Search

Defects in crystals can have a transformative effect on the properties and functionalities of solid-state systems. Dopants in semiconductors are core components in electronic and optoelectronic devices. The control of single color centers is at the basis of advanced applications for quantum technologies. Unintentional defects can also be detrimental to the crystalline structure and hinder the development of novel materials. Whatever the research perspective, the identification of defects is a key but complicated, and often long-standing issue. Here, we present a general methodology to identify point defects by combining isotope substitution and polytype control, with a systematic comparison between experiments and first-principles calculations. We apply this methodology to hexagonal boron nitride (hBN) and its ubiquitous color center emitting in the ultraviolet spectral range. From isotopic purification of the host hBN matrix, a local vibrational mode of the defect is uncovered, and isotope-selective carbon doping proves that this mode belongs to a carbon-based center. Then, by varying the stacking sequence of the host hBN matrix, we unveil different optical responses to hydrostatic pressure for the non-equivalent configurations of this ultraviolet color center. We conclude that this defect is a carbon dimer in the honeycomb lattice of hBN. Our results show that tuning the stacking sequence in different polytypes of a given crystal provides unique fingerprints contributing to the identification of defects in 2D materials.

The negatively-charged boron vacancy (V$_\text{B}^-$) center in hexagonal boron nitride (hBN) is currently garnering considerable attention for the design of two-dimensional (2D) quantum sensing units. Such developments require a precise understanding of the spin-dependent optical response of V$_\text{B}^-$ centers, which still remains poorly documented despite its key role for sensing applications. Here we investigate the spin-dependent photodynamics of V$_\text{B}^-$ centers in hBN by a series of time-resolved photoluminescence (PL) measurements. We first introduce a robust all-optical method to infer the spin-dependent lifetime of the excited states and the electron spin polarization of V$_\text{B}^-$ centers under optical pumping. Using these results, we then analyze PL time traces recorded at different optical excitation powers with a seven-level model of the V$_\text{B}^-$ center and we extract all the rates involved in the spin-dependent optical cycles, both under ambient conditions and at liquid helium temperature. These findings are finally used to study the impact of a vector magnetic field on the optical response. More precisely, we analyze PL quenching effects resulting from electron spin mixing induced by the magnetic field component perpendicular to the V$_\text{B}^-$ quantization axis. All experimental results are well reproduced by the seven-level model, illustrating its robustness to describe the spin-dependent photodymanics of V$_\text{B}^-$ centers. This work provides important insights into the properties of V$_\text{B}^-$ centers in hBN, which are valuable for future developments of 2D quantum sensing units., Comment: 11 pages, 9 figures

Under high electrical current, some materials can emit electromagnetic radiation beyond incandescence. This phenomenon, referred to as electroluminescence, leads to the efficient emission of visible photons and is the basis of domestic lighting devices (e.g., light-emitting diodes). In principle, electroluminescence can lead to mid-infrared (mid-IR) emission of confined light-matter excitations called phonon-polaritons, resulting from the coupling of photons with crystal lattice vibrations (optical phonons). In particular, phonon-polaritons arising in the van der Waals crystal hexagonal boron nitride (hBN) exhibit hyperbolic dispersion, which enhances light-matter coupling. For this reason, electroluminescence of hyperbolic phonon-polaritons (HPhPs) has been proposed as an explanation for the peculiar radiative energy transfer within hBN-encapsulated graphene transistors. However, since HPhPs are confined, they are inaccessible in the far-field, so that any hint of electroluminescence is only based on indirect electronic signatures and needs to be confirmed by direct observation. Here, we demonstrate far-field mid-IR ({\lambda} = 6.5 {\mu}m) electroluminescence of HPhPs excited by strongly biased high-mobility graphene within a van der Waals heterostructure, and we quantify the associated radiative energy transfer through the material. The presence of HPhPs is revealed via far-field mid-IR spectroscopy due to their elastic scattering at discontinuities in the heterostructure. The associated radiative flux is quantified by mid-IR pyrometry of the substrate receiving the energy. This radiative energy transfer is shown to be reduced in hBN with nanoscale inhomogeneities, demonstrating the central role of the electromagnetic environment in this process., Comment: 32 pages including Extended Data and Supplementary Material (Main text: 7 pages, 4 figures)

We report on electron spin resonance (ESR) spectroscopy of boron-vacancy (V$_\text{B}^-$) centers hosted in isotopically-engineered hexagonal boron nitride (hBN) crystals. We first show that isotopic purification of hBN with $^{15}$N yields a simplified and well-resolved hyperfine structure of V$_\text{B}^-$ centers, while purification with $^{10}$B leads to narrower ESR linewidths. These results establish isotopically-purified h$^{10}$B$^{15}$N crystals as the optimal host material for future use of V$_\text{B}^-$ spin defects in quantum technologies. Capitalizing on these findings, we then demonstrate optically-induced polarization of $^{15}$N nuclei in h$^{10}$B$^{15}$N, whose mechanism relies on electron-nuclear spin mixing in the V$_\text{B}^-$ ground state. This work opens up new prospects for future developments of spin-based quantum sensors and simulators on a two-dimensional material platform., Comment: 6 pages, 3 figure

