Search

Bimetallic Cu on Au nanoparticles with controllable morphology and optical properties were obtained via electrochemical synthesis. In particular, multilobed structures with good homogeneity were achieved through the optimization of experimental parameters such as deposition current, charge transfer, and metal ion concentration. A hyperspectral dark field scattering setup was used to characterize the electrodeposition on a single particle level, with changes in localized surface plasmon resonance frequency correlated with deposition charge transfer and amount of Cu deposited as determined by electron microscopy. This demonstrated the ability to tune morphology and spectra through electrochemical parameters alone. Time-resolved in situ measurements of single particle spectra were obtained, giving an insight into the kinetics of the deposition process. Nucleation of multiple cubes of Cu initially occurs preferentially on the tips of Au nanoparticles, before growing and coalescing to form a multilobed, lumpy shell. Modifying the surface of Au nanoparticles by plasma treatment resulted in thicker and more uniform Cu shells.

Acknowledgements: Support for this project was provided by the EU Framework Programme for Research and Innovation Horizon 2020 (ERC starting grant SPECs 804523). E. R. H. acknowledges financial support from the EPSRC NanoDTC Cambridge (EP/L015978/1)., Bimetallic Pd-Mg nanoparticles were synthesized by partial galvanic replacement of plasmonic Mg nanoparticles, and their catalytic and photocatalytic properties in selective hydrogenation of acetylene have been investigated. Electron probe studies confirm that the Mg-Pd structures mainly consist of metallic Mg and sustain several localized plasmon resonances across a broad wavelength range. We demonstrate that, even without light excitation, the Pd-Mg nanostructures exhibit an excellent catalytic activity with selectivity to ethylene of 55% at 100% acetylene conversion achieved at 60 °C. With laser excitation at room temperature over a range of intensities and wavelengths, the initial reaction rate increased up to 40 times with respect to dark conditions and a 2-fold decrease of the apparent activation energy was observed. A significant wavelength-dependent change in hydrogenation kinetics strongly supports a catalytic behavior affected by plasmon excitation. This report of coupling between Mg's plasmonic and Pd's catalytic properties paves the way for sustainable catalytic structures for challenging, industrially relevant selective hydrogenation processes.

Materials that sustain localized surface plasmon resonances have a broad technology potential as attractive platforms for surface-enhanced spectroscopies, chemical and biological sensing, light-driven catalysis, hyperthermal cancer therapy, waveguides, and so on. Most plasmonic nanoparticles studied to date are composed of either Ag or Au, for which a vast array of synthetic approaches are available, leading to controllable size and shape. However, recently, alternative materials capable of generating plasmonically enhanced light-matter interactions have gained prominence, notably Cu, Al, In, and Mg. In this Perspective, we give an overview of the attributes of plasmonic nanostructures that lead to their potential use and how their performance is dictated by the choice of plasmonic material, emphasizing the similarities and differences between traditional and emerging plasmonic compositions. First, we discuss the materials limitation encapsulated by the dielectric function. Then, we evaluate how size and shape maneuver localized surface plasmon resonance (LSPR) energy and field distribution and address how this impacts applications. Next, biocompatibility, reactivity, and cost, all key differences underlying the potential of non-noble metals, are highlighted. We find that metals beyond Ag and Au are of competitive plasmonic quality. We argue that by thinking outside of the box, i.e., by looking at nonconventional materials such as Mg, one can broaden the frequency range and, more importantly, combine the plasmonic response with other properties essential for the implementation of plasmonic technologies.

The reduction of 4-nitrophenol (4-NiP) to 4-aminophenol (4-AP) with an excess of sodium borohydride is commonly used as a model reaction to assess the catalytic activity of metallic nanoparticles. This reaction is considered both a potentially important step in industrial water treatment and an attractive, commercially relevant synthetic pathway. Surprisingly, an important factor, the role of the reaction medium on the reduction performance, has so far been overlooked. Here, we report a pronounced effect of the solvent on the reaction kinetics in the presence of silver and gold nanoparticles. We demonstrate that the addition of methanol, ethanol, or isopropanol to the reaction mixture leads to a dramatic decrease in the reaction rate. For typical concentrations of reactants, the reduction is completely suppressed in the presence of 50 vol% alcohols. 4-NiP reduction rate in aqueous alcohol mixtures can, however, be improved noticeably by increasing the borohydride concentration or the reaction temperature. The analysis of various factors responsible for solvent effects reveals that the decrease in the reduction rate in the presence of alcohols is related, amongst others, to a substantially higher oxygen solubility in alcohols compared to water. The results of this work show that the effects of solvent properties on reaction kinetics must be considered for unambiguous comparison and optimization of the catalytic performance of metallic nanoparticles in the liquid phase 4-NiP reduction.

