Surface Plasmon Resonance Of Nanoparticles Research Articles

Copper nanoparticle and point defect formation in Cu+-Na+ ion-exchanged glass using protons of 2 MeV energy.

There are several applications for irradiating materials with protons that could provide alternative methodologies to synthesize and induce the formation of new compounds of different size scales. In this study, we explored the effects of proton irradiation oncommercial glass silicate that was previously subjected to a Cu+-Na+ ion exchange (IE) treatment at 600 °C for a duration of 60 min. The ion-exchanged glass samples were irradiated with protons (p+) of 2 MeV energy at doses in the range of thousands of grays (3.3 × 103, 7.9 × 103 Gy) and hundreds of thousands of grays (3.6 × 105 Gy). Significant changes in the optical and structural properties were observed post the radiation treatment. The UV-Visible absorption spectra of the irradiated samples revealed the appearance of overlapping absorption bands, which could be deconvoluted into three Gaussian-shaped bands peaking at 566, 620 and 680 nm. These three bands could be attributed to the surface plasmon resonance (SPR) of copper nanoparticles, non-bridging oxygen hole centers (NBOHCs) and self-trapped hole (STH) defects, respectively. Prominent photoluminescence (PL) was observed in the Cu-exchanged and irradiated samples, mainly induced by the presence of both Cu+ and Cu2O. Increasing the irradiation dose led to an increase in the PL intensity due to the conversion of Cu2+ ions into Cu+. This result was confirmed by electron paramagnetic resonance (EPR) spectroscopy that shows a decrease in the Cu2+ signal when increasing the dose of proton exposure. Transmission electron microscopy (TEM) and high-resolution TEM (TEM and HRTEM) observations confirmed the presence of copper nanoparticles (CuNPs) in the doped and p+ irradiated Cu-exchanged glass silicate samples. These CuNPs were found to be crystalline with an average size of 12.39 nm.

Utility of Localized Surface Plasmon Resonance of Gold Nanoparticles for Spectrophotometric Determination of Dobutamine in Pharmaceutical Formulations

Utility of Localized Surface Plasmon Resonance of Gold Nanoparticles for Spectrophotometric Determination of Dobutamine in Pharmaceutical Formulations

Miniature computational spectrometer with a plasmonic nanoparticles-in-cavity microfilter array

Optical spectrometers are essential tools for analysing light‒matter interactions, but conventional spectrometers can be complicated and bulky. Recently, efforts have been made to develop miniaturized spectrometers. However, it is challenging to overcome the trade-off between miniaturizing size and retaining performance. Here, we present a complementary metal oxide semiconductor image sensor-based miniature computational spectrometer using a plasmonic nanoparticles-in-cavity microfilter array. Size-controlled silver nanoparticles are directly printed into cavity-length-varying Fabry‒Pérot microcavities, which leverage strong coupling between the localized surface plasmon resonance of the silver nanoparticles and the Fabry‒Pérot microcavity to regulate the transmission spectra and realize large-scale arrayed spectrum-disparate microfilters. Supported by a machine learning-based training process, the miniature computational spectrometer uses artificial intelligence and was demonstrated to measure visible-light spectra at subnanometre resolution. The high scalability of the technological approaches shown here may facilitate the development of high-performance miniature optical spectrometers for extensive applications.

Coupling of Phthalocyanines with Plasmonic Gold Nanoparticles by Click Chemistry for an Enhanced Singlet Oxygen Based Photoelectrochemical Sensing

AbstractCoupling photosensitizers (PSs) with plasmonic nanoparticles increases the photocatalytic activity of PSs as the localized surface plasmon resonance (LSPR) of plasmonic nanoparticles leads to extreme concentration of light in their vicinity known as the near‐field enhancement effect. To realize this in a colloidal phase, efficient conjugation of the PS molecules with the plasmonic nanoparticle surface is critical. In this work, we demonstrate the coupling of phthalocyanine (Pc) molecules with gold nanoparticles (AuNPs) in the colloidal phase via click chemistry. This conjugated Pc‐AuNPs colloidal system is shown to enhance the photocatalytic singlet oxygen (1O2) production over non‐conjugated Pcs and hence improve the photoelectrochemical detection of phenols. The plasmonic enhancement of the 1O2 generation by Pcs was clearly elucidated by complementary experimental and computational classical electromagnetic models. The dependence of plasmonic enhancement on the spectral position of the excitation laser wavelength and the absorbance of the Pc molecules with respect to the wavelength specific near‐field enhancement is clearly demonstrated. A high ∼ 8 times enhancement is obtained with green laser (532 nm) at the LSPR due to the maximum near‐field enhancement at the resonance wavelength.

