Plasmonic Metal Nanoparticles Research Articles

Plasmonic metal/doped-semiconductor nanocomposites for high-efficiency solar-driven clean water production

Despite their strong light absorption capacity, the narrow absorption bandwidth of plasmonic metal materials has impeded their application in solar-driven freshwater production. To address this limitation, we grew copper sulfide (Cu7S4) shell on gold nanorod (Au NR) core to construct a plasmonic nanocomposite Au NR@Cu7S4, which exhibited broad and intense absorption of solar radiation due to the integration of their individually visible (Au NR) and near-infrared (Cu7S4) plasmons, with this absorption being further broadened and enhanced by the coupling of these two plasmons. This strategy is conceptually distinct from aggregating plasmonic metal nanoparticles, which is subject to a trade-off between the breadth and intensity of their absorption. The Au NR@Cu7S4-impregnated hydrogel delivered an evaporation rate of 2.35 kg m−2 h−1 under 1 sun illumination despite having a Au areal density of only 28 μg cm−2. Moreover, it showed excellent volatile organic compound removal performance.

Computational investigation of the effect ZnS buffer layer on the hole transport of polymer solar cell

Semiconductor organic solar absorber exhibits poor charge transport process because of exciton short diffusion length, short life time, and poor carrier mobilities in the medium. Such transport properties have negatively impacted the performance of organic solar cells (OSC). This article is designed to investigate the effect of solar absorber thickness and metal plasmonic nanoparticles using the most popular polymer blend (P3HT:PCBM) via SCAPS device simulation program. Bulk hetero-junction (BHJ) design of OSC has partially addressed the challenges by increasing inter-facial area of the acceptor/donor (A/D) molecules, which boosts the generation of free charges. However, the collection of these charges hindered due to low carrier mobilities in polymer medium. Significant influence of the Zinc Sulfide (ZnS) metal nanoparticles (NPs) have been observed on the performance of OSC at various concentrations. Thus, we are reporting here the effect of absorber layer thickness and ZnS NPs on the charge transport process in OSC.

Inkjet Patterning of Plasmonic Metal Nanoparticles in Silicone Elastomers

AbstractThe incorporation of the plasmonic metal nanoparticles (NPs) in microfluidic systems is highly desirable since their unique characteristic such as localized plasmonic resonance can be largely beneficial to many biomedical applications; however, the typical incorporation process requires a long immersion time and totally lacks patterning capability. This work develops a method for embedding patterned plasmonic AuNPs and AgNPs in silicone elastomer by inkjet printing metal ion solution into uncured silicone elastomer. This work finds that both energetics and kinetics of the solvent's mixing behaviors are critical to successful patterning, both experimentally and theoretically. Based on these results, patterned metal NPs are literally “embedded” in silicon elastomers efficiently, not formed just on surfaces. This work demonstrates the patterning capability by reproducing pixel arts with metal NPs in silicone elastomer. In addition, an AuNPs‐based photothermal microfluidic pump that responds to light at a specific wavelength is fabricated, demonstrating the potential utility of the inkjet patterned metal NPs in silicone elastomer.

Boosting the Photocatalysis of Plasmonic Au-Cu Nanocatalyst by AuCu-TiO2 Interface Derived from O2 Plasma Treatment.

Plasmonic gold (Au) and Au-based nanocatalysts have received significant attention over the past few decades due to their unique visible light (VL) photocatalytic features for a wide variety of chemical reactions in the fields of environmental protection. However, improving their VL photocatalytic activity via a rational design is prevalently regarded as a grand challenge. Herein we boosted the VL photocatalysis of the TiO2-supported Au-Cu nanocatalyst by applying O2 plasma to treat this bimetallic plasmonic nanocatalyst. We found that O2 plasma treatment led to a strong interaction between the Au and Cu species compared with conventional calcination treatment. This interaction controlled the size of plasmonic metallic nanoparticles and also contributed to the construction of AuCu-TiO2 interfacial sites by forming AuCu alloy nanoparticles, which, thus, enabled the plasmonic Au-Cu nanocatalyst to reduce the Schottky barrier height and create numbers of highly active interfacial sites. The catalyst's characterizations and density functional theory (DFT) calculations demonstrated that boosted VL photocatalytic activity over O2 plasma treated Au-Cu/TiO2 nanocatalyst arose from the favorable transfer of hot electrons and a low barrier for the reaction between CO and O with the construction of large numbers of AuCu-TiO2 interfacial sites. This work provides an efficient approach for the rational design and development of highly active plasmonic Au and Au-based nanocatalysts and deepens our understanding of their role in VL photocatalytic reactions.

