arXiv subjects

Giulia Tagliabue

Publications and source records attributed to Giulia Tagliabue.

At least 19 recordsLinked to original sources

arXiv2026

Metaphotonic Catalysis: Amorphous silicon metasurfaces encode photochemical activity

Solar-to-fuel conversion can benefit from photoelectrodes with engineered light-matter interactions, yet most nanostructured designs provide limited control over the spatial and spectral distribution of photochemical activity. Here, we present an all-dielectric amorphous-silicon metasurface photoelectrode that confines resonant light-matter interactions within a 220-nm-thick active layer. Tunable Mie-type and guided-mode resonances spectrally encode chemical reactivity and produce absorptance above 80% near the silicon band edge, compared with less than 30% for an unpatterned film of the same thickness. The metasurface simultaneously functions as the light absorber, carrier-transport layer, and catalytic interface without an added co-catalyst or engineered passivation layer. Operando photo-scanning electrochemical microscopy reveals wavelength- and structure-dependent redox activity and a tenfold enhancement in internal quantum efficiency near the silicon band edge relative to planar films. Power-dependent measurements support a photon-driven rather than nonlinear photothermal origin of the enhancement, while surface-sensitive ultrafast transient-reflectivity measurements probe the underlying carrier dynamics. Light-coupled scanning electrochemical cell microscopy further shows hydrogen-evolution enhancements of up to 21-fold under photocatalytic conditions and 15-fold under photoelectrochemical bias, corresponding to 11.2-fold and 7.7-fold enhancements after accounting for the estimated surface-area increase. The metasurfaces remain stable during more than 10 hours of immersion and prolonged laser illumination. These results establish amorphous silicon as a stable and versatile platform for resonantly programmed photocatalysis and solar-fuel generation.

physics.optics↗

arXiv2026

Determining Electron Beam Lateral Coherence in a Scanning Electron Microscope Using Electron Diffraction

We develop and characterize scanning transmission electron microscopy (STEM) capabilities within a scanning electron microscope (SEM) to investigate the effective lateral coherence of the electron beam (e-beam) in the specimen plane. Using single-crystalline Au flakes and a sample composed of a monolayer of graphene, we obtain high-quality selected-area electron diffraction (SAED) maps and convergent-beam electron diffraction (CBED) patterns, validating the systems ability to probe crystallographic information at an acceleration voltage of 30 keV. Building on these capabilities, we implement a method, which is adapted from techniques traditionally used in transmission electron microscopy, to measure the degree of lateral coherence of the e-beam in the specimen plane of the SEM. By analyzing interference between electrons with two different wave vectors separated by 0.031 per angstrom, we extract a lower limit for the degree of lateral coherence over 5% of the e-beam diameter of approximately 60%. These coherence values are sufficient to enable quantum-coherent electron-light-matter interaction experiments in the SEM.

cond-mat.mes-hall↗

arXiv2026

Spin-Polarized Oxygen Evolution in Chiral-Molecule-Modified Plasmonic Photoanodes

Photoelectrochemical oxygen evolution is limited not only by multi-electron charge-transfer kinetics but also by the spin constraints associated with forming triplet O2. Here, we used a hybrid photoanode architecture to demonstrate spin-polarization of plasmonic hot holes through a chiral molecular layer. TiO2 photoanodes were modified with achiral Au nanoparticles to introduce visible-light plasmonic absorption, functionalized with cysteine as a chiral molecular interface, and coated with a NiFe-based oxygen-evolution catalyst. Wavelength-resolved photo-scanning electrochemical microscopy was used to directly detect locally evolved O2 under operando illumination while simultaneously monitoring the photoanode current. Chiral functionalization with homochiral L-cysteine enhanced both photocurrent and local O2 evolution relative to racemic DL-cysteine controls. The chirality-dependent enhancement was most pronounced under visible excitation overlapping the Au plasmon resonance, including a 130% photocurrent increase. These results provide evidence that chiral molecular layers, often used for chiral nanoparticle synthesis, can directly modulate plasmon-derived hot-carrier transfer through the chiral induced spin selectivity (CISS) effect. This work establishes a chiral plasmonic photoelectrochemical platform for coupling hot-carrier generation to spin-dependent water oxidation.

