Active Tuning of Plasmon Damping via Light Induced Magnetism.

Circularly polarized optical excitation of plasmonic nanostructures causes coherent circulating motion of their electrons, which in turn gives rise to strong optically induced magnetization, a phenomenon known as the inverse Faraday effect (IFE). In this study we report how the IFE also significantly decreases plasmon damping. By modulating the optical polarization state incident on achiral plasmonic nanostructures from linear to circular, we observe reversible increases of reflectance by up to 8% and simultaneous increases of optical field concentration by 35.7% under 109 W/m2 continuous wave (CW) optical excitation. These signatures of decreased plasmon damping were also monitored in the presence of an external magnetic field (0.2 T). We rationalize the observed decreases in plasmon damping in terms of the Lorentz forces acting on the circulating electron trajectories. Our results outline strategies for actively modulating intrinsic losses in the metal via optomagnetic effects encoded in the polarization state of incident light.

Optoelectronic phenomena in gold metal nanostructures due to the inverse Faraday effect.

The inverse Faraday effect (IFE) is an opto-magnetic phenomenon that produces static magnetic fields in a wide range of materials during illumination with circularly polarized light. This study analyzes non-magnetic gold (Au) metal nanostructures, providing insight into plasmonic enhancement of the magnetic and optoelectronic phenomena associated with the IFE. We report a simple numerical approach in combination with full-wave optical simulations (finite-difference time-domain method) for tracking the optically-induced motion of electrons inside plasmonic nanostructures that gives rise to the IFE. In addition to static magnetic fields, a circulating drift current is observed, where the direction of current is the same as the chirality of the circularly polarized light. Our results indicate a significant enhancement of this drift current by ~100 times in Au nanoparticles due to larger optical field gradients in comparison with bulk Au films. We also report on the size, geometry, and spectral dependence of the induced drift currents and static magnetic fields, which we predict can exceed 1×10-3 T under 1015 W m-2 optical intensity for spherical Au nanoparticles. Our results inform the development of new classes of magneto-optic and optoelectronic behavior that can be obtained via direct manipulation of electron dynamics by the optical fields inside metals.

Hot Electrons in a Steady State: Interband vs Intraband Excitation of Plasmonic Gold.

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.

Thermal Activation of Anti-Stokes Photoluminescence in CsPbBr3 Perovskite Nanocrystals: The Role of Surface Polaron States.

Optically driven cooling of a material, or optical refrigeration, is possible when optical up-conversion via anti-Stokes photoluminescence (ASPL) is achieved with near-unity quantum yield. The recent demonstration of optical cooling of CsPbBr3 perovskite nanocrystals (NCs) has provided a path forward in the development of semiconductor-based optical refrigeration strategies. However, the mechanism of ASPL in CsPbBr3 NCs is not yet settled, and the prospects for cooling technologies strongly depend on details of the mechanism. By analyzing the Arrhenius behavior of ASPL in CsPbBr3 NCs, we investigated the relationship between the average energy gained per photon during up conversion, ΔE, and the thermal activation energy, Ea. We find that Ea is systematically larger than ΔE, and that Ea increases for larger ΔE. We suggest that the additional energetic cost is due to a rearrangement of the crystal lattice as charge carriers pass from surface localized, structurally distinct sub-gap polaron states to the free exciton state during up-conversion. Our interpretation is further corroborated by quantifying the impact of ligand coverage on the NC surface. These findings help inform the development of CsPbBr3 NCs for applications in optical refrigeration.

Chemical and Structural Stability of CsPbX3 Nanorods during Postsynthetic Anion-Exchange: Implications for Optoelectronic Functionality.

We examine halide anion-exchange reactions on CsPbX3 nanorods (NRs), and we identify reaction conditions that provide complete anion exchange while retaining both the highly quantum-confined 1-D morphology and metastable crystal lattice configurations that span a range between tetragonal structures and thermodynamically preferred orthorhombic structures. We find that the chemical stability of CsPbBr3 NRs is degraded by the presence of alkyl amines that etch CsPbBr3 and result in the formation of Cs4PbBr6 and 2-D bromoplumbates. Our study outlines strategies for maintaining metastable states of the soft lattices of perovskite nanocrystals undergoing exchange reactions, despite the thermodynamic driving force toward more stable lattice configurations during this disruptive chemical transformation. These strategies can be used to fine-tune the band gap of LHP-based nanostructures while preserving structure-property relationships that are contingent on metastable shapes and crystal configurations, aiding optoelectronic applications of these materials.

The Anisotropic Complex Dielectric Function of CsPbBr3 Perovskite Nanorods Obtained via an Iterative Matrix Inversion Method.

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.

Quantifying Order during Field-Driven Alignment of Colloidal Semiconductor Nanorods.