Recent Progresses in Plasmonic Biosensors for Point-of-Care (POC) Devices: A Critical Review

The recent progresses in the research of plasmonic phenomena and materials paved the route toward the development of optical sensing platforms based on metal nanostructures with a great potential to be integrated into point-of-care (POC) devices for the next generation of sensing platforms, thus enabling real-time, highly sensitive and accurate diagnostics. In this review, firstly, the optical properties of plasmonic metal nanoparticles will be illustrated, whereafter the engineering of POC platforms, such as microfluidics and readout systems, will be considered with another critical point which is surface functionalization. Attention will also be given to their potential in multiplexed analysis. Finally, the limitations for effective implementation in real diagnostics will be illustrated with a special emphasis on the latest trend in developing cutting-edge sensing systems.

Laser-Induced Chirality of Plasmonic Nanoparticles Embedded in Porous Matrix.

Chiral plasmonic nanostructures have emerged as promising objects for numerous applications in nanophotonics, optoelectronics, biosensing, chemistry, and pharmacy. Here, we propose a novel method to induce strong chirality in achiral ensembles of gold nanoparticles via irradiation with circularly-polarized light of a picosecond Nd:YAG laser. Embedding of gold nanoparticles into a nanoporous silicate matrix leads to the formation of a racemic mixture of metal nanoparticles of different chirality that is enhanced by highly asymmetric dielectric environment of the nanoporous matrix. Then, illumination with intense circularly-polarized light selectively modifies the particles with the chirality defined by the handedness of the laser light, while their "enantiomers" survive the laser action almost unaffected. This novel modification of the spectral hole burning technique leads to the formation of an ensemble of plasmonic metal nanoparticles that demonstrates circular dichroism up to 100 mdeg. An unforeseen peculiarity of the chiral nanostructures obtained in this way is that 2D and 3D nanostructures contribute almost equally to the observed circular dichroism signals. Thus, the circular dichroism is neither even nor odd under reversal of direction of light propagation. These findings will help guide the development of a passive optical modulator and nanoplatform for enhanced chiral sensing and catalysis.

Two-dimensional Pd-Cellulose with optimized morphology for the effective solar to steam generation

Nanosized plasmonic metallic nanoparticles such as Pd have gained significant attention due to their diverse applications in catalysis, sensing, and light-to-heat conversion. However, the development of scalable and environmentally friendly synthesis routes for such nanoparticles is crucial for the sustainable development of industrial applications. In this work, we address this challenge by synthesizing Pd-nanoparticles on the cellulose filter paper (Pd-Cellulose) via two scalable green synthesis routes: low-temperature thermal and plasma synthesis. We found that adjusting synthesis conditions allowed us to achieve an optimum morphology that maximizes light absorptance. The nature of the reduction species during synthesis significantly impacts the morphology and heat-transfer properties of the resulting material. Compared to thermally synthesized Pd-Cellulose, the absorbers synthesized with plasma have smaller particles size and higher coverage, which leads to higher broadband light absorptance and more intense heat transfer to the surroundings. The optimized Pd-based light absorbers were utilized in a solar-to-steam desalination system, resulting in an evaporation rate of 1.30 kg/m2h for the open system and a filtration rate of 0.7 kg/m2h for the closed system. Our findings provide insights into the green and scalable synthesis and optimization of Pd-based light absorbers and their potential application in sustainable renewable energy systems.