physics.chem-ph↗

arXiv2026

From Loss Diagnosis to Rational Design: A Unified Analytical Model for Photoelectrochemical Cells

Photoelectrochemical (PEC) cells are a compelling route to solar-driven chemical energy storage and feedstock synthesis, yet their deployment is hindered by coupled losses spanning light absorption, carrier transport, interfacial charge transfer, and semiconductor-electrolyte matching. Existing models address these losses in an architecture-specific manner and fall short of quantitative experimental diagnosis or actionable design guidance. Here, we introduce a unified loss-analysis framework applicable to both built-in junction (BIJ) and semiconductor-electrolyte junction (SEJ) photoelectrodes within a consistent set of physically meaningful parameters. The framework delivers current-voltage curves and efficiency metrics under ideal and real conditions, constructing efficiency maps to delineate theoretical limits and material-selection windows. Critically, by fitting experimental current-voltage data, it enables quantitative energy-loss decomposition into thermodynamic, optical, recombination, and interfacial contributions, pinpointing performance bottlenecks in real devices and mapping them directly onto optimization strategies such as co-catalyst integration or nanostructuring. Energy flows are visualized through Sankey diagrams, providing an intuitive picture of how incident solar energy is absorbed, dissipated, or converted into chemical output. Validated against state-of-the-art literature results spanning solar water splitting, CO2 reduction, NH3 synthesis, and solar redox flow batteries, the framework further enables systematic comparison of photovoltaic-grade absorbers (e.g., Si, perovskites) with intermediate-bandgap semiconductors (e.g., hematite, BiVO4), identifying key factors limiting each material class. Together, these capabilities support a paradigm shift from empirical optimization to mechanism-informed rational design of high-efficiency PEC energy-conversion systems.

physics.chem-ph↗

arXiv2026

Revealing Wavelength- and Size-Dependent CO2 Reduction Selectivity via Operando Scanning Photo-Electrochemical Microscopy

Controlling product selectivity in plasmonic catalysis, particularly in CO2 reduction (CO2R), remains a central unsolved challenge with direct implications for light-driven fuel and chemical synthesis. Here, we deploy quantitative operando scanning photoelectrochemical microscopy (photo-SECM) to provide a direct demonstration that tuning photon energy switches CO2R selectivity through an electronically driven pathway. On plasmonic Au/p-GaN photocathodes, interband excitation (460-560 nm) drives selective CO production while intraband excitation (640-800 nm) favors H2 evolution. By maintaining constant absorbed power across wavelengths and confirming linear power dependence, we isolate the role of hot-carrier energy from photonic and photothermal contributions. Density functional theory calculations reveal that higher-energy interband excitation progressively increases the overlap between hot-electron-accessible states and the CO-producing intermediate, selectively promoting CO over formate, in excellent agreement with experiment. We further show that selectivity is geometrically gated by hot-carrier transport: sub-100 nm nanostructures sustain CO2R activity, while ~300 nm nanodisks suffer transport losses that suppress it, consistent with ab initio hot-carrier transport calculations. Together, these results establish photon energy, carrier transport, and nanostructure geometry as coupled design parameters for plasmonic CO2R selectivity, resolve a longstanding debate on the origin of plasmon-driven selectivity effects, and position photo-SECM as a broadly applicable operando platform for photo(electro)catalysis.

physics.chem-ph↗

arXiv2026

Plasmon Induced Delocalized Second-Harmonic Generation Towards Buried-Interface Spectroscopy

Second-harmonic generation microscopy is a powerful technique capable of probing local crystal symmetries and electric fields at interfaces. However, it often suffers from weak signal strength and is difficult to understand in multilayer systems where many materials can give competing signal contributions. In this work we present direct observation of delocalized, surface plasmon polariton-mediated second-harmonic generation on gold monocrystalline surfaces and structures. We generate second-harmonic light up to 35 um from the excitation spot and, excitingly, we obtain signal from atomically flat surfaces without a fundamental excitation beam present in the same region. We reveal that this process arises from the interaction of two counter-propagating surface plasmon polaritons, which we believe to be the first observation of this process at the microscale. This signal has the same polarisation dependence as localised second-harmonic generation and is emitted in a collimated beam travelling perpendicular to the sample surface. In part due to local electric field enhancements, we were able to observe these signals on a CMOS camera with 1 s exposure and no gain using an industrial-grade pulsed laser. Our results enable wide area multilayer samples to be probed using a single excitation beam, with applications including in energy, catalysis and single particle surface sensing.

