Accelerated Nano-Optical Imaging through Sparse Sampling.

The integration time and signal-to-noise ratio are inextricably linked when performing scanning probe microscopy based on raster scanning. This often yields a large lower bound on the measurement time, for example, in nano-optical imaging experiments performed using a scanning near-field optical microscope (SNOM). Here, we utilize sparse scanning augmented with Gaussian process regression to bypass the time constraint. We apply this approach to image charge-transfer polaritons in graphene residing on ruthenium trichloride (α-RuCl3) and obtain key features such as polariton damping and dispersion. Critically, nano-optical SNOM imaging data obtained via sparse sampling are in good agreement with those extracted from traditional raster scans but require 11 times fewer sampled points. As a result, Gaussian process-aided sparse spiral scans offer a major decrease in scanning time.

Quenched Excitons in WSe2/α-RuCl3 Heterostructures Revealed by Multimessenger Nanoscopy.

We investigate heterostructures composed of monolayer WSe2 stacked on α-RuCl3 using a combination of Terahertz (THz) and infrared (IR) nanospectroscopy and imaging, scanning tunneling spectroscopy (STS), and photoluminescence (PL). Our observations reveal itinerant carriers in the heterostructure prompted by charge transfer across the WSe2/α-RuCl3 interface. Local STS measurements show the Fermi level is shifted to the valence band edge of WSe2 which is consistent with p-type doping and verified by density functional theory (DFT) calculations. We observe prominent resonances in near-IR nano-optical and PL spectra, which are associated with the A-exciton of WSe2. We identify a concomitant, near total, quenching of the A-exciton resonance in the WSe2/α-RuCl3 heterostructure. Our nano-optical measurements show that the charge-transfer doping vanishes while excitonic resonances exhibit near-total recovery in "nanobubbles", where WSe2 and α-RuCl3 are separated by nanometer distances. Our broadband nanoinfrared inquiry elucidates local electrodynamics of excitons and an electron-hole plasma in the WSe2/α-RuCl3 system.

Curvature-Induced One-Dimensional Phonon Polaritons at Edges of Folded Boron Nitride Sheets.

Generation and manipulation of phonon polaritons are of paramount importance for understanding the interaction between an electromagnetic field and dielectric materials and furthering their application in mid-infrared optical communication. However, the formation of tunable one-dimensional phonon polaritons has been rarely realized in van der Waals layered structures. Here we report the discovery of curvature-induced phonon polaritons localized at the crease of folded hexagonal boron nitrides (h-BNs) with a few atomic layers using monochromated electron energy-loss spectroscopy. Compared to bulk regions, the creased-localized signals undergo an abnormal blue-shift of 1.4 meV. First-principles calculations reveal that the energy shift arises from the optical phonon hardening in the curled region. Interestingly, the curvature-induced phonon polariton can also be controllably achieved via an electron-beam etching approach. This work opens an avenue of tailoring local electromagnetic response and creating unique phonon polariton modes in van der Waals layered materials for diverse applications.

Long-Lived Phonon Polaritons in Hyperbolic Materials.

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-MoO3 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-MoO3 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.

Unzipping hBN with ultrashort mid-infrared pulses.

Manipulating the nanostructure of materials is critical for numerous applications in electronics, magnetics, and photonics. However, conventional methods such as lithography and laser writing require cleanroom facilities or leave residue. We describe an approach to creating atomically sharp line defects in hexagonal boron nitride (hBN) at room temperature by direct optical phonon excitation with a mid-infrared pulsed laser from free space. We term this phenomenon "unzipping" to describe the rapid formation and growth of a crack tens of nanometers wide from a point within the laser-driven region. Formation of these features is attributed to the large atomic displacement and high local bond strain produced by strongly driving the crystal at a natural resonance. This process occurs only via coherent phonon excitation and is highly sensitive to the relative orientation of the crystal axes and the laser polarization. Its cleanliness, directionality, and sharpness enable applications such as polariton cavities, phonon-wave coupling, and in situ flake cleaving.

Programming twist angle and strain profiles in 2D materials.

