Plasmon Energy Research Articles

Upconversion luminescence enhancement of the ytterbium oxide with gold nanoparticles on anodized titanium surface

This paper presents a study of the cooperative luminescence (upconversion) process of Yb2O3 with gold nanoparticles on the anodized titanium surface. The luminescence of the samples was registered under two-photon excitation with using infrared laser (λ = 980 nm) and a quasi-continuous femtosecond laser (λ = 1030 nm). It was found that the quantum yield of luminescence in the presence of gold nanoparticles increases in 5.6 times fold as a result of non-radiative plasmon energy transfer. The constant of non-radiative dipole-dipole energy transfer was calculated with using the Förster model under the plasmon energy generation. It is also shown that under photoexcitation with wavelength of 980 nm at low temperatures (80 K), the intensity of upconversion luminescence increases according to the quadratic function of the excitation energy, which confirms the existence of upconversion luminescence generation by the mechanism of simultaneous energy transfer involving two Yb3+ ions in the oxide crystal.

Effect of hydrogen coverage on elastic and optical properties of silicene: a first-principle study.

The structural, electronic, and optical properties of hydrogenated silicene have been investigated using first-principles DFT calculations. Compared to pristine silicene, hydrogenated silicene exhibits high stability, reduced anisotropy, and less birefringence. Hydrogenated silicene shows a constant refractive index in the visible region, increasing exponentially in silicene. The elastic and optical parameters such as Young's modulus (Y), Poisson's ratio (ν), bulk modulus (B), shear modulus (G), dielectric constant ε(0), refractive index n(0), conductivity threshold (Eth), birefringence Δn(0), and plasmon energy (ħωp) were calculated for the first time for different hydrogen coverage on silicene, which is crucial in the applications of linear and non-linear optoelectronic devices. The estimated parameters agree well with the available experimental and reported values.

Boosted radiative energy transfer of plasmonic electrodes enables flexible organic photovoltaics with efficiency over 18%

The light extinction caused by plasmonic effects is the bottleneck of developing the highly transparent silver nanowires (AgNWs)-based electrode in the applications of flexible organic photovoltaics. Here, a new electrode architecture is proposed to remit the surface plasmon polaritons (SPPs) of AgNWs through hot-nanoimprint introduced lateral buds, which can couple SPPs to radiation via non-radiative damping and thus reduce the plasmonic energy loss. The boosted radiative energy transfer generates a broadband increase in optical transmittance of AgNWs, yielding the highest value of 91.2% and an average one of 87.56%. Due to the synergetic effect of plasmon out-coupling, anti-reflection, and morphological improvement of the deformed AgNWs electrode, flexible organic photovoltaics obtain an 8.7% increase in power conversion efficiency as compared to their counterpart, achieving a state-of-the-art efficiency of 18.1%.

Uncovering strong π-metal interactions on Ag and Au nanosurfaces under ambient conditions via in-situ surface-enhanced Raman spectroscopy

Uncovering strong π-metal interactions on Ag and Au nanosurfaces under ambient conditions via in-situ surface-enhanced Raman spectroscopy

Structure Specific Adsorbate Interactions at Electrodepositing Cu Interfaces

Mechanistic understanding of interfaces during additive based electrochemical deposition of thin films is limited by lack of tools to discretely probe given features of deposits. Modern spectroelectrochemical methods that have enabled significant understanding, like surface-enhanced Raman and infrared spectroscopies (SERS and SEIRAS, respectively), are restricted by specimen geometry; SERS is closely linked to the use of rough plasmonically active surfaces while SEIRAS measurements is constrained to thin IR transparent metal films. More recently, the application of Au@SiO2 core-shell nanoparticles as “vibrational reporters” on plasmonically inactive surfaces has enabled collection of site-specific vibrational data on well-defined single crystal surfaces whereby the nanoparticle serves to channel the plasmonic energy to the nanoparticle-substrate interface. The present work utilizes this technique, Shell-Isolated Nanoparticle Enhanced Raman Spectroscopy (SHINERS) to track relative coverages of sulfonate, chloride and methylene moieties following super-conformal Cu electrodeposition on a patterned interface (Figure 1 a,b,d). Corroborated by computational finite-element results (Figure 1 c,d) and x-ray photoelectron spectroscopy measurements, the SHINERS measurements demonstrate that during early stages of electrodeposition, on an accelerator functionalized surface, the regions with more deposition have higher coverage of sulfonate species. As deposition continues dilation of the sulfonate concentration occurs following the continual decrease in surface area of the interface. Ultimately, this work reveals the benefit from the combined use of SHINERs, photoelectron spectroscopy and computational models to further our understanding of composite electroplating and resolve complex site-specific interfacial interactions. Figure 1

