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Refraction between isotropic media is characterized by light bending towards the normal to the boundary when passing from a low- to a high-refractive-index medium. However, refraction between anisotropic media is a more exotic phenomenon which remains barely investigated, particularly at the nanoscale. Here, we visualize and comprehensively study the general case of refraction of electromagnetic waves between two strongly anisotropic (hyperbolic) media, and we do it with the use of nanoscale-confined polaritons in a natural medium: α-MoO 3 . The refracted polaritons exhibit non-intuitive directions of propagation as they traverse planar nanoprisms, enabling to unveil an exotic optical effect: bending-free refraction. Furthermore, we develop an in-plane refractive hyperlens, yielding foci as small as λ p /6, being λ p the polariton wavelength (λ 0 /50 compared to the wavelength of free-space light). Our results set the grounds for planar nano-optics in strongly anisotropic media, with potential for effective control of the flow of energy at the nanoscale., (© 2021. The Author(s).)

Natural hyperbolic materials with dielectric permittivities of opposite signs along different principal axes can confine long-wavelength electromagnetic waves down to the nanoscale, well below the diffraction limit. Confined electromagnetic waves coupled to phonons in hyperbolic dielectrics including hexagonal boron nitride (hBN) and α-MoO 3 are referred to as hyperbolic phonon polaritons (HPPs). HPP dissipation at ambient conditions is substantial, and its fundamental limits remain unexplored. Here, we exploit cryogenic nanoinfrared imaging to investigate propagating HPPs in isotopically pure hBN and naturally abundant α-MoO 3 crystals. Close to liquid-nitrogen temperatures, losses for HPPs in isotopic hBN drop significantly, resulting in propagation lengths in excess of 8 μm, with lifetimes exceeding 5 ps, thereby surpassing prior reports on such highly confined polaritonic modes. Our nanoscale, temperature-dependent imaging reveals the relevance of acoustic phonons in HPP damping and will be instrumental in mitigating such losses for miniaturized mid-infrared technologies operating at liquid-nitrogen temperatures.

Coherent optical excitations in two-dimensional (2D) materials, 2D polaritons, can generate a plethora of optical phenomena that arise from the extraordinary dispersion relations that do not exist in regular materials. Probing of the dynamical phenomena of 2D polaritons requires simultaneous spatial and temporal imaging capabilities and could reveal unknown coherent optical phenomena in 2D materials. Here, we present a spatiotemporal measurement of 2D wave packet dynamics, from its formation to its decay, using an ultrafast transmission electron microscope driven by femtosecond midinfrared pulses. The ability to coherently excite phonon-polariton wave packets and probe their evolution in a nondestructive manner reveals intriguing dispersion-dependent dynamics that includes splitting of multibranch wave packets and, unexpectedly, wave packet deceleration and acceleration. Having access to the full spatiotemporal dynamics of 2D wave packets can be used to illuminate puzzles in topological polaritons and discover exotic nonlinear optical phenomena in 2D materials., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Dragging of light by moving media was predicted by Fresnel 1 and verified by Fizeau's celebrated experiments 2 with flowing water. This momentous discovery is among the experimental cornerstones of Einstein's special relativity theory and is well understood 3,4 in the context of relativistic kinematics. By contrast, experiments on dragging photons by an electron flow in solids are riddled with inconsistencies and have so far eluded agreement with the theory 5-7 . Here we report on the electron flow dragging surface plasmon polaritons 8,9 (SPPs): hybrid quasiparticles of infrared photons and electrons in graphene. The drag is visualized directly through infrared nano-imaging of propagating plasmonic waves in the presence of a high-density current. The polaritons in graphene shorten their wavelength when propagating against the drifting carriers. Unlike the Fizeau effect for light, the SPP drag by electrical currents defies explanation by simple kinematics and is linked to the nonlinear electrodynamics of Dirac electrons in graphene. The observed plasmonic Fizeau drag enables breaking of time-reversal symmetry and reciprocity 10 at infrared frequencies without resorting to magnetic fields 11,12 or chiral optical pumping 13,14 . The Fizeau drag also provides a tool with which to study interactions and nonequilibrium effects in electron liquids.

