Anti-Stokes Emission from Hot Carriers in Gold Nanorods.

The origin of light emission from plasmonic nanoparticles has been strongly debated lately. It is present as the background of surface-enhanced Raman scattering and, despite the low yield, has been used for novel sensing and imaging applications because of its photostability. Although the role of surface plasmons as an enhancing antenna is widely accepted, the main controversy regarding the mechanism of the emission is its assignment to either radiative recombination of hot carriers (photoluminescence) or electronic Raman scattering (inelastic light scattering). We have previously interpreted the Stokes-shifted emission from gold nanorods as the Purcell effect enhanced radiative recombination of hot carriers. Here we specifically focused on the anti-Stokes emission from single gold nanorods of varying aspect ratios with excitation wavelengths below and above the interband transition threshold while still employing continuous wave lasers. Analysis of the intensity ratios between Stokes and anti-Stokes emission yields temperatures that can only be interpreted as originating from the excited electron distribution and not a thermally equilibrated phonon population despite not using pulsed laser excitation. Consistent with this result as well as previous emission studies using ultrafast lasers, the power-dependence of the upconverted emission is nonlinear and gives the average number of participating photons as a function of emission wavelength. Our findings thus show that hot carriers and photoluminescence play a major role in the upconverted emission.

Observation and Manipulation of Visible Edge Plasmons in Bi2Te3 Nanoplates.

Noble metals, like Ag and Au, are the most intensively studied plasmonic materials in the visible range. Plasmons in semiconductors, however, are usually believed to be in the infrared wavelength region due to the intrinsic low carrier concentrations. Herein, we observe the edge plasmon modes of Bi2Te3, a narrow-band gap semiconductor, in the visible spectral range using photoemission electron microscopy (PEEM). The Bi2Te3 nanoplates excited by 400 nm femtosecond laser pulses exhibit strong photoemission intensities along the edges, which follow a cos4 dependence on the polarization state of incident beam. Because of the phase retardation effect, plasmonic response along different edges can be selectively exited. The thickness-dependent photoemission intensities exclude the spin-orbit induced surface states as the origin of these plasmonic modes. Instead, we propose that the interband transition-induced nonequilibrium carriers might play a key role. Our results not only experimentally demonstrate the possibility of visible plasmons in semiconducting materials but also open up a new avenue for exploring the optical properties of topological insulator materials using PEEM.

Aluminum Nanocrystals as a Plasmonic Photocatalyst for Hydrogen Dissociation.

Hydrogen dissociation is a critical step in many hydrogenation reactions central to industrial chemical production and pollutant removal. This step typically utilizes the favorable band structure of precious metal catalysts like platinum and palladium to achieve high efficiency under mild conditions. Here we demonstrate that aluminum nanocrystals (Al NCs), when illuminated, can be used as a photocatalyst for hydrogen dissociation at room temperature and atmospheric pressure, despite the high activation barrier toward hydrogen adsorption and dissociation. We show that hot electron transfer from Al NCs to the antibonding orbitals of hydrogen molecules facilitates their dissociation. Hot electrons generated from surface plasmon decay and from direct photoexcitation of the interband transitions of Al both contribute to this process. Our results pave the way for the use of aluminum, an earth-abundant, nonprecious metal, for photocatalysis.

Interband Absorption Enhanced Optical Activity in Discrete Au@Ag Core-Shell Nanocuboids: Probing Extended Helical Conformation of Chemisorbed Cysteine Molecules.

Detailed understanding of the interaction between a chiral molecule and a noble metal surface is essential to rationalize and advance interfacial self-assembly of amino acids and metal-mediated anchoring of proteins. Here we demonstrate that individual Au@Ag core-shell nanocuboids can serve as a plasmonic reporter of an extended helical network formed among chemisorbed cysteine molecules, through generating an interband absorption enhanced, Ag-surface-exclusive circular dichroism (CD) band in the UV region. The observed unusual, strong CD response in the hybrid Au@Ag-cysteine system can be used to probe in real time conformational evolution and structural rearrangement of biomolecules in general and also monitor the interfacial interaction between a metal surface and an adsorbed molecule, opening up the possibility of using Ag nanostructures as promising stereochemically attuned nanosensors.