Galvanic Restructuring of Exsolved Nanoparticles for Plasmonic and Electrocatalytic Energy Conversion (Small 29/2022)

Photoelectrochemical Water Splitting In article number 2201106, Athanasios Chatzitakis and co-workers combine in situ metal exsolution and the galvanic replacement reaction for the synthesis of advanced catalysts for diverse energy conversion applications. Exsolved Ni nanoparticles are galvanically restructured and a wealth of bimetallic nanostructures are facilely synthesized. Among them are well adhered and supported AuNi antenna-reactor nanoconfigurations with improved plasmonic activity for photoelectrochemical water splitting in alkaline conditions.

Influence of oxygen plasma treatment on structural and spectral changes in gold nanorods immobilized on indium tin oxide surfaces.

Oxygen plasma treatment is commonly used to sterilize gold nanoparticles by removing chemical contaminants from their surface while simultaneously inducing surface activation and functionalization of nanoparticles for biological, electrocatalytic, or electrochemical studies. In this study, we investigate the influence of oxygen plasma treatment on structural and localized surface plasmon resonance (LSPR) spectral changes of anisotropic gold nanorods (AuNRs) immobilized on an indium tin oxide (ITO) glass substrate. Unlike AuNRs deposited on a glass slide, no noticeable structural change or deformation of AuNRs on ITO was observed while increasing the oxygen plasma treatment time. This result indicates that ITO provides structural stability to AuNRs immobilized on its surface. Additionally, single-particle scattering spectra of AuNRs showed the broadening of LSPR linewidth within 60s of oxygen plasma treatment as a result of the plasmon energy loss contributed from plasmon damping to ITO due to the removal of capping material from the AuNR surface. Nevertheless, an increase in the surface charge on the AuNR surface was observed by narrowing the LSPR linewidth after 180s of plasma treatment. The electrochemical study of AuNRs immobilized on ITO electrodes revealed the surface activation and functionalization of AuNRs by increasing plasma treatment. Hence, in this study, a significant understanding of oxygen plasma treatment on AuNRs immobilized on ITO surfaces is provided.

Compositional analysis of oxide-embedded III–V nanostructures

Nanowire growth enables creation of embedded heterostructures, where one material is completely surrounded by another. Through materials-selective post-growth oxidation it is also possible to combine amorphous oxides and crystalline, e.g. III–V materials. Such oxide-embedded structures pose a challenge for compositional characterization through transmission electron microscopy since the materials will overlap in projection. Furthermore, materials electrically isolated by an embedding oxide are more sensitive to electron beam-induced alterations. Methods that can directly isolate the embedded material, preferably at reduced electron doses, will be required in this situation. Here, we analyse the performance of two such techniques—local lattice parameter measurements from high resolution micrographs and bulk plasmon energy measurements from electron energy loss spectra—by applying them to analyse InP-AlInP segments embedded in amorphous aluminium oxide. We demonstrate the complementarity of the two methods, which show an overall excellent agreement. However, in regions with residual strain, which we analyse through molecular dynamics simulations, the two techniques diverge from the true value in opposite directions.

Lithium-plasmon-based low-powered dynamic color display.