Efficient control of photons is enabled by hybridizing light with matter. The resulting light-matter quasi-particles can be readily programmed by manipulating either their photonic or matter constituents. Here, we hybridized infrared photons with graphene Dirac electrons to form surface plasmon polaritons (SPPs) and uncovered a previously unexplored means to control SPPs in structures with periodically modulated carrier density. In these periodic structures, common SPPs with continuous dispersion are transformed into Bloch polaritons with attendant discrete bands separated by bandgaps. We explored directional Bloch polaritons and steered their propagation by dialing the proper gate voltage. Fourier analysis of the near-field images corroborates that this on-demand nano-optics functionality is rooted in the polaritonic band structure. Our programmable polaritonic platform paves the way for the much-sought benefits of on-the-chip photonic circuits., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

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 E 2g 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 WSe 2 epitaxy. WSe 2 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.

Silicon waveguides have enabled large-scale manipulation and processing of near-infrared optical signals on chip. Yet, expanding the bandwidth of guided waves to other frequencies will further increase the functionality of silicon as a photonics platform. Frequency multiplexing by integrating additional architectures is one approach to the problem, but this is challenging to design and integrate within the existing form factor due to scaling with the free-space wavelength. This paper demonstrates that a hexagonal boron nitride (hBN)/silicon hybrid waveguide can simultaneously enable dual-band operation at both mid-infrared (6.5-7.0 µm) and telecom (1.55 µm) frequencies, respectively. The device is realized via the lithography-free transfer of hBN onto a silicon waveguide, maintaining near-infrared operation. In addition, mid-infrared waveguiding of the hyperbolic phonon polaritons (HPhPs) supported in hBN is induced by the index contrast between the silicon waveguide and the surrounding air underneath the hBN, thereby eliminating the need for deleterious etching of the hyperbolic medium. The behavior of HPhP waveguiding in both straight and curved trajectories is validated within an analytical waveguide theoretical framework. This exemplifies a generalizable approach based on integrating hyperbolic media with silicon photonics for realizing frequency multiplexing in on-chip photonic systems., (© 2021 Wiley-VCH GmbH.)

The limited memory retention for a ferroelectric field-effect transistor has prevented the commercialization of its nonvolatile memory potential using the commercially available ferroelectrics. Here, we show a long-retention ferroelectric transistor memory cell featuring a metal-ferroelectric-metal-insulator-semiconductor architecture built from all van der Waals single crystals. Our device exhibits 17 mV dec -1 operation, a memory window larger than 3.8 V, and program/erase ratio greater than 10 7 . Thanks to the trap-free interfaces and the minimized depolarization effects via van der Waals engineering, more than 10 4 cycles endurance, a 10-year memory retention and sub-5 μs program/erase speed are achieved. A single pulse as short as 100 ns is enough for polarization reversal, and a 4-bit/cell operation of a van der Waals ferroelectric transistor is demonstrated under a 100 ns pulse train. These device characteristics suggest that van der Waals engineering is a promising direction to improve ferroelectronic memory performance and reliability for future applications.

Polaritons allow for strong light-matter coupling and for highly sensitive analysis of (bio)chemical substances and processes. Nanoimaging of the polaritons' evanescent fields is critically important for experimental mode identification and field confinement studies. Here we describe two setups for polariton nanoimaging and spectroscopy in liquid. We first demonstrate the mapping of localized plasmon polaritons in metal antennas with a transflection infrared scattering-type scanning near-field optical microscope (s-SNOM), where the tip acts as a near-field scattering probe. We then demonstrate a total internal reflection (TIR)-based setup, where the tip is both launching and probing ultraconfined polaritons in van der Waals materials (here phonon polaritons in hexagonal boron nitride flakes), laying the foundation for s-SNOM-based polariton interferometry in liquid. Our results promise manifold applications, for example, in situ studies of strong coupling between polaritons and molecular vibrations or chemical reactions at the bare or functionalized surfaces of polaritonic materials.

