arXiv subjects

Levi D. Palmer

Publications and source records attributed to Levi D. Palmer.

5 recordsLinked to original sources

arXiv2026

Imaging nanoscale photocarrier traps in solar water-splitting catalysts

Defects trap photocarriers and hinder solar water splitting. The nanoscale photocarrier transport, trapping, and recombination mechanisms are usually inferred from ensemble-averaged measurements and remain elusive. Because an individual high-performing nanoparticle photocatalyst may outperform the ensemble average, design rules that would otherwise enhance catalytic efficiency remain unclear. Here, we introduce photomodulated electron energy-loss spectroscopy (EELS) in an optically coupled scanning transmission electron microscope (STEM) to map photocarrier localization. Using rhodium-doped strontium titanate (SrTiO3:Rh) solar water-splitting nanoparticles, we directly image the carrier densities concentrated at oxygen-vacancy surface trap states. This is achieved by separating photothermal heating from photocarrier populations through experimental and computational analyses of low-loss spectra. Photomodulated STEM-EELS enables angstrom-scale imaging of defect-induced photocarrier traps and their impact on photocatalytic efficiency.

physics.chem-ph↗

arXiv2025

Imaging Nanoscale Carrier, Thermal, and Structural Dynamics with Time-Resolved and Ultrafast Electron Energy-Loss Spectroscopy

Time-resolved and ultrafast electron energy-loss spectroscopy (EELS) is an emerging technique for measuring photoexcited carriers, lattice dynamics, and near-fields across femtosecond to microsecond timescales. When performed in either a specialized scanning transmission electron microscope or ultrafast electron microscope (UEM), time-resolved and ultrafast EELS can directly image charge carriers, lattice vibrations, and heat dissipation following photoexcitation or applied bias. Yet recent advances in theoretical calculations and electron optics are often required to realize the full potential of ultrafast EEL spectrum imaging. In this review, we present a comprehensive overview of the recent progress in the theory and instrumentation of time-resolved and ultrafast EELS. We begin with an introduction to the technique, followed by a physical description of the loss function. We outline approaches for calculating and interpreting ground-state and transient EEL spectra spanning low-loss plasmons to core-level excitations analogous to X-ray absorption. We then survey the current state of time-resolved and ultrafast EELS techniques beyond photon-induced near-field electron microscopy, highlighting abilities to image carrier and thermal dynamics. Finally, we examine future directions enabled by emerging technologies, including electron beam monochromation, in situ and operando cells, laser-free UEM, and high-speed direct electron detectors. These advances position time-resolved and ultrafast EELS as a critical tool for uncovering nanoscale dynamic processes in quantum materials and solar energy conversion devices.

cond-mat.mtrl-sci↗

arXiv2025

Nanoscale and Element-Specific Lattice Temperature Measurements using Core-Loss Electron Energy-Loss Spectroscopy

Measuring nanoscale local temperatures, particularly in vertically integrated and multi-component systems, remains challenging. Spectroscopic techniques like X-ray absorption and core-loss electron energy-loss spectroscopy (EELS) are sensitive to lattice temperature, but understanding thermal effects is nontrivial. This work explores the potential for nanoscale and element-specific core-loss thermometry by comparing the Si L2,3 edge's temperature-dependent redshift against plasmon energy expansion thermometry (PEET) in a scanning TEM. Using density functional theory (DFT), time-dependent DFT, and the Bethe-Salpeter equation, we ab initio model both the Si L2,3 and plasmon redshift. We find that the core-loss redshift occurs due to bandgap reduction from electron-phonon renormalization. Our results indicate that despite lower core-loss signal intensity compared to plasmon features, core-loss thermometry has key advantages and can be more accurate through standard spectral denoising. Specifically, we show that the Varshni equation easily interprets the core-loss redshift for semiconductors, which avoids plasmon spectral convolution for PEET in complex junctions and interfaces. We also find that core-loss thermometry is more accurate than PEET at modeling thermal lattice expansion in semiconductors, unless the specimen's temperature-dependent dielectric properties are fully characterized. Furthermore, core-loss thermometry has the potential to measure nanoscale heating in multi-component materials and stacked interfaces with elemental specificity at length scales smaller than the plasmon's wavefunction.

cond-mat.mtrl-sci↗

arXiv2024

Determining Quasi-Equilibrium Electron and Hole Distributions of Plasmonic Photocatalysts using Photomodulated X-ray Absorption Spectroscopy

Most photocatalytic and photovoltaic devices operate under broadband, constant illumination. Electron and hole dynamics in these devices, however, are usually measured using ultrafast pulsed lasers in a narrow wavelength range. In this work, we prove that steady-state, photomodulated X-ray spectra from a non-time-resolved synchrotron beamline can be used to estimate electron and hole distributions. A set of plasmonic metal core-shell nanoparticles is designed to systematically isolate photothermal, hot electron, and thermalized electron-hole pairs in a TiO2 shell. Steady-state changes in the Ti L2,3 edge are measured with and without continuous-wave illumination of the nanoparticle's localized surface plasmon resonance. Ab initio excited-state X-ray theory developed for transient X-ray measurements is then applied to model the experimental spectra in an attempt to extract the resultant steady-state carrier distributions. The results suggest that, within error, the quasi-equilibrium carrier distribution can be determined even from relatively noisy data with mixed excited-state phenomena.

physics.chem-ph↗

arXiv2023

Using Electron Energy-Loss Spectroscopy to Measure Nanoscale Electronic and Vibrational Dynamics in a TEM

Electron energy-loss spectroscopy (EELS) can measure similar information to X-ray, UV-Vis, and IR spectroscopies but with atomic resolution and increased scattering cross sections. Recent advances in electron monochromators have expanded EELS capabilities from chemical identification to the realms of synchrotron-level core-loss measurements and to low-loss, 10-100 meV excitations such as phonons, excitons, and valence structure. EELS measurements are easily correlated with electron diffraction and atomic-scale real-space imaging in a transmission electron microscope (TEM) to provide detailed local pictures of quasiparticle and bonding states. This perspective provides an overview of existing high-resolution EELS (HR-EELS) capabilities while also motivating the powerful next step in the field - ultrafast EELS in a TEM. Ultrafast EELS aims to combine atomic level, element specific, and correlated temporal measurements to better understand spatially specific excited state phenomena. Ultrafast EELS measurements also add to the abilities of steady-state HR-EELS by being able to image the electromagnetic field and use electrons to excite photon-forbidden and momentum-specific transitions. We discuss the technical challenges ultrafast HR-EELS currently faces, as well as how integration with in situ and cryo measurements could expand the technique to new systems of interest, especially molecular and biological samples.

physics.chem-ph↗