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Understanding the dynamics of hot, highly energetic electrons resulting from nonradiative plasmon decay is crucial for optimizing applications in photocatalysis and energy conversion. This study presents an analysis of electron kinetics within plasmonic metals, focusing on the steady-state behavior during continuous-wave (CW) illumination. Using an inelastic spectroscopy technique, we quantify the temperature and lifetimes of distinct carrier populations during excitation. A significant finding is the monotonic increase in hot electron lifetime with decreases in electronic temperature. We also observe a 1.22× increase in hot electron temperature during intraband excitation compared to interband excitation and a corresponding 2.34× increase in carrier lifetime. The shorter lifetimes during interband excitation are hypothesized to result from direct recombination of nonthermal holes and hot electrons, highlighting steady-state kinetics. Our results help bridge the knowledge gap between ultrafast and steady-state spectroscopies, offering critical insights for optimizing plasmonic applications.

Colloidal lead halide perovskite nanorods have recently emerged as promising optoelectronic materials. However, more information about how shape anisotropy impacts their complex dielectric function is required to aid the development of applications that take advantage of the strongly polarized absorption and emission. Here, we have determined the anisotropy of the complex dielectric function of CsPbBr3 nanorods by analyzing the ensemble absorption spectra in conjunction with the ensemble spectral fluorescence anisotropy. This strategy allows us to distinguish the absorption of light parallel and perpendicular to the main axis so that the real and imaginary components of the dielectric function along each direction can be determined by the use of an iterative matrix inversion (IMI) methodology. We find that quantum confinement gives rise to unique axis-dependent electronic features in the dielectric function that increase the overall fluorescence anisotropy in addition to the optical anisotropy that results from particle shape, even in the absence of quantum confinement. Further, the procedure outlined here provides a strategy for obtaining anisotropic complex dielectric functions of colloidal materials of varying composition and aspect ratios using ensemble solution-phase spectroscopy.

Recent studies have established that the anti-Stokes Raman signal from plasmonic metal nanostructures can be used to determine the two separate temperatures that characterize carriers inside the metal—the temperature of photoexcited "hot carriers" and carriers that are thermalized with the metal lattice. However, the related signal in the Stokes spectral region has historically impeded surface enhanced Raman spectroscopy, as the vibrational peaks of adsorbed molecules are always accompanied by the broad background of the metal substrate. The fundamental source of the metal signal, and hence its contribution to the spectrum, has been unclear. Here, we outline a unified theoretical model that describes both the temperature-dependent behavior and the broad spectral distribution. We suggest that the majority of the Raman signal is from inelastic scattering directly with carriers in a non-thermal energy distribution that have been excited via damping of surface plasmon. In addition, a significant spectral component (∼1%) is due to a sub-population of hot carriers with an energy distribution that is well approximated by an elevated temperature distribution, about 2000 K greater than the lattice temperature of the metal. We have performed temperature- and power-dependent Raman experiments to show how a simple fitting procedure reveals the plasmon dephasing time as well as the temperatures of the hot carriers and the metal lattice, in order to correlate these parameters with the quantitative Raman analysis of chemical species adsorbed on the metal surface. [ABSTRACT FROM AUTHOR]

Colloidal lead halide perovskite nanorods have recently emerged as promising optoelectronic materials. However, more information about how shape anisotropy impacts their complex dielectric function is required to aid the development of applications that take advantage of the strongly polarized absorption and emission. Here, we have determined the anisotropy of the complex dielectric function of CsPbBr 3 nanorods by analyzing the ensemble absorption spectra in conjunction with the ensemble spectral fluorescence anisotropy. This strategy allows us to distinguish the absorption of light parallel and perpendicular to the main axis so that the real and imaginary components of the dielectric function along each direction can be determined by the use of an iterative matrix inversion (IMI) methodology. We find that quantum confinement gives rise to unique axis-dependent electronic features in the dielectric function that increase the overall fluorescence anisotropy in addition to the optical anisotropy that results from particle shape, even in the absence of quantum confinement. Further, the procedure outlined here provides a strategy for obtaining anisotropic complex dielectric functions of colloidal materials of varying composition and aspect ratios using ensemble solution-phase spectroscopy., Competing Interests: The authors declare no competing financial interest., (© 2023 American Chemical Society.)