Excitation Of Surface Plasmon Resonance Research Articles

Hot Carrier Lifetimes and Electrochemical Water Dissociation Enhanced by Nickel Doping of a Plasmonic Electrocatalyst

Hot carriers generated by localized surface plasmon resonance (LSPR) excitation of plasmonic metal nanoparticles are known to enhance electrocatalytic reactions. However, the participation of plasmonically generated carriers in interfacial electrochemical reactions is often limited by fast relaxation of these carriers. Herein, we address this challenge by tuning the electronic structure of a plasmonic electrocatalyst. Specifically, we design an electrocatalyst for alkaline hydrogen evolution reaction (HER) that consists of nanoparticles of a ternary Cu-Pt-Ni ternary alloy. The CuPt alloy has both plasmonic attributes and electrocatalytic HER activity. Ni doping contributes an electron-deficient 3d band and fully filled 4s band, which promotes water adsorption and prolongs the lifetimes of excited carriers generated by plasmonic excitation. As an outcome, the Cu-Pt-Ni nanoparticles exhibit boosted activity for electrochemical water dissociation and HER under LSPR excitation.

Dual-functional copper (Cu0/Cu2+)-modified SrTiO3-δ nanosheets with enhanced photothermal catalytic performance for CO2 reduction and H2 evolution

In recent years, metal–semiconductor heterojunctions have been intensively researched in the field of photocatalysis due to the effective spatial separation of photo-induced electron-hole pairs. Here, the dual-functional copper (Cu0/Cu2+)-modified SrTiO3-δ nanosheets (Cu/STCO) are successfully synthesized by a two-step route. First, Cu2+-doped SrTiO3-δ (STCO) nanosheets are synthesized by a hydrothermal method and then Cu0 nanoparticles (NPs) are in situ formed from the STCO under H2 atmosphere at 500 °C. The optimized ratio 6 %-Cu/STCO photocatalyst exhibits the best photothermal catalytic performance for CO2 reduction reaction (CO2RR) and H2 evolution performance. The detailed characterization demonstrate that the Cu2+ dopant extend the light absorption range and the in situ generated Cu0 NPs effectively improve the separation ability of photogenerated charge carriers by forming the Schottky contact with STCO. The excited localized surface plasmon resonance (LSPR) effect of metallic Cu0 in Cu/STCO shows a considerable catalysis performance even under 600 nm monochromatic light irradiation. The density functional theory (DFT) calculations suggest that the Cu/STCO diminishes the barrier of the rate-determining steps of the CO2RR and H2 evolution thus perform the outstanding catalysis ability in two filed. This work presents the synergistic effect of Cu0 and Cu2+ on enhancing the photothermal catalytic performance for CO2RR and H2 evolution and offers a novel strategy to synthesize the metal–semiconductor nanostructures for efficient harnessing of solar energy into fuel.

Plasmonic Hot-Electron-Painted Au@Pt Nanoparticles as Efficient Electrocatalysts for Detection of H2O2.

Plasmon-driven catalysis of metal nanostructures has garnered wide interest. Here, a photogenerated plasmonic hot-electron painting strategy was reported to form Au@Pt composite nanoparticles (Au@Pt NPs) with high catalytic reactivity without using reducing agents. Au nanoparticles, including Au nanospheres (Au NSs), Au nanorods (Au NRs), and Au nanobipyramids (Au NBPs), generated hot electrons under localized surface plasmon resonance (LSPR) excitation, which made the platinum precursor reduced as a consequence that Pt(0) atoms were painted on the surface of Au NPs to form an asymmetric Pt shell outside the plasmonic Au core. Compared with bare Au NPs, Au@Pt NPs exhibited significantly enhanced electrocatalytic activity toward reduction of H2O2 due to the bimetallic synergistic effect and great dispersion of Au@Pt NP-modified indium tin oxide (Au@Pt NPs/ITO). It exhibited a linear detection of H2O2 in a wide concentration range from 0.5 to 1000 μM with a low detection limit of 0.11 μM (S/N = 3). Therefore, the plasmonic hot-electron-painted Au@Pt NPs represent a novel and simple method for the design of advanced noble asymmetric metal nanomaterials.

