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The nature of the insulator-to-metal phase transition in vanadium dioxide (VO2) is one of the longest-standing problems in condensed-matter physics. Ultrafast spectroscopy has long promised to determine whether the transition is primarily driven by the electronic or structural degree of freedom, but measurements to date have been stymied by their sensitivity to only one of these components and/or their limited temporal resolution. Here we use ultra-broadband few-femtosecond pump-probe spectroscopy to resolve the electronic and structural phase transitions in VO2 at their fundamental time scales. We find that the system transforms into a bad-metallic phase within 10 fs after photoexcitation, but requires another 100 fs to complete the transition, during which we observe electronic oscillations and a partial re-opening of the bandgap, signalling a transient semi-metallic state. Comparisons with tensor-network simulations and density-functional theory calculations show these features originate from oscillations around the equilibrium high-symmetry atomic positions during an unprecedentedly fast structural transition, in which the vanadium dimers separate and untwist with two different timescales. Our results resolve the complete structural and electronic nature of the light-induced phase transition in VO2 and establish ultra-broadband few-femtosecond spectroscopy as a powerful new tool for studying quantum materials out of equilibrium., Comment: 20 pages, 12 figures

Reconfigurable optical systems are the object of continuing, intensive research activities, as they hold great promise for realizing a new generation of compact, miniaturized, and flexible optical devices. However, current reconfigurable systems often tune only a single state variable triggered by an external stimulus, thus, leaving out many potential applications. Here we demonstrate a reconfigurable multistate optical system enabled by phase transitions in vanadium dioxide (VO2). By controlling the phase-transition characteristics of VO2 with simultaneous stimuli, the responses of the optical system can be reconfigured among multiple states. In particular, we show a quadruple-state dynamic plasmonic display that responds to both temperature tuning and hydrogen-doping. Furthermore, we introduce an electron-doping scheme to locally control the phase-transition behavior of VO2, enabling an optical encryption device encoded by multiple keys. Our work points the way toward advanced multistate reconfigurable optical systems, which substantially outperform current optical devices in both breadth of capabilities and functionalities.

Achieving ultrafast all-optical switching in a silicon waveguide geometry is a key milestone on the way to an integrated platform capable of handling the increasing demands for higher speed and higher capacity for information transfer. Given the weak electro-optic and thermo-optic effects in silicon, there has been intense interest in hybrid structures in which that switching could be accomplished by integrating another material into the waveguide, including the phase-changing material, vanadium dioxide (VO2). It has long been known that the phase transition in VO2 can be triggered by ultrafast laser pulses, and that pump-laser fluence is a critical parameter governing the recovery time of thin films irradiated by femtosecond laser pulses near 800 nm. However, thin-film experiments are not a priori reliable guides to using VO2 for all-optical switching in on-chip silicon photonics because of the large changes in VO2 optical constants in the telecommunications band, the requirement of low insertion loss, and the limits on switching energy permissible in integrated photonic systems. Here we report the first measurements to show that the reversible, ultrafast photo-induced phase transition in VO2 can be harnessed to achieve sub-picosecond switching when small VO2 volumes are integrated in a silicon waveguide as a modulating element. Switching energies above threshold are of order 600 fJ/switch. These results suggest that VO2 can now be pursued as a strong candidate for all-optical switching with sub-picosecond on-off times., Comment: Main text 6 pages, 4 figures. Supplementary Information 9 pages, 7 figures

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. In this paper, 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. Such effects may therefore be used to spatially separate hyperbolic modes of different orders, and indicates that for index-based sensing schemes that HPhPs can be more sensitive than surface polaritons in the thin film limit. Our results advance our understanding of fundamental polariton excitations and their potential for on-chip photonics and planar metasurface optics.

