Particle Plasmon Resonance Research Articles

Effect of temperature on the photoreactions of ethanol over Ag/TiO2 in steady state catalytic conditions

The photo-thermal reaction of ethanol to hydrogen and acetaldehyde over Ag/TiO2 is studied in flow conditions. Hydrogen production is mostly photo driven below 170 °C, and thermally driven above 250 °C. An increase in the overall reaction rates is observed when both photons and heat (photo-thermal effect) are present in the 125−225 °C temperature window for acetaldehyde and hydrogen production (via ethanol dehydrogenation; C2H5OH → CH3CHO + H2). The activation energies for photo-thermal and thermal reactions, measured in steady state conditions, are 31 and 40 kJmol−1, respectively. The maximum enhancement in reaction rates is 1.5× for acetaldehyde and 10× for hydrogen production. The enhancement for these two product should be the same. Reasons for these discrepancies are discussed. Other minor reaction products including ethylene and acetone appeared above 225 °C. Possible reasons for the enhanced rate of ethanol reaction under photo-thermal conditions, linked to plasmon resonance of Ag particles of Ag/TiO2, are discussed. Light to Chemical Energy Conversion (LCEC) was found equal to 0.12 % and 0.25 % at 170 °C and 225 °C, respectively.

A fiber optic nanoplasmonic biosensor for the sensitive detection of ampicillin and its analogs.

A novel optical immunosensor for the screening of ampicillin (Amp) residues has been developed. The biosensor is based on fiber optic particle plasmon resonance detection and uses an enhancement method called as fiber optic nanogold-linked immunosorbent assay (FONLISA) for the sensitive detection of antibiotics. A commercial antibody which had a higher affinity for ampicillin than for other β-lactam antibiotics was chosen. A surface competitive binding assay was used in which a fixed concentration of antibiotic-conjugated gold nanoparticles (AuNPs) competes with free unlabeled antibiotic molecules to measure the amount of binding with antibody molecules immobilized on an optical fiber. The synthesis of the 11-mercaptoundecanoic acid (MUA)-ampicillin conjugate facilitates the attachment of the Amp molecules to AuNPs via MUA which acts as a linker between them. This AuNP-Amp conjugate was then used for the detection of β-lactam antibiotics. The practical limit of detection obtained for Amp was 0.74ppb (7.4 × 10-10g/mL) which is lower than the recommended maximum residue limit (MRL) for β-lactams. The method also shows a wide linear range of 4 orders. Its applicability to the determination of ampicillin in spiked milk samples has been demonstrated with good recovery and reproducibility. Graphical abstract.

Fiber Optic Particle Plasmon Resonance Biosensor for Label-Free Detection of Nucleic Acids and Its Application to HLA-B27 mRNA Detection in Patients with Ankylosing Spondylitis.

We developed a label-free, real-time, and highly sensitive nucleic acid biosensor based on fiber optic particle plasmon resonance (FOPPR). The biosensor employs a single-strand deoxyoligonucleotides (ssDNA) probe, conjugated to immobilized gold nanoparticles on the core surface of an optical fiber. We explore the steric effects on hybridization affinity and limit of detection (LOD), by using different ssDNA probe designs and surface chemistries, including diluent molecules of different lengths in mixed self-assembled monolayers, ssDNA probes of different oligonucleotide lengths, ssDNA probes in different orientations to accommodate target oligonucleotides with a hybridization region located unevenly in the strand. Based on the optimized ssDNA probe design and surface chemistry, we achieved LOD at sub-nM level, which makes detection of target oligonucleotides as low as 1 fmol possible in the 10-μL sensor chip. Additionally, the FOPPR biosensor shows a good correlation in determining HLA-B27 mRNA, in extracted blood samples from patients with ankylosing spondylitis (AS), with the clinically accepted real-time reverse transcription-polymerase chain reaction (RT-PCR) method. The results from this fundamental study should guide the design of ssDNA probe for anti-sense sensing. Further results through application to HLA-B27 mRNA detection illustrate the feasibility in detecting various nucleic acids of chemical and biological relevance.

Fiber Optic Particle Plasmon Resonance-Based Immunoassay Using a Novel Multi-Microchannel Biochip.