physics.optics↗

arXiv2025

All-Dielectric Photo-thermo-optical Metasurfaces for Thermal Landscaping at the Nanoscale

Precise control of temperature fields at the micro- and nanoscale is essential for emerging applications in nanophotonics, catalysis, and microfluidics, yet remains difficult due to the diffusive nature of heat. While inverse-design algorithms have advanced thermoplasmonic metasurfaces, their extension to all-dielectric systems has not been explored. Here, an inverse thermal design framework is introduced for dielectric metasurfaces composed of thermo-optical amorphous silicon (a-Si) nanoresonators. By leveraging a precomputed library of absorption spectra as a function of geometry and temperature, target thermal profiles are directly mapped onto metasurfaces, enabling both uniform and complex temperature shaping. Unlike plasmonic platforms that require multi-resonator unit cells for tunability, dielectric nanoresonators provide intrinsic reconfigurability: at wavelengths where the thermo-optical coefficient is negligible (e.g., ~500 nm), absorption is temperature-invariant, whereas at other wavelengths it becomes strongly temperature-dependent, allowing illumination intensity to reshape the thermal landscape. This multifunctionality permits a single metasurface to yield distinct profiles under different excitation conditions without added structural complexity. As a proof of concept, photothermal catalysis on such metasurfaces is modeled, predicting over 30% enhancement in reaction rates. The presented framework establishes a scalable strategy for engineering nanoscale temperature fields with broad implications for catalysis, thermal management, and photothermal energy conversion.

physics.optics↗

arXiv2025

Revealing Light-Driven Dynamics at Nanostructured Solid-Liquid Interfaces with In-Situ SHG

Light and heat drive interfacial chemistry at solid-liquid interfaces, underpinning processes central to sustainable energy conversion, including photoelectrochemical and hydrovoltaic systems. Yet, non-invasive probing of light-induced interfacial dynamics remains challenging due to the weak and spatially complex nature of optical signals. Here, we introduce a nanophotonic platform that enhances second harmonic generation (SHG) from nanostructured interfaces by over two orders of magnitude, enabling real-time, all-optical access to interfacial processes. We develop a rigorous overlap-integral formalism that provides a general quantitative framework for SHG in nanostructured geometries. By accounting for spatially inhomogeneous electromagnetic fields, this approach links the nonlinear response to geometry-dependent near-field and reveals new degrees of freedom, namely independent control of attenuation and phase, which are absent in planar systems. This enables deterministic tuning of surface and electric-field-induced contributions through nanophotonic design. Using in situ SHG at silicon-oxide-electrolyte interfaces, we resolve subtle spectral shifts of ~1.3 nm with electrolyte concentration, indicating coupling between electrical double layer potential and semiconductor polarizability. Under controlled optical excitation, we observe reversible, intensity-dependent modulation of interfacial susceptibility, with a decrease at low intensities consistent with photocharging and an increase at higher intensities due to photothermal effects. These results establish nanophotonic-enhanced SHG as a quantitative and tunable probe of interfacial phenomena, providing a unified framework linking optical response, electrostatics, and geometry, and opening new avenues for controlling interfacial charge and potential with light for applications in energy conversion, catalysis, and nanophotonic devices.

physics.chem-ph↗

arXiv2025

Photo-Thermally Tunable Photon-Pair Generation in Dielectric Metasurfaces

Photon-pair sources based on spontaneous four-wave mixing (SFWM) in integrated photonics are often spectrally static. We demonstrate and model a fundamental thermo-optical mechanism that modulates photon-pair generation in amorphous silicon (a-Si) thin films and metasurfaces via SFWM. Femtosecond-pulsed excitation yields g2(0) higher than 400 in unpatterned a-Si, confirming high-purity nonclassical emission. Resonant a-Si metasurfaces produce photon pairs at rates exceeding 3.8 kHz under 0.6 mW pump power through Mie-type modes. Pump absorption induces localized heating that redshifts resonances, altering modal overlap and SFWM efficiency, leading to deviations from the quadratic power scaling expected in the undepleted regime. Coupled electromagnetic and heat-transfer simulations quantitatively reproduce these trends. Polarization-resolved measurements show nearly isotropic nonlinear responses, with 3 times higher third-order susceptibility of a-Si compared to poly-Si. This work positions a-Si as a bright, CMOS-compatible quantum photonics platform and identifies thermo-optical detuning as a key mechanism that should be considered-and potentially harnessed-in integrated photon-pair sources.