A scalable and anti-fouling silver-nickel/cellulose paper with synergy photothermal effect for efficient solar distillation.

Solar interfacial evaporation is one of the most efficient and environmentally-friendly clean freshwater production technologies. Plasma metal nanoparticles are excellent optical absorption materials, but their high cost and inherent resonance narrow bandwidth absorption limit their application. In this work, commercial cellulose papers are used as substrates to synthesize Ag-Ni/cellulose paper by the seed-mediated method. The Ag-Ni/cellulose paper exhibits high light absorption at the full wavelength (200-2500 nm) resulting from the synergistic effect of localized surface plasmon resonance (LSPR) of Ag NPs and the interband transitions (IBTs) of Ni. Under one-sun irradiation (1 kW m-2), the energy utilization efficiency of Ag-Ni/cellulose paper is as high as 93.8%, and the water evaporation rate is 1.87 kg m-2 h-1. Diffusion inhibition experiment results show that the Ag-Ni/cellulose paper exhibits excellent antibacterial performance, and the antibacterial performance is highly related with Ag NPs content. These provide new opportunities for commercial production of competitive cost, green, and portable solar evaporators for different application sceneries.

Determination of the Concentration of Silver Atoms in Hydrosol Nanoparticles.

In this work, we propose a new method for determining the concentration of silver atoms in hydrosols of nanoparticles (NPs) stabilized with various capping agents. The proposed method is based on the determination of IBT absorption in the UV region (a broad band with a weakly pronounced shoulder at ~250 nm). To determine the extinction coefficient at 250 nm, we synthesized silver nanoparticles with average sizes of 5, 10, and 25 nm, respectively. The prepared nanoparticles were characterized by TEM, HRTEM, electron diffraction, XRD, DLS, and UV-Vis spectroscopy. It has been shown that the absorption characteristics of spherical NPs are not significantly influenced by the hydrosol preparation method and the type of stabilizer used. For particles with a size of 5-25 nm, the molar extinction coefficient of Ag0 atoms was found to be equal to 3500 ± 100 L mol-1 cm-1 at a wavelength of 250 nm. The results of the theoretical calculations of the molar extinction coefficients for spherical nanoparticles are in good agreement with the experimental values. ICP-MS analysis confirmed the applicability of this method in the concentration range of 5 × 10-7-1 × 10-4 mol L-1.

Increased Intraband Transitions in Smaller Gold Nanorods Enhance Light Emission.

Photoinduced light emission from plasmonic nanoparticles has attracted considerable interest within the scientific community because of its potential applications in sensing, imaging, and nanothermometry. One of the suggested mechanisms for the light emission from plasmonic nanoparticles is the plasmon-enhanced radiative recombination of hot carriers through inter- and intraband transitions. Here, we investigate the nanoparticle size dependence on the photoluminescence through a systematic analysis of gold nanorods with similar aspect ratios. Using single-particle emission and scattering spectroscopy along with correlated scanning electron microscopy and electromagnetic simulations, we calculate the emission quantum yields and Purcell enhancement factors for individual gold nanorods. Our results show strong size-dependent quantum yields in gold nanorods, with higher quantum yields for smaller gold nanorods. Furthermore, by determining the relative contributions to the photoluminescence from inter- and intraband transitions, we deduce that the observed size dependence predominantly originates from the size dependence of intraband transitions. Specifically, within the framework of Fermi's golden rule for radiative recombination of excited charge carriers, we demonstrate that the Purcell factor enhancement alone cannot explain the emission size dependence and that changes in the transition matrix elements must also occur. Those changes are due to electric field confinement enhancing intraband transitions. These results provide vital insight into the intraband relaxation in metallic nanoconfined systems and therefore are of direct importance to the rapidly developing field of plasmonic photocatalysis.

Remarkable Visible-Light Photocatalytic Activity Enhancement over Au/p-type TiO2 Promoted by Efficient Interfacial Charge Transfer.

