Mechanical decoupling of quantum emitters in hexagonal boron nitride from low-energy phonon modes
ABSTRACT: We unravel the mystery of mechanically decoupled defect centers in hexagonal boron nitride. Quantum emitters in hexagonal boron nitride were recently reported to hold unusual narrow homogeneous linewidths of tens of megahertz within the Fourier transform limit at room temperature. This unique observation was traced back to decoupling from in-plane phonon modes. Here, we investigate the origins for the mechanical decoupling. New sample preparation improved spectral diffusion, which allowed us to reveal a gap in the electron-phonon spectral density for low phonon frequencies. This sign for mechanical decoupling persists up to room temperature and explains the observed narrow lines at 300 kelvin. We investigate the dipole emission directionality and reveal preferred photon emission through channels between the layers supporting the claim for out-of-plane distorted defect centers. Our work provides insights into the underlying physics for the persistence of Fourier transform limit lines up to room temperature and gives a guide to the community on how to identify the exotic emitters.
Project description:Hexagonal boron nitride has been proposed as an excellent candidate to achieve subwavelength infrared light manipulation owing to its polar lattice structure, enabling excitation of low-loss phonon polaritons with hyperbolic dispersion. We show that strongly subwavelength hexagonal boron nitride planar nanostructures can exhibit ultra-confined resonances and local field enhancement. We investigate strong light-matter interaction in these nanoscale structures via photo-induced force microscopy, scattering-type scanning near-field optical microscopy, and Fourier transform infrared spectroscopy, with excellent agreement with numerical simulations. We design optical nano-dipole antennas and directly image the fields when bright- or dark-mode resonances are excited. These modes are deep subwavelength, and strikingly, they can be supported by arbitrarily small structures. We believe that phonon polaritons in hexagonal boron nitride can play for infrared light a role similar to that of plasmons in noble metals at visible frequency, paving the way for a new class of efficient and highly miniaturized nanophotonic devices.
Project description:Layered van der Waals materials are emerging as compelling two-dimensional platforms for nanophotonics, polaritonics, valleytronics and spintronics, and have the potential to transform applications in sensing, imaging and quantum information processing. Among these, hexagonal boron nitride (hBN) is known to host ultra-bright, room-temperature quantum emitters, whose nature is yet to be fully understood. Here we present a set of measurements that give unique insight into the photophysical properties and level structure of hBN quantum emitters. Specifically, we report the existence of a class of hBN quantum emitters with a fast-decaying intermediate and a long-lived metastable state accessible from the first excited electronic state. Furthermore, by means of a two-laser repumping scheme, we show an enhanced photoluminescence and emission intensity, which can be utilized to realize a new modality of far-field super-resolution imaging. Our findings expand current understanding of quantum emitters in hBN and show new potential ways of harnessing their nonlinear optical properties in sub-diffraction nanoscopy.
Project description:Enhanced light-matter interactions are the basis of surface-enhanced infrared absorption (SEIRA) spectroscopy, and conventionally rely on plasmonic materials and their capability to focus light to nanoscale spot sizes. Phonon polariton nanoresonators made of polar crystals could represent an interesting alternative, since they exhibit large quality factors, which go far beyond those of their plasmonic counterparts. The recent emergence of van der Waals crystals enables the fabrication of high-quality nanophotonic resonators based on phonon polaritons, as reported for the prototypical infrared-phononic material hexagonal boron nitride (h-BN). In this work we use, for the first time, phonon-polariton-resonant h-BN ribbons for SEIRA spectroscopy of small amounts of organic molecules in Fourier transform infrared spectroscopy. Strikingly, the interaction between phonon polaritons and molecular vibrations reaches experimentally the onset of the strong coupling regime, while numerical simulations predict that vibrational strong coupling can be fully achieved. Phonon polariton nanoresonators thus could become a viable platform for sensing, local control of chemical reactivity and infrared quantum cavity optics experiments.
Project description:Optically addressable spins associated with defects in wide-bandgap semiconductors are versatile platforms for quantum information processing and nanoscale sensing, where spin-dependent inter-system crossing transitions facilitate optical spin initialization and readout. Recently, the van der Waals material hexagonal boron nitride (h-BN) has emerged as a robust host for quantum emitters, promising efficient photon extraction and atom-scale engineering, but observations of spin-related effects have remained thus far elusive. Here, we report room-temperature observations of strongly anisotropic photoluminescence patterns as a function of applied magnetic field for select quantum emitters in h-BN. Field-dependent variations in the steady-state photoluminescence and photon emission statistics are consistent with an electronic model featuring a spin-dependent inter-system crossing between triplet and singlet manifolds, indicating that optically-addressable spin defects are present in h-BN.
Project description:Two-dimensional van der Waals materials have emerged as promising platforms for solid-state quantum information processing devices with unusual potential for heterogeneous assembly. Recently, bright and photostable single photon emitters were reported from atomic defects in layered hexagonal boron nitride (hBN), but controlling inhomogeneous spectral distribution and reducing multi-photon emission presented open challenges. Here, we demonstrate that strain control allows spectral tunability of hBN single photon emitters over 6?meV, and material processing sharply improves the single photon purity. We observe high single photon count rates exceeding 7?×?106 counts per second at saturation, after correcting for uncorrelated photon background. Furthermore, these emitters are stable to material transfer to other substrates. High-purity and photostable single photon emission at room temperature, together with spectral tunability and transferability, opens the door to scalable integration of high-quality quantum emitters in photonic quantum technologies.Inhomogeneous spectral distribution and multi-photon emission are currently hindering the use of defects in layered hBN as reliable single photon emitters. Here, the authors demonstrate strain-controlled wavelength tuning and increased single photon purity through suitable material processing.
