Spectroscopic and Interferometric Sum-Frequency Imaging of Strongly Coupled Phonon Polaritons in SiC Metasurfaces.

Phonon polaritons enable waveguiding and localization of infrared light with extreme confinement and low losses. The spatial propagation and spectral resonances of such polaritons are usually probed with complementary techniques such as near-field optical microscopy and far-field reflection spectroscopy. Here, infrared-visible sum-frequency spectro-microscopy is introduced as a tool for spectroscopic imaging of phonon polaritons. The technique simultaneously provides sub-wavelength spatial resolution and highly-resolved spectral resonance information. This is implemented by resonantly exciting polaritons using a tunable infrared laser and wide-field microscopic detection of the upconverted light. The technique is employed to image hybridization and strong coupling of localized and propagating surface phonon polaritons in a metasurface of SiC micropillars. Spectro-microscopy allows to measure the polariton dispersion simultaneously in momentum space by angle-dependent resonance imaging, and in real space by polariton interferometry. Notably, it is possible to directly image how strong coupling affects the spatial localization of polaritons, inaccessible with conventional spectroscopic techniques. The formation of edge states is observed at excitation frequencies where strong coupling prevents polariton propagation into the metasurface. The technique is applicable to the wide range of polaritonic materials with broken inversion symmetry and can be used as a fast and non-perturbative tool to image polariton hybridization and propagation.

Compact oblique-incidence nonlinear widefield microscopy with paired-pixel balanced imaging.

Nonlinear (vibrational) microscopy has emerged as a successful tool for the investigation of molecular systems as it combines label-free chemical characterization with spatial resolution on the sub-micron scale. In addition to the molecular recognition, the physics of the nonlinear interactions allows in principle to obtain structural information on the molecular level such as molecular orientations. Due to technical limitations such as the relatively complex imaging geometry with the required oblique sample irradiation and insufficient sensitivity of the instrument this detailed molecular information is typically not accessible using widefield imaging. Here, we present, what we believe to be, a new microscope design that addresses both challenges. We introduce a simplified imaging geometry that enables the measurement of distortion-free widefield images with free space oblique sample irradiation achieving high spatial resolution (∼1 µm). Furthermore, we present a method based on a paired-pixel balanced detection system for sensitivity improvement. With this technique, we demonstrate a substantial enhancement of the signal-to-noise ratio of up to a factor of 10. While both experimental concepts presented in this work are very general and can, in principle, be applied to various microscopy techniques, we demonstrate their performance for the specific case of heterodyned, sum frequency generation (SFG) microscopy.

Controlling the propagation asymmetry of hyperbolic shear polaritons in beta-gallium oxide.

Structural anisotropy in crystals is crucial for controlling light propagation, particularly in the infrared spectral regime where optical frequencies overlap with crystalline lattice resonances, enabling light-matter coupled quasiparticles called phonon polaritons (PhPs). Exploring PhPs in anisotropic materials like hBN and MoO3 has led to advancements in light confinement and manipulation. In a recent study, PhPs in the monoclinic crystal ß-Ga2O3 (bGO) were shown to exhibit strongly asymmetric propagation with a frequency dispersive optical axis. Here, using scanning near-field optical microscopy (s-SNOM), we directly image the symmetry-broken propagation of hyperbolic shear polaritons in bGO. Further, we demonstrate the control and enhancement of shear-induced propagation asymmetry by varying the incident laser orientation and polariton momentum using different sizes of nano-antennas. Finally, we observe significant rotation of the hyperbola axis by changing the frequency of incident light. Our findings lay the groundwork for the widespread utilization and implementation of polaritons in low-symmetry crystals.

Observation of directional leaky polaritons at anisotropic crystal interfaces.

Extreme anisotropy in some polaritonic materials enables light propagation with a hyperbolic dispersion, leading to enhanced light-matter interactions and directional transport. However, these features are typically associated with large momenta that make them sensitive to loss and poorly accessible from far-field, being bound to the material interface or volume-confined in thin films. Here, we demonstrate a new form of directional polaritons, leaky in nature and featuring lenticular dispersion contours that are neither elliptical nor hyperbolic. We show that these interface modes are strongly hybridized with propagating bulk states, sustaining directional, long-range, sub-diffractive propagation at the interface. We observe these features using polariton spectroscopy, far-field probing and near-field imaging, revealing their peculiar dispersion, and - despite their leaky nature - long modal lifetime. Our leaky polaritons (LPs) nontrivially merge sub-diffractive polaritonics with diffractive photonics onto a unified platform, unveiling opportunities that stem from the interplay of extreme anisotropic responses and radiation leakage.