Polarization insensitive metamaterial based electromagnetic multiband absorber in the long-wave infrared (LWIR) region

In this paper, we propose a design of metamaterials-based polarization insensitive, broadband electromagnetic (EM) wavebands absorber in the long-wave infrared (LWIR) region. The proposed model consists multilayer of gold-magnesium oxide-germanium-gold-germanium layers from the bottom to the top of the structure. The top surface of our proposed metamaterial structure consists of rings and disk-shape resonators. Using the finite element method, the electromagnetic properties of the metamaterials are investigated in terms of reflectance and absorbance. We find that excitation of localized surface plasmon resonance gives rise to highly localized electromagnetic resonance with the structure. Due to the circularly symmetric nature of the ring resonator, the numerical results show that the proposed design of metamaterial has average absorption (above 90 %) from 12.8 μm to 17.8 μm for both transverse electric (TE) and transverse magnetic (TM) polarization over a wide range of incidence angle. Along with this, it can absorb EM waves completely (100 %) at a particular wavelength of 9.1 μm and 17.8 μm. These results show the proposed model configuration may have wide application in energy harvesting and another optoelectronic area.

Deep-ultraviolet plasmon resonance of Ni nanoparticles embedded in BaTiO3 matrix

A tunable nanocomposite structure, consisting of Ni nanoparticles (NPs) with various morphologies and controllable BaTiO3 (BTO) films, was designed using a pulse laser deposition method. The morphological transformation of NPs and the crystal structure of BTO could be modulated by the Ni NP concentration. The experimental demonstration of absorption and photoluminescence enhancement using surface plasmon resonance (SPR) excitation in the deep-ultraviolet (DUV) region was investigated. The splitting of the Ni SPR peak was found in the DUV region, accompanied by decreased band gaps as the Ni NP concentration increased. By photoluminescence analysis, more Ni NPs embedding could provide more electron-hole recombination possibilities, enhancing the optical emission intensity and widening the emission range from red to ultraviolet luminescence. The DUV optical response of Ni NPs with various morphologies was further verified by finite-difference time-domain calculations. Compared with the reported metal NPs using the DUV SPR effect, the smaller Ni NPs provide a new non-noble metal NPs alternative with a high performance SPR excitation in the DUV region beyond the previous Al-based materials, giving new opportunities for manipulating high-energy photons.

Single-Particle Insights into Plasmonic Hot Carrier Separation Augmenting Photoelectrochemical Ethanol Oxidation with Photocatalytically Synthesized Pd-Au Bimetallic Nanorods.

Understanding the nature of hot carrier pathways following surface plasmon excitation of heterometallic nanostructures and their mechanistic prevalence during photoelectrochemical oxidation of complex hydrocarbons, such as ethanol, remains challenging. This work studies the fate of carriers from Au nanorods before and after the presence of reductively photodeposited Pd at the single-particle level using scattering and emission spectroscopy, along with ensemble photoelectrochemical methods. A sub-2 nm epitaxial Pd0 shell was reductively grown onto colloidal Au nanorods via hot carriers generated from surface plasmon resonance excitation in the presence of [PdCl4]2-. These bimetallic Pd-Au nanorod architectures exhibited 14% quenched emission quantum yields and 9% augmented plasmon damping determined from their scattering spectra compared to the bare Au nanorods, consistent with injection/separation of intraband hot carriers into the Pd. Absorbed photon-to-current efficiency in photoelectrochemical ethanol oxidation was enhanced 50× from 0.00034% to 0.017% due to the photodeposited Pd. Photocurrent during ethanol oxidation improved 13× under solar-simulated AM1.5G and 40× for surface plasmon resonance-targeted irradiation conditions after photodepositing Pd, consistent with enhanced participation of intraband-excited sp-band holes and desorption of ethanol oxidation reaction intermediates owing to photothermal effects.

Design of photonic crystal fiber to excite surface plasmon resonance for highly sensitive magnetic field sensing.