Moiré superlattices in twisted two-dimensional materials have generated tremendous excitement as a platform for achieving quantum properties on demand. However, the moiré pattern is highly sensitive to the interlayer atomic registry, and current assembly techniques suffer from imprecise control of the average twist angle, spatial inhomogeneity in the local twist angle, and distortions caused by random strain. We manipulated the moiré patterns in hetero- and homobilayers through in-plane bending of monolayer ribbons, using the tip of an atomic force microscope. This technique achieves continuous variation of twist angles with improved twist-angle homogeneity and reduced random strain, resulting in moiré patterns with tunable wavelength and ultralow disorder. Our results may enable detailed studies of ultralow-disorder moiré systems and the realization of precise strain-engineered devices.

Hyperbolic exciton polaritons in a van der Waals magnet.

Exciton polaritons are quasiparticles of photons coupled strongly to bound electron-hole pairs, manifesting as an anti-crossing light dispersion near an exciton resonance. Highly anisotropic semiconductors with opposite-signed permittivities along different crystal axes are predicted to host exotic modes inside the anti-crossing called hyperbolic exciton polaritons (HEPs), which confine light subdiffractionally with enhanced density of states. Here, we show observational evidence of steady-state HEPs in the van der Waals magnet chromium sulfide bromide (CrSBr) using a cryogenic near-infrared near-field microscope. At low temperatures, in the magnetically-ordered state, anisotropic exciton resonances sharpen, driving the permittivity negative along one crystal axis and enabling HEP propagation. We characterize HEP momentum and losses in CrSBr, also demonstrating coupling to excitonic sidebands and enhancement by magnetic order: which boosts exciton spectral weight via wavefunction delocalization. Our findings open new pathways to nanoscale manipulation of excitons and light, including routes to magnetic, nonlocal, and quantum polaritonics.

Enhanced tunable second harmonic generation from twistable interfaces and vertical superlattices in boron nitride homostructures.

Broken symmetries induce strong even-order nonlinear optical responses in materials and at interfaces. Unlike conventional covalently bonded nonlinear crystals, van der Waals (vdW) heterostructures feature layers that can be stacked at arbitrary angles, giving complete control over the presence or lack of inversion symmetry at a crystal interface. Here, we report highly tunable second harmonic generation (SHG) from nanomechanically rotatable stacks of bulk hexagonal boron nitride (BN) crystals and introduce the term twistoptics to describe studies of optical properties in twistable vdW systems. By suppressing residual bulk effects, we observe SHG intensity modulated by a factor of more than 50, and polarization patterns determined by moiré interface symmetry. Last, we demonstrate greatly enhanced conversion efficiency in vdW vertical superlattice structures with multiple symmetry-broken interfaces. Our study paves the way for compact twistoptics architectures aimed at efficient tunable frequency conversion and demonstrates SHG as a robust probe of buried vdW interfaces.

Visualization of moiré superlattices.

Moiré superlattices in van der Waals heterostructures have given rise to a number of emergent electronic phenomena due to the interplay between atomic structure and electron correlations. Indeed, electrons in these structures have been recently found to exhibit a number of emergent properties that the individual layers themselves do not exhibit. This includes superconductivity1,2, magnetism3, topological edge states4,5, exciton trapping6 and correlated insulator phases7. However, the lack of a straightforward technique to characterize the local structure of moiré superlattices has thus far impeded progress in the field. In this work we describe a simple, room-temperature, ambient method to visualize real-space moiré superlattices with sub-5-nm spatial resolution in a variety of twisted van der Waals heterostructures including, but not limited to, conducting graphene, insulating boron nitride and semiconducting transition metal dichalcogenides. Our method uses piezoresponse force microscopy, an atomic force microscope modality that locally measures electromechanical surface deformation. We find that all moiré superlattices, regardless of whether the constituent layers have inversion symmetry, exhibit a mechanical response to out-of-plane electric fields. This response is closely tied to flexoelectricity wherein electric polarization and electromechanical response is induced through strain gradients present within moiré superlattices. Therefore, moiré superlattices of two-dimensional materials manifest themselves as an interlinked network of polarized domain walls in a non-polar background matrix.

Rapid Growth of Nanocrystalline Diamond on Single Crystal Diamond for Studies on Materials under Extreme Conditions.