Total internal reflection (TIR) infrared spectroscopy is a convenient measurement tool for collecting spectra for chemical identification. However, TIR infrared microscopy lacks high spatial resolution due to the optical diffraction limit and difficulty to preserve a high-quality wave front for focus. In this article, we present the peak force infrared microscopy in the TIR geometry to achieve a 10 nm spatial resolution. Instead of optical detection, photothermal responses of the sample are collected in the peak force tapping mode of atomic force microscopy. We demonstrate the technique on two representative samples: structured polymers for soft matters and a hexagonal boron nitride flake for two-dimensional materials. As an extension of the apparatus, we also demonstrate nanoinfrared imaging with the TIR excitation for photoinduced force microscopy. The combination of TIR geometry with nanoinfrared microscopies simplifies the optical alignment, providing alternative instrument-designing principles for atomic force microscopy-based infrared microscopy.

Materials with high thermal conductivities (κ) are valuable to solve the challenge of waste heat dissipation in highly integrated and miniaturized modern devices. Herein, we report the first synthesis of atomically thin isotopically pure hexagonal boron nitride (BN) and its one of the highest κ among all semiconductors and electric insulators. Single atomic layer (1L) BN enriched with ^{11}B has a κ up to 1009  W/mK at room temperature. We find that the isotope engineering mainly suppresses the out-of-plane optical (ZO) phonon scatterings in BN, which subsequently reduces acoustic-optical scatterings between ZO and transverse acoustic (TA) and longitudinal acoustic phonons. On the other hand, reducing the thickness to a single atomic layer diminishes the interlayer interactions and hence umklapp scatterings of the out-of-plane acoustic (ZA) phonons, though this thickness-induced κ enhancement is not as dramatic as that in naturally occurring BN. With many of its unique properties, atomically thin monoisotopic BN is promising on heat management in van der Waals devices and future flexible electronics. The isotope engineering of atomically thin BN may also open up other appealing applications and opportunities in 2D materials yet to be explored.

Polaritons - coupled excitations of photons and dipolar matter excitations - can propagate along anisotropic metasurfaces with either hyperbolic or elliptical dispersion. At the transition from hyperbolic to elliptical dispersion (corresponding to a topological transition), various intriguing phenomena are found, such as an enhancement of the photonic density of states, polariton canalization and hyperlensing. Here, we investigate theoretically and experimentally the topological transition, the polaritonic coupling and the strong nonlocal response in a uniaxial infrared-phononic metasurface, a grating of hexagonal boron nitride (hBN) nanoribbons. By hyperspectral infrared nanoimaging, we observe a synthetic transverse optical phonon resonance (strong collective near-field coupling of the nanoribbons) in the middle of the hBN Reststrahlen band, yielding a topological transition from hyperbolic to elliptical dispersion. We further visualize and characterize the spatial evolution of a deeply subwavelength canalization mode near the transition frequency, which is a collimated polariton that is the basis for hyperlensing and diffraction-less propagation.

Polaritons in two-dimensional materials provide extreme light confinement that is difficult to achieve with metal plasmonics. However, such tight confinement inevitably increases optical losses through various damping channels. Here we demonstrate that hyperbolic phonon polaritons in hexagonal boron nitride can overcome this fundamental trade-off. Among two observed polariton modes, featuring a symmetric and antisymmetric charge distribution, the latter exhibits lower optical losses and tighter polariton confinement. Far-field excitation and detection of this high-momenta mode become possible with our resonator design that can boost the coupling efficiency via virtual polariton modes with image charges that we dub 'image polaritons'. Using these image polaritons, we experimentally observe a record-high effective index of up to 132 and quality factors as high as 501. Further, our phenomenological theory suggests an important role of hyperbolic surface scattering in the damping process of hyperbolic phonon polaritons.

Phonon polaritons (PhPs) are collective phonon oscillations with hybridized electromagnetic fields, which concentrate mid-infrared optical fields that can match molecular vibrations. The utilization of PhPs holds the promise for chemical sensing tools and polariton-enhanced nanospectroscopy. However, investigations and innovations on PhPs in the aqueous phase remain stagnant because of the lack of in situ mid-infrared nanoimaging methods in water. Strong infrared absorption from water prohibits optical delivery and detection in the mid-infrared for scattering-type near-field microscopy. Here, we present our solution: the detection of photothermal responses caused by the excitation of PhPs by liquid phase peak force infrared (LiPFIR) microscopy. Characteristic interference fringes of PhPs in 10 B isotope-enriched h -BN were measured in the aqueous phase and their dispersion relationship extracted. LiPFIR enables the measurement of mid-infrared PhPs in the fluid phase, opening possibilities and facilitating the development of mid-IR phonon polaritonics in water.

