Decay Of Surface Plasmons Research Articles

Plasmonic hot carrier dynamics in solid-state and chemical systems for energy conversion

Abstract Surface plasmons provide a pathway to efficiently absorb and confine light in metallic nanostructures, thereby bridging photonics to the nano scale. The decay of surface plasmons generates energetic ‘hot’ carriers, which can drive chemical reactions or be injected into semiconductors for nano-scale photochemical or photovoltaic energy conversion. Novel plasmonic hot carrier devices and architectures continue to be demonstrated, but the complexity of the underlying processes make a complete microscopic understanding of all the mechanisms and design considerations for such devices extremely challenging.Here,we review the theoretical and computational efforts to understand and model plasmonic hot carrier devices.We split the problem into three steps: hot carrier generation, transport and collection, and review theoretical approaches with the appropriate level of detail for each step along with their predictions.We identify the key advances necessary to complete the microscopic mechanistic picture and facilitate the design of the next generation of devices and materials for plasmonic energy conversion.

Unraveling Surface Plasmon Decay in Core-Shell Nanostructures toward Broadband Light-Driven Catalytic Organic Synthesis.

Harnessing surface plasmon of metal nanostructures to promote catalytic organic synthesis holds great promise in solar-to-chemical energy conversion. High conversion efficiency relies not only on broadening the absorption spectrum but on coupling the harvested energy into chemical reactions. Such coupling undergoes hot-electron transfer and photothermal conversion during the decay of surface plasmon; however, the two plasmonic effects are unfortunately entangled, making their individual roles still under debate. Here, we report that in a model system of bimetallic Au-Pd core-shell nanostructures the two effects can be disentangled through tailoring the shell thickness at atomic-level precision. As demonstrated by our ultrafast absorption spectroscopy characterizations, the achieved tunability of the two effects in a model reaction of Pd-catalyzed organic hydrogenation offers a knob for enhancing energy coupling. In addition, the two intrinsic plasmonic modes at 400-700 and 700-1000 nm in the bar-shaped nanostructures allow for utilizing photons to a large extent in full solar spectrum. This work establishes a paradigmatic guidance toward designing plasmonic-catalytic nanomaterials for enhanced solar-to-chemical energy conversion.

(Invited) Plasmonic Hot Carrier Injection in Wide Bandgap Nitride Semiconductors

Despite more than a decade of intensive scientific exploration, new plasmonic phenomena continue to be discovered, including quantum interference of plasmons, observation of quantum coupling of plasmons to single particle excitations, and quantum confinement of plasmons in single-nm scale plasmonic particles. Simultaneously, plasmonic structures find widening applications in integrated nanophotonics, biosensing, photovoltaic devices, single photon transistors and single molecule spectroscopy. Decay of surface plasmons to hot carriers is a new direction that has attracted considerable fundamental and application interest, yet a theoretical understanding of ultrafast plasmon decay processes and the underlying microscopic mechanisms remain incomplete. Recently we analyzed the quantum decay of surface plasmon polaritons and found that the prompt distribution of generated carriers is extremely sensitive to the energy band structure of the plasmonic material. A theoretical understanding of plasmon-driven hot carrier generation and relaxation dynamics at femtosecond timescales is presented here. We report the first ab initio calculations of phonon-assisted optical excitations in metals, which are critical to bridging the frequency range between resistive losses at low frequencies and direct interband transitions at high frequencies. We also present calculations of energy-dependent lifetimes and mean free paths of hot carriers, accounting for electron-electron and electron-phonon scattering, lending insight towards transport of plasmonically-generated carriers at the nanoscale. We will discuss calculations for multiplasmon and nonlinear processes in the ultrafast regime from the mid-IR to visible and in different geometries. Employing a Feynman diagram approach here has been critical to determine the relevant processes. Based on these theoretical predictions, we designed a solid-state system with wide-bandgap semiconductors and studied the photocurrent generated upon plasmon decay across the extended UV and visible regime for different metals and plasmonic structures. Direct comparison with ab-initio calculations allow us to assess the contribution of direct and indirect transitions and identify guidelines for engineering the generation of plasmonic hot-carriers in the UV-VIS regime.