A novel multi-microchannel biochip fiber-optic particle plasmon resonance (FOPPR) sensor system for the simultaneous detection of multiple samples. The system integrates a novel photoelectric system, a lock-in module, and an all-in-one platform incorporating optical design and mechanical design together to improve system stability and the sensitivity of the FOPPR sensor. The multi-microchannel FOPPR biochip has been developed by constructing a multi-microchannel flow-cell composed of plastic material to monitor and analyze five samples simultaneously. The sensor system requires only 30 μL of sample for detection in each microchannel. Moreover, the total size of the multi-microchannel FOPPR sensor chip is merely 40 mm × 30 mm × 4 mm; thus, it is very compact and cost-effective. The analysis was based on calibration curves obtained from real-time sensor response data after injection of sucrose solution, streptavidin and anti-dinitrophenyl (anti-DNP) antibody of known concentrations over the chips. The results show that the multi-microchannel FOPPR sensor system not only has good reproducibility (coefficient of variation (CV) < 10%), but also excellent refractive index resolution (6.23 ± 0.10 × 10−6 refractive index unit (RIU)). The detection limits are 2.92 ± 0.28 × 10−8 g/mL (0.53 ± 0.01 nM) and 7.48 ± 0.40 × 10−8 g/mL (0.34 ± 0.002 nM) for streptavidin and anti-DNP antibody, respectively.

Fiber optic particle plasmon resonance immunosensor for rapid and sensitive detection of methamphetamine based on competitive inhibition

We report the study of methamphetamine (MA) sensing in urine samples using fiber optic particle plasmon resonance (FOPPR) biosensor. This approach is intended for on-site analysis of low-molecular-weight compounds. High sensitivity detection of MA at ultra-low concentration is realized by using a competitive inhibition immunoreaction scheme based on the competition of free MA in solution for anti-MA molecules that bind to the bovine serum albumin (BSA)–MA conjugate on the gold nanoparticle surface.With the BSA–MA functionalized sensor fiber, in the presence of a fixed concentration of anti-MA and various concentrations of MA in sample, the change of transmitted light intensity through the sensor fiber relative to that in a buffer solution decreases when the MA concentration increases because of the inhibition effect of MA. Based on this sensing method, the MA-functionalized FOPPR biosensor is capable for determining the concentration of MA with high sensitivity and wide linear dynamic range of 1–1000 ng/mL. The limit of detection for MA is 0.16 ng/mL. In addition, the MA functionalized FOPPR biosensor can detect MA in diluted human urine samples without nonspecific adsorption interference.

Tuning of surface plasmon resonance of silver nano particles by shock waves for plasmonic device applications

The present research article demonstrates the findings of the fine tuning of surface plasmon resonance (SPR) and the relationship between structural, optical and morphological properties of shock wave loaded silver nanoparticles (Ag NPs). The characteristics of structural, optical and morphological properties of Ag NPs are evaluated by powder XRD (X-ray powder diffraction), UV–Vis (ultra violet- visible) spectroscopy and SEM (scanning electron microscopy) technique, respectively. The test material of Ag NPs is subjected to the shock wave loading with 50,100 and 150 shock pulses, respectively. The PXRD results reveal that the degree of crystalline nature and grain size of the crystal is significantly reduced by the impact of shock waves. The UV–Visible spectrum reveals that the control Ag NPs absorption band at 514 nm has given rise to blue shift (514–403 nm) at 150 shock wave loaded samples. The SEM images reveal that the particle size is considerably reduced by the impact of shock waves with respect to number of shock waves. The tri-angle correlation of structural, optical and morphological properties of shock wave loaded Ag NPs is explored.

Effect of ArF excimer laser annealing on morphology and surface plasmon resonance properties of Ag nanoparticles

Ag nanoparticles were obtained in AZO/Ag and AZO/Ag/AZO films by magnetron sputtering method at room temperature. These as-deposited films are then annealed by ArF excimer laser system operated at λ = 193 nm. The effect of two different laser annealing processes on surface plasmon resonance (SPR) of Ag particles and photoelectric properties of these films can be discussed detailedly. AZO film substrates where the thermally active surface diffusion of Ag occurs play an important role in determining the morphologies of Ag particles. Ag films irradiated directly by laser annealing in AZO/Ag films tend to form spherical particles, while Ag films deposited on laser-irradiated AZO film substrates are likely to form irregular long particles. The results show that irregular long Ag particles can be obtained on AZO films with small and dense grains as nucleation centers induced by high laser energy densities, which can exhibit redshift of SPR peaks and optimize photoelectric properties. The SPR peak of irregular long Ag particles based on laser-irradiated AZO substrate can reach to 750 nm with an optical average transmittance of 83% and a $$ R_{\text{S}} $$ value of 16 Ω/sq at a laser energy density of 250 mJ/cm2.