The phonon linewidth of isotopically controlled hexagonal boron nitride (h-BN) single crystals has been determined by Raman scattering. The scattering by isotopic mass disorder induces a phonon broadening that is largest for boron 11 fractions around 0.65. Lowest-order perturbation theory does not suffice to explain the dependence of the isotopic broadening on isotopic composition. A multiple-scattering theory based on the coherent potential approximation provides a good quantitative account of the phonon shift and broadening with isotopic composition observed in the experiments. Isotopic-disorder scattering is shown to have a prominent role in limiting the optical-phonon lifetime in h-BN.

Hexagonal boron nitride (hBN) supports two types of hyperbolic phonon polaritons (HPPs), whose properties of strong electromagnetic field confinement and low propagation loss have been proposed for various applications in nanophotonics. Conventionally, real-space imaging of HPPs by scattering-type scanning near-field optical microscopy (s-SNOM) with vertical polarization excitation contains both tip and edge launched polariton modes, which leads to hybrid interference fringes. In this work, we symmetrically study the tip and edge excited HPPs in both boron nitride with the natural distribution of boron isotopes (natural hBN) and 11 B isotope-enriched boron nitride (99.2% 11 B hBN). The intrinsic HPPs excited in 99.2% 11 B hBN exhibit a lower damping rate and longer propagation length than that in natural hBN. We experimentally realize a tuning from tip-dominated to edge-dominated excited HPPs by rotating the polarization of incident light. The near-field electric field intensity (NEFI) of edge-excited HPPs E edge and the angle β (between the hBN edge and the projective direction of the incident electric field on the hBN plane) present a sine function relationship as E edge ∝|sin β| under an s-polarized incident light. The NEFI of edge-excited HPPs in 99.2% 11 B hBN shows a 10% enhancement compared to natural hBN under the same measurement conditions. Our findings demonstrate an effective approach to reducing phonon polariton damping and manipulating phonon polariton excitation in hBN, which are beneficial for developing HPPs-based nanophotonic applications.

Van der Waals (vdW) materials host a variety of polaritons, which make them an emerging material platform for manipulating light at the nanoscale. Due to the layered structure of vdW materials, the polaritons can exhibit a hyperbolic dispersion and propagate as nanoscale-confined volume modes in thin flakes. On the other hand, surface-confined modes can be found at the flake edges. Surprisingly, the guiding of these modes in ribbons-representing typical linear waveguide structures-is widely unexplored. Here, a detailed study of hyperbolic phonon polaritons propagating in hexagonal boron nitride ribbons is reported. Employing infrared nanoimaging, a variety of modes are observed. Particularly, the fundamental volume waveguide mode that exhibits a cutoff width is identified, which, interestingly, can be lowered by reducing the waveguide thickness. Further, hybridization of the surface modes and their evolution with varying frequency and waveguide width are observed. Most importantly, it is demonstrated that the symmetrically hybridized surface mode does not exhibit a cutoff width, and thus enables linear waveguiding of the polaritons in arbitrarily narrow ribbons. The experimental data, supported by simulations, establish a solid basis for the understanding of hyperbolic polaritons in linear waveguides, which is of critical importance for their application in future photonic devices., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Scattering-type scanning near-field optical microscopy (s-SNOM) is instrumental in exploring polaritonic behaviors of two-dimensional (2D) materials at the nanoscale. A sharp s-SNOM tip couples momenta into 2D materials through phase matching to excite phonon polaritons, which manifest as nanoscale interference fringes in raster images. However, s-SNOM lacks the ability to detect the progression of near-field properties along the perpendicular axis to the surface. Here, we perform near-field analysis of a micro-disk and a reflective edge made of isotopically pure hexagonal boron nitride (h-11BN), by using three-dimensional near-field response cubes obtained by peak force scattering-type near-field optical microscopy (PF-SNOM). Momentum quantization of polaritons from the confinement of the circular structure is revealed in situ. Moreover, tip-sample distance is found to be capable of fine-tuning the momentum of polaritons and modifying the superposition of quantized polaritonic modes. The PF-SNOM-based three-dimensional near-field analysis provides detailed characterization capability with a high spatial resolution to fully map three-dimensional near-fields of nano-photonics and polaritonic structures.