Surface plasmon-enhanced photo-driven CO2 hydrogenation by hydroxy-terminated nickel nitride nanosheets

The majority of visible light-active plasmonic catalysts are often limited to Au, Ag, Cu, Al, etc., which have considerations in terms of costs, accessibility, and instability. Here, we show hydroxy-terminated nickel nitride (Ni3N) nanosheets as an alternative to these metals. The Ni3N nanosheets catalyze CO2 hydrogenation with a high CO production rate (1212 mmol g−1 h−1) and selectivity (99%) using visible light. Reaction rate shows super-linear power law dependence on the light intensity, while quantum efficiencies increase with an increase in light intensity and reaction temperature. The transient absorption experiments reveal that the hydroxyl groups increase the number of hot electrons available for photocatalysis. The in situ diffuse reflectance infrared Fourier transform spectroscopy shows that the CO2 hydrogenation proceeds via the direct dissociation pathway. The excellent photocatalytic performance of these Ni3N nanosheets (without co-catalysts or sacrificial agents) is suggestive of the use of metal nitrides instead of conventional plasmonic metal nanoparticles.

Hydrothermally synthesized Ag decorated β-Ga2O3 heterostructures as low cost, reusable SERS substrates for the nanomolar detection of rhodamine 6G

Metal oxide semiconductors and plasmonic metal nanoparticles have received extensive research interest due to their superior optical properties resulting from the combination of semiconductor and plasmonic properties. Herein, we demonstrate the synthesis of Ag decorated β-Ga2O3 heterostructures utilizing a cost effective and eco-friendly hydrothermal method. The decoration of Ag endows plasmonic features to the hybrid material resulting in broad absorption in the visible light region of the electromagnetic spectrum, which is not possible for bare β-Ga2O3 due to its wide bandgap. The peculiar nature of the hybrid material was then utilized to fabricate an efficient substrate for surface enhanced Raman scattering (SERS) applications. The recyclability and prolonged stability of the substrate indicate its potential application toward the fabrication of versatile and low-cost SERS substrates.

On Damping of Plasmons and Plasmon-Polaritons in Metallic Nanostructures and Its Influence onto Numerical Simulations

AbstractWe show that the damping of plasmons in metallic nanoparticles highly exceeds that caused by scattering of electrons on defects, phonons, and other electrons and on boundaries of particles. The radiation losses in far-field zone due to the Lorentz friction is especially high at nanometre scale of metal confinement (e.g. attains the maximum at ca. 100 nm diameter of particle, Au in vacuum). This causes a different e-m response of such size structures in comparison to conventional solution of Maxwell-Fresnel equations using the bulk dielectric function for metal. The strong discrepancy occurs also if plasmons are coupled in near-field zone to nearby-located absorbing medium, e.g. semiconductor substrate. This coupling cannot be accounted for by classical electrodynamic treatment (e.g. by numerical solution of Maxwell equations by finite element method for differential equation solution) and needs the application of quantum Fermi golden rule to estimate plasmon damping and related modifications of dielectric functions both of metallic nanoparticles and of absorbing medium. Similarly, the perfect cancellation of radiative losses of plasmon-polaritons in metallic nano-chains is beyond classical Maxwell equation modelling, as it reveals the perfect vanishing of Lorentz friction losses in chain segments by radiative contribution from other segments in near-, medium- and far-field zones. This demonstrates that nano-plasmonic effects cannot be reliably numerically modelled using material parameters from conventional packets referred to optical constants measured in bulk.

Synthesis Methods and Optical Sensing Applications of Plasmonic Metal Nanoparticles Made from Rhodium, Platinum, Gold, or Silver.

The purpose of this paper is to provide an in-depth review of plasmonic metal nanoparticles made from rhodium, platinum, gold, or silver. We describe fundamental concepts, synthesis methods, and optical sensing applications of these nanoparticles. Plasmonic metal nanoparticles have received a lot of interest due to various applications, such as optical sensors, single-molecule detection, single-cell detection, pathogen detection, environmental contaminant monitoring, cancer diagnostics, biomedicine, and food and health safety monitoring. They provide a promising platform for highly sensitive detection of various analytes. Due to strongly localized optical fields in the hot-spot region near metal nanoparticles, they have the potential for plasmon-enhanced optical sensing applications, including metal-enhanced fluorescence (MEF), surface-enhanced Raman scattering (SERS), and biomedical imaging. We explain the plasmonic enhancement through electromagnetic theory and confirm it with finite-difference time-domain numerical simulations. Moreover, we examine how the localized surface plasmon resonance effects of gold and silver nanoparticles have been utilized for the detection and biosensing of various analytes. Specifically, we discuss the syntheses and applications of rhodium and platinum nanoparticles for the UV plasmonics such as UV-MEF and UV-SERS. Finally, we provide an overview of chemical, physical, and green methods for synthesizing these nanoparticles. We hope that this paper will promote further interest in the optical sensing applications of plasmonic metal nanoparticles in the UV and visible ranges.