Display and power supply have been two essential and independent cornerstones of modern electronics. Here, we report a lithium-plasmon-based low-powered dynamic color display with intrinsic dual functionality (plasmonic display and energy recycling unit) which is a result of the electric-field-driven transformation of nanostructured lithium metals. Dynamic color displays are enabled by plasmonic transformation through electrodeposition (electrostripping) of lithium metals during the charging (discharging) process, while the consumed energy for coloring can be retrieved in the inverse process respectively. Energy recycling of lithium metals brings energy consumption down to 0.390mW cm-2 (0.105mW cm-2) for the active (static) coloration state of a proof-of-concept display/battery device, which approaches nearly-zero-energy-consumption in the near-100%-energy-efficiency limit of commercial lithium batteries. Combining the subwavelength feature of plasmonics with effective energy recycling, the lithium-plasmon-based dynamic display offers a promising route towards next-generation integrated photonic devices, with the intriguing advantages of low energy consumption, a small footprint and high resolution.

Flat-band plasmons in twisted bilayer transition metal dichalcogenides

Twisted bilayer transition metal dichalcogenides are ideal platforms to study flat-band phenomena. In this paper, we investigate flat-band plasmons in the hole-doped twisted bilayer ${\mathrm{MoS}}_{2}$ (tb-${\mathrm{MoS}}_{2}$) by employing a full tight-binding model and the random phase approximation. When considering lattice relaxations in tb-${\mathrm{MoS}}_{2}$, the flat band is not separated from remote valence bands, which makes the contribution of interband transitions in transforming the plasmon dispersion and energy significantly different. In particular, low-damped and quasiflat plasmons emerge if we only consider intraband transitions in the doped flat band, whereas a $\sqrt{q}$ plasmon dispersion emerges if we also take into account interband transitions between the flat band and remote bands. Furthermore, the plasmon energies are tunable with twist angles and doping levels. However, in a rigid sample that suffers no lattice relaxations, lower-energy quasiflat plasmons and higher-energy interband plasmons can coexist. For rigid tb-${\mathrm{MoS}}_{2}$ with a high doping level, strongly enhanced interband transitions quench the quasiflat plasmons. Based on the lattice relaxation and doping effects, we conclude that two conditions, the isolated flat band and a proper hole-doping level, are essential for observing the low-damped and quasiflat plasmon mode in twisted bilayer transition metal dichalcogenides. We hope that our study on flat-band plasmons can be instructive for studying the possibility of plasmon-mediated superconductivity in twisted bilayer transition metal dichalcogenides in the future.

Plasmon spectroscopy for the determination of Ti3C2T x MXene few layer stacks architecture

Like many 2D materials, numerous properties of MXene multilayers, and especially the most popular one Ti3C2T x , have been shown to significantly depend on their architecture, i.e. the number of layers and interlayer distance. These structural parameters are thus key elements to be characterized for the analysis of MXene properties. Focusing on valence electron energy-loss spectroscopy (VEELS) as performed in a transmission electron microscope (TEM), and using density functional theory (DFT) simulations, we here analyze the layer dependent large changes in the VEEL spectra of Ti3C2T x multilayers as a probe of their total thickness, and emphasize the bulk plasmon energy sensitivity to interlayer distance. Together these findings allow to directly quantify the absolute number of layers in a Ti3C2T x stack up to ∼10 nm thickness and give access to interlayer distance modifications with sub-angström sensitivity, evidencing VEELS as a powerful method for the characterization of MXene multilayers on the nanometer scale. We expect these results to be relevant for the study of structure/properties correlations in this class of materials, especially with the development of in situ or environmental TEM experiments.

Galvanic Restructuring of Exsolved Nanoparticles for Plasmonic and Electrocatalytic Energy Conversion.