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.

Plasmon resonances in semiconductor materials for detecting photocatalysis at the single-particle level.

Hot carriers, generated via the non-radiative decay of localized surface plasmon, can be utilized in photovoltaic and photocatalytic devices. In recent years, most studies have focused on conventional plasmon materials like Au and Ag. However, they suffer from several drawbacks like low energy of the generated hot carriers and a high charge-carrier recombination rate. To resolve these problems, here, we propose the plasmon resonances in heavily self-doped titanium oxide (TiO1.67) to realize effective hot carrier generation. Since the plasmon resonant energy of TiO1.67 nanoparticles (2.56 eV) is larger than the bandgap (2.15 eV), plasmon resonances through interband transition can realize both the generation and separation of hot carriers and bring a new strategy for visible-light photodegradation. The photodegradation rate for methyl orange was about 0.034 min(-1). More importantly, the combination of plasmonic and catalytic properties makes it feasible to investigate the degradation process of different materials and different structures at the single particle level in situ. By detecting the scattering shift, we demonstrated that the TiO1.67 dimer (Δλ/ΔλRIU = 0.16) possesses a higher photodegradation rate than an individual nanoparticle (Δλ/ΔλRIU = 0.09). We hope this finding may be a beginning, paving the way toward the development of semiconductor plasmonic materials for new applications beyond noble metals.

Nonradiative Plasmon Decay and Hot Carrier Dynamics: Effects of Phonons, Surfaces, and Geometry.

The behavior of metals across a broad frequency range from microwave to ultraviolet frequencies is of interest in plasmonics, nanophotonics, and metamaterials. Depending on the frequency, losses of collective excitations in metals can be predominantly classical resistive effects or Landau damping. In this context, we present first-principles calculations that capture all of the significant microscopic mechanisms underlying surface plasmon decay and predict the initial excited carrier distributions so generated. Specifically, we include ab initio predictions of phonon-assisted optical excitations in metals, which are critical to bridging the frequency range between resistive losses at low frequencies and direct interband transitions at high frequencies. In the commonly used plasmonic materials, gold, silver, copper, and aluminum, we find that resistive losses compete with phonon-assisted carrier generation below the interband threshold, but hot carrier generation via direct transitions dominates above threshold. Finally, we predict energy-dependent lifetimes and mean free paths of hot carriers, accounting for electron-electron and electron-phonon scattering, to provide insight toward transport of plasmonically generated carriers at the nanoscale.

Effective Energy Transfer via Plasmon-Activated High-Energy Water Promotes Its Fundamental Activities of Solubility, Ionic Conductivity, and Extraction at Room Temperature.

Water is a ubiquitous solvent in biological, physical, and chemical processes. Unique properties of water result from water’s tetrahedral hydrogen-bonded (HB) network (THBN). The original THBN is destroyed when water is confined in a nanosized environment or localized at interfaces, resulting in corresponding changes in HB-dependent properties. In this work, we present an innovative idea to validate the reserve energy of high-energy water and applications of high-energy water to promote water’s fundamental activities of solubility, ionic conductivity, and extraction at room temperature. High-energy water with reduced HBs was created by utilizing hot electrons with energies from the decay of surface plasmon excited at gold (Au) nanoparticles (NPs). Compared to conventional deionized (DI) water, solubilities of alkali metal-chloride salts in high-energy water were significantly increased, especially for salts that release heat when dissolved. The ionic conductivity of NaCl in high-energy water was also markedly higher, especially when the electrolyte’s concentration was extremely low. In addition, antioxidative components, such as polyphenols and 2,3,5,4’-tetrahydroxystilbene-2-O-beta-d-glucoside (THSG) from teas, and Polygonum multiflorum (PM), could more effectively be extracted using high-energy water. These results demonstrate that high-energy water has emerged as a promising innovative solvent for promoting water’s fundamental activities via effective energy transfer.

Quantum-Spillover-Enhanced Surface-Plasmonic Absorption at the Interface of Silver and High-Index Dielectrics.