To improve the sensing performance of optical fiber magnetic field sensor based on magneto-refractive effect, a D-shaped photonic crystal fiber-surface plasmon resonance (PCF-SPR) sensor based on magneto-refractive effect is proposed and its magnetic field sensing characteristics are investigated. The designed D-shaped PCF has a core-analyte-gold structure. Within the D-shaped PCF, the side polishing surface is coated with the gold film and the special hole is sandwiched between the core and the gold film. To realize the high magnetic field sensitivity for the fiber SPR magnetic field sensor, the special hole is filled with magnetic fluid (MF). In this paper, we analyze the mode transmission characteristics and magnetic field sensing characteristics of this fiber sensor by finite element method. We also obtain a general rule for the optimization of PCF-SPR sensors by analyzing the dispersion curves, the energy of the surface plasmon polariton mode and the core mode on the sensing performance of the designed fiber sensor. The maximum refractive index sensitivity and magnetic field sensitivity of the optimized fiber are 59714.3 nm/RIU and 21750 pm/mT (50-130 Oe), respectively. Compared with optical fiber magnetic field sensors based on magneto-refractive effect reported previously, the magnetic field sensitivity in this paper is nearly two orders of magnitude higher and it can initially achieve nT magnitude magnetic field resolution and testing capability. The proposed fiber sensor has the advantages of simple structure, easy production, high sensitivity, and strong environmental adaptability. It not only improves the sensing performance of optical fiber magnetic field sensors, but also provides an ideal alternative platform for biosensors like microfluidics because of its high refractive index sensitivity and the special structure.

Lifetime of Photogenerated Positive Charges in Hybrid Cerium Oxide-Based Materials from Space and Mirror Charge Effects in Time-Resolved Photoemission Spectroscopy

Space and mirror charge effects in time-resolved photoemission spectroscopy can be modeled to obtain relevant information on the recombination dynamics of charge carriers. We successfully extracted from these phenomena the reneutralization characteristic time of positive charges generated by photoexcitation in CeO2-based films. For the above-band-gap excitation, a large fraction of positive carriers with a lifetime that exceeds 100 ps are generated. Otherwise, the sub-band-gap excitation induces the formation of a significantly smaller fraction of charges with lifetimes of tens of picoseconds, ascribed to the excitation of defect sites or to multiphoton absorption. When the oxide is combined with Ag nanoparticles, the sub-band-gap excitation of localized surface plasmon resonances leads to reneutralization times longer than 300 ps. This was interpreted by considering the electronic unbalance at the surface of the nanoparticles generated by the injection of electrons, via localized surface plasmon resonance (LSPR) decay, into CeO2. This study represents an example of how to exploit the space charge effect in gaining access to the surface carrier dynamics in CeO2 within the picosecond range of time, which is fundamental to describe the photocatalytic processes.

Plasmon Mediated Electron Transfer and Temperature Dependent Electron-Phonon Scattering in Gold Nanoparticles Embedded in Dielectric Films.

Excitation of localized surface plasmon resonance in metal nanoparticles (NPs) embedded in a glassy matrix generates hot electrons, which can be extracted for different optoelectronic applications. The insights of plasmon relaxation dynamics with varying surrounding dielectric environments and temperature dependence electron-phonon scattering process in gold (Au) NPs are still not very clear. Here, we have employed ultrafast transient absorption (TA) spectroscopy to explore the hot plasmon mediated electron transfer (PMET) and electron-phonon dynamics of photo-excited Au NPs in glassy film matrix with variable SiO2 /TiO2 compositions at cryogenic (5 K) to room temperature (300 K). Herein, we have chosen two pump excitation wavelengths (400 and 700 nm). The 400 nm excitation (d→sp) generates hot electron and the 700 nm excitation (sp→sp) provide information of direct plasmon relaxation. Drastic reduction of the transient signal of Au NPs in the high TiO2 content film as compared to pure SiO2 confirm hot electron transfer (HET) from Au plasmon to TiO2 . Electron-phonon scattering time constant (τe-ph ) of Au NPs in the glassy film is found to be faster in presence of TiO2 due to facile electron transfer/injection. Temperature dependent TA studies suggest that electron-phonon scattering time decreases with temperature. These findings would assist to develop more advanced photo-voltaic, opto-electronic and quantum optic-based devices using the plasmonic metal NPs.

Enhancing electromagnetic field gradient in tip-enhanced Raman spectroscopy with a perfect radially polarized beam.