Synthesis of hexagonal‐like ZnO/Ag composite with excellent photocatalytic activity

Hexagonal-like zinc oxide (ZnO)/silver (Ag) composite was successfully synthesised by a flux/solvothermal route, and Ag nanoparticles are loaded on ZnO. Compared with pure ZnO, the attachment of Ag on ZnO can significantly increase visible-light absorption and reduce photoluminescence emission intensity. The photocatalytic performance of ZnO/Ag composite was evaluated by the degradation of Rhodamine B solution under ultraviolet (UV) light and visible light irradiation. The degradation rate of ZnO/Ag composite is obviously improved compared with pure ZnO and the commercial TiO2 (P25) and is more than 2.5 and 2.9 times faster than that of pure ZnO under the UV and visible light irradiation, respectively. The enhanced photocatalytic activity of ZnO/Ag composite under UV irradiation was ascribed to the formation of Schottky barriers between Ag particles and ZnO. However, the superior photocatalytic activity under visible light irradiation could be attributed to the surface plasmon resonance of Ag particles.

Spectral Screening of the Energy of Hot Holes over a Particle Plasmon Resonance.

Plasmonic hot carriers have been recently identified as key elements for photocatalysis at visible wavelengths. The possibility to transfer energy between metal plasmonic nanoparticles and nearby molecules depends not only on carrier generation and collection efficiencies but also on their energy at the metal-molecule interface. Here an energy screening study was performed by monitoring the aniline electro-polymerization reaction via an illuminated 80 nm gold nanoparticle. Our results show that plasmon excitation reduces the energy required to start the polymerization reaction as much as 0.24 eV. Three possible photocatalytic mechanisms were explored: the enhanced near field of the illuminated particle, the temperature increase at the metal-liquid interface, and the excited electron-hole pairs. This last phenomenon is found to be the one contributing most prominently to the observed energy reduction.

Enhanced second harmonic generation by double plasmon resonances in mesoscale flower-like silver particles

We investigate second harmonic generation (SHG) response of mesoscale silver (Ag) particles. The flower-like Ag mesoparticles and Ag micro-hemispheres on an indium tin oxide coated glass substrate were prepared by a simple electrochemical deposition method. We find that the mesoscale Ag particles show a strong SHG response associated with their geometries. The dependence of the SHG on the excitation wavelength reveals that the multi-resonant response occurring at the emission wavelengths plays an important role in SHG enhancement.

Investigation of valence electron excitation and plasmonic enhancement in sputter grown NMZO thin films: For energy harvesting applications

We report a novel approach of sputter-stimulated plasmonic generation in Na-doped MgZnO (NMZO) thin films. Sputtering of material during film growth by utilizing secondary direct-coupled ion-source present in dual-ion beam sputtering system leads to the generation of nanoclusters of its constituent elements due to different sputtering-out rates of various elements present in the films. The authentication of plasmonic generation in NMZO is conducted as follows a) identification of plasmonic signature in electron energy loss spectra obtained by ultraviolet photoelectron spectroscopy measurement, b) valence bulk, valence surface, and particle plasmon resonance energy calculations are performed, and each plasmon peak is indexed with corresponding plasmon energy peak of different nanoclusters, and c) spectroscopic ellipsometric measurement is deployed to verify plasmonic behavior by investigating different optical properties. Additionally, incorporation of the plasmonic feature along with alkali metals plays a crucial role in the improvement of the performance of solar cells. Therefore, plasmon enhanced NMZO as a backscattering layer in between CIGSe/back contact is probed to ascertain the additional benefits of 1) Na incorporation into the absorber layer as a result of the Na diffusion from the NMZO layer, and 2) improvement in the morphology of the CIGSe thin film with the incorporation of NMZO layer in between the back-contact and CIGSe. The diffusion of Na into the absorber layer is probed by deploying secondary ion mass spectroscopy measurements, and improvement in the morphology of CIGSe with the incorporation of NMZO layer between the back-contact/absorber is investigated using field-emission scanning electron microscope analysis.

All-Metal Broadband Optical Absorbers Based on Block Copolymer Nanolithography.