Aligning large populations of colloidal nanorods (NRs) into ordered assemblies provides a strategy for engineering macroscopic functional materials with strong optical anisotropy. The bulk optical properties of such systems depend not only on the individual NR building blocks but also on their meso- and macroscale ordering, in addition to more complex interparticle coupling effects. Here, we investigate the dynamic alignment of colloidal CdSe/CdS NRs in the presence of AC electric fields by measuring concurrent changes in optical transmission. Our work identifies two distinct scales of interaction that give rise to the field-driven optical response: (1) the spontaneous mesoscale self-assembly of colloidal NRs into structures with increased optical anisotropy and (2) the macroscopic ordering of NR assemblies along the direction of the applied AC field. By modeling the alignment of NR ensembles using directional statistics, we experimentally quantify the maximum degree of order in terms of the average deviation angle relative to the field axis. Results show a consistent improvement in alignment as a function of NR concentration─with a minimum average deviation of 36.2°â”€indicating that mesoscale assembly helps facilitate field-driven alignment of colloidal NRs.

Kinetic Control for Continuously Tunable Lattice Parameters, Size, and Composition during CsPbX3 (X = Cl, Br, I) Nanorod Synthesis.

The fast kinetics of all-inorganic CsPbX3 (X = Cl, Br, or I) nanocrystal growth entail that many synthetic strategies for structural control established in other semiconductor systems do not apply. Rather, products are often determined by thermodynamic factors, limiting the range of synthetic outcomes and functionality. In this study, we show how reaction kinetics are significantly slowed if nanocrystals are prepared using a dual injection strategy that moderates the crucial interaction between cesium and halide during nucleation and growth. The result is highly uniform nanorod or cuboid nanocrystals with a controllable size and aspect ratio across the quantum confinement regime, obtainable for both pure and mixed halide compositions. Further, the crystal lattice is continuously tunable between the tetragonal (I4/mcm) and orthorhombic (Pbnm) phases, independent of the overall nanorod morphology, enabling significantly more sophisticated structure-property relationships that can be tailored during this kinetically controlled synthesis.

Enhanced semiconductor nanocrystal conductance via solution grown contacts.

We report a 100000-fold increase in the conductance of individual CdSe nanorods when they are electrically contacted via direct solution phase growth of Au tips on the nanorod ends. Ensemble UV-vis and X-ray photoelectron spectroscopies indicate this enhancement does not result from alloying of the nanorod. Rather, low temperature tunneling and high temperature (250-400 K) thermionic emission across the junction at the Au contact reveal a 75% lower interface barrier to conduction compared to a control sample. We correlate this barrier lowering with the electronic structure at the Au-CdSe interface. Our results emphasize the importance of a nanocrystal surface structure for robust device performance and the advantage of this contact method.

The role of gold oxidation state in the synthesis of Au-CsPbX3 heterostructure or lead-free Cs2AuIAuIIIX6 perovskite nanoparticles.

Here, we report that the oxidation state of gold plays a dominant role in determining the reaction products when gold halide salts are mixed with all-inorganic lead halide perovskite nanocrystals. When CsPbX3 nanocrystals react with Au(i) halide salts, Au nanoparticles are deposited on the surface of the perovskites through the reduction of Au1+ ions by the surfactant ligand shell, to produce Au-CsPbX3 heterostructures. These heterostructures preserve comparably high photoluminescence quantum yield (PLQY) and show identical XRD diffractograms as the parent CsPbX3 nanocrystals. In contrast, the reaction of CsPbX3 nanocrystals with Au(iii) halide salts promotes complete cation exchange of Pb ions by Au ions in the nanocrystal perovskite lattice. The cation exchange products, Cs2AuIAuIIIBr6 or Cs2AuIAuIIICl6, show XRD patterns corresponding to a tetragonal mixed halide perovskite crystal structure and show no visible photoluminescence. This crucial dependence on the oxidation state of the Au ion informs synthetic strategies for producing and optimizing metal-perovskite heterostructures and lead-free perovskite nanoparticles.

Thermodynamic theory of the plasmoelectric effect.

Resonant metal nanostructures exhibit an optically induced electrostatic potential when illuminated with monochromatic light under off-resonant conditions. This plasmoelectric effect is thermodynamically driven by the increase in entropy that occurs when the plasmonic structure aligns its resonant absorption spectrum with incident illumination by varying charge density. As a result, the elevated steady-state temperature of the nanostructure induced by plasmonic absorption is further increased by a small amount. Here, we study in detail the thermodynamic theory underlying the plasmoelectric effect by analyzing a simplified model system consisting of a single silver nanoparticle. We find that surface potentials as large as 473 mV are induced under 100 W/m(2) monochromatic illumination, as a result of a 11 mK increases in the steady-state temperature of the nanoparticle. Furthermore, we discuss the applicability of this analysis for realistic experimental geometries, and show that this effect is generic for optical structures in which the resonance is linked to the charge density.

Nanophotonics. Plasmoelectric potentials in metal nanostructures.

The conversion of optical power to an electric potential is of general interest for energy applications and is typically obtained via optical excitation of semiconductor materials. We developed a method for achieving electric potential that uses an all-metal geometry based on the plasmon resonance in metal nanostructures. In arrays of gold nanoparticles on an indium tin oxide substrate and arrays of 100-nanometer-diameter holes in 20-nanometer-thick gold films on a glass substrate, we detected negative and positive surface potentials during monochromatic irradiation at wavelengths below or above the plasmon resonance, respectively. We observed plasmoelectric surface potentials as large as 100 millivolts under illumination of 100 milliwatts per square centimeter. Plasmoelectric devices may enable the development of all-metal optoelectronic devices that can convert light into electrical energy.