Tip-enhanced Raman spectroscopy (TERS) is a promising label-free super-resolving imaging technique, and the electric field gradient of nanofocusing plays a role in TERS performance. In this paper, we theoretically investigated the enhancement and manipulation of the electric field gradient in a bottom-illumination TERS configuration through a tightly focused perfect radially polarized beam (PRPB). Improvement and manipulation in electric field enhancement and field gradient of the gap-plasmon mode between a plasmonic tip and a virtual surface plasmons (SPs) probe are achieved by adjusting the ring radius of the incident PRPB. Our results demonstrate that the method of optimizing the ring radius of PRPB is to make the illumination angle of incident light as close to the surface plasmon resonance (SPR) excitation angle as possible. Under the excitation of optimal parameters, more than 10 folds improvement of field enhancement and 3 times of field gradient of the gap-plasmon mode is realized compared with that of the conventional focused RPB. By this feat, our results indicate that such a method can further enhance the gradient Raman mode in TERS. We envision that the proposed method, to achieve the dynamic manipulation and enhancement of the nanofocusing field and field gradient, can be more broadly used to control light-matter interactions and extend the reach of tip-enhanced spectroscopy.

SERS and EC-SERS detection of local anesthetic procaine using Pd loaded highly reduced graphene oxide nanocomposite substrate

The localized surface plasmon resonance (LSPR) excitations are critical towards achieving sizable spectral enhancements of the Raman scattered light. Herein, the synthesis of palladium-based highly reduced graphene oxide (Pd-HRG) with LSPR properties as an effective surface-enhanced Raman scattering (SERS) substrate and its utility in the highly sensitive detection of procaine are reported. The concentration detection of procaine samples was optimized by applying a set of pre-concentration parameters. The Pd-HRG nanocomposite showed a remarkable LSPR response with a Raman enhancement factor of 8.7 × 102. The Pd-HRG is employed to modify fluorine doped tin oxide electrode (Pd-HRG/FTO), resulted with an enhancement factor of 7.5 × 104 corresponding to the EC-SERS technique. The electronic and surface properties of synthesized Pd-HRG and functionalized FTO electrode were evaluated using Raman, infrared, EIS, XRD, FESEM and EDX techniques. Quantum chemical calculations were carried out to elaborate on the nature of interaction of procaine molecules with a nanostructured surface model. Pd-HRG, with an efficient and cost-effective fabrication, can be considered as a promising EC-SERS substrate for the detection of organic therapeutic drugs.

Reconfigurable switching between reflecting/absorbing modes in VO2 assisted graphene-coated hemispherical dielectric hole arrays

In this paper, a graphene-coated dielectric hole array is used to design a reconfigurable switchable optical reflector/absorber device. The design benefits from the collective excitation of localized surface plasmon resonances of graphene-coated hole array, providing simpler fabrication fellow and more compact structure with respect to graphene-coated spherical nanoparticle array with similar plasmonic behavior. Geometrical parametric study of the reflecting mode shows that the device has lots of degrees of freedom for spectrum tuning and can highly tolerate fabrication imperfections. Moreover, the reflection rate is slightly affected by the dielectric substrate height, which can be tuned to achieve strong absorption by backing it with a metallic mirror. The designed absorber efficiently captures a wide range of obliquely incident transverse electric (TE) and transverse magnetic (TM) waves. Also, the operating frequency of both reflecting and absorbing modes can be tuned after fabrication, thanks to the two-dimensional nature of graphene material. Finally, using vanadium dioxide (VO2) phase change material, the switchable reflector\\absorber mode of the device is also exhibited.

Dimensional Design for Surface-Enhanced Raman Spectroscopy.

Surface-enhanced Raman spectroscopy (SERS) is a vibrational spectroscopy technique that enables specific identification of target analytes with sensitivity down to the single-molecule level by harnessing metal nanoparticles and nanostructures. Excitation of localized surface plasmon resonance of a nanostructured surface and the associated huge local electric field enhancement lie at the heart of SERS, and things will become better if strong chemical enhancement is also available simultaneously. Thus, the precise control of surface characteristics of enhancing substrates plays a key role in broadening the scope of SERS for scientific purposes and developing SERS into a routine analytical tool. In this review, the development of SERS substrates is outlined with some milestones in the nearly half-century history of SERS. In particular, these substrates are classified into zero-dimensional, one-dimensional, two-dimensional, and three-dimensional substrates according to their geometric dimension. We show that, in each category of SERS substrates, design upon the geometric and composite configuration can be made to achieve an optimized enhancement factor for the Raman signal. We also show that the temporal dimension can be incorporated into SERS by applying femtosecond pulse laser technology, so that the SERS technique can be used not only to identify the chemical structure of molecules but also to uncover the ultrafast dynamics of molecular structural changes. By adopting SERS substrates with the power of four-dimensional spatiotemporal control and design, the ultimate goal of probing the single-molecule chemical structural changes in the femtosecond time scale, watching the chemical reactions in four dimensions, and visualizing the elementary reaction steps in chemistry might be realized in the near future.