physics.optics↗

arXiv2025

Cross-polarized and Stable Second Harmonic Generation from Monocrystalline Copper

Second-harmonic generation (SHG) is a powerful surface-specific probe for centrosymmetric materials, with broad relevance to energy and biological interfaces. Plasmonic nanomaterials have been extensively utilized to amplify this nonlinear response. Yet, material instability has constrained most studies to gold, despite the significance of plasmonic metals such as copper for catalysis. Here, we demonstrate stable and anisotropic SHG from monocrystalline copper, overcoming long-standing challenges associated with surface degradation. By leveraging an on-substrate synthesis approach that yields atomically flat and oxidation-resistant Cu microflakes, we enable reliable SHG measurements and reveal a strong cross-polarized response with C3v surface symmetry. The SHG signal remains stable over several minutes of continuous femtosecond excitation, highlighting the optical robustness of the Cu microflakes. These results reinforce the viability of monocrystalline Cu as a robust platform for nonlinear nanophotonics and surface-sensitive spectroscopy, expanding the range of copper-based optical applications.

physics.optics↗

arXiv2025

Thin-wall Single-crystal Gold Nanoelectrodes towards Advanced Chemical Probing and Imaging

Thin-wall metal ultramicro- and nanoelectrodes (UMEs/NEs), especially gold NEs, are indispensable for high-resolution electrochemical microscopy, biosensing, and fundamental research. However, their damage susceptibility and the lack of scalable fabrication methods hinder broader adoption. We present a versatile wet-chemical approach for high-throughput fabrication of thin-wall Au NEs/UMEs and multifunctional NEs with ~80% reproducibility. This method is based on a unique template-assisted 1D growth of single-crystalline Au in borosilicate nanopipettes followed by electrochemical contacting with tungsten microwires, and focused ion beam milling, ensuring precise control over NEs dimensions. Adaptable to various metals and integrable in multifunctional probes, the method facilitates batch production of high-quality NEs with standardized electrical connections. Structural and electrochemical characterization reveals a twinned single-crystalline Au core, a seamless Au/glass interface, and highly stable electrochemical performance. Notably, smaller electrodes exhibit higher current densities, enhancing chemical detection sensitivity. Specifically, we demonstrate outstanding spatial (< 200 nm) and current (< 1 pA) resolutions, low limit of detection (~11.0 {\mu}M) and high stability (7 h) in scanning photoelectrochemical microscopy (photo-SECM), by detecting photo-oxidation reaction on atomically smooth Au micro-flakes. We also demonstrate growth in double-barrel pipettes for SECM/SICM probes as well as Pt NEs. Overall, this scalable method addresses longstanding challenges in NEs, paving the way for advanced electrochemical and spectro-electrochemical microscopy, including SERS/TERS integration. With single-crystalline surfaces, these electrodes open new frontiers in catalysis, interfacial electrochemistry, biosensing, and molecular-scale investigations.

physics.chem-ph↗

arXiv2025

Large area monocrystalline and surfactant-free copper microflake synthesis

Copper is one of the most extensively studied materials for energy conversion and catalytic systems, with a wide range of other applications from nanophotonics to biotechnology. However, existing synthesis methods are limited with many undesirable by-products and poorly defined morphologies. Here, we report a surfactant-free on-substrate wet synthesis approach that yields monocrystalline metallic Cu microflakes with (111) crystalline exposed surface. By systematically studying the growth mechanism, we achieve unprecedented sizes of more than 130 {\mu}m, which is two orders of magnitude larger than reported in most previous studies, along with higher aspect ratios of over 400. Furthermore, we show distinctly higher stability against oxidation provided by the halide adlayer. Overall, our facile synthesis approach delivers an exciting venue for the emerging fields of catalysis and nanophotonics.