There is a growing need to control and tune nanoparticles (NPs) to increase their stability and effectiveness, especially for photo- and electrochemical energy conversion applications. Exsolved particles are well anchored and can be re-shaped without changing their initial location and structural arrangement. However, this usually involves lengthy treatments and use of toxic gases. Here, the galvanic replacement/deposition method is used, which is simpler, safer, and leads to a wealth of new hybrid nanostructures with a higher degree of tailorability. The produced NiAu bimetallic nanostructures supported on SrTiO3 display exceptional activity in plasmon-assisted photoelectrochemical (PEC) water oxidation reactions. In situ scanning transmission electron microscopy is used to visualize the structural evolution of the plasmonic bimetallic structures, while theoretical simulations provide mechanistic insight and correlate the surface plasmon resonance effects with structural features and enhanced PEC performance. The versatility of this concept in shifting catalytic modes to the hydrogen evolution reaction is demonstrated by preparing hybrid NiPt bimetallic NPs of low Pt loadings on highly reduced SrTiO3 supports. This powerful methodology enables the design of supported bimetallic nanomaterials with tunable morphology and catalytic functionalities through minimal engineering.

Plasmonic Gold Trimers and Dimers with Air-Filled Nanogaps.

The subwavelength confinement of light energy in the nanogaps formed between adjacent plasmonic nanostructures provides the foundational basis for nanophotonic applications. Within this realm, air-filled nanogaps are of central importance because they present a cavity where application-specific nanoscale objects can reside. When forming such configurations on substrate surfaces, there is an inherent difficulty in that the most technologically relevant nanogap widths require closely spaced nanostructures separated by distances that are inaccessible through standard electron-beam lithography techniques. Herein, we demonstrate an assembly route for the fabrication of aligned plasmonic gold trimers with air-filled vertical nanogaps having widths that are defined with spatial controls that exceed those of lithographic processes. The devised procedure uses a sacrificial oxide layer to define the nanogap, a glancing angle deposition to impose a directionality on trimer formation, and a sacrificial antimony layer whose sublimation regulates the gold assembly process. By further implementing a benchtop nanoimprint lithography process and a glancing angle ion milling procedure as additional controls over the assembly, it is possible to deterministically position trimers in periodic arrays and extend the assembly process to dimer formation. The optical response of the structures, which is characterized using polarization-dependent spectroscopy, surface-enhanced Raman scattering, and refractive index sensitivity measurements, shows properties that are consistent with simulation. This work, hence, forwards the wafer-based processing techniques needed to form air-filled nanogaps and place plasmonic energy at site-specific locations.

Temperature and inhomogeneity combination effects on collective excitations in three-layer graphene structures

Temperature and the inhomogeneity of background dielectric combination effects on the collective excitations in a multilayer graphene structure consisting of three monolayer graphene sheets are investigated, within the random-phase approximation. Numerical calculations present that three weakly damped plasmon modes exist and continue in inter single-particle excitation region. Our investigations show that as temperature increases, the acoustic plasmon frequencies slightly decrease and then increase after getting the lowest peak. Dissimilarly, the optical plasmon frequency increases with the increasing temperature in the large wave vector regions. Besides, temperature effects cause the energy loss to plasmon modes even nearby the Dirac points, outside the single-particle excitation region of the system. We also observe that the inhomogeneity of background dielectric declines the plasmon energy, the damping rate of plasma oscillations , and the effects of temperature and interlayer separation on the collective excitations in the system. • Three plasmon modes exist and continue in SPE region of the system. • Acoustic modes decrease and then increase with increasing temperature. • Optical mode increases as temperature increases. • Temperature causes the energy loss to plasmon modes outside the SPE region. • The inhomogeneity declines the plasmon energy, the damping rate and the effects of temperature and separation on the collective excitations.