Rapid and efficient antibacterial activity of Molybdenum-Tungsten oxide from n-n heterojunctions and localized surface plasmon resonance

With a surge in bacteria encroaching on our daily life, exacerbated antimicrobial resistance toward antibiotics, and sagacious short- and long-term responses of bacteria toward novel antibacterial nanoparticles, the need for developing rapid and effective antibacterial agents is increasing. Herein, Mo0.55W0.45O3–x samples are synthesized through a coprecipitation process, followed by annealing at 450–600 °C. Mo0.55W0.45O3–x samples showed outstanding activity after 10 min of incubation against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) under the compact fluorescent lamp irradiation; the activities were 98.948 ± 1.890 and 98.413 ± 1.080% for S. aureus and E. coli, respectively. The role of each reactive oxygen species (ROS) in suppressing bacteria was studied. The strikingly fast antibacterial rate was discovered with respect to semiconducting features of Mo0.55W0.45O3–x samples, including band positions, trap state, and band gap. We found that well-formed n-n heterojunctions and localized surface plasmon resonance (LSPR) excitation are responsible for antibacterial performance. Accordingly, we believe that a band position-considered system with numerous n-n heterojunctions and LSPR excitation will lead to efficient generation and separation of electron–hole pairs, facilitating the generation of ROS and subsequently resulting in the enhanced antibacterial performance.

Gold–rhodium nanoflowers for the plasmon enhanced ethanol electrooxidation under visible light for tuning the activity and selectivity

Direct ethanol fuel cells (DEFCs) are a promising power source, but the low selectivity to ethanol complete oxidation is still challenging. The localized surface plasmon resonance (LSPR) excitation has been reported to accelerate and drive several chemical reactions, including the ethanol oxidation reaction (EOR), coming as a strategy to improve catalysts performance. Nonetheless, metallic nanoparticles (NPs) that present the LSPR excitation in the visible range are known for leading to the incomplete oxidation of ethanol. Thus, we report here the application of gold-rhodium nanoflowers (Au@Rh NFs) towards the plasmon-enhanced EOR. These hybrid materials consist of a Au spherical nucleus covered by Rh branches shell, combining plasmonic and catalytic properties. Firstly, the Au@Rh NFs metallic ratio was investigated in dark conditions to obtain an optimal catalyst. Experiments were also performed under light irradiation. Our data demonstrated an improvement of 352% in current density and 36% in selectivity to complete ethanol oxidation under 533 nm laser incidence. Moreover, the current density showed a linear increase with the laser power density, indicating a photochemical effect and thus enhancement due to the LSPR properties.

Surface-Plasmon-Assisted Growth, Reshaping and Transformation of Nanomaterials.

Excitation of surface plasmon resonance of metal nanostructures is a promising way to break the limit of optical diffraction and to achieve a great enhancement of the local electromagnetic field by the confinement of optical field at the nanoscale. Meanwhile, the relaxation of collective oscillation of electrons will promote the generation of hot carrier and localized thermal effects. The enhanced electromagnetic field, hot carriers and localized thermal effects play an important role in spectral enhancement, biomedicine and catalysis of chemical reactions. In this review, we focus on surface-plasmon-assisted nanomaterial reshaping, growth and transformation. Firstly, the mechanisms of surface-plasmon-modulated chemical reactions are discussed. This is followed by a discussion of recent advances on plasmon-assisted self-reshaping, growth and etching of plasmonic nanostructures. Then, we discuss plasmon-assisted growth/deposition of non-plasmonic nanostructures and transformation of luminescent nanocrystal. Finally, we present our views on the current status and perspectives on the future of the field. We believe that this review will promote the development of surface plasmon in the regulation of nanomaterials.