Photocatalytic performance of Au/Bi4Ti3O12 composite improved by synergistic piezoelectric effect and exciton-plasmon

Bi4Ti3O12 (BiTO) is a typical bismuth-layered Aurivillius ferroelectric material for its potential application in photocatalysis. In this study, Au/BiTO hybrid was fabricated by precipitating Au nanoparticles onto BiTO nanoflake using a sodium citrate reduction route. This integration has led to a remarkable enhancement in the photocatalytic efficiency, which is attributed to the synergistic coupling of piezoelectric effect of BiTO with the localized surface plasmon resonance (LSPR) of Au nanoparticles. The incorporation of Au nanoparticles onto the BiTO matrix has significantly boosted the light absorption and charge carrier separation, thereby augmenting the photocatalytic activity. Notably, Au/BiTO-2 composite exhibits exceptional photocatalytic performance, demonstrating the complete degradation of RhB within 40 min under full-spectrum light irradiation. Moreover, Au/BiTO-2 displays a robust photocatalytic action against other organic pollutants, including methyl orange (MO), ofloxacin (OFLX) and tetracycline hydrochloride (TC). Further enhancement of photocatalytic process is achieved when combing light irradiation with ultrasonic excitation. The ultrasonic waves break the static spontaneous polarization through alternating piezoelectric potential, which accelerates the catalytic reaction. The photocatalytic action rate of Au/BiTO-2 toward RhB reaches a value as high as 0.0984 min−1, which is nearly 2.3 folds increasement compared to that of pristine BiTO. The possible synergistic mechanism caused by piezoelectric effect and exciton-plasmon effect is discussed in detail. The work not only enriches our understanding of the underlying principles but also supply a new strategy to design high-performance catalysts in the field of environmental remediation and energy conversion.

Photocatalytic H2O2 production and fuel cell performance based on PDI nanobelts enhanced by surface plasmon resonance of gold nanoparticles

The photocatalytic hydrogen peroxide (H2O2) fuel cell represents an innovative self-powered apparatus amalgamating the production and conversion of H2O2 to supply electricity. Using efficient photocatalyst as photoanode to realize two-electron water oxidation to produce H2O2 is considered as a key factor to improve the performance of fuel cell. In this study, perylene imide nanobelts decorated with gold nanoparticles (Au/PDI) were synthesized and subsequently employed as the photoanode to construct a photocatalytic H2O2 fuel cell. This cell can produce H2O2 under irradiation and store it, subsequently utilizing the stored H2O2 to generate electricity in the absence of light. The maximum power density of Au/PDI-based cell could reach 1.07 mW·cm−2 under AM 1.5G solar light, which has around 1.7 times enhancement compared to PDI-based cell. Meanwhile, a specific capacitance of 5661 mF·cm−2 was obtained after 3 h irradiation. After operating the cell for 12 h, the specific capacitance remained at 50.2% of its initial value. It is indicated that PDI-based photocatalysts hold considerable promise in water oxidation for H2O2 production. The incorporation of noble nanometals has shown effective enhancement in photocatalytic H2O2 production through the localized surface plasmon resonance (LSPR) effects, thereby enriching the photoanode materials designed for H2O2 fuel cell application.

Complementary absorption effect to improve the optical efficiency of dual-absorption-layered PSCs

By taking advantage of the complementary absorption effect of germanium (Ge) and perovskite, a novel perovskite solar cell (PSC) was proposed by stacking Ge and perovskite thin films to serve as the dual absorption layer. Its absorption spectra and photocurrent were calculated and optimized as a function of the thickness of Ge film by finite element method (FEM). Then, the optical efficiency was further boosted by embedding an array of Ge semi-ellipsoidal nanoparticles within the perovskite film. The predicted maximum photocurrent is revealed to reach 45.72 mA/cm2, which is 2.55 times larger than that of planar referenced PSC. Besides the complementary absorption effect, the localized surface plasmon resonance (LSPR) of Ge nanoparticles and the grating effects of Ge nanoparticle array are revealed to contribute to the obtained Jsc improvement. The present work is insightful for future design and applications of PSCs by introducing Ge thin film and Ge nanoparticles.