Molecules intercalating two-dimensional (2D) materials form complex structures that have been mostly characterized by spatially averaged techniques. Here we use aberration-corrected scanning transmission electron microscopy and density-functional-theory (DFT) calculations to study the atomic structure of bilayer graphene (BLG) and few-layer graphene (FLG) intercalated with FeCl$_3$. In BLG we discover two distinct intercalated structures that we identify as monolayer-FeCl$_3$ and monolayer-FeCl$_2$. The two structures are separated by atomically sharp boundaries and induce large but different free-carrier densities in the graphene layers, $7.1\times10^{13}$ cm$^{-2}$ and $7.1\times10^{13}$ cm$^{-2}$ respectively. In FLG, we observe multiple FeCl$_3$ layers stacked in a variety of possible configurations with respect to one another. Finally, we find that the microscope's electron beam can convert the FeCl$_3$ monolayer into FeOCl monolayers in a rectangular lattice. These results reveal the need for a combination of atomically-resolved microscopy, spectroscopy, and DFT calculations to identify intercalated structures and study their properties.

Metasurfaces offer the potential to control light propagation at the nanoscale for applications in both free-space and surface-confined geometries. Existing metasurfaces frequently utilize metallic polaritonic elements with high absorption losses, and/or fixed geometrical designs that serve a single function. Here we overcome these limitations by demonstrating a reconfigurable hyperbolic metasurface comprising of a heterostructure of isotopically enriched hexagonal boron nitride (hBN) in direct contact with the phase-change material (PCM) vanadium dioxide (VO2). Spatially localized metallic and dielectric domains in VO2 change the wavelength of the hyperbolic phonon polaritons (HPhPs) supported in hBN by a factor 1.6 at 1450cm-1. This induces in-plane launching, refraction and reflection of HPhPs in the hBN, proving reconfigurable control of in-plane HPhP propagation at the nanoscale15. These results exemplify a generalizable framework based on combining hyperbolic media and PCMs in order to design optical functionalities such as resonant cavities, beam steering, waveguiding and focusing with nanometric control.

Nanoscale control over the second-order photon correlation function $g^{(2)}(\tau)$ is critical to emerging research in nonlinear nanophotonics and integrated quantum information science. Here we report on quasiparticle control of photon bunching with $g^{(2)}(0)>45$ in the cathodoluminescence of nanodiamond nitrogen vacancy (NV$^0$) centers excited by a converged electron beam in an aberration-corrected scanning transmission electron microscope. Plasmon-mediated NV$^0$ cathodoluminescence exhibits a 16-fold increase in luminescence intensity correlated with a three fold reduction in photon bunching compared with that of uncoupled NV$^0$ centers. This effect is ascribed to the excitation of single temporally uncorrelated NV$^0$ centers by single surface plasmon polaritons. Spectrally resolved Hanbury Brown--Twiss interferometry is employed to demonstrate that the bunching is mediated by the NV$^0$ phonon sidebands, while no observable bunching is detected at the zero-phonon line. The data are consistent with fast phonon-mediated recombination dynamics, a conclusion substantiated by agreement between Bayesian regression and Monte Carlo models of superthermal NV$^0$ luminescence., Comment: 4 pages, 4 figures

We utilize near-infrared pump and mid-infrared probe spectroscopy to investigate the ultrafast electronic response of pressurized VO$_2$. Distinct pump-probe signals and a pumping threshold behavior are observed even in the pressure-induced metallic state showing a noticeable amount of localized electronic states. Our results are consistent with a scenario of a bandwidth-controlled Mott-Hubbard transition., Comment: 10 pages, 9 figures

Phase-change materials (PCMs) have emerged as promising active elements in silicon (Si) photonic systems. In this work, we design, fabricate, and characterize a hybrid Si-PCM optical modulator. By integrating vanadium dioxide (a PCM) within a Si photonic waveguide, in a non-resonant geometry, we demonstrate ~ 10 dB broadband modulation with a PCM length of 500 nm.