Hyperbolic phonon polaritons (HPhPs) are generated when infrared photons couple to polar optic phonons in anisotropic media, confining long-wavelength light to nanoscale volumes. However, to realize the full potential of HPhPs for infrared optics, it is crucial to understand propagation and loss mechanisms on substrates suitable for applications from waveguiding to infrared sensing. We employ scattering-type scanning near-field optical microscopy (s-SNOM) and nano-Fourier transform infrared (FTIR) spectroscopy, in concert with analytical and numerical calculations, to elucidate HPhP characteristics as a function of the complex substrate dielectric function. We consider propagation on suspended, dielectric and metallic substrates to demonstrate that the thickness-normalized wavevector can be reduced by a factor of 25 simply by changing the substrate from dielectric to metallic behavior. Moreover, by incorporating the imaginary contribution to the dielectric function in lossy materials, the wavevector can be dynamically controlled by small local variations in loss or carrier density. Counterintuitively, higher-order HPhP modes are shown to exhibit the same change in the polariton wavevector as the fundamental mode, despite the drastic differences in the evanescent ranges of these polaritons. However, because polariton refraction is dictated by the fractional change in the wavevector, this still results in significant differences in polariton refraction and reduced sensitivity to substrate-induced losses for the higher-order HPhPs. Such effects may therefore be used to spatially separate hyperbolic modes of different orders and for index-based sensing schemes. Our results advance our understanding of fundamental hyperbolic polariton excitations and their potential for on-chip photonics and planar metasurface optics.

Polaritons formed by the coupling of light and material excitations enable light-matter interactions at the nanoscale beyond what is currently possible with conventional optics. However, novel techniques are required to control the propagation of polaritons at the nanoscale and to implement the first practical devices. Here we report the experimental realization of polariton refractive and meta-optics in the mid-infrared by exploiting the properties of low-loss phonon polaritons in isotopically pure hexagonal boron nitride interacting with the surrounding dielectric environment comprising the low-loss phase change material Ge 3 Sb 2 Te 6 . We demonstrate rewritable waveguides, refractive optical elements such as lenses, prisms, and metalenses, which allow for polariton wavefront engineering and sub-wavelength focusing. This method will enable the realization of programmable miniaturized integrated optoelectronic devices and on-demand biosensors based on high quality phonon resonators.

At very small twist angles of ∼0.1°, bilayer graphene exhibits a strain-accompanied lattice reconstruction that results in submicron-size triangular domains with the standard, Bernal stacking. If the interlayer bias is applied to open an energy gap inside the domain regions making them insulating, such marginally twisted bilayer graphene is expected to remain conductive due to a triangular network of chiral one-dimensional states hosted by domain boundaries. Here we study electron transport through this helical network and report giant Aharonov-Bohm oscillations that reach in amplitude up to 50% of resistivity and persist to temperatures above 100 K. At liquid helium temperatures, the network exhibits another kind of oscillations that appear as a function of carrier density and are accompanied by a sign-changing Hall effect. The latter are attributed to consecutive population of the narrow minibands formed by the network of one-dimensional states inside the gap.

Van der Waals materials and their heterostructures offer a versatile platform for studying a variety of quantum transport phenomena due to their unique crystalline properties and the exceptional ability in tuning their electronic spectrum. However, most experiments are limited to devices that have lateral dimensions of only a few micrometres. Here, we perform magnetotransport measurements on graphene/hexagonal boron-nitride Hall bars and show that wider devices reveal additional quantum effects. In devices wider than ten micrometres we observe distinct magnetoresistance oscillations that are caused by resonant scattering of Landau-quantised Dirac electrons by acoustic phonons in graphene. The study allows us to accurately determine graphene's low energy phonon dispersion curves and shows that transverse acoustic modes cause most of phonon scattering. Our work highlights the crucial importance of device width when probing quantum effects and also demonstrates a precise, spectroscopic method for studying electron-phonon interactions in van der Waals heterostructures.