Real-space nanoimaging of hyperbolic shear polaritons in a monoclinic crystal.

Various optical crystals possess permittivity components of opposite signs along different principal directions in the mid-infrared regime, exhibiting exotic anisotropic phonon resonances. Such materials with hyperbolic polaritons-hybrid light-matter quasiparticles with open isofrequency contours-feature large-momenta optical modes and wave confinement that make them promising for nanophotonic on-chip technologies. So far, hyperbolic polaritons have been observed and characterized in crystals with high symmetry including hexagonal (boron nitride), trigonal (calcite) and orthorhombic (α-MoO3 or α-V2O5) crystals, where they obey certain propagation patterns. However, lower-symmetry materials such as monoclinic crystals were recently demonstrated to offer richer opportunities for polaritonic phenomena. Here, using scanning near-field optical microscopy, we report the direct real-space nanoscale imaging of symmetry-broken hyperbolic phonon polaritons in monoclinic CdWO4 crystals, and showcase inherently asymmetric polariton excitation and propagation associated with the nanoscale shear phenomena. We also introduce a quantitative theoretical model to describe these polaritons that leads to schemes to enhance crystal asymmetry via the damping loss of phonon modes. Ultimately, our findings show that polaritonic nanophotonics is attainable using natural materials with low symmetry, favouring a versatile and general way to manipulate light at the nanoscale.

Hyperbolic shear polaritons in low-symmetry crystals.

The lattice symmetry of a crystal is one of the most important factors in determining its physical properties. Particularly, low-symmetry crystals offer powerful opportunities to control light propagation, polarization and phase1-4. Materials featuring extreme optical anisotropy can support a hyperbolic response, enabling coupled light-matter interactions, also known as polaritons, with highly directional propagation and compression of light to deeply sub-wavelength scales5. Here we show that monoclinic crystals can support hyperbolic shear polaritons, a new polariton class arising in the mid-infrared to far-infrared due to shear phenomena in the dielectric response. This feature emerges in materials in which the dielectric tensor cannot be diagonalized, that is, in low-symmetry monoclinic and triclinic crystals in which several oscillators with non-orthogonal relative orientations contribute to the optical response6,7. Hyperbolic shear polaritons complement previous observations of hyperbolic phonon polaritons in orthorhombic1,3,4 and hexagonal8,9 crystal systems, unveiling new features, such as the continuous evolution of their propagation direction with frequency, tilted wavefronts and asymmetric responses. The interplay between diagonal loss and off-diagonal shear phenomena in the dielectric response of these materials has implications for new forms of non-Hermitian and topological photonic states. We anticipate that our results will motivate new directions for polariton physics in low-symmetry materials, which include geological minerals10, many common oxides11 and organic crystals12, greatly expanding the material base and extending design opportunities for compact photonic devices.

Controlling the Infrared Dielectric Function through Atomic-Scale Heterostructures.

Surface phonon polaritons (SPhPs), the surface-bound electromagnetic modes of a polar material resulting from the coupling of light with optic phonons, offer immense technological opportunities for nanophotonics in the infrared (IR) spectral region. However, once a particular material is chosen, the SPhP characteristics are fixed by the spectral positions of the optic phonon frequencies. Here, we provide a demonstration of how the frequency of these optic phonons can be altered by employing atomic-scale superlattices (SLs) of polar semiconductors using AlN/GaN SLs as an example. Using second harmonic generation (SHG) spectroscopy, we show that the optic phonon frequencies of the SLs exhibit a strong dependence on the layer thicknesses of the constituent materials. Furthermore, new vibrational modes emerge that are confined to the layers, while others are centered at the AlN/GaN interfaces. As the IR dielectric function is governed by the optic phonon behavior in polar materials, controlling the optic phonons provides a means to induce and potentially design a dielectric function distinct from the constituent materials and from the effective-medium approximation of the SL. We show that atomic-scale AlN/GaN SLs instead have multiple Reststrahlen bands featuring spectral regions that exhibit either normal or extreme hyperbolic dispersion with both positive and negative permittivities dispersing rapidly with frequency. Apart from the ability to engineer the SPhP properties, SL structures may also lead to multifunctional devices that combine the mechanical, electrical, thermal, or optoelectronic functionality of the constituent layers. We propose that this effort is another step toward realizing user-defined, actively tunable IR optics and sources.

Dissecting spin-phonon equilibration in ferrimagnetic insulators by ultrafast lattice excitation.