Investigation of Melphalan interaction as an alkylating agent with nucleotides by using surface enhanced Raman spectroscopy (SERS)

SERS (Surface Enhanced Raman Spectroscopy) is a new Raman spectroscopy which relies on Surface Plasmon Resonance (SPR) of metal nanoparticles. We have applied colloidal silver and gold nanoparticles as amplifier agents to enhance nucleotide Raman signals. It is observed that without these enhancing agents, it is impossible to investigate nucleotide spectrum due to weak Raman signals. Interaction mechanism of Melphalan, an anticancer drug with four nucleotides (Adenine, Cytosine, Guanine, Thymine) was investigated using SERS to detect and identify changes due to alkylating process in Raman spectra. After incubating Melphalan drug with nucleotides for 24 h at 37 °C, some changes occurred in SERS spectrum and interpretation of SERS spectra revealed the influence of the alkyl substitution on peaks and Raman shifts. After incubation of Melphalan with each nucleotide, intensity of relevant SERS signals assigned to Amid III group of Cytosine and Amid I of Thymine decreased significantly, confirming alkylating taking place. In this study, we also investigated the effect of nanoparticles type on nucleotide spectrum. We could not obtain useful information in the cases of guanine nucleotide. The SERS spectrum of Cytosine as an example of nucleotides in aqueous solution compared to solid state and results demonstrated that in solid state better signals were obtained than in liquid state.

Comparing silver and gold nanoislands’ surface plasmon resonance for bisacodyl and its metabolite quantification in human plasma

Gold and silver nanoparticles have witnessed increased scientific interest due to their colourful colloidal solutions and exceptional applications. Comparing the localized surface plasmon resonance (LSPR) of gold and silver nanoparticles is crucial for understanding and optimizing their optical properties. This comparison informs the design of highly sensitive plasmonic sensors, aids in selecting the most suitable nanoparticles for applications like surface-enhanced infrared spectroscopy (SEIRA) and biomedical imaging, and guides the choice between gold and silver nanoparticles based on their catalytic and photothermal properties. Ultimately, the study of LSPR facilitates the tailored use of these nanoparticles in diverse scientific and technological applications. Two SEIRA methods combined with partial least squares regression (PLSR) chemometric tools were developed. This development is based on the synthesis of homogeneous, high-dense deposited metal nanoparticle islands over the surface of glass substrates to be used as lab-on-chip SEIRA sensors for the determination of bisacodyl (BIS) and its active metabolite in plasma. SEM micrographs revealed the formation of metallic islands of colloidal citrate-capped gold and silver nanoparticles of average sizes of 29.7 and 15 nm, respectively. BIS and its active metabolite were placed on the nanoparticles’ coated substrates to be directly measured, then PLSR chemometric modelling was used for the quantitative determinations. Plasmonic citrate-capped gold nanoparticle substrates showed better performance than those prepared using citrate-capped silver nanoparticles in terms of preparation time, enhancement factor, PLSR model prediction, and quantitative results. This study offers a way to determine BIS and its active metabolite in the concentration range 15–240 ng/mL in human plasma using inexpensive disposable glass-coated substrates that can be prepared in 1 h to get results in seconds with good recovery between 98.77 and 100.64%. The sensors provided fast, simple, selective, molecular-specific and inexpensive procedures to determine molecules in their pure form and biological fluid.