Herein, we report the cooperative self-assembly of nanoparticles and block copolymers at the air-water interface, which can generate highly uniform and readily transferable composite films with tunable nanoscale architecture and functionalities. Interestingly, the incorporation of nanoparticles significantly affects the self-assembly of block copolymers at the interface. The nanoparticle-induced morphology change occurs through distinct mechanisms depending on the volume fraction of the hydrophobic block. For block copolymers with a relatively small hydrophobic volume fraction, the morphology transition occurs through the nanoparticle-induced swelling of a selective block. When the hydrophobic volume fraction is large enough, added nanoparticles promote the breath figure assembly, which generates uniform honeycomb-like porous structures with unusual nanoscale periodicity. This approach is generally applicable to various types of nanoparticles, constituting a simple one-step method to porous thin films with various functionalities.

Nanoparticles of plasmonic materials can sustain oscillations of their free electron density, called localized surface plasmon resonances (LSPRs), giving them a broad range of potential applications. Mg is an earth-abundant plasmonic material attracting growing attention owing to its ability to sustain LSPRs across the ultraviolet, visible, and near-infrared wavelength range. Tuning the LSPR frequency of plasmonic nanoparticles requires precise control over their size and shape; for Mg, this control has previously been achieved using top-down fabrication or gas-phase methods, but these are slow and expensive. Here, we systematically probe the effects of reaction parameters on the nucleation and growth of Mg nanoparticles using a facile and inexpensive colloidal synthesis. Small NPs of 80 nm were synthesized using a low reaction time of 1 min and ∼100 nm NPs were synthesized by decreasing the overall reaction concentration, replacing the naphthalene electron carrier with biphenyl or using metal salt additives of FeCl3 or NiCl2 at longer reaction times of 17 h. Intermediate sizes up to 400 nm were further selected via the overall reaction concentration or using other metal salt additives with different reduction potentials. Significantly larger particles of over a micrometer were produced by reducing the reaction temperature and, thus, the nucleation rate. We showed that increasing the solvent coordination reduced Mg NP sizes, while scaling up the reaction reduced the mixing efficiency and produced larger NPs. Surprisingly, varying the relative amounts of Mg precursor and electron carrier had little impact on the final NP sizes. These results pave the way for the large-scale use of Mg as a low-cost and sustainable plasmonic material.

This work describes two different core–shell architectures based on Mg nanoparticles (NPs) synthesised in order to improve Mg's stability in aqueous solutions. The shell thickness in Mg–polydopamine NPs can be modulated from 5 to >50 nm by ending the polymerization at different times; the resulting structures stabilize the metallic, plasmonic core in water for well over an hour. Mg–silica NPs with shells ranging from 5 to 30 nm can also be prepared via a modified Stöber procedure and they retain optical properties in 5% water-in-isopropanol solutions. These new architectures allow Mg nanoplasmonics to be investigated as an alternative to Ag and Au in a broader range of experimental conditions for a rich variety of applications., Plasmonic Mg nanoparticles can be stabilised up to a few hours in aqueous suspensions by protecting them inside core–shell architectures, which are prepared by condensation of either polydopamine or sol–gel silica.

Unlike in the bulk, at the nanoscale shape dictates properties. The imperative to understand and predict nanocrystal shape led to the development, over several decades, of a large number of mathematical models and, later, their software implementations. In this review, the various mathematical approaches used to model crystal shapes are first overviewed, from the century-old Wulff construction to the year-old (2020) approach to describe supported twinned nanocrystals, together with a discussion and disambiguation of the terminology. Then, the multitude of published software implementations of these Wulff-based shape models are described in detail, describing their technical aspects, advantages and limitations. Finally, a discussion of the scientific applications of shape models to either predict shape or use shape to deduce thermodynamic and/or kinetic parameters is offered, followed by a conclusion. This review provides a guide for scientists looking to model crystal shape in a field where ever-increasingly complex crystal shapes and compositions are required to fulfil the exciting promises of nanotechnology. Supplementary Information The online version contains supplementary material available at 10.1186/s40580-021-00275-6.

Electronic circuits, the backbone of modern electronic devices, require precise integration of conducting, insulating, and semiconducting materials in two- and three-dimensional space to control the flow of electric current. Alternative strategies to pattern these materials outside of a cleanroom environment, such as additive manufacturing, have enabled rapid prototyping and eliminated design constraints imposed by traditional fabrication. In this work, a transformative manufacturing approach using laser processing is implemented to directly realize conducting, insulating, and semiconducting phases within an amorphous molybdenum disulfide thin film precursor. This is achieved by varying the incident visible (514 nm) laser intensity and raster-scanning the thin film a-MoS2 sample (900 nm thick) at different speeds for micro-scale control of the crystallization and reaction kinetics. The overall result is the transformation of select regions of the a-MoS2 film into MoO2, MoO3, and 2H-MoS2 phases, exhibiting conducting, insulating, and semiconducting properties, respectively. A mechanism for this precursor transformation based on crystallization and oxidation is developed using a thermal model paired with a description of the reaction kinetics. Finally, by engineering the architecture of the three crystalline phases, electrical devices such as a resistor, capacitor, and chemical sensor were laser-written directly within the precursor film, representing an entirely transformative manufacturing approach for the fabrication of electronic circuitry.