A Photocatalytic Hydrolysis and Degradation of Toxic Dyes by Using Plasmonic Metal–Semiconductor Heterostructures: A Review

Converting solar energy to chemical energy through a photocatalytic reaction is an efficient technique for obtaining a clean and affordable source of energy. The main problem with solar photocatalysts is the recombination of charge carriers and the large band gap of the photocatalysts. The plasmonic noble metal coupled with a semiconductor can give a unique synergetic effect and has emerged as the leading material for the photocatalytic reaction. The LSPR generation by these kinds of materials has proved to be very efficient in the photocatalytic hydrolysis of the hydrogen-rich compound, photocatalytic water splitting, and photocatalytic degradation of organic dyes. A noble metal coupled with a low bandgap semiconductor result in an ideal photocatalyst. Here, both the noble metal and semiconductor can absorb visible light. They tend to produce an electron–hole pair and prevent the recombination of the generated electron–hole pair, which ultimately reacts with the chemicals in the surrounding area, resulting in an enhanced photocatalytic reaction. The enhanced photocatalytic activity credit could be given to the shared effect of the strong SPR and the effective separation of photogenerated electrons and holes supported by noble metal particles. The study of plasmonic metal nanoparticles onto semiconductors has recently accelerated. It has emerged as a favourable technique to master the constraint of traditional photocatalysts and stimulate photocatalytic activity. This review work focuses on three main objectives: providing a brief explanation of plasmonic dynamics, understanding the synthesis procedure and examining the main features of the plasmonic metal nanostructure that dominate its photocatalytic activity, comparing the reported literature of some plasmonic photocatalysts on the hydrolysis of ammonia borane and dye water treatment, providing a detailed description of the four primary operations of the plasmonic energy transfer, and the study of prospects and future of plasmonic nanostructures.

Visible light driven robust photocatalytic activity in vanadium-doped ZnO/SnS core-shell nanocomposites for decolorization of MB dye towards wastewater treatment

Vanadium metal oxide (V2O5) doped ZnO/SnS core-shell nanocomposites are fabricated by hydrothermal method at 2200C for 10 hours. All synthesized Nanocomposites were optically, structurally, morphologically and magnetically examined by different techniques such as UV-DRS, XRD, TEM, electron paramagnetic resonance (EPR), XPS and PL techniques. The photocatalytic activity (PCA) was studied for methylene blue (MB) model pollutant dye under 300 W visible light illumination. XRD peaks confirmed the mixed phase abundance with hexagonal ZnO and orthorhombic SnS. TEM micrographs inferred uneven surface with more agglomeration. XPS conclude V4+ oxidation state for vanadyl atoms along with constitutes elements. The UV-DRS inferred red shift in bandgap. EPR argued that vanadyl ions perform tetragonal compression distorted octahedral site symmetry. PL study described quantum confinement effect. The achieved MB dye degradation under visible light illumination is more than 96% in 2 hours. Enhanced PCA argued owing to plasmonic effect and tunable energy bandgap nature of heterogeneous semiconducting materials.

Emitted secondary Electrons: In vacuo plasmon energy gain observation using a Three-Point probe method

A surface plasmon energy gain for emitted secondary electrons (SEs) was recently observed in SE spectroscopy measurements from a tailor-made nanostructured Au specimen as a satellite on the high energy side of the vacuum level. However, thus far, this plasmon energy gain phenomenon has been observed only for Au samples because surface plasmons in Au arise at 2.3 eV, which is relatively far from the strong background cascade peak of SEs. Here, we report a brand-new three-point probe method, for enlarging the surface plasmon energy gain structure in SE spectra. Using this scheme, three different SE energy spectra were measured from nanostructured samples of Au and Ag. By combining their spectra, the surface plasmon energy gain structure of Au and Ag can be clearly observed. The observed structures revealed that the plasmon energy gain process for SEs contributing to a potentially observable feature in a spectrum occurs only in vacuum above the sample surface and is naturally related only to surface plasmons. This unusual plasmon energy gain phenomenon observed by the three-point probe method suggests the potential for development of a new physical image directly in space based on surface plasmons in vacuum above the surface of a medium.

DFT investigations of AgMC7H10N2 (M = Cl, Br, and I) metal organic molecules: NMR, optoelectronic, and transport properties.