Construction of ternary AuPt/Bi2WO6/ZnIn2S4 heterostructures for photocatalytic degradation of tetrabromobisphenol A

How to fascinate the separation of the photogenerated electrons and holes is very crucial to enhance the photocatalysis of semiconductors. Herein we have prepared AuPt/BWO/ZIS heterostructured photocatalysts by decorating Bi2WO6 (BWO) nanoflakes and AuPt nanoparticles on the surface of ZnIn2S4 (ZIS) hierarchical microspheres. The photocatalysis of the samples was evaluated by degrading tetrabromobisphenol A under simulated-sunlight illumination. It is demonstrated that the ternary AuPt/BWO/ZIS photocatalysts exhibit obviously enhanced photocatalysis in comparison with bare BWO and ZIS as well as the binary BWO/ZIS photocatalysts. The highest photocatalysis is observed for 3%AuPt/40%BWO/ZIS, whose photodegradation performance is improved by 3.9 and 6.2 times over that of single BWO and ZIS, respectively. This phenomenon can be explained due to several reasons: the photocarriers are efficiently separated due to the charge transfer across the BWO/ZIS and AuPt/ZIS interfaces, surface plasmon resonance of AuPt nanoparticles stimulate ZIS to produce additional electron/hole pairs, and the SPR-induced electrons in the AuPt nanoparticles could also take part in the photocatalysis. Additionally, the effect of various factors on the tetrabromobisphenol A degradation was investigated; the degradation pathways of tetrabromobisphenol A and the potential toxicity of the degradation by-products were evaluated.

Development of excitation power-responsive anti-stokes emission wavelength switching and their energy saving induced by localized surface plasmon resonance

We designed an external stimulus-responsive anti-Stokes emission switching using dual-annihilator-based triplet–triplet annihilation upconversion systems. This system, which was constructed by incorporating a palladium porphyrin derivative as a sensitizer and 9,10-diphenylanthracene (DPA) and 9,10-bis(triisopropylsilyl)ethynylanthracene (TIPS) as annihilators into polymer thin films, produced TIPS- and DPA-based anti-Stokes emission under low and high excitation powers, respectively. The mechanism involves the following: under low excitation power, triplet energy transfer from triplet-excited PdOEP to DPA is induced, followed by relay to TIPS. This results in the generation of triplet-excited TIPS, and the subsequent triplet–triplet annihilation between them produces TIPS-based anti-Stokes emission. Conversely, under high excitation power, the high-density triplet-excited DPA, generated through triplet energy transfer from PdOEP, undergoes triplet–triplet annihilation among themselves, resulting in the generation of DPA-based anti-Stokes emission. Additionally, we achieved energy savings by reducing the required excitation power for switching through the utilization of plasmonic metal nanoparticles. The strong local electromagnetic fields associated with the localized surface plasmon resonance of metal nanoparticles enhance the photoexcitation efficiency of PdOEP, subsequently increasing the density of triplet-excited DPA. As a result, anti-Stokes emission switching becomes feasible at lower excitation powers.

Localize surface plasmon resonance of gold nanoparticles and their effect on the polyethylene oxide nanocomposite films

Colloidal Gold nanoparticles (AuNPs) with sodium citrate coating were successfully synthesized using a chemical reduction method with an average spherical size of about 20 nm dispersed in the water with high stability. The localized surface plasmon resonance (LSPR) peak was studied by experimental measurement and Mie theory. The absorbance spectrum of AuNPs exhibits a fingerprint peak in the 500–600 nm range, corresponding to the LSPR of AuNPs. Moreover, PEO/AuNPs nanocomposite films with different concentrations of AuNPs were also prepared to evaluate the effect of LSPR of AuNPs on the electrical conductivity and photoconductivity of nanocomposite films. The degree of crystallinity (Xcrys) and melting enthalpy (ΔHm) increase as the AuNPs content in the polymer matrix increases up to 0.5 wt% due to the enhanced nucleation points. The electrical conductivity of pure PEO film is 1.93×10−6 S.cm−1. Increasing the AuNPs concentration to 0.5 wt% in the PEO matrix leads to an increase in the electrical conductivity to 2.28×10−3 S.cm−1 as AuNPs.

Plasmons Enhancing Sub-Bandgap Photoconductivity in TiO2 Nanoparticles Film.

The coupling between sub-bandgap defect states and surface plasmon resonances in Au nanoparticles and its effects on the photoconductivity performance of TiO2 are investigated in both the ultraviolet (UV) and visible spectrum. Incorporating a 2 nm gold nanoparticle layer in the photodetector device architecture creates additional trapping pathways, resulting in a faster current decay under UV illumination and a significant enhancement in the visible photocurrent of TiO2, with an 8-fold enhancement of the defects-related photocurrent. We show that hot electron injection (HEI) and plasmonic resonance energy transfer (PRET) jointly contribute to the observed photoconductivity enhancement. In addition to shedding light on the below-band-edge photoconductivity of TiO2, our work provides insight into new methods to probe and examine the surface defects of metal oxide semiconductors using plasmonic resonances.