Effects of "defective" plasmonic metal nanoparticle arrays on the opto-electronic performance of thin-film solar cells: computational study.

This computational study investigates the effects of common defects that occur while fabricating arrays of plasmonic metal nanoparticles (NPs) on the absorbing layer of the solar cells for enhancing their opto-electronic performance. Several "defects" in an array of plasmonic NP arrays on solar cells were studied. The results demonstrated no major changes in the performance of solar cells in the presence of "defective" arrays when compared to a "perfect" array with defect-free NPs. The results indicate that relatively inexpensive techniques may be used to fabricate "defective" plasmonic NP arrays on solar cells and still obtain a significant enhancement in opto-electronic performance.

Nonreleasing AgNP Colloids Composite Hydrogel with Potent Hemostatic, Photodynamic Bactericidal and Wound Healing-Promoting Properties.

Reactive oxygen species (ROS) produced by noble metallic nanoparticles under visible light is an effective way to combat drug-resistant bacteria colonized on the wound. However, the photocatalytic efficiency of noble metallic nanoparticles is limited by its self-aggregation in water media. Moreover, the fast release of noble metallic ions from nanoparticles might engender cellular toxicity and hazardous environmental issues. Herein, we chose AgNPs, the most common plasmonic noble metallic nanoparticles, as an example, modifying the surface of AgNPs with oleic acid and n-butylamine and imbedded them into calcium alginate (CA) hydrogel that holds tissue adhesion, rapid hemostatic, sunlight-sensitive antibacterial and anti-inflammatory abilities, and thus effectively promotes the healing of wounds. Unlike conventional AgNP-based materials, the constrain of colloids and hydrogel networks hinders the leach of Ag+. Nonetheless, the CA/Ag hydrogels exhibit on-demand photodynamic antibacterial efficacy due to the generation of ROS under visible light. In addition, the CA/Ag hydrogel can effectively stop the hemorrhage in a mouse liver bleeding model due to their skin-adaptive flexibility and tissue adhesiveness. The potent sunlight-responsive antibacterial activity of the CA/Ag hydrogel can effectively kill multidrug-resistant bacteria both in vitro (>99.999%) and in vivo (>99.9%), while the diminished Ag+ release guarantees its biocompatibility. The CA/Ag hydrogel significantly promotes the wound healing process by the downregulation of proinflammatory cytokines (TNF-α and IL-6) in a rodent full-thickness cutaneous wound model. Overall, the proposed multifunctional CA/Ag nanocomposite hydrogel has excellent prospects as an advanced wound dressing.

Basics of the LSPR Sensors for Soft Matter at Interfaces

An important class of localized surface plasmon resonance (LSPR)–based sensors implies the fabrication of an array of plasmonic metal nanoparticles on the support in combination with a thin protective dielectric layer. If needed, this layer can be covered, e.g., by a suitable thin biological layer, e.g., a lipid bilayer with receptors. The attachment of analyte (e.g., protein molecules or vesicles) to such interfaces is tracked via its indirect optical effect on the LSPR-related peak extinction wavelength. Such sensors have been commercialized and are now used to study biological soft matter. The length scale of the local field able in probing analyte around plasmonic nanoparticles is in this case on the order of 20 nm. Conceptually, these LSPR sensors are similar to the SPR sensors which were developed much earlier. Herein, the similarities and differences in the formalisms used to interpret SPR and LSPR measurements are discussed in detail. In particular, the exponential and power-law attenuation functions employed in these formalisms to describe the drop of the field are compared from various perspectives. The applicability of the power-law attenuation function in the context of LSPR is illustrated by using a generic model describing spherically shaped plasmonic metal nanoparticles. This model is also employed to illustrate the sensitivity of LSPR sensors with respect to various quantities. Among more specific results, the available expressions for the signal reduction factor for analyte nanoparticles of various shapes are collected and complemented by new ones. In addition, the equation describing the LSPR signal related to analyte attachment to a rough surface is presented.