Early stage nucleation morphologies of spatially localized nanocrystalline diamond (NCD) micro-anvils grown on (100)-oriented single crystal diamond (SCD) anvil surfaces were analyzed and investigated for applications in high pressure studies on materials. NCD was grown on SCD using Microwave Plasma Chemical Vapor Deposition (MPCVD) for brief time intervals ranging from 1-15 minutes. Early stage film morphologies were characterized using scanning electron microscopy (SEM) and Raman spectroscopy and were compared to films grown for several hours. Rapid nucleation and growth of NCD on SCD is demonstrated without any pre-growth seeding of the substrate surface. As grown NCD diamond micro-anvils on SCD were used to generate static pressure of 0.5 Terapascal (TPa) on a tungsten sample as measured by synchrotron x-ray diffraction in a diamond anvil cell. Atomic force microscopy (AFM) analysis after decompression from ultrahigh pressures showed that the detachment of the NCD stage occurred in the bulk of the SCD and not at the interface, suggesting significant adhesive bond strength between nanocrystalline and single crystal diamond.

Epitope specificities of the group Y and W-135 polysaccharides of Neisseria meningitidis.

Previous studies have identified the length dependency of several polysaccharide (PS) protective epitopes. We have investigated whether meningococcal polysaccharides Y and W-135 possess such epitopes. Oligosaccharides (OSs) consisting of one or more disaccharide repeating units (RU) were derived from the capsular PSs of group Y and W-135 meningococci (GYMP and GWMP, respectively) by mild acid hydrolysis. The relative affinities of anticapsular antibodies binding to derivative OSs of different chain lengths were measured in inhibition enzyme-linked immunosorbent assays. As OS size increased from two to three RU, there was a notable increase in binding inhibition of rabbit anti-group Y antiserum. This pattern of antibody binding inhibition was also observed for rabbit antiserum to group W-135, though the inhibition increase was much more pronounced. In the cases of both OS species, the concentration of inhibiting antigen required to achieve 50% inhibition of rabbit immunoglobulin binding increased progressively as the inhibiting disaccharide chain length increased from 1 RU through greater than 50 RU. These data suggest that antibodies directed against both of these meningococcal PSs recognize conformational epitopes only fully expressed in higher-molecular-weight forms of these antigens.

Doubly branched hexasaccharide epitope on the cell wall polysaccharide of group A streptococci recognized by human and rabbit antisera.

A number of epitope specificities associated with the cell wall polysaccharide antigen of group A streptococci were identified in a polyclonal rabbit antiserum induced in rabbits by whole group A streptococci and in polyclonal convalescent human antisera from children that had recovered from streptococcal A infections. The identification was achieved by using a series of synthetic oligosaccharides, glycoconjugates, and bacterial polysaccharide inhibitors to inhibit the binding of the group A helical polysaccharide to the polyclonal antisera. The exclusively dominant epitope expressed in the convalescent human antisera was the doubly branched extended helical hexasaccharide with the structure alpha-L-Rhap(1-->2)[beta-D-GlcpNAc(1-->3)]alpha-L-Rhap(1-->3)alpha-L-Rhap(1-->2)[beta-D-GlcpNAc(1-->3)]alpha-L-Rhap. The hexasaccharide epitope also bound with the highest immunoreactivity to the rabbit antiserum. In contrast, the human antisera did not show significant binding to the singly branched pentasaccharide with the structure alpha-L-Rhap(1-->2)alpha-L-Rhap(1-->3)alpha-L-Rhap(1-->2)[beta-D-GlcpNAc(1-->3)]alpha-L-Rhap or the branched trisaccharide alpha-L-Rhap(1-->2)[beta-D-GlcpNAc(1-->3)]alpha-l-Rhap, although both these haptens bound significantly to the same rabbit antiserum, albeit with less immunoreactivity than the hexasaccharide. Inhibition studies using streptococcal group A and B rabbit antisera and the inhibitors indicated above also suggested that the group A carbohydrate, unlike the group B streptococcal polysaccharide, does not contain the disaccharide alpha-L-Rhap(1-->2)alpha-L-Rhap motif at its nonreducing chain terminus, stressing the importance of mapping the determinant specificities of these two important streptococcal subcapsular group polysaccharides to fully understand the serological relationships between group A and group B streptococci.