Formation of hollow silver nanoparticles under irradiation with ultrashort laser pulses

Abstract We have studied the formation of cavities in spherical silver nanoparticles embedded in silica, irradiated with fs laser pulses that produce an intense electronic excitation. Experimentally determined aspect ratio, i.e. the ratio between the cavity and nanoparticle size, for hollow structures formed under different irradiation conditions shows a very good agreement with values obtained by means of atomistic simulations. According to the predictions of the atomistic model, one can produce at will hollow silver nanoparticles with cavities of tailored dimensions, having an accurate control. Hence, laser irradiation can be used to control and design the optical response by tuning the localized surface plasmon resonances of the hollow nanoparticles.

Watermelon (Citrullus lanatus) Rind Extract-Mediated Synthesis of Manganese (II, III) Oxide Nanoparticles for Potential Theranostic Applications

Plant extracts and microorganisms are widely utilized for the green synthesis of Mn3O4 nanoparticles. In this study, green synthesis of Mn3O4 nanoparticles for theranostic applications was performed using watermelon (Citrullus lanatus) rind extract as a reducing and stabilizing agent. The UV-visible absorption of the nanoparticles at 196 nm is associated with the surface plasmon resonance of Mn3O4 nanoparticles. FT-IR spectra presented the key chemical functional groups associated with the Mn–O vibrations and phytoconstituents of the watermelon rind extract. XRD analysis revealed the single-phase hausmannite crystalline structure of the Mn3O4 nanoparticles with an average crystallite size of 35.2 nm. SEM and TEM images of the synthesized Mn3O4 nanoparticles showed quasi-spherical shapes and a core size of 52.90 ± 8.19 nm and 35.89 ± 0.83 nm, respectively. EDS analysis indicated that the nanoparticles mainly comprised Mn, O, and C. Furthermore, the radical scavenging activity through the DPPH assay showed that the nanoparticles have significant antioxidant therapeutic potential, with an IC50 value of 20.62 ± 0.69 ppm. T1 and T2 relaxivities of Mn3O4 nanoparticles were 5.34 ± 0.11 mM–1s–1 and 63.47 ± 0.60 mM–1s–1, respectively, when measured at a clinically relevant field strength of 1.5 T, confirming their suitability as an MRI contrast agent for diagnostic imaging. These findings imply that the green synthesized Mn3O4 nanoparticles could be used as a theranostic agent for MRI applications.

Unconventional Breathing Currents Far beyond the Quantum Tunneling Distances in Large-Gapped Nanoplasmonic Systems.

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles propels the field of plasmo-electronics, holding promise for transformative optoelectronic devices through efficient light-to-current conversion. Plasmonic excitations strongly influence the charge distribution within nanoparticles, giving rise to electromagnetic fields that can significantly impact the macroscopic charge flows within the nanoparticle housing material. In this study, we present evidence of ultralow, unconventional breathing currents resulting from dynamic irradiance interactions between widely separated nanoparticles, extending far beyond conventional electron (quantum) tunneling distances. We develop an electric analogue model and derive an empirical expression to elucidate the generation of these unconventional breathing currents in cascaded nanoplasmonic systems under irradiance modulation. This technique and theoretical model have significant potential for applications requiring a deeper understanding of current dynamics, particularly on large nanostructured surfaces relevant to photocatalysis, energy harvesting, sensing, imaging, and the development of future photonic devices.

Realization of ultrastrong coupling between LSPR and Fabry–Pérot mode via self-assembly of Au-NPs on p-NiO/Au film

