arXiv subjects

Giulia Carini

Publications and source records attributed to Giulia Carini.

6 recordsLinked to original sources

arXiv2026

Tailoring phonon-driven responses in {\alpha}-MoO3 through isotopic enrichment

The implementation of polaritonic materials into nanoscale devices requires selective tuning of parameters to realize desired spectral or thermal responses. One robust material is {\alpha}-MoO3, which as an orthorhombic crystal boasts three distinct phonon dispersions, providing three polaritonic dispersions of hyperbolic phonon polaritons (HPhPs) across the mid-infrared (MIR). Here, the tunability of both optical and thermal responses in isotopically enriched {\alpha}-MoO3 (98MoO3, Mo18O3 and 98Mo18O3) are explored. A uniform ~5 % spectral redshift from 18O enrichment is observed in both Raman- and IR-active TO phonons. Both the in- and out-of-plane thermal conductivities for the isotopic variations are reported. Ab initio calculations both replicate experimental findings and analyze the select-mode three-phonon scattering contributions. The HPhPs from each isotopic variation are probed with s-SNOM and their Q- factors are reported. A Q-factor maxima increase of ~50 % along the [100] in the RB2 and ~100 % along the [001] in the RB3 are reported for HPhPs supported in 98Mo18O3. Observations in both real and Fourier space of higher-order HPhP modes propagating in single slabs of isotopically enriched {\alpha}-MoO3 without the use of a subdiffractional surface scatterer are presented here. This work illustrates the tunability of {\alpha}-MoO3 for thermal and nanophotonic applications.

cond-mat.mtrl-sci↗

arXiv2025

Non-equilibrium state during proton-deuteron exchange at a liquid-liquid interface

Proton-deuteron exchange is a very fast process, even across macroscopic length scales. Here we directly and quantitatively measure the formation of HDO within the first 100 microseconds of the reaction at the liquid-liquid interface between D$_2$O and H$_2$O, using a fast-flowing liquid flat jet combined with infrared spectroscopic imaging. We demonstrate that, at early stages HDO formation is reaction-limited, set by the low concentration of the hydroxide and hydronium ions that mediate the exchange. As the ion concentration rises, the rate rapidly approaches the diffusion limit. The reaction rate constant we extract is consistent with the picosecond timescale of the elementary proton-deuteron exchange. Access to these microsecond kinetics reveals a non-equilibrium state in the early H$_2$O/D$_2$O interface: the two liquids are fully mixed by diffusion, yet the HDO concentration remains well below equilibrium. Quantitative imaging of reactant and product concentrations at well-defined liquid-liquid interfaces, as introduced here, will enable the study of fast kinetics across a wide range of chemical reactions.

physics.chem-ph↗

arXiv2025

Spectral tuning of hyperbolic shear polaritons in monoclinic gallium oxide via isotopic substitution

Hyperbolic phonon polaritons - hybridized modes arising from the ultrastrong coupling of infrared light to strongly anisotropic lattice vibrations in uniaxial or biaxial polar crystals - enable to confine light to the nanoscale with low losses and high directionality. In even lower symmetry materials, such as monoclinic $\beta$-Ga$_2$O$_3$ (bGO), hyperbolic shear polaritons (HShPs) further enhance the directionality. Yet, HShPs are intrinsically supported only within narrow frequency ranges defined by the phonon frequencies of the host material. Here, we report spectral tuning of HShPs in bGO by isotopic substitution. Employing near-field optical microscopy to image HShPs in $^{18}$O bGO films homo-epitaxially grown on a $^{16}$O bGO substrate, we demonstrate a spectral redshift of $\sim~40~$cm$^{-1}$ for the $^{18}$O bGO, compared to $^{16}$O bGO. The technique allows for direct observation and a model-free estimation of the spectral shift driven by isotopic substitution without the need for knowledge of the dielectric tensor. Complementary far-field measurements and ab initio calculations - in good agreement with the near-field data - confirm the effectiveness of this estimation. This multifaceted study demonstrates a significant isotopic substitution induced spectral tuning of HShPs into a previously inaccessible frequency range, creating new avenues for technological applications of such highly directional polaritons.