The growing interest in solar energy during recent years has spurred on the development of high-efficiency optical absorbers using emerging concepts in plasmonics and metamaterials. Most absorber designs require patterning on a subwavelength scale, making large-scale fabrication expensive or impractical. This study presents an all-metal metasurface with tightly packed, sub-80 nm nanodomes fabricated by template-stripping thin gold films from reusable silicon templates. Subwavelength patterning was achieved via molecular self-assembly of block copolymers, which enables large-area, periodic patterning with nanometer precision. The proposed nanodome surface acts as an optical absorber capable of absorbing 97% of incident light in the visible range 320-650 nm, and still more than 90% at high incidence angles. We demonstrate both experimentally and theoretically that the absorption behavior of the thin film can be controlled by changing the size of the nanodomes, namely, the gap between the structures. The enhanced absorption of light is attributed to localized particle plasmon and gap plasmon resonances. This research provides a straightforward and cost-effective strategy to design and fabricate thin, large-area, light-absorbing coatings that can be transferred onto nearly any rigid or flexible substrate. The all-metal metasurfaces are a promising candidate for plasmon-induced hot electron generation for efficient solar energy conversion in photovoltaic and photocatalytic devices.

Synthesis and light-induced aggregation of benzoate-stabilized silver nanoparticles

We report the influence of LED light irradiation on the colloids of silver nanoparticles synthesized in the presence of sodium benzoate. Scanning electron and atomic force microscopy measurements showed progressive aggregation and agglomeration of the particles during the irradiation with the light which energy is close to particle plasmon resonance. We consider local heating phenomenon caused due to the plasmon excitation as the main reason for the aggregation of the particles. A specific role of the benzoate and irradiation wavelength in these processes are discussed. This plasmon-induced aggregation opens new opportunities for the creation of metallic nanoparticle clusters.

Nanoscale Hydrogenography on Single Magnesium Nanoparticles.

Active plasmonics is enabling novel devices such as switchable metasurfaces for active beam steering or dynamic holography. Magnesium with its particle plasmon resonances in the visible spectral range is an ideal material for this technology. Upon hydrogenation, metallic magnesium switches reversibly into dielectric magnesium hydride (MgH2), turning the plasmonic resonances off and on. However, up until now, it has been unknown how exactly the hydrogenation process progresses in the individual plasmonic nanoparticles. Here, we introduce a new method, namely nanoscale hydrogenography, that combines near-field scattering microscopy, atomic force microscopy, and single-particle far-field spectroscopy to visualize the hydrogen absorption process in single Mg nanodisks. Using this method, we reveal that hydrogen progresses along individual single-crystalline nanocrystallites within the nanostructure. We are able to monitor the spatially resolved forward and backward switching of the phase transitions of several individual nanoparticles, demonstrating differences and similarities of that process. Our method lays the foundations for gaining a better understanding of hydrogen diffusion in metal nanoparticles and for improving future active nano-optical switching devices.

Effect of Surface Coverage of Gold Nanoparticles on the Refractive Index Sensitivity in Fiber-Optic Nanoplasmonic Sensing.

A simple theoretical model was developed to analyze the extinction spectrum of gold nanoparticles (AuNPs) on the fiber core and glass surfaces in order to aid the determination of the surface coverage and surface distribution of the AuNPs on the fiber core surface for sensitivity optimization of the fiber optic particle plasmon resonance (FOPPR) sensor. The extinction spectrum of AuNPs comprises of the interband absorption of AuNPs, non-interacting plasmon resonance (PR) band due to isolated AuNPs, and coupled PR band of interacting AuNPs. When the surface coverage is smaller than 12.2%, the plasmon coupling effect can almost be ignored. This method is also applied to understand the refractive index sensitivity of the FOPPR sensor with respect to the non-interacting PR band and the coupled PR band. In terms of wavelength sensitivity at a surface coverage of 18.6%, the refractive index sensitivity of the coupled PR band (205.5 nm/RIU) is greater than that of the non-interacting PR band (349.1 nm/RIU). In terms of extinction sensitivity, refractive index sensitivity of the coupled PR band (−3.86/RIU) is similar to that of the non-interacting PR band (−3.93/RIU). Both maximum wavelength and extinction sensitivities were found at a surface coverage of 15.2%.

Rapid degradation of naproxen by AgBr-α-NiMoO4 composite photocatalyst in visible light: Mechanism and pathways