The unique physical, mechanical, chemical, optical, and electronic properties of hexagonal boron nitride (hBN) make it a promising two-dimensional material for electronic, optoelectronic, nanophotonic, and quantum devices. Here we report on the changes in hBN's properties induced by isotopic purification in both boron and nitrogen. Previous studies on isotopically pure hBN have focused on purifying the boron isotope concentration in hBN from its natural concentration (approximately 20 at$\%$ $^{10}$B, 80 at$\%$ $^{11}$B) while using naturally abundant nitrogen (99.6 at$\%$ $^{14}$N, 0.4 at$\%$ $^{15}$N), i.e. almost pure $^{14}$N. In this study, we extend the class of isotopically-purified hBN crystals to $^{15}$N. Crystals in the four configurations, namely h$^{10}$B$^{14}$N, h$^{11}$B$^{14}$N, h$^{10}$B$^{15}$N, and h$^{11}$B$^{15}$N, were 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 h$^{10}$B$^{14}$N, h$^{11}$B$^{14}$N, h$^{10}$B$^{15}$N, and h$^{11}$B$^{15}$N opens exciting perspectives for thermal conductivity control in heat management, as well as for advanced functionalities in quantum technologies., Comment: 13 pages, 7 figures

Graphite is one of the most chemically inert materials. Its elementary constituent, monolayer graphene, is generally expected to inherit most of the parent material's properties including chemical inertness. Here we show that, unlike graphite, defect-free monolayer graphene exhibits a strong activity with respect to splitting molecular hydrogen, which is comparable to that of metallic and other known catalysts for this reaction. We attribute the unexpected catalytic activity to surface corrugations (nanoscale ripples), a conclusion supported by theory. Nanoripples are likely to play a role in other chemical reactions involving graphene and, because nanorippling is inherent to atomically thin crystals, can be important for two dimensional materials in general.

Strong coupling (SC) between light and matter excitations such as excitons and molecular vibrations bear intriguing potential for controlling chemical reactivity, conductivity or photoluminescence. So far, SC has been typically achieved either between mid-infrared (mid-IR) light and molecular vibrations or between visible light and excitons. Achieving SC simultaneously in both frequency bands may open unexplored pathways for manipulating material properties. Here, we introduce a polaritonic nanoresonator (formed by h-BN layers placed on Al ribbons) hosting surface plasmon polaritons (SPPs) at visible frequencies and phonon polaritons (PhPs) at mid-IR frequencies, which simultaneously couple to excitons and atomic vibration in an adjacent molecular layer (CoPc). Employing near-field optical nanoscopy, we first demonstrate the co-localization of strongly confined near-fields at both visible and mid-IR frequencies. After covering the nanoresonator structure with a layer of CoPc molecules, we observe clear mode splittings in both frequency ranges by far-field transmission spectroscopy, unambiguously revealing simultaneous SPP-exciton and PhP-vibron coupling. Dual-band SC may be exploited for manipulating the coupling between excitons and molecular vibrations in future optoelectronics, nanophotonics, and quantum information applications.

We derive a dielectric function tensor model approach to render the optical response of monoclinic and triclinic symmetry materials with multiple uncoupled infrared and farinfrared active modes. We apply our model approach to monoclinic $\beta$-Ga$_2$O$_3$ single crystal samples. Surfaces cut under different angles from a bulk crystal, (010) and ($\bar{2}$01), are investigated by generalized spectroscopic ellipsometry within infrared and farinfrared spectral regions. We determine the frequency dependence of 4 independent $\beta$-Ga$_2$O$_3$ Cartesian dielectric function tensor elements by matching large sets of experimental data using a point by point data inversion approach. From matching our monoclinic model to the obtained 4 dielectric function tensor components, we determine all infared and farinfrared active transverse optic phonon modes with $A_u$ and $B_u$ symmetry, and their eigenvectors within the monoclinic lattice. We find excellent agreement between our model results and results of density functional theory calculations. We derive and discuss the frequencies of longitudinal optical phonons in $\beta$-Ga$_2$O$_3$. We derive and report density and anisotropic mobility parameters of the free charge carriers within the tin doped crystals. We discuss the occurrence of longitudinal phonon plasmon coupled modes in $\beta$-Ga$_2$O$_3$ and provide their frequencies and eigenvectors. We also discuss and present monoclinic dielectric constants for static electric fields and frequencies above the reststrahlen range, and we provide a generalization of the Lyddane-Sachs-Teller relation for monoclinic lattices with infrared and farinfrared active modes. We find that the generalized Lyddane-Sachs-Teller relation is fulfilled excellently for $\beta$-Ga$_2$O$_3$., Comment: 18 pages, 12 figures, 105 references; Presented at IWGO 2015 Nov. 4th, Kyoto, Japan

The phonon mode parameters and anisotropic mid-infrared dielectric function tensor components of high- Al-content Al$_x$Ga$_{1-x}$N alloys in dependence of the Al content $x$ are precisely determined from mid-infrared spectroscopic ellipsometry measurements for a set of high-quality Si-doped Al$_x$Ga$_{1-x}$N epitaxial layers on 4H-SiC substrates. Two-mode behavior of the $E_1$(TO) modes and one-mode behavior of the $A_1$(LO) mode are found in agreement with previous Raman scattering spectroscopy reports. The composition dependencies of the IR active phonon frequency parameters are established and a discussion on the silent $B_1$ mode that may be disorder activated is provided. The static dielectric constants in dependence of $x$ are determined by using the best-match model derived phonon mode frequency and high-frequency dielectric constant parameters and applying the Lydanne-Sachs-Teller relation. The effective mass parameter in high-Al-content Al$_x$Ga$_{1-x}$N alloys and its composition dependence are determined from mid-infrared optical Hall effect measurements. Furtheremore, the free electron concentration $N$ and mobility parameters $\mu$ of Al$_x$Ga$_{1-x}$N films with similar Si doping levels are investigated as function of the Al content, $x$ and discussed., Comment: 12 pages, 10 figures