Understanding the near-field electromagnetic interactions that produce optical orbital angular momentum (OAM) is central to the integration of twisted light into nanotechnology. Here, we examine the cathodoluminescence (CL) of plasmonic vortices carrying OAM generated in spiral nanostructures through scanning transmission electron microscopy (STEM). The nanospiral geometry defines the photonic local density of states (LDOS) sampled by STEM-CL, which provides access to the phase and amplitude of the plasmonic vortex with nanometer spatial and meV spectral resolution. We map the full spectral dispersion of the plasmonic vortex in the spiral structure and examine the effects of increasing topological charge on the plasmon phase and amplitude in the detected CL signal. The vortex is mapped in CL over a broad spectral range, and deviations between the predicted and detected positions of near-field optical signatures of as much as 5 per cent are observed. Finally, enhanced luminescence is observed from concentric spirals of like handedness compared to that from concentric spirals of opposite handedness, indicating the potential to couple plasmonic vortices to chiral nanostructures for sensitive detection and manipulation of optical OAM.

The debate about whether the insulating phases of vanadium dioxide (VO2) can be described by band theory or must be described by a theory of strong electron correlations remains unresolved even after decades of research. Energy-band calculations using hybrid exchange functionals or including self-energy corrections account for the insulating or metallic nature of different phases, but have not yet successfully accounted for the observed magnetic orderings. Strongly-correlated theories have had limited quantitative success. Here we report that, by using hard pseudopotentials and an optimized hybrid exchange functional, the energy gaps and magnetic orderings of both monoclinic VO2 phases and the metallic nature of the high-temperature rutile phase are consistent with available experimental data, obviating an explicit role for strong correlations. We also report a potential candidate for the newly-found metallic monoclinic phase and present a detailed magnetic structure of the M2 monoclinic phase.

Nanophotonic (nanoplasmonic) structures confine, guide, and concentrate light on the nanoscale. Advancement of nanophotonics critically depends on active nanoscale control of these phenomena. Localized control of the insulator and metallic phases of vanadium dioxide (VO2) would open up a universe of applications in nanophotonics via modulation of the local dielectric environment of nanophotonic structures allowing them to function as active devices. Here we show dynamic reversible control of VO2 insulator-to-metal transition (IMT) locally on the scale of 15 nm or less and control of nanoantennas, observed in the near-field for the first time. Using polarization-selective near-field imaging techniques, we monitor simultaneously the IMT in VO2 and the change of plasmons on gold infrared nanoantennas. Structured nanodomains of the metallic VO2 locally and reversibly transform infrared plasmonic dipolar antennas to monopole antennas. Fundamentally, the IMT in VO2 can be triggered on femtosecond timescale to allow ultrafast nanoscale control of optical phenomena. These unique capabilities open up exciting novel applications in active nanophotonics.

We present recent measurements of excited-atom and ion emission from KCl surfaces illuminated by vacuum-ultraviolet synchrotron radiation (h-nu = 8-28 eV) and ultraviolet laser light (h-nu = 4 eV). At low intensities characteristic of the synchrotron experiments, excited atoms are desorbed by simple valence-band excitation process involving the metallization of the KCl surface. At the higher intensities typical of laser desorption and ablation, we observe a strong decrease in K emission as a function of the number of laser shots, but an essentially constant yield of Cl. K(+) and Cl(-) emission at high intensities show similar behavior. The energetics of these desorption phenomena can be treated in a bond-orbital model which shows that creation of a single valence hole is sufficient to excite an ion to an anti-bonding state.

Experimental studies of desorption induced by electronic transitions (DIET) are described. Such studies are producing an increasingly complete picture of the dynamical pathways through which incident electronic energy is absorbed and rechanneled to produce macroscopic erosion and glow. These mechanistic studies can determine rate constants for erosion and glow processes in model materials and provide valuable guidance in materials selection and development. Extensive experiments with electron, photon, and heavy particle irradiation of alkali halides and other simple model materials have produced evidence showing that: (1) surface erosion, consisting primarily in the ejection or desorption of ground-state neutral atoms, occurs with large efficiencies for all irradiated species; (2) surface glow, resulting from the radiative decay of desorbed atoms, likewise occurs for all irradiating species; (3) the typical mechanism for ground-state neutral desorption is exciton formation, followed by relaxation to a permanent, mobile electronic defect which is the precursor to bond-breaking in the surface or near-surface bulk of the material; and (4) the mechanisms for excited atom formation may include curve crossing in atomic collisions, interactions with surface defect or impurity states, or defect diffusion.