An understanding of the nucleation and growth of hexagonal boron nitride (hBN) on nickel substrates is essential to its development as a functional material. In particular, fundamental insights into the formation of the hexagonal lattices with alternating boron (B) and nitrogen (N) atoms could be exploited to control hBN lattice morphologies for targeted applications. In this study, the preferred shapes and edge configurations of atomically smooth hBN on Ni(111) were investigated using molecular dynamics (MD) simulations, along with reactive force field (ReaxFF) developed to represent the Ni/B/N system and the lattice-building B-N bond formation. The obtained hBN lattices, from different B : N feed ratios, are able to confirm that hBN domain geometries can indeed be tuned by varying thermodynamic parameters (i.e., chemical potentials of N and B) - a finding that has only been predicted using quantum mechanical theories. Here, we also showed that the nitrogen fed to the system plays a more crucial role in dictating the size of hBN lattices. With an increase of the relative N content, the simulated hBN domain shapes also transition from equilateral triangles to hexagons, again, consistent with the anticipation based on Density Functional Theory (DFT) calculations. Hence, a plausible approach to acquire a desired hBN nanostructure depends on careful control over the synthesis conditions, which now can benefit from reliable molecular simulations.

Metasurfaces control light propagation at the nanoscale for applications in both free-space and surface-confined geometries. However, dynamically changing the properties of metasurfaces can be a major challenge. Here we demonstrate a reconfigurable hyperbolic metasurface comprised of a heterostructure of isotopically enriched hexagonal boron nitride (hBN) in direct contact with the phase-change material (PCM) single-crystal vanadium dioxide (VO 2 ). Metallic and dielectric domains in VO 2 provide spatially localized changes in the local dielectric environment, enabling launching, reflection, and transmission of hyperbolic phonon polaritons (HPhPs) at the PCM domain boundaries, and tuning the wavelength of HPhPs propagating in hBN over these domains by a factor of 1.6. We show that this system supports in-plane HPhP refraction, thus providing a prototype for a class of planar refractive optics. This approach offers reconfigurable control of in-plane HPhP propagation and exemplifies a generalizable framework based on combining hyperbolic media and PCMs to design optical functionality.

Hexagonal boron nitride (hBN) mono and multilayers are promising hosts for room-temperature single photon emitters (SPEs). In this work we explore high-energy (∼MeV) electron irradiation as a means to generate stable SPEs in hBN. We investigate four types of exfoliated hBN flakes-namely, high-purity multilayers, isotopically pure hBN, carbon-rich hBN multilayers and monolayered material-and find that electron irradiation increases emitter concentrations dramatically in all samples. Furthermore, the engineered emitters are located throughout hBN flakes (not only at flake edges or grain boundaries) and do not require activation by high-temperature annealing of the host material after electron exposure. Our results provide important insights into controlled formation of hBN SPEs and may aid in identification of their crystallographic origin.

Artificial atomic systems in solids are becoming increasingly important building blocks in quantum information processing and scalable quantum nanophotonic networks. Amongst numerous candidates, 2D hexagonal boron nitride has recently emerged as a promising platform hosting single photon emitters. Here, we report a number of robust plasma and thermal annealing methods for fabrication of emitters in tape-exfoliated hexagonal boron nitride (hBN) crystals. A two-step process comprising Ar plasma etching and subsequent annealing in Ar is highly robust, and yields an eight-fold increase in the concentration of emitters in hBN. The initial plasma-etching step generates emitters that suffer from blinking and bleaching, whereas the two-step process yields emitters that are photostable at room temperature with emission wavelengths greater than ∼700 nm. Density functional theory modeling suggests that the emitters might be associated with defect complexes that contain oxygen. This is further confirmed by generating the emitters via annealing hBN in air. Our findings advance the present understanding of the structure of quantum emitters in hBN and enhance the nanofabrication toolkit needed to realize integrated quantum nanophotonic circuits.