We demonstrate an unexpectedly strong surface-plasmonic absorption at the interface of silver and high-index dielectrics based on electron and photon spectroscopy. The measured bandwidth and intensity of absorption deviate significantly from the classical theory. Our density-functional calculation well predicts the occurrence of this phenomenon. It reveals that due to the low metal-to-dielectric work function at such interfaces, conduction electrons can display a drastic quantum spillover, causing the interfacial electron-hole pair production to dominate the decay of surface plasmons. This finding can be of fundamental importance in understanding and designing quantum nanoplasmonic devices that utilize noble metals and high-index dielectrics.

Hot Electron-Based Near-Infrared Photodetection Using Bilayer MoS2.

Recently, there has been much interest in the extraction of hot electrons generated from surface plasmon decay, as this process can be used to achieve additional bandwidth for both photodetectors and photovoltaics. Hot electrons are typically injected into semiconductors over a Schottky barrier between the metal and semiconductor, enabling generation of photocurrent with below bandgap photon illumination. As a two-dimensional semiconductor single and few layer molybdenum disulfide (MoS2) has been demonstrated to exhibit internal photogain and therefore becomes an attractive hot electron acceptor. Here, we investigate hot electron-based photodetection in a device consisting of bilayer MoS2 integrated with a plasmonic antenna array. We demonstrate sub-bandgap photocurrent originating from the injection of hot electrons into MoS2 as well as photoamplification that yields a photogain of 10(5). The large photogain results in a photoresponsivity of 5.2 A/W at 1070 nm, which is far above similar silicon-based hot electron photodetectors in which no photoamplification is present. This technique is expected to have potential use in future ultracompact near-infrared photodetection and optical memory devices.

Photoluminescence of a Plasmonic Molecule.

Photoluminescent Au nanoparticles are appealing for biosensing and bioimaging applications because of their non-photobleaching and non-photoblinking emission. The mechanism of one-photon photoluminescence from plasmonic nanostructures is still heavily debated though. Here, we report on the one-photon photoluminescence of strongly coupled 50 nm Au nanosphere dimers, the simplest plasmonic molecule. We observe emission from coupled plasmonic modes as revealed by single-particle photoluminescence spectra in comparison to correlated dark-field scattering spectroscopy. The photoluminescence quantum yield of the dimers is found to be surprisingly similar to the constituent monomers, suggesting that the increased local electric field of the dimer plays a minor role, in contradiction to several proposed mechanisms. Aided by electromagnetic simulations of scattering and absorption spectra, we conclude that our data are instead consistent with a multistep mechanism that involves the emission due to radiative decay of surface plasmons generated from excited electron-hole pairs following interband absorption.

Hot electron-induced reduction of small molecules on photorecycling metal surfaces.

Noble metals are important photocatalysts due to their ability to convert light into chemical energy. Hot electrons, generated via the non-radiative decay of localized surface plasmons, can be transferred to reactants on the metal surface. Unfortunately, the number of hot electrons per molecule is limited due to charge–carrier recombination. In addition to the reduction half-reaction with hot electrons, also the corresponding oxidation counter-half-reaction must take place since otherwise the overall redox reaction cannot proceed. Here we report on the conceptual importance of promoting the oxidation counter-half-reaction in plasmon-mediated catalysis by photorecycling in order to overcome this general limitation. A six-electron photocatalytic reaction occurs even in the absence of conventional chemical reducing agents due to the photoinduced recycling of Ag atoms from hot holes in the oxidation half-reaction. This concept of multi-electron, counter-half-reaction-promoted photocatalysis provides exciting new opportunities for driving efficient light-to-energy conversion processes.

Theoretical predictions for hot-carrier generation from surface plasmon decay.

Decay of surface plasmons to hot carriers finds a wide variety of applications in energy conversion, photocatalysis and photodetection. However, a detailed theoretical description of plasmonic hot-carrier generation in real materials has remained incomplete. Here we report predictions for the prompt distributions of excited ‘hot’ electrons and holes generated by plasmon decay, before inelastic relaxation, using a quantized plasmon model with detailed electronic structure. We find that carrier energy distributions are sensitive to the electronic band structure of the metal: gold and copper produce holes hotter than electrons by 1–2 eV, while silver and aluminium distribute energies more equitably between electrons and holes. Momentum-direction distributions for hot carriers are anisotropic, dominated by the plasmon polarization for aluminium and by the crystal orientation for noble metals. We show that in thin metallic films intraband transitions can alter the carrier distributions, producing hotter electrons in gold, but interband transitions remain dominant.