To gain control over magnetic order on ultrafast time scales, a fundamental understanding of the way electron spins interact with the surrounding crystal lattice is required. However, measurement and analysis even of basic collective processes such as spin-phonon equilibration have remained challenging. Here, we directly probe the flow of energy and angular momentum in the model insulating ferrimagnet yttrium iron garnet. After ultrafast resonant lattice excitation, we observe that magnetic order reduces on distinct time scales of 1 ps and 100 ns. Temperature-dependent measurements, a spin-coupling analysis, and simulations show that the two dynamics directly reflect two stages of spin-lattice equilibration. On the 1-ps scale, spins and phonons reach quasi-equilibrium in terms of energy through phonon-induced modulation of the exchange interaction. This mechanism leads to identical demagnetization of the ferrimagnet's two spin sublattices and to a ferrimagnetic state of increased temperature yet unchanged total magnetization. Finally, on the much slower, 100-ns scale, the excess of spin angular momentum is released to the crystal lattice, resulting in full equilibrium. Our findings are relevant for all insulating ferrimagnets and indicate that spin manipulation by phonons, including the spin Seebeck effect, can be extended to antiferromagnets and into the terahertz frequency range.

Strong Coupling of Epsilon-Near-Zero Phonon Polaritons in Polar Dielectric Heterostructures.

We report the first observation of epsilon-near-zero (ENZ) phonon polaritons in an ultrathin AlN film fully hybridized with surface phonon polaritons (SPhP) supported by the adjacent SiC substrate. Employing a strong coupling model for the analysis of the dispersion and electric field distribution in these hybridized modes, we show that they share the most prominent features of the two precursor modes. The novel ENZ-SPhP coupled polaritons with a highly propagative character and deeply subwavelength light confinement can be utilized as building blocks for future infrared and terahertz nanophotonic integration and communication devices.

Terahertz Sum-Frequency Excitation of a Raman-Active Phonon.

In stimulated Raman scattering, two incident optical waves induce a force oscillating at the difference of the two light frequencies. This process has enabled important applications such as the excitation and coherent control of phonons and magnons by femtosecond laser pulses. Here, we experimentally and theoretically demonstrate the so far neglected up-conversion counterpart of this process: THz sum-frequency excitation of a Raman-active phonon mode, which is tantamount to two-photon absorption by an optical transition between two adjacent vibrational levels. Coherent control of an optical lattice vibration of diamond is achieved by an intense terahertz pulse whose spectrum is centered at half the phonon frequency of 40 THz. Remarkably, the carrier-envelope phase of the THz pulse is directly transferred into the phase of the lattice vibration. New prospects in general infrared spectroscopy, action spectroscopy, and lattice trajectory control in the electronic ground state emerge.

Resonant Enhancement of Second-Harmonic Generation in the Mid-Infrared Using Localized Surface Phonon Polaritons in Subdiffractional Nanostructures.

We report on the strong enhancement of mid-infrared second-harmonic generation (SHG) from SiC nanopillars due to the resonant excitation of localized surface phonon polaritons within the Reststrahlen band. A strong dependence of the SHG enhancement upon the optical mode distribution was observed. One such mode, the monopole, exhibits an enhancement that is beyond what is anticipated from field localization and dispersion of the linear and nonlinear SiC optical properties. Comparing the results for the identical nanostructures made of 4H and 6H SiC polytypes, we demonstrate the interplay of localized surface phonon polaritons with zone-folded weak phonon modes of the anisotropic crystal. Tuning the monopole mode in and out of the region where the zone-folded phonon is excited in 6H-SiC, we observe a further prominent increase of the already enhanced SHG output when the two modes are coupled. Envisioning this interplay as one of the showcase features of mid-infrared nonlinear nanophononics, we discuss its prospects for the effective engineering of nonlinear-optical materials with desired properties in the infrared spectral range.

Femtosecond electrons probing currents and atomic structure in nanomaterials.

The investigation of ultrafast electronic and structural dynamics in low-dimensional systems such as nanowires and two-dimensional materials requires femtosecond probes providing high spatial resolution and strong interaction with small volume samples. Low-energy electrons exhibit large scattering cross-sections and high sensitivity to electric fields, but their pronounced dispersion during propagation in vacuum so far prevented their use as femtosecond probe pulses in time-resolved experiments. Here, employing a laser-triggered point-like source of either divergent or collimated electron wave packets, we developed a hybrid approach for femtosecond point projection microscopy and femtosecond low-energy electron diffraction. We investigate ultrafast electric currents in nanowires with sub-100 femtosecond temporal and few 10 nm spatial resolutions, and demonstrate the potential of our approach for studying structural dynamics in crystalline single-layer materials.