Metal-induced photocatalysis has emerged as a promising approach for exploiting visible-light-responsive composite materials for solar energy conversion, which is generally hindered by low photocatalytic efficiency. Herein, for the first time, an Au/p-TiO2 (p-type TiO2) strategy with the hole transfer mechanism is developed, remarkably promoting visible-light photocatalytic performance. An efficient acetone evolution rate (138 µmol·g-1·h-1) in the photocatalytic isopropyl alcohol (IPA) degradation under λex = 500 nm light (light intensity, 5.5 mW/cm2) was achieved over Au/p-TiO2, which is approximately 5 times as high as that over Au/n-TiO2 under the same conditions. Photoluminescence and electrochemical impedance spectroscopy measurements indicate enhanced charge carrier separation and transfer for Au/p-TiO2. In an elaborate study, apparent quantum efficiency and transmission electron microscopy characterization on selective PbO2 deposition over p-TiO2 revealed that visible-light-excited holes other than electrons generated in the Au interband transition transferred to p-TiO2, which is opposite to the general route in Au/n-TiO2 (n-type TiO2). Energetic holes generated in the d band of Au led to a fluent transfer across the Schottky barrier, which is further confirmed by the IPA photodegradation mechanism study with different scavengers over Au/p-TiO2. This discovery opens up new opportunities in designing and developing efficient metal semiconductor composite materials with visible-light response.

Interband Transitions in Monolayer and Few-Layer WSe2 Probed Using Photoexcited Charge Collection Spectroscopy.

Transition-metal dichalcogenides are currently under rigorous investigation because of their distinct layer-dependent physical properties originating from the corresponding evolution of the band structure. Here, we report the highly resolved probing of layer-dependent band structure evolution for WSe2 using photoexcited charge collection spectroscopy (PECCS). Monolayer, few-layer, and multilayer WSe2 can be probed in top-gate field-effect transistor platforms, and their interband transitions are efficiently observed. Our theoretical calculations show a great coincidence with the PECCS results, proving that the indirect Γ-K and Γ-Λ transitions as well as the direct K-K transition are clearly resolved in multilayer WSe2 by PECCS.

Photoluminescence of Gold Nanorods: Purcell Effect Enhanced Emission from Hot Carriers.

We demonstrate, experimentally and theoretically, that the photon emission from gold nanorods can be viewed as a Purcell effect enhanced radiative recombination of hot carriers. By correlating the single-particle photoluminescence spectra and quantum yields of gold nanorods measured for five different excitation wavelengths and varied excitation powers, we illustrate the effects of hot carrier distributions evolving through interband and intraband transitions and the photonic density of states on the nanorod photoluminescence. Our model, using only one fixed input parameter, describes quantitatively both emission from interband recombination and the main photoluminescence peak coinciding with the longitudinal surface plasmon resonance.

Near-infrared-to-visible highly selective thermal emitters based on an intrinsic semiconductor.

Control of the thermal emission spectra of emitters will result in improved energy utilization efficiency in a broad range of fields, including lighting, energy harvesting, and sensing. In particular, it is challenging to realize a highly selective thermal emitter in the near-infrared-to-visible range, in which unwanted thermal emission spectral components at longer wavelengths are significantly suppressed, whereas strong emission in the near-infrared-to-visible range is retained. To achieve this, we propose an emitter based on interband transitions in a nanostructured intrinsic semiconductor. The electron thermal fluctuations are first limited to the higher-frequency side of the spectrum, above the semiconductor bandgap, and are then enhanced by the photonic resonance of the structure. Theoretical calculations indicate that optimized intrinsic Si rod-array emitters with a rod radius of 105 nm can convert 59% of the input power into emission of wavelengths shorter than 1100 nm at 1400 K. It is also theoretically indicated that emitters with a rod radius of 190 nm can convert 84% of the input power into emission of <1800-nm wavelength at 1400 K. Experimentally, we fabricated a Si rod-array emitter that exhibited a high peak emissivity of 0.77 at a wavelength of 790 nm and a very low background emissivity of <0.02 to 0.05 at 1100 to 7000 nm, under operation at 1273 K. Use of a nanostructured intrinsic semiconductor that can withstand high temperatures is promising for the development of highly efficient thermal emitters operating in the near-infrared-to-visible range.