Metamaterial perfect absorber based hot electron photodetection.

While the nonradiative decay of surface plasmons was once thought to be only a parasitic process that limits the performance of plasmonic devices, it has recently been shown that it can be harnessed in the form of hot electrons for use in photocatalysis, photovoltaics, and photodetectors. Unfortunately, the quantum efficiency of hot electron devices remains low due to poor electron injection and in some cases low optical absorption. Here, we demonstrate how metamaterial perfect absorbers can be used to achieve near-unity optical absorption using ultrathin plasmonic nanostructures with thicknesses of 15 nm, smaller than the hot electron diffusion length. By integrating the metamaterial with a silicon substrate, we experimentally demonstrate a broadband and omnidirectional hot electron photodetector with a photoresponsivity that is among the highest yet reported. We also show how the spectral bandwidth and polarization-sensitivity can be manipulated through engineering the geometry of the metamaterial unit cell. These perfect absorber photodetectors could open a pathway for enhancing hot electron based photovoltaic, sensing, and photocatalysis systems.

Coupling surface plasmon resonance of gold nanoparticles with slow-photon-effect of TiO2 photonic crystals for synergistically enhanced photoelectrochemical water splitting

The slow photon effect of a photonic crystal (PC) is a promising characteristic for tuning light–matter interactions through material structure designing. A TiO2 bi-layer structure photoanode was constructed by fabricating a TiO2 PC layer through a template-assisted sol–gel process on a TiO2 nanorod array (NR) layer. Gold nanoparticles (Au NPs) with an average size of about 10 nm were deposited in situ into the TiO2 bi-layer structure. The extended photoelectrochemical (PEC) water splitting activity in visible light was ascribed to the energetic hot electrons and holes that were generated in the Au NPs through the excitation and decay of surface plasmons. By alternating the characteristic pore size of the TiO2 PC layer, the slow photon region at the red edge of the photonic band gap could be purposely tuned to overlap with the strong localized surface plasmon resonance (SPR) region of Au NPs. The matching slow photon effect of TiO2 PC (with a characteristic pore size of 250 nm) intensified the SPR responses (central at 536 nm) of Au NPs. Consequently, more hot electrons were generated in the Au NPs and injected into the conduction band of TiO2, resulting in improved PEC water splitting efficiency in the visible light region. Under simulated sunlight illumination, the photoconversion efficiency of the well matching Au/TiO2 photoanode approached 0.71%, which is one of the highest values ever reported in Au/TiO2 PEC systems. The work reported here provides support for designing coupling plasmonic nanostructures with PC-based materials to synergistically enhance PEC water splitting efficiency.

Mechanistic understanding of surface plasmon assisted catalysis on a single particle: cyclic redox of 4-aminothiophenol

Surface plasmon assisted catalysis (SPAC) reactions of 4-aminothiophenol (4ATP) to and back from 4,4′-dimercaptoazobenzene (DMAB) have been investigated by single particle surface enhanced Raman spectroscopy, using a self-designed gas flow cell to control the reductive/oxidative environment over the reactions. Conversion of 4ATP into DMAB is induced by energy transfer (plasmonic heating) from surface plasmon resonance to 4ATP, where O2 (as an electron acceptor) is essential and H2O (as a base) can accelerate the reaction. In contrast, hot electron (from surface plasmon decay) induction drives the reverse reaction of DMAB to 4ATP, where H2O (or H2) acts as the hydrogen source. More interestingly, the cyclic redox between 4ATP and DMAB by SPAC approach has been demonstrated. This SPAC methodology presents a unique platform for studying chemical reactions that are not possible under standard synthetic conditions.