Ultrafast evolution of the excited-state potential energy surface of TiO2 single crystals induced by carrier cooling.

We investigate the influence of carrier cooling dynamics in TiO(2) on the excited-state potential energy surface along the A(1g) optical phonon coordinate after above band-gap excitation using ultrashort ultraviolet pulses. The large amplitude coherent oscillation observed in a pump-probe transient reflectivity measurement shows a phase shift of -0.2π with respect to a purely instantaneous displacive excitation. The dynamic evolution of the potential energy surface minimum of the coherent phonon coordinate is explored using accurate density functional theory calculations, which confirm a shift of the potential energy surface minimum upon resonant laser excitation and reveal a significant positive contribution to the displacive force due to the cooling of the excited hot electron-hole plasma. We show that this noninstantaneous effect can quantitatively explain the experimentally observed phase using reasonable assumptions for the parameters characterizing the excited carriers. Our work demonstrates that the fast equilibration dynamics of laser-excited nonequilibrium carrier populations can have a pronounced effect on the initial structural response of crystalline solids.

Excitonic effects in two-dimensional vibrational spectra of liquid formamide.

The linear and two-dimensional infrared (2DIR) responses of the amide I vibrational mode in liquid formamide are investigated experimentally and theoretically using molecular dynamics simulations. The recent method based on the numerical integration of the Schrödinger equation is employed to calculate the 2DIR spectra. Special attention is devoted to the interplay of the structural dynamics and the excitonic nature of the amide I modes in determining the optical response of the studied system. In particular, combining experimental data, simulated spectra and analysis of the simulated atomic trajectory in terms of a transition dipole coupling model, we provide a convincing explanation of the peculiar features of the 2DIR spectra, which show a substantial increase of the antidiagonal bandwidth with increasing frequency. We point out that, at variance with liquid water, the 2DIR spectral profile of formamide is determined more by the excitonic nature of the vibrational states than by the fast structural dynamics responsible for the frequency fluctuations.

Diffractive optics based four-wave, six-wave, ..., nu-wave nonlinear spectroscopy.

A detailed understanding of chemical processes requires information about both structure and dynamics. By definition, a reaction involves nonstationary states and is a dynamic process. Structure describes the atomic positions at global minima in the nuclear potential energy surface. Dynamics are related to the anharmonicities in this potential that couple different minima and lead to changes in atomic positions (reactions) and correlations. Studies of molecular dynamics can be configured to directly access information on the anharmonic interactions that lead to chemical reactions and are as central to chemistry as structural information. In this regard, nonlinear spectroscopies have distinct advantages over more conventional linear spectroscopies. Because of this potential, nonlinear spectroscopies could eventually attain a comparable level of importance for studying dynamics on the relevant time scales to barrier crossings and reactive processes as NMR has for determining structure. Despite this potential, nonlinear spectroscopy has not attained the same degree of utility as linear spectroscopy largely because nonlinear studies are more technically challenging. For example, unlike the linear spectrometers that exist in almost all chemistry departments, there are no "black box" four-wave mixing spectrometers. This Account describes recent advances in the application of diffractive optics (DOs) to nonlinear spectroscopy, which reduces the complexity level of this technology to be closer to that of linear spectroscopy. The combination of recent advances in femtosecond laser technology and this single optic approach could bring this form of spectroscopy out of the exclusive realm of specialists and into the general user community. However, the real driving force for this research is the pursuit of higher sensitivity limits, which would enable new forms of nonlinear spectroscopy. This Account chronicles the research that has now extended nonlinear spectroscopy to six-wave processes and to a completely generalized "nu-wave" mixing form to fully control state preparation and coherences. For example, direct observation of global protein motions and energetics has led to the collective mode coupling model to understand structure-function correlations in biological systems. Direct studies of the hydrogen bond network of liquid H(2)O have recently shown that both intramolecular and intermolecular degrees of freedom are strongly coupled so that the primary excitations of water have an excitonic-like character. This fundamentally different view of liquid water has now resolved a 100-year-old problem of homogeneous versus inhomogeneous broadening of the vibrational line shapes. By adding programmable pulse shaping, we can access new information about the many-body interactions directly relevant to chemical reaction dynamics. We can also steer the course of the reaction along multidimensional surfaces to provide information about fluctuations far from the equilibrium, which are most relevant to chemical reactivity.