A Facile and Rational Method to Tailor the Symmetry of Au@Ag Nanoparticles.

Precisely controlling the morphologies of plasmonic metal nanoparticles (NPs) is of great importance for many applications. Here, a facile seed-mediated growth method is demonstrated that tailors the morphologies of Au@Ag NPs from cubes/cuboids to chiral truncated cuboids/octahedra, well-defined octahedra, and tetrahedra, via simply increasing the concentrations of AgNO3 and cysteine in the halide surfactant systems. Accordingly, the particle symmetries are also tuned. The method is quite robust where seeds with distinct shapes including irregular ones can all lead to uniform Au@Ag NPs. The evolution of these shapes can be illustrated by a recently proposed symmetry-based kinematic theory (SBKT). Furthermore, SBKT shows a strategy to optimize the preparation of chiral/dissymmetric NPs, and the experimental results confirm such a dissymmetric synthesis strategy. Cuboids and octahedra with corners differently truncated are identified as two different chiral forms. The chirality of the NPs is additionally probed by electrochemistry, where the chiral NPs show enantioselectivity in the oxidation of d- and l-glucose. Altogether, the results gain fundamental insights into tailoring the plasmonic NP morphologies, and also suggest strategies to obtain chiral NPs.

In-situ formation of electron-deficient Pd sites on AuPd alloy nanoparticles under irradiation enabled efficient photocatalytic Heck reaction

Plasmonic metal nanoparticles have emerged as important candidates for photocatalysis. Numerous studies have shown that coupling of a plasmonic component (such as Au) as the light energy harvester with a catalytically active metal component (such as Pd) to form hybrid or alloy structures could achieve enhanced catalytic performance. However, the microscopic mechanism relative to the multicomponent plasmonic photocatalysis is still elusive. Here, we find that the electron-deficient Pd sites (Pdδ+) on AuPd alloy nanoparticle were formed under visible light irradiation, which play a decisive role in the AuPd alloy nanoparticle photocatalysis. The in-situ formed Pdδ+ under irradiation offers ideal platform for the catalytic reaction which is comparable to that under thermal heating conditions (>100 °C). The AuPd alloy nanoparticles show excellent conversion and selectivity for visible-light-driven Heck cross-coupling reaction under ambient conditions. The combination of experimental and density functional theory results suggest that the photocatalytic Heck reaction proceeds via a new radical-based single-electron transfer pathway on the AuPd alloy, and the in-situ formed Pdδ+ sites ideally provided efficient catalytic sites for the activation of reactant with much lower activation energy barrier under irradiation. The present work sheds light on the new mechanistic understandings of bimetallic plasmonic photocatalysis.

Mechanistic Insights into Plasmonic Catalysis by Dynamic Calculations: O2 and N2 on Au and Ag Nanoparticles

Plasmonic metal nanoparticles offer an interesting alternative to traditional heterogeneous catalytic processes due to their ability to harness energy from light. While plasmonic photocatalysis is a well-known phenomenon, the exact mechanism of these reactions is still debated. Understanding the precise workings of plasmon-driven reactions is crucial for the rational design of novel catalytic structures. Here, we utilize real-time, time-dependent density functional theory (RT-TD-DFT) to excite systems with oscillating electric fields and track the subsequent excited state dynamics in real time. We find that RT-TD-DFT with Ehrenfest dynamics gives results that are consistent with experimental tests of plasmonic excitations, in that the presence of nanoparticles facilitates light-induced molecular dissociation. Our results also demonstrate that the electric-field enhancement is the primary driving factor for the plasmon-driven dissociation of O2 on Au and Ag nanoparticles, while for N2 dissociation, both charge transfer and field enhancement appear to play important roles. Additionally, charge density and density of states calculations indicate that these excitations are π → π* on short time scales and a mixture of π, σ → π*, σ* over time.