Tunable and Sensitive Detection of Cortisol Using Anisotropic Phosphorene with a Surface Plasmon Resonance Technique: Numerical Investigation

Tunable and ultrasensitive surface plasmon resonance (SPR) sensors are highly desirable for monitoring stress hormones such as cortisol, a steroid hormone formed in the human body’s adrenal glands. This paper describes the detection of cortisol using a bimetallic SPR sensor based on a highly anisotropic two-dimensional material, i.e., phosphorene. Thicknesses of bi-metal layers, such as copper (Cu) and nickel (Ni), are optimized to achieve strong SPR excitation. The proposed sensor is rotated in-plane with a rotation angle (φ) around the z-axis to obtain the phosphorene anisotropic behavior. The performance parameters of the sensor are demonstrated in terms of higher sensitivity (347.78 °/RIU), maximum angular figure of merit (FOM* = 1780.3), and finer limit of detection (0.026 ng/mL). Furthermore, a significant penetration depth (203 nm) is achieved for the proposed sensor. The obtained results of the above parameters indicate that the proposed sensor outperforms the previously reported papers in the literature on cortisol detection using the SPR technique.

Optical properties of nanostructured bimetallic films from the Ag-In and Ag-Sb systems and their surface-enhanced fluorescence application

The possibility for tuned excitation of surface plasmon resonance in Ag-In and Ag-Sb films with different compositions and thicknesses was studied in terms of preparation and microstructural and optical properties. The analyses show that plasmon excitation can be achieved both by changing the thickness of the deposited bimetallic films and by varying their composition. The imaginary ε'' part of the complex permittivity of the thin films has a maximum due to the transverse oscillations of free electrons in the range of 1 eV to 3.5 eV. The films’ applicability as amplifying substrates in surface-enhanced fluorescence was tested. Tryptophan and Cu (II)-phthalocyanine (CuPc) dye were used to analyze the efficiency of the localized surface plasmon resonance excitation in the ultraviolet spectral region. Amplification enhancing coefficient of 4.17 times was obtained in the case of CuPc dye.

High-resolution surface plasmon resonance holographic microscopy based on symmetrical excitation

Surface plasmon resonance holographic microscopy (SPRHM) is able to simultaneously obtain the amplitude- and phase-contrast surface plasmon resonance (SPR) images, showing great potentials in imaging near-field targets with high sensitivity. However, suffered by the decaying length of surface plasmon wave which can be as long as tens of microns, the spatial resolution of SPRHM is lower than that of traditional holographic microscopy. In this work, we propose to enhance the spatial resolution in SPRHM by exciting surface plasmon resonance in two symmetrical directions and detecting the complex amplitudes of the reflected light symmetrically. Through the Fourier analysis of the recorded composite hologram, the reconstruction schemes for high-resolution amplitude- and phase-contrast SPR images are established, respectively. The feasibility and advantages of the proposed method is verified by numerical simulations and experimental demonstrations of small-size particles and micro-structures.

Surface plasmon resonance enhanced transverse magneto-optical Kerr effect and the detection performance of nanopore arrays

The introduction of a magnetic component to the surface plasmon resonance (SPR) structure to form a magneto-optical surface plasmonic resonance (MOSPR) detector is an effective method for enhancing the detection limit for small molecules at low concentrations. This is important for biosensing, early disease diagnosis, drug discovery, and the detection of contamination in solutions and gases. In this study, an MOSPR crystal composed of a Co6Ag94 slab covered by a subwavelength periodic square array of gold (Au) nanopores was designed to theoretically examine the mechanism by which MOSPR crystals detect glucose concentrations through the transverse magneto-optical Kerr effect (T-MOKE). Owing to the excitation of SPR at the interface between the glucose solution and Au film, a Fano-like sharp T-MOKE spectrum with a narrow linewidth and a high amplitude was obtained, thus producing a high sensitivity of 159° RIU−1 and a high figure of merit of the order of 103 RIU−1. This corresponds to a glucose detection limit of 0.0066 g ml−1, which is more accurate than that previously reported. This design provides an alternative method for detecting analytes’ concentrations in aqueous environments.