A novel strategy for fabrication of visible light driven AgBr-α-NiMoO4 composite photocatalyst has been developed, including microwave hydrothermal and precipitation-deposition method. The fabrication of heterojunction photocatalyst was proved by XRD, FESEM mapping, HRTEM, SAED, EDS, and XPS techniques. The composite photocatalyst degraded naproxen drug around 84% within 20 min under visible light irradiation. The active species trapping experiment confirmed that OH, O2−, and h+ play a crucial role for naproxen degradation. Due to efficient charge separation, well matched energy band of AgBr and α-NiMoO4 as well as surface plasmon resonance of silver particles, the composite revealed the high photocatalytic performance with excellent stability up to fifth cycle. In addition, the composite is photochemical stable. Furthermore, the five degradation pathways were proposed on the basis of retention time and theoretical/observed molecular masses of 19 degraded organic fragments that was confirmed by high-performance liquid chromatography-photodiode array (HPLC-PDA) and high resolution-quadruple time of flight electrospray ionization mass spectroscopy (HR-QTOF ESI/MS) techniques. The different reactions (methylation, demethylation, decarboxylation, hydroxylation, oxidation, and coupling) were observed during NPX degradation by photocatalyst. TOC (total organic carbon) analysis revealed that naproxen drug was completely mineralized by composite photocatalyst within 100 min. So, this work represents the fabrication of visible light induced novel composite photocatalyst for rapid degradation of pharmaceutical pollutant with detailed mechanism and pathways.

Q-switched Yb3+:YAG laser using plasmonic Cu2-xSe quantum dots as saturable absorbers

Cu2-xSe quantum dots (QDs) were synthesized by organometallic synthesis methods. Due to heavy self-doping, the Cu2-xSe QDs exhibit particle plasmon resonance in the near-infrared. Transient absorption spectroscopic investigation revealed strong nonlinear optical absorption and bleaching performance of the QDs under femtosecond pulse excitation, which enabled the Cu2-xSe QDs to be excellent saturable absorbers and applied in Q-switched or mode-locked lasers. A passively Q-switched Yb3+:YAG solid-state laser at 1.03 μm was achieved by coating Cu2-xSe QDs as saturable absorbers onto one of the output coupler of the V-shaped linear cavity.

Investigation of Dual-Ion Beam Sputter-Instigated Plasmon Generation in TCOs: A Case Study of GZO.

The use of the high free-electron concentration in heavily doped semiconductor enables the realization of plasmons. We report a novel approach to generate plasmons in Ga:ZnO (GZO) thin films in the wide spectral range of ∼1.87-10.04 eV. In the grown GZO thin films, dual-ion beam sputtering (DIBS) instigated plasmon is observed because of the formation of different metallic nanoclusters are reported. Moreover, formation of the nanoclusters and generation of plasmons are verified by field emission scanning electron microscope, electron energy loss spectra obtained by ultraviolet photoelectron spectroscopy, and spectroscopic ellipsometry analysis. Moreover, the calculation of valence bulk, valence surface, and particle plasmon resonance energies are performed, and indexing of each plasmon peaks with corresponding plasmon energy peak of the different nanoclusters is carried out. Further, the use of DIBS-instigated plasmon-enhanced GZO can be a novel mean to improve the performance of photovoltaic, photodetector, and sensing devices.

Evolution of structural and optical properties of Ag implanted CrN thin films with annealing temperature

This study reports on the changes of the structural and optical properties occurring in CrN thin films upon Ag ion implantation. The films were grown by reactive sputtering on top of Si (100) wafers at a temperature of around 150 °C. Subsequently, the films were implanted with Ag ion fluences in the range of 0.5 × 1016 ions/cm2 ‒ 2 × 1016 ions/cm2 with energy of 200 keV. The structural and morphological changes, promoted by in-vacuum annealing of the as-implanted thin films at 200 °C, 400 °C and 700 °C, resulted in different optical responses of the CrN:Ag films due to the formation of Ag nanoparticles. The nanoparticles were inhomogenously distributed through the layer, which is related to the implantation distribution of silver in CrN. Apart from this, Ag nanoparticles with a size of 20–25 nm were formed at the surface of the layer. These structural properties are responsible for the formation of a broad optical absorption peak. This peak is located at ∼420 nm and can be associated with the plasmon resonance of Ag particles embedded in the CrN matrix.

Nondestructive Probing of a Photoswitchable Dithienylethene Coupled to Plasmonic Nanostructures

We demonstrate the read-out of the conformational state of photoswitchable molecules, without modifying that state by the read-out process itself. The ring-opening and ring-closing reactions change not only the absorption spectrum of a molecular layer but also its index of refraction. A thin layer of a dithienylethene derivative was combined with well-designed gold nanostructures. The particle plasmon resonance of these nanostructures is extremely sensitive to the photoinduced change in the environment and can therefore be used to probe the state of the photochromic switch. The probing wavelength now interrogates the plasmonic structure, not the molecular film, and can thus be conveniently placed in a transparent spectral range, e.g., the near-infrared. We find good agreement between experiments and numerical simulations with regard to spectral signatures of the plasmon resonance.