Project description:Disordered structures of boron nitride (BN), graphite, boron carbide (BC), and boron carbon nitride (BCN) systems are considered important precursor materials for synthesis of superhard phases in these systems. However, phase transformation of such materials can be achieved only at extreme pressure-temperature conditions, which is irrelevant to industrial applications. Here, the phase transition from disordered nanocrystalline hexagonal (h)BN to superhard wurtzitic (w)BN was found at room temperature under a pressure of 6.7 GPa after applying large plastic shear in a rotational diamond anvil cell (RDAC) monitored by in situ synchrotron X-ray diffraction (XRD) measurements. However, under hydrostatic compression to 52.8 GPa, the same hBN sample did not transform to wBN but probably underwent a reversible transformation to a high-pressure disordered phase with closed-packed buckled layers. The current phase-transition pressure is the lowest among all reported direct-phase transitions from hBN to wBN at room temperature. Usually, large plastic straining leads to disordering and amorphization; here, in contrast, highly disordered hBN transformed to crystalline wBN. The mechanisms of strain-induced phase transformation and the reasons for such a low transformation pressure are discussed. Our results demonstrate a potential of low pressure-room temperature synthesis of superhard materials under plastic shear from disordered or amorphous precursors. They also open a pathway of phase transformation of nanocrystalline materials and materials with disordered and amorphous structures under extensive shear.
Project description:Hyperbolic materials exhibit sub-diffractional, highly directional, volume-confined polariton modes. Here we report that hyperbolic phonon polaritons allow for a flat slab of hexagonal boron nitride to enable exciting near-field optical applications, including unusual imaging phenomenon (such as an enlarged reconstruction of investigated objects) and sub-diffractional focusing. Both the enlarged imaging and the super-resolution focusing are explained based on the volume-confined, wavelength dependent propagation angle of hyperbolic phonon polaritons. With advanced infrared nanoimaging techniques and state-of-art mid-infrared laser sources, we have succeeded in demonstrating and visualizing these unexpected phenomena in both Type I and Type II hyperbolic conditions, with both occurring naturally within hexagonal boron nitride. These efforts have provided a full and intuitive physical picture for the understanding of the role of hyperbolic phonon polaritons in near-field optical imaging, guiding, and focusing applications.
Project description:We selectively excite and study two new types of phonon-polariton guided modes that are found in hexagonal boron nitride thin flakes on a gold substrate. Such modes show substantially improved confinement and a group velocity that is hundreds of times slower than the speed of light, thereby providing a new way to create slow light in the mid-infrared range with a simple structure that does not require nano-patterning. One mode is the fundamental mode in the first Restrahlen band of hexagonal boron nitride thin crystals on a gold substrate; the other mode is equivalent to the second mode of the second Restrahlen band of hexagonal boron nitride flakes that are suspended in vacuum. The new modes also couple efficiently with incident light at the hexagonal boron nitride edges, as we demonstrate experimentally using photo-induced force microscopy and scanning near-field optical microscopy. The high confinement of these modes allows for Purcell factors that are on the order of tens of thousands directly above boron nitride and a wide band, with new perspectives for enhanced light-matter interaction. Our findings demonstrate a new approach to engineering the dispersion of polaritons in 2D materials to improve confinement and light-matter interaction, thereby paving the way for new applications in mid-infrared nano-optics.
Project description:Directly mapping local phonon dispersion in individual nanostructures can advance our understanding of their thermal, optical, and mechanical properties. However, this requires high detection sensitivity and combined spatial, energy and momentum resolutions, thus has been elusive. Here, we demonstrate a four-dimensional electron energy loss spectroscopy technique, and present position-dependent phonon dispersion measurements in individual boron nitride nanotubes. By scanning the electron beam in real space while monitoring both the energy loss and the momentum transfer, we are able to reveal position- and momentum-dependent lattice vibrations at nanometer scale. Our measurements show that the phonon dispersion of multi-walled nanotubes is locally close to hexagonal-boron nitride crystals. Interestingly, acoustic phonons are sensitive to defect scattering, while optical modes are insensitive to small voids. This work not only provides insights into vibrational properties of boron nitride nanotubes, but also demonstrates potential of the developed technique in nanoscale phonon dispersion measurements.
Project description:Van der Waals materials exhibit intriguing structural, electronic, and photonic properties. Electron energy loss spectroscopy within scanning transmission electron microscopy allows for nanoscale mapping of such properties. However, its detection is typically limited to energy losses in the eV range-too large for probing low-energy excitations such as phonons or mid-infrared plasmons. Here, we adapt a conventional instrument to probe energy loss down to 100?meV, and map phononic states in hexagonal boron nitride, a representative van der Waals material. The boron nitride spectra depend on the flake thickness and on the distance of the electron beam to the flake edges. To explain these observations, we developed a classical response theory that describes the interaction of fast electrons with (anisotropic) van der Waals slabs, revealing that the electron energy loss is dominated by excitation of hyperbolic phonon polaritons, and not of bulk phonons as often reported. Thus, our work is of fundamental importance for interpreting future low-energy loss spectra of van der Waals materials.Here the authors adapt a STEM-EELS system to probe energy loss down to 100?meV, and apply it to map phononic states in hexagonal boron nitride, revealing that the electron loss is dominated by hyperbolic phonon polaritons.