Metasurfaces with strongly anisotropic optical properties can support deep subwavelength-scale confined electromagnetic waves (polaritons), which promise opportunities for controlling light in photonic and optoelectronic applications. We developed a mid-infrared hyperbolic metasurface by nanostructuring a thin layer of hexagonal boron nitride that supports deep subwavelength-scale phonon polaritons that propagate with in-plane hyperbolic dispersion. By applying an infrared nanoimaging technique, we visualize the concave (anomalous) wavefronts of a diverging polariton beam, which represent a landmark feature of hyperbolic polaritons. The results illustrate how near-field microscopy can be applied to reveal the exotic wavefronts of polaritons in anisotropic materials and demonstrate that nanostructured van der Waals materials can form a highly variable and compact platform for hyperbolic infrared metasurface devices and circuits., (Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Hexagonal boron nitride is a model lamellar compound where weak, non-local van der Waals interactions ensure the vertical stacking of two-dimensional honeycomb lattices made of strongly bound boron and nitrogen atoms. We study the isotope engineering of lamellar compounds by synthesizing hexagonal boron nitride crystals with nearly pure boron isotopes ( 10 B and 11 B) compared to those with the natural distribution of boron (20 at% 10 B and 80 at% 11 B). On the one hand, as with standard semiconductors, both the phonon energy and electronic bandgap varied with the boron isotope mass, the latter due to the quantum effect of zero-point renormalization. On the other hand, temperature-dependent experiments focusing on the shear and breathing motions of adjacent layers revealed the specificity of isotope engineering in a layered material, with a modification of the van der Waals interactions upon isotope purification. The electron density distribution is more diffuse between adjacent layers in 10 BN than in 11 BN crystals. Our results open perspectives in understanding and controlling van der Waals bonding in layered materials.

Atomistic-scale insights into the growth of a continuous, atomically thin hexagonal boron nitride (hBN) lattice from elemental boron and nitrogen on Ni substrates were obtained from multiscale modeling combining density functional theory (DFT) and reactive molecular dynamics. The quantum mechanical calculations focused on the adsorption and reaction energetics for the hBN building-block species, i.e., atomic B, N, B x N y (x, y = 1, 2), on Ni(111) and Ni(211), and the diffusion pathways of elemental B and N on these slab model surfaces and in the sublayer. B can diffuse competitively on both the surface and in the sublayer, while N diffuses strictly on the substrate surface. The DFT data were then used to generate a classical description of the Ni-B and Ni-N pair interactions within the formulation of the reactive force field, ReaxFF. Using the potential developed from this work, the elementary nucleation and growth process of an hBN monolayer structure from elemental B and N is shown at the atomistic scale. The nucleation initiates from the growth of linear BN chains, which evolve into branched and then hexagonal lattices. Subsequent DFT calculations confirmed the structure evolution energetically and validate the self-consistency of this multiscale modeling framework. On the basis of this framework, the fundamental aspects regarding crystal quality and the role of temperature and substrates used during hBN growth can also be understood.

We employ X-ray absorption near-edge spectroscopy at the boron K-edge and the phosphorus L 2,3 -edge to study the structural properties of cubic boron phosphide (c-BP) samples. The X-ray absorption spectra are modeled from first-principles within the density functional theory framework using the excited electron core-hole (XCH) approach. A simple structural model of a perfect c-BP crystal accurately reproduces the P L 2,3 -edge, however it fails to describe the broad and gradual onset of the B K-edge. Simulations of the spectroscopic signatures in boron 1s excitations of intrinsic point defects and the hexagonal BP crystal phase show that these additions to the structural model cannot reproduce the broad pre-edge of the experimental spectrum. Calculated formation enthalpies show that, during the growth of c-BP, it is possible that amorphous boron phases can be grown in conjunction with the desired boron phosphide crystalline phase. In combination with experimental and theoretically obtained X-ray absorption spectra of an amorphous boron structure, which have a similar broad absorption onset in the B K-edge spectrum as the cubic boron phosphide samples, we provide evidence for the presence of amorphous boron clusters in the synthesized c-BP samples.

Mechanical exfoliation from bulk layered crystal is widely used for preparing two-dimensional (2D) layered materials, which involves not only out-of-plane interlayer cleavage but also in-plane fracture. Through a statistical analysis on the exfoliated 2D flakes, we reveal the in-plane cleavage behaviors of six representative layered materials, including graphene, h-BN, 2H phase MoS2, 1T phase PtS2, FePS3, and black phosphorus. In addition to the well-known interlayer cleavage, these 2D layered materials show a distinctive tendency to fracture along certain in-plane crystallography orientations. With theoretical modeling and analysis, these distinct in-plane cleavage behaviors can be understood as a result of the competition between the release of the elastic energy and the increase of the surface energy during the fracture process. More importantly, these in-plane cleavage behaviors provide a fast and noninvasive method using optical microscopy to identify the lattice direction of mechanical exfoliated 2D layered materials.