Aspects of the interaction of pectin-coated Ag nanoparticles with methylene blue with regard to photodynamic applications

The promising future of photodynamic therapy has led to progress in the design of highly effective new-generation photosensitizers based on the combination of plasmonic metal nanoparticles and fluorescent molecules to kill cancer cells and bacteria. In this work, the details of the interaction of pectin-coated Ag nanocomposites (NCs) of different sizes (8, 10, 13, and 28 nm) and various types of pectin shells with the classical photosensitizer methylene blue (MB) were investigated. Pectin-Ag NCs were characterized by UV–vis spectroscopy, DLS, TEM, and XPS. The enhanced singlet oxygen generation effect of pectin-Ag@MB complexes was size-dependent (the smaller the size of the plasmonic particles, the higher the 1O2 generation) and associated with the local concentration of the dye in different molecular forms in the pectin shell of nanoparticles. In cell experiments, the pectin-Ag@MB complexes did not show enhanced phototoxicity or cellular uptake towards cancer cells, compared to free MB. The prolonged release of MB from the complex in a phosphate-buffered saline solution (pH 7.4) was observed. The amount of irreversibly bound MB depended on the type of pectin shell and equaled 1.13, 1.45, and 2.57 µg per mg pectin for Citrus25-Ag, Classic25-Ag, and Classic10-Ag NCs, respectively. The obtained physicochemical insights supplement the present understanding of the fundamental aspects of the interaction between plasmonic polymer-capped nanoparticles and MB and could be important for the rational design of new theranostic agents.

Role of Tunable Gold Nanostructures in Cancer Nanotheranostics: Implications on Synthesis, Toxicity, Clinical Applications and Their Associated Opportunities and Challenges

The existing diagnosis and treatment modalities have major limitations related to their precision and capability to understand several stages of disease development. A superior therapeutic system consists of a multifunctional approach in early diagnosis of the disease with a simultaneous progressive cure, using a precise medical approach towards complex treatment. These challenges can be addressed via nanotheranostics and explore suitable approaches to improve health care. Nanotechnology in combination with theranostics as an unconventional platform paved the way for developing novel strategies and modalities leading to diagnosis and therapy for complex disease conditions, ranging from acute to chronic levels. Among the metal nanoparticles, gold nanoparticles are being widely used for theranostics due to their inherent non-toxic nature and plasmonic properties. The unique optical and chemical properties of plasmonic metal nanoparticles along with theranostics have led to a promising era of plausible early detection of disease conditions, and they enable real-time monitoring with enhanced non-invasive or minimally invasive imaging of several ailments. This review aims to highlight the improvement and advancement brought to nanotheranostics by gold nanoparticles in the past decade. The clinical use of the metal nanoparticles in nanotheranostics is explained, along with the future perspectives on addressing the key applications related to diagnostics and therapeutics, respectively. The scope of gold nanoparticles and their realistic potential to design a sophisticated theranostic system is discussed in detail, along with their implications in clinical advancements which are the needs of the hour. The review concluded with the challenges, opportunities, and implications on translational potential of using gold nanoparticles in nanotheranostics.

Carbon Dot Emission Enhancement in Covalent Complexes with Plasmonic Metal Nanoparticles.

Carbon dots can be used for the fabrication of colloidal multi-purpose complexes for sensing and bio-visualization due to their easy and scalable synthesis, control of their spectral responses over a wide spectral range, and possibility of surface functionalization to meet the application task. Here, we developed a chemical protocol of colloidal complex formation via covalent bonding between carbon dots and plasmonic metal nanoparticles in order to influence and improve their fluorescence. We demonstrate how interactions between carbon dots and metal nanoparticles in the formed complexes, and thus their optical responses, depend on the type of bonds between particles, the architecture of the complexes, and the degree of overlapping of absorption and emission of carbon dots with the plasmon resonance of metals. For the most optimized architecture, emission enhancement reaching up to 5.4- and 4.9-fold for complexes with silver and gold nanoparticles has been achieved, respectively. Our study expands the toolkit of functional materials based on carbon dots for applications in photonics and biomedicine to photonics.