physics.optics↗

arXiv2024

Surface Phonon Polariton Ellipsometry

Surface phonon polaritons (SPhPs) have become a key ingredient for infrared nanophotonics, owing to their long lifetimes and the large number of polar dielectric crystals supporting them. While these evanescent modes have been thoroughly characterized by near-field mapping or far-field intensity measurements over the last decade, far-field optical experiments also providing phase information are less common. In this paper, we study surface phonon polaritons at the gallium phosphide (GaP)-air interface in the momentum domain using the Otto-type prism coupling geometry. We combine this method with spectroscopic ellipsometry to obtain both amplitude and phase information of the reflected waves across the entire reststrahlen band of GaP. By adjusting the prism-sample air gap width, we systematically study the dependence of the ellipsometry parameters on the optical coupling efficiency. In particular, we show that the combined observation of both ellipsometry parameters - amplitude and phase - provides a powerful tool for the detection of SPhPs, even in the presence of high optical losses. Finally, we theoretically study how surface phonon polariton ellipsometry can reveal the emergence of vibrational strong coupling through changes in the topology of their complex plane trajectories, opening up a new perspective on light-matter coupling.

physics.optics↗

arXiv2023

Extreme light confinement and control in low-symmetry phonon-polaritonic crystals

Polaritons are a hybrid class of quasiparticles originating from the strong and resonant coupling between light and matter excitations. Recent years have witnessed a surge of interest in novel polariton types, arising from directional, long-lived material resonances, and leading to extreme optical anisotropy that enables novel regimes of nanoscale, highly confined light propagation. While such exotic propagation features may also be in principle achieved using carefully designed metamaterials, it has been recently realized that they can naturally emerge when coupling infrared light to directional lattice vibrations, i.e., phonons, in polar crystals. Interestingly, a reduction in crystal symmetry increases the directionality of optical phonons and the resulting anisotropy of the response, which in turn enables new polaritonic phenomena, such as hyperbolic polaritons with highly directional propagation, ghost polaritons with complex-valued wave vectors, and shear polaritons with strongly asymmetric propagation features. In this Review, we develop a critical overview of recent advances in the discovery of phonon polaritons in low-symmetry crystals, highlighting the role of broken symmetries in dictating the polariton response and associated nanoscale-light propagation features. We also discuss emerging opportunities for polaritons in lower-symmetry materials and metamaterials, with connections to topological physics and the possibility of leveraging anisotropic nonlinearities and optical pumping to further control their nanoscale response.

physics.optics↗

arXiv2022

Layer-Resolved Resonance Intensity of Evanescent Polariton Modes in Anisotropic Multilayers

Phonon polariton modes in layered anisotropic heterostructures are a key building block for modern nanophotonic technologies. The light-matter interaction for evanescent excitation of such a multilayer system can be theoretically described by a transfer matrix formalism. This method allows to compute the imaginary part of the p-polarized reflection coefficient Im$(r_{pp})$, which is typically used to analyze the polariton dispersion of the multilayer structure, but lacks the possibility to access the layer-resolved polaritonic response. We present an approach to compute the layer-resolved polariton resonance intensity in aribtrarily anisotropic layered heterostructures, based on calculating the Poynting vector extracted from a transfer matrix formalism. Our approach is independent of the experimental excitation conditions, and fulfills an empirical conservation law. As a test ground, we study two state-of-the-art nanophotonic multilayer systems, covering strong coupling and tunable hyperbolic surface phonon polaritons in twisted \MoO~double layers. Providing a new level of insight into the polaritonic response, our method holds great potential for understanding, optimizing and predicting new forms of polariton heterostructures in the future.

physics.optics↗