The full-potential linearized augmented plane wave (FP-LAPW) method was used for the calculation of the structural, nuclear magnetic resonance (NMR), optoelectronic, and thermoelectric properties of AgMC7H10N2 (M = Cl, Br, and I) compounds. The calculated wide band gap of AgMC7H10N2 (M = Cl, Br, and I) metal organic molecules with the density of states approach were 3.32, 3.29, and 3.10eV, respectively. The NMR parameters are calculated for the Ag, Cl, Br, I, C, N, O, and H elements. It is found that by decreasing bandgap, the isotropic NMR chemical shielding values of Cl, Br, and I elements increase. The strong hybridization of Ag-4d, Cl-3p, Br-4p, and I-5p states are observed at the top of the valence band. The birefringence and anisotropic properties are observed in the optical spectra with high plasmon energies, and the figure of merit, ZT, of 0.98 for AgCl(C7H10N2) compound is found at 300K. Hence, these compounds are attractive flexible metal organic molecules for optoelectronic and transport applications.

Resonant defect recombination-localized surface plasmon energy transfer and exciton dominated fluorescence in ZnO-Au-ZnO multi-interfaced heteronanocrystals.

The semiconductor-metal heteronanocrystals (HNCs) that possess a perfect epitaxial interface can accommodate novel and interesting physical phenomena owing to the strong interaction and coupling between the semiconductor excitons and metal plasmons at the interface. Here, we fabricate the pyramidal ZnO-Au HNCs and study their unique photophysical properties. Several Au nanospheres are perfectly epitaxially bound with a single ZnO NC owing to the small lattice mismatch between them and there are also ZnO-Au-ZnO sandwiched HNCs. There is a strong coupling between the green defect-associated recombination in the ZnO NC and the localized surface plasmon resonance (LSPR) of the Au nanosphere at the interface of the HNC. This leads to resonant defect recombination-LSPR energy transfer and resultant nearly complete quenching of the green defect luminescence of the ZnO NCs in the HNCs, leaving only the UV exciton luminescence. The lifetimes of both the green and UV emission bands decrease significantly in the ZnO-Au HNCs relative to that of the pure ZnO NCs owing to the combined effect of resonance energy transfer and surface plasmon enhanced radiative transition. The exponent of the luminescence intensity-excitation intensity power function for the green emission band is remarkably smaller than unity, and this suggests that the involved defects have an intermediate concentration.

Photothermal/NO combination therapy from plasmonic hybrid nanotherapeutics against breast cancer.

In this study, a plasmon-semiconductor nanotheranostic system comprising Au nanostars/graphene quantum dots (AuS/QD) hybrid nanoparticles loaded with BNN6 and surface modified with PEG-pyrene was developed for the photo-triggered hyperthermia effect and NO production as the dual modality treatment against orthotopic triple-negative breast cancer. The structure and morphology of the hybrid nanodevice was characterized and the NIR-II induced thermal response and NO production was determined. The hybrid nanodevice has shown enhanced plasmonic energy transfer from localized surface plasmonic resonance of Au nanostars to QD semiconductor that activates the BNN6 species loaded on QD surfaces, leading to the effective NO production and the gas therapy in addition to the photothermal response. The increased accumulation of the NIR-II-responsive hybrid nanotheranostic in tumor via the enhanced permeation and retention effects was confirmed by both in vivo fluorescence and photoacoustic imaging. The prominent therapeutic efficacy of the photothermal/NO combination therapy from the BNN6-loaded AuS@QD nanodevice with the NIR-II laser irradiation at 1064nm against 4T1 breast cancer was observed both in vitro and in vivo. The NO therapy for the cancer treatment was evidenced with the increased cellular nitrosative and oxidative stress, nitration of tyrosine residues of mitochondrial proteins, vessel eradication and cell apoptosis. The efficacy of the photothermal treatment was corroborated directly by severe tissue thermal ablation and tumor growth inhibition. The NIR-II triggered thermal/NO combination therapy along with the photoacoustic imaging-guided therapeutic accumulation in tumor shows prominent effect to fully inhibit tumor growth and validates the promising strategy developed in this study.