physics.chem-ph↗

arXiv2024

Enhancing Hydrovoltaic Power Generation through Coupled Heat and Light-Driven Surface Charge Dynamics

Harnessing natural evaporation offers a sustainable and untapped pathway for next-generation energy technologies. Here, we present a unified physical and experimental framework for evaporation-driven hydrovoltaic (EDHV) systems that decouples and systematically controls the key interfacial processes underlying electricity generation from ambient heat and sunlight. By introducing an intermediate ion-conducting layer, we spatially and functionally separate the evaporative top interface from the silicon-dielectric nanopillar array at the bottom, enabling independent modulation of evaporation, ion transport, and interfacial chemical equilibrium. This decoupling strategy enhances device performance, facilitating the study of thermal and photo-induced charge generation, and improving ion migration and electricity generation. We develop a predictive equivalent electrical circuit model that captures the coupling between these processes through a transfer capacitance term, which we derive analytically as a function of geometric and material parameters. Our study reveals that capacitive photocharging and thermally modulated surface equilibria, rather than Faradaic or photothermal effects, are the dominant drivers of energy conversion when interfacial environments are adequately engineered. The device achieves a state-of-the-art open-circuit voltage of 1 V and a peak power density of 0.25 W/m2 at a 0.1 M salt concentration. Strategic variation of doping reveals that increasing silicon doping enhances voltage by 28% and power by 1.6 times, while switching the dielectric shell from TiO2 to Al2O3 boosts voltage (power) by up to 1.9 times (3.6 times). These findings offer insights for enhancing EDHV devices and suggest strategies that consider environmental conditions, water salinity, and material engineering to better harness waste heat and sunlight.

physics.chem-ph↗

arXiv2024

Decoupling Optical and Thermal Responses: Thermo-optical Nonlinearities Unlock MHz Transmission Modulation in Dielectric Metasurfaces

Thermo-optical nonlinearities (TONL) in metasurfaces enable dynamic control of optical properties like transmission, reflection, and absorption through external stimuli such as laser irradiation or temperature. As slow thermal dynamics of extended systems are expected to limit modulation speeds ultimately, research has primarily focused on steady-state effects. In this study, we investigate photo-driven TONL in amorphous silicon (a-Si) metasurfaces both under steady-state and, most importantly, dynamic conditions (50 kHz modulation) using a 488 nm continuous-wave pump laser. First, we show that a non-monotonic change in the steady-state transmission occurs at wavelengths longer than the electric-dipole resonance (800 nm). In particular, at 815 nm transmission first decreases by 30% and then increases by 30% as the laser intensity is raised to 5 mW/{\mu}m2. Next, we demonstrate that TONL decouple the thermal and optical characteristic times, the latter being up to 7 times shorter in the tested conditions (i.e {\tau}opt =0.5 {\mu}s vs {\tau}th =3.5 {\mu}s). Most remarkably, we experimentally demonstrate that combining these two effects enables optical modulation at twice the speed (100 kHz) of the excitation laser modulation. We finally show how to achieve all-optical transmission modulation at MHz speeds with large amplitudes (85%). Overall, these results show that photo-driven TONL produce large and fully reversible transmission modulation in dielectric metasurfaces with fast and adjustable speeds. Therefore, they open completely new opportunities toward exploiting TONL in dynamically reconfigurable systems, from optical switching to wavefront manipulation.

physics.optics↗

arXiv2024

All-water supercapacitor enabled by 1-nm clay channels

Water confined to channels one nanometer thick exhibits electrochemical behavior distinct from bulk water, including enhanced protonic conductivity and large dielectric anisotropy. Here, we exploit these characteristics to design a scalable electrochemical energy-storage system ("blue capacitor") constructed entirely from naturally abundant materials. By assembling layered clays and conductive graphene, we produce 1-nm-thick channels in which confined water acts as the sole electrolyte. We systematically study different clay types, the electrode composition, and separator thickness using complementary physicochemical and electrochemical techniques. The device operates stably up to 1.6 V, achieves specific capacitances of up to 40 F/g, nearly 100% coulombic efficiency, and stable performance over more than 60,000 charge-discharge cycles. Structural and dynamic analyses validate the device architecture, water purity, and proton transport in the nanopores. These results demonstrate that nanoconfined water can function as an electrolyte in a macroscopic electrochemical device, providing a platform for exploring sustainable aqueous energy-storage systems.