Hot-electron nanoscopy using adiabatic compression of surface plasmons

Surface plasmon polaritons are a central concept in nanoplasmonics and have been exploited to develop ultrasensitive chemical detection platforms, as well as imaging and spectroscopic techniques at the nanoscale. Surface plasmons can decay to form highly energetic (or hot) electrons in a process that is usually thought to be parasitic for applications, because it limits the lifetime and propagation length of surface plasmons and therefore has an adverse influence on the functionality of nanoplasmonic devices. Recently, however, it has been shown that hot electrons produced by surface plasmon decay can be harnessed to produce useful work in photodetection, catalysis and solar energy conversion. Nevertheless, the surface-plasmon-to-hot-electron conversion efficiency has been below 1% in all cases. Here we show that adiabatic focusing of surface plasmons on a Schottky diode-terminated tapered tip of nanoscale dimensions allows for a plasmon-to-hot-electron conversion efficiency of ∼30%. We further demonstrate that, with such high efficiency, hot electrons can be used for a new nanoscopy technique based on an atomic force microscopy set-up. We show that this hot-electron nanoscopy preserves the chemical sensitivity of the scanned surface and has a spatial resolution below 50nm, with margins for improvement.

Polarimetric measurement of optically perturbed surface plasmonic field

A surface plasmon (SP) field excited at the metal–air interface by a TM-polarized laser and perturbed by an unpolarized, weakly absorbing laser beam leads to an understanding of the SP decay field’s contribution to specular reflection at the near field. The locally perturbed near field results in a spatial variation of the magnitude of the SP decay field due to the photo-thermal effect on the excited SP wave. The SP decay field of different magnitude interferes with the specular reflected field, affecting its polarization and phase characteristics. The changes in the resulting far field are polarimetrically analyzed to extract the polarization ellipse parameters and the phase changes in the entire plasmonic field region. The obtained results are promising for potential applications in all-optical polarization modulators and switches for optical computing.

Contribution of Surface Plasmon Decay to Secondary Electron Emission from an Al Surface

Secondary electron spectra emitted from polycrystalline Al have been measured in coincidence with 500 eV electrons reflected after undergoing a given energy loss. Contributions from bulk- and surface-plasmon decay have been observed, as well as contributions from LVV Auger electrons and electron-electron scattering.

Plasmonic Photoanodes for Solar Water Splitting with Visible Light

We report a plasmonic water splitting cell in which 95% of the effective charge carriers derive from surface plasmon decay to hot electrons, as evidenced by fuel production efficiencies up to 20-fold higher at visible, as compared to UV, wavelengths. The cell functions by illuminating a dense array of aligned gold nanorods capped with TiO(2), forming a Schottky metal/semiconductor interface which collects and conducts the hot electrons to an unilluminated platinum counter-electrode where hydrogen gas evolves. The resultant positive charges in the Au nanorods function as holes and are extracted by an oxidation catalyst which electrocatalytically oxidizes water to oxygen gas.

Plasmonic Photosensitization of a Wide Band Gap Semiconductor: Converting Plasmons to Charge Carriers

A fruitful paradigm in the development of low-cost and efficient photovoltaics is to dope or otherwise photosensitize wide band gap semiconductors in order to improve their light harvesting ability for light with sub-band-gap photon energies.(1-8) Here, we report significant photosensitization of TiO2 due to the direct injection by quantum tunneling of hot electrons produced in the decay of localized surface-plasmon polaritons excited in gold nanoparticles (AuNPs) embedded in the semiconductor (TiO2). Surface plasmon decay produces electron-hole pairs in the gold.(9-15) We propose that a significant fraction of these electrons tunnel into the semiconductor's conduction band resulting in a significant electron current in the TiO2 even when the device is illuminated with light with photon energies well below the semiconductor's band gap. Devices fabricated with (nonpercolating) multilayers of AuNPs in a TiO2 film produced over 1000-fold increase in photoconductance when illuminated at 600 nm over what TiO2 films devoid of AuNPs produced. The overall current resulting from illumination with visible light is ∼50% of the device current measured with UV (ℏω>Eg band gap) illumination. The above observations suggest that plasmonic nanostructures (which can be fabricated with absorption properties that cover the full solar spectrum) can function as a viable alternative to organic photosensitizers for photovoltaic and photodetection applications.