The dielectric response function of epitaxial B(12)As(2) films on 4H-SiC was determined at room temperature and at 10 K in the spectral region of 3.6-9.8 eV, i.e., in the vacuum ultraviolet (VUV) spectral region, by synchrotron ellipsometry. The experimental dielectric function was simulated with the critical point parabolic band model. The parameters of the dispersive structures were derived by numerical fitting of the experimental data to the proposed model. New high energy optical transitions are resolved at 5.95, 7.8 and 8.82 eV and their lineshape and origin are discussed. The temperature dependence of the critical point energies and transition strengths was determined, and the excitonic effect is considered.

This paper describes the fabrication and characterization of photopolymerizable alkylphosphonate self-assembled monolayers (SAMs) on group-III nitride substrates including GaN and Al(x)Ga(1-x)N (AlGaN; x = 0.2 and 0.25). Contact angle goniometry, visible absorption spectroscopy, and atomic force microscopy were used to assess the formation, desorption, and photopolymerization of SAMs of diacetylenic alkylphosphonic acids (CH(3)(CH(2))(n)-C[triple bond]C-C[triple bond]C-(CH(2))(m)PO(OH)(2); (m, n) = (3, 11), (6, 8), and (9, 5)). As with GaN substrates (Ito, T.; Forman, S. M.; Cao, C.; Li, F.; Eddy, C. R., Jr.; Mastro, M. A.; Holm, R. T.; Henry, R. L.; Hohn, K.; Edgar, J. H. Langmuir 2008, 24, 6630-6635), alkylphosphonic acids formed SAMs on UV/O(3)-treated AlGaN substrates from their toluene solutions in contrast to other primary substituted hydrocarbons with a terminal -COOH, -NH(2), -OH, or -SH group. Diacetylenic alkylphosphonate SAMs on group-III nitrides could be polymerized by UV irradiation (254 nm), as indicated by the appearance of a visible absorption band around 640 nm and also by their significantly reduced desorption from the surface in a 0.1 M aqueous NaOH solution. A longer UV irradiation time was required to maximize the photopolymerization of a SAM having a diacetylene group close to the terminal phosphonate moiety, probably because of the hindrance of the topochemical polymerization due to the limited flexibility of the cross-linking moieties on an atomically rough substrate surface.

In this paper we describe the formation and characterization of self-assembled monolayers of octadecylphosphonic acid (ODPA) on epitaxial (0001) GaN films on sapphire. By immersing the substrate in its toluene solution, ODPA strongly adsorbed onto UV/O 3-treated GaN to give a hydrophobic surface. Spectroscopic ellipsometry verified the formation of a well-packed monolayer of ODPA on the GaN substrate. In contrast, adsorption of other primarily substituted hydrocarbons (C n H 2 n+1 X; n = 16-18; X = -COOH, -NH 2, -SH, and -OH) offered less hydrophobic surfaces, reflecting their weaker interaction with the GaN substrate surfaces. A UV/O 3-treated N-polar GaN had a high affinity to the -COOH group in addition to ODPA, possibly reflecting the basic properties of the surface. These observations suggested that the molecular adsorption was primarily based on hydrogen bond interactions between the surface oxide layer on the GaN substrate and the polar functional groups of the molecules. The as-prepared ODPA monolayers were desorbed from the GaN substrates by soaking in an aqueous solution, particularly in a basic solution. However, ODPA monolayers heated at 160 degrees C exhibited suppressed desorption in acidic and neutral aqueous solution maybe due to covalent bond formation between ODPA and the surface. X-ray photoelectron spectroscopy provided insight into the effect of the UV/O 3 treatment on the surface composition of the GaN substrate and also the ODPA monolayer formation. These results demonstrate that the surface of a GaN substrate can be tailored with organic molecules having an alkylphosphonic acid moiety for future sensor and device applications.