cond-mat.soft↗

arXiv2024

Nanostructured Fe2O3/CuxO Heterojunction for Enhanced Solar Redox Flow Battery Performance

Solar redox flow batteries (SRFB) have received much attention as an alternative integrated technology for simultaneous conversion and storage of solar energy. Yet, the photocatalytic efficiency of semiconductor-based single photoelectrode, such as hematite, remains low due to the trade-off between fast electron hole recombination and insufficient light utilization, as well as inferior reaction kinetics at the solid/liquid interface. Herein, we present an {\alpha}-Fe2O3/CuxO p-n junction, coupled with a readily scalable nanostructure, that increases the electrochemically active sites and improves charge separation. Thanks to light-assisted scanning electrochemical microscopy (Photo-SECM), we elucidate the morphology-dependent carrier transfer process involved in the photo-oxidation reaction at a {\alpha}-Fe2O3 photoanode. The optimized nanostructured is then exploited in the {\alpha}-Fe2O3/CuxO p-n junction, achieving an outstanding unbiased photocurrent density of 0.46 mA/cm2, solar-to-chemical (STC) efficiency over 0.35% and a stable photocharge-discharge cycling. The average solar-to-output energy efficiency (SOEE) for this unassisted {\alpha}-Fe2O3-based SRFB system reaches 0.18%, comparable to previously reported DSSC-assisted hematite SRFBs. The use of earth-abundant materials and the compatibility with scalable nanostructuring and heterojunction preparation techniques, offer promising opportunities for cost-effective device deployment in real-world applications.

physics.chem-ph↗

arXiv2024

Nanophotonic-Enhanced Thermal Circular Dichroism for Chiral Sensing

Circular Dichroism (CD) can distinguish the handedness of chiral molecules. However, it is typically very weak due to vanishing absorption at low molecular concentrations. Here, we suggest Thermal Circular Dichroism (TCD) for chiral detection, leveraging the temperature difference in the chiral sample when subjected to right and left-circularly polarized excitations. The TCD combines the enantiospecificity of circular dichroism with the higher sensitivity of thermal measurements, while introducing new opportunities in the thermal domain that can be synergistically combined with optical approaches. We propose a theoretical framework to understand the TCD of individual and arrays of resonators covered by chiral molecules. To enhance the weak TCD of chiral samples, we first use individual dielectric Mie resonators and identify chirality transfer and self-heating as the underlying mechanisms giving rise to the differential temperature. However, inherent limitations imposed by the materials and geometries of such resonators make it challenging to surpass a certain level in enhancements. To overcome this, we suggest nonlocal thermal and electromagnetic interactions in arrays. We predict that a combination of chirality transfer to Mie resonators, collective thermal effects, and optical lattice resonance could, in principle, offer more than 4 orders of magnitude enhancement in TCD. Our thermonanophotonic-based approach thus establishes key concepts for ultrasensitive chiral detection.

physics.optics↗

arXiv2024

Distinguishing Inner and Outer-Sphere Hot Electron Transfer in Au/p-GaN Photocathodes

Exploring nonequilibrium hot carriers from plasmonic metal nanostructures is a dynamic field in optoelectronics, driving photochemical reactions such as solar fuel generation. The hot carrier injection mechanism and the reaction rate are highly impacted by the metal/molecule interaction. However, determining the primary type of the reaction and thus the injection mechanism of the hot carriers has remained elusive. In this work, we reveal an electron injection mechanism deviating from a purely outersphere process for the reduction of ferricyanide redox molecule in a gold/p-type gallium nitride (Au/p- GaN) photocathode system. Combining our experimental approach with ab initio simulations, we discover that the efficient inner-sphere transfer of low-energy electrons leads to a continuous enhancement in the photocathode device performance in the interband regime. These findings provide important mechanistic insights, showing our methodology as a powerful tool for analyzing and engineering hot-carrier-driven processes in plasmonic photocatalytic systems and optoelectronic devices.

physics.chem-ph↗