an incorporation of Al since the base of the nanopyramid, and a decrease of the deposition height on the mask. These results can be explained by the desorption of Ga species, due to the presence of H2 in the reactor chamber during the step without the metal precursors, leading to a higher Al/Ga ratio. It is even enhanced inside the holes by the reduced pitch.

Boron and Nitrogen Isotope Effects on Hexagonal Boron Nitride Properties.

The unique physical, mechanical, chemical, optical, and electronic properties of hexagonal boron nitride (hBN) make it a promising 2D material for electronic, optoelectronic, nanophotonic, and quantum devices. Here, the changes in hBN's properties induced by isotopic purification in both boron and nitrogen are reported. Previous studies on isotopically pure hBN have focused on purifying the boron isotope concentration in hBN from its natural concentration (≈20 at% 10 B, 80 at% 11 B) while using naturally abundant nitrogen (99.6 at% 14 N, 0.4 at% 15 N), that is, almost pure 14 N. In this study, the class of isotopically purified hBN crystals to 15 N is extended. Crystals in the four configurations, namely h10 B14 N, h11 B14 N, h10 B15 N, and h11 B15 N, are grown by the metal flux method using boron and nitrogen single isotope (> 99%) enriched sources, with nickel plus chromium as the solvent. In-depth Raman and photoluminescence spectroscopies demonstrate the high quality of the monoisotopic hBN crystals with vibrational and optical properties of the 15 N-purified crystals at the state-of-the-art of currently available 14 N-purified hBN. The growth of high-quality h10 B14 N, h11 B14 N, h10 B15 N, and h11 B15 N opens exciting perspectives for thermal conductivity control in heat management, as well as for advanced functionalities in quantum technologies.

Cathodoluminescence spectroscopy of monolayer hexagonal boron nitride.

Cathodoluminescence (CL) spectroscopy is a suitable technique for studying the luminescent properties of optoelectronic materials because CL has no limitation on the excitable bandgap energy and eliminates ambiguous signals due to simple light scattering and resonant Raman scattering potentially involved in the photoluminescence spectra. However, direct CL measurements of atomically thin two-dimensional materials have been difficult due to the small excitation volume that interacts with high-energy electron beams. Herein, distinct CL signals from a monolayer hexagonal BN (hBN), namely mBN, epitaxial film grown on a graphite substrate are shown by using a CL system capable of large-area and surface-sensitive excitation. Spatially resolved CL spectra at 13 K exhibited a predominant 5.5-eV emission band, which has been ascribed to originate from multilayered aggregates of hBN, markedly at thicker areas formed on the step edges of the substrate. Conversely, a faint peak at 6.04 ± 0.01 eV was routinely observed from atomically flat areas, which is assigned as being due to the recombination of phonon-assisted direct excitons of mBN. The CL results support the transition from indirect bandgap in bulk hBN to direct bandgap in mBN. The results also encourage one to elucidate emission properties of other low-dimensional materials by using the present CL configuration.

High p doped and robust band structure in Mg-doped hexagonal boron nitride.

In two dimensional materials, substitutional doping during growth can be used to alter the electronic properties. Here, we report on the stable growth of p-type hexagonal boron nitride (h-BN) using Mg-atoms as substitutional impurities in the h-BN honeycomb lattice. We use micro-Raman spectroscopy, angle-resolved photoemission measurements (nano-ARPES) and Kelvin probe force microscopy (KPFM) to study the electronic properties of Mg-doped h-BN grown by solidification from a ternary Mg-B-N system. Besides the observation of a new Raman line at ∼1347 cm-1 in Mg-doped h-BN, nano-ARPES reveals p-type carrier concentration. Our nano-ARPES experiments demonstrate that the Mg dopants can significantly alter the electronic properties of h-BN by shifting the valence band maximum about 150 meV toward higher binding energies with respect to pristine h-BN. We further show that, Mg doped h-BN exhibits a robust, almost unaltered, band structure compared to pristine h-BN, with no significant deformation. Kelvin probe force microscopy (KPFM) confirms the p-type doping, with a reduced Fermi level difference between pristine and Mg-doped h-BN crystals. Our findings demonstrate that conventional semiconductor doping by Mg as substitutional impurities is a promising route to high-quality p-type doped h-BN films. Such stable p-type doping of large band h-BN is a key feature for 2D materials applications in deep ultra-violet light emitting diodes or wide bandgap optoelectronic devices.

Bernal Boron Nitride Crystals Identified by Deep-Ultraviolet Cryomicroscopy.

The presence of metastable Bernal stacking boron nitride is verified by combining second harmonic generation (SHG) and photoluminescence (PL) spectroscopy. The scanning confocal cryomicroscope, operating in the deep-ultraviolet range, shows a one-to-one correlation between inversion symmetry breaking probed by SHG and the detection of an intense PL line at ∼6.035 eV, the specific signature of the noncentrosymmetric Bernal stacking. The coherent character of the Bernal phase in boron nitride crystals is demonstrated by two-photon excitation spectroscopy. Direct and indirect excitons are simultaneously detected in the emission spectrum; they are quasi-degenerate, in agreement with theoretical predictions for Bernal boron nitride. The transition from AA' to AB stacking is characterized by an intense emission from stacking faults at the grain boundaries of hexagonal and Bernal boron nitride crystals.

Hexagonal Boron Nitride Crystal Growth from Iron, a Single Component Flux.

The highest quality hexagonal boron nitride (hBN) crystals are grown from molten solutions. For hBN crystal growth at atmospheric pressure, typically the solvent is a combination of two metals, one with a high boron solubility and the other to promote nitrogen solubility. In this study, we demonstrate that high-quality hBN crystals can be grown at atmospheric pressure using pure iron as a flux. The ability to produce excellent-quality hBN crystals using pure iron as a solvent is unexpected, given its low solubility for nitrogen. The properties of crystals produced with this flux matched the best values ever reported for hBN: a narrow Raman E2g vibration peak (7.6 cm-1) and strong phonon-assisted peaks in the photoluminescence spectra. To further test their quality, the hBN crytals were used as a substrate for WSe2 epitaxy. WSe2 was deposited with a low nucleation density, indicating the low defect density of the hBN. Lastly, the carrier tunneling through our hBN thin layers (3.5 nm) follows the Fowler-Nordheim model, with a barrier height of 3.7 eV, demonstrating hBN's superior electrical insulating properties. This ability to produce high-quality hBN crystals in such a simple, environmentally friendly and economical process will advance two-dimensional material research by enabling integrated devices.

Enhanced excitonic emission efficiency in porous GaN.

We investigate the optical properties of porous GaN films of different porosities, focusing on the behaviors of the excitonic features in time-integrated and time-resolved photoluminescence. A substantial enhancement of both excitonic emission intensity and recombination rate, along with insignificant intensity weakening under temperature rise, is observed in the porous GaN films. These observations are in line with (i) the local concentration of electric field at GaN nanoparticles and pores due to the depolarization effect, (ii) the efficient light extraction from the nanoparticles. Besides, the porosification enlarges the surface of the air/semiconductor interface, which further promotes the extraction efficiency and suppresses non-radiative recombination channels. Our findings open a way to increasing the emission efficiency of nanophotonic devices based on porous GaN.