Abstract The realization of higher coupling strengths between coupled resonant modes enables exploration of compelling phenomena in diverse fields of physics and chemistry. In this study, we focus on the modal coupling between localized surface plasmon resonance (LSPR) of Au nanoparticles (Au-NPs) and Fabry–Pérot mode (p-NiO/Au film). The effects of nanoparticle size, projected surface coverage (PSC), interparticle distance (IPD), and arrangement to the coupling strength between the two modes are theoretically investigated using finite-difference time-domain (FDTD) method. Au-NPs/p-NiO/Au film (ANA) nanostructures with NPs size of 10 nm, 30 nm, and 50 nm are considered. Numerical calculations point to larger size and higher projected surface coverage (also smaller IPD) of NPs as pre-eminent factors in enhancing the strength of modal coupling. ANA nanostructure with NPs size of 30 nm (ANA-30) and 50 nm (ANA-50) are experimentally fabricated via a facile air–liquid interface self-assembly. The fabricated nanodevices exhibit immense Rabi splitting energies of 655 meV (ANA-30) and 770 meV (ANA-50), and thus fulfill the ultrastrong coupling condition with remarkable splitting energy to bare (plasmon) energy ratio of 0.35 (ANA-30) and 0.4 (ANA-50). The physical insights presented in this study, together with the simple and scalable fabrication process, establish a viable approach to realize stronger coupling between LSPR and Fabry–Pérot mode in metal NPs/dielectric/metal film systems. This will be vital to take advantage of the promising performance enhancements of plasmonic-based nanostructures under strongly coupled regimes in areas such as solar to fuel conversion, sensing, opto-electronics, and quantum applications.

High‐Performance UV Photodetector via Energy Band Engineering and LSPR‐Enhanced Pyro‐Phototronic Effect in Au Decorated 2D‐PbI2/1D‐ZnO Heterojunction

AbstractUltraviolet (UV) photodetectors have attracted extensive attention in various applications, including aerospace, optical communication, and fire warning. However, the intrinsic coupling of high responsivity and fast response as well as imperfect interface transmission impede the further improvement of UV photodetector. Here, a high‐performance Au‐decorated PbI2/ZnO pn junction UV photodetector with a one‐dimensional (1D) and two‐dimensional (2D) interspersed structure is presented. The pyro‐phototronic effect and energy band engineering effect from the localized pn junction generated by the layered p‐type PbI2 nanosheets along the c‐axis of ZnO are coupled to modulate the separation and transport of photogenerated carriers. Furthermore, the localized surface plasmon resonance of Au nanoparticles produces transient thermal power to raise temperature fast to enhance pyroelectric current. The self‐powered Au@PbI2/ZnO photodetector displays a high responsivity of 0.21 A W−1, excellent detectivity of 7.9 × 1012 Jones, and fast response/recovery time of 25/31 ms, under the illumination of 325 nm light with the power density of 0.08 µW cm−2. This work offers an effective strategy for designing high‐performance next‐generation optoelectronic devices.

ZnO Matrices as a Platform for Tunable Localized Surface Plasmon Resonances of Silver Nanoparticles

In this study, the localized surface plasmon resonances (LSPRs) of Ag nanoparticles (NPs) embedded in ZnO dielectric matrices were studied. Initially, continuous Ag thin films were deposited on Corning glass substrates via magnetron sputtering, followed by post annealing, resulting in the formation of self-assembled nanoparticles. In some cases, a heated substrate holder was employed to induce NP formation during the deposition. The morphology of nanoparticles was studied using atomic force microscopy (AFM). Ultraviolet–visible spectroscopy (UV-Vis) probed the LSPRs. Subsequently, a 70 nm thick ZnO layer was deposited on top of the Ag thin films. For the Ag films, LSPR characteristics were found to depend on the initial film thickness. The ZnO capping layer induced an intense red shift, suggesting its potential as a mechanism for tailoring LSPRs. Lastly, theoretical calculations with the rigorous coupled-wave analysis (RCWA) method were carried out for comparison with the experimental results.

Highly stable localized surface plasmon resonance of Cu nanoparticles obtained via oxygen plasma irradiation.

Copper nanoparticles (CuNPs) possess strong localized surface plasmon resonance (LSPR) in visible light. However, CuNPs are not chemically stable in air, which has seriously hindered the applications based on the LSPR of CuNPs. We developed an artificial method to passivate CuNPs as Al naturally does in air, preventing the oxidation of CuNPs through swift oxidation of the surface atoms via oxygen plasma irradiation. A hemispheric core-shell structure of CuNPs uniformly covered by a dense CuO shell (CuNPs@d-CuO) was constructed. The 4 nm d-CuO shell can prevent CuNPs from further oxidation. As a result, the LSPR of the CuNPs is stable in air over 180 days.