Many metals and alloys, including Fe and W, adopt body-centred cubic (BCC) crystal structures and nanoparticles of these metals are gaining significant scientific and industrial relevance. Twinning has a marked effect on catalytic activity, yet there is little evidence for or against the presence of twinning in BCC nanoparticles. Here, we explore the potential shapes of twinned BCC nanoparticles, and predict their electron microscopy and diffraction signatures. BCC single crystal and twinned shapes often appear similar and diffraction patterns along common, low-index zone axes are often indistinguishable, casting doubt on many claims of single crystallinity. We conclude by outlining how nanoparticles can be characterized to conclusively prove the presence or absence of twinning.

Iron oxide nanorings have great promise for biomedical applications because of their magnetic vortex state, which endows them with a low remanent magnetization while retaining a large saturation magnetization. Here we use micromagnetic simulations to predict the exact shapes that can sustain magnetic vortices, using a toroidal model geometry with variable diameter, ring thickness, and ring eccentricity. Our model phase diagram is then compared with simulations of experimental geometries obtained by electron tomography. High axial eccentricity and low ring thickness are found to be key factors for forming vortex states and avoiding net-magnetized metastable states. We also find that while defects from a perfect toroidal geometry increase the stray field associated with the vortex state, they can also make the vortex state more energetically accessible. These results constitute an important step toward optimizing the magnetic behavior of toroidal iron oxide nanoparticles.

As elemental main group materials (i.e., silicon and germanium) have dominated the field of modern electronics, their monolayer 2D analogues have shown great promise for next-generation electronic materials as well as potential game-changing properties for optoelectronics, energy, and beyond. These atomically thin materials composed of single atomic variants of group III through group VI elements on the periodic table have already demonstrated exciting properties such as near-room-temperature topological insulation in bismuthene, extremely high electron mobilities in phosphorene and silicone, and substantial Li-ion storage capability in borophene. Isolation of these materials within the postgraphene era began with silicene in 2010 and quickly progressed to the experimental identification or theoretical prediction of 15 of the 18 main group elements existing as solids at standard pressure and temperatures. This review first focuses on the significance of defects/functionalization, discussion of different allotropes, and overarching structure-property relationships of 2D main group elemental materials. Then, a complete review of emerging applications in electronics, sensing, spintronics, plasmonics, photodetectors, ultrafast lasers, batteries, supercapacitors, and thermoelectrics is presented by application type, including detailed descriptions of how the material properties may be tailored toward each specific application.

[Image: see text] Localized surface plasmon resonances have attracted much attention due to their ability to enhance light–matter interactions and manipulate light at the subwavelength level. Recently, alternatives to the rare and expensive noble metals Ag and Au have been sought for more sustainable and large-scale plasmonic utilization. Mg supports plasmon resonances, is one of the most abundant elements in earth’s crust, and is fully biocompatible, making it an attractive framework for plasmonics. This feature article first reports the hexagonal, folded, and kite-like shapes expected theoretically from a modified Wulff construction for single crystal and twinned Mg structures and describes their excellent match with experimental results. Then, the optical response of Mg nanoparticles is overviewed, highlighting Mg’s ability to sustain localized surface plasmon resonances across the ultraviolet, visible, and near-infrared electromagnetic ranges. The various resonant modes of hexagons, leading to the highly localized electric field characteristic of plasmonic behavior, are presented numerically and experimentally. The evolution of these modes and the associated field from hexagons to the lower symmetry folded structures is then probed, again by matching simulations, optical, and electron spectroscopy data. Lastly, results demonstrating the opportunities and challenges related to the high chemical reactivity of Mg are discussed, including surface oxide formation and galvanic replacement as a synthetic tool for bimetallics. This Feature Article concludes with a summary of the next steps, open questions, and future directions in the field of Mg nanoplasmonics.

Plasmonic structures have attracted much interest in science and engineering disciplines, exploring a myriad of potential applications owing to their strong light-matter interactions. Recently, the plasmonic concentration of energy in subwavelength volumes has been used to initiate chemical reactions, for instance by combining plasmonic materials with catalytic metals. In this work, we demonstrate that plasmonic nanoparticles of earth-abundant Mg can undergo galvanic replacement in a nonaqueous solvent to produce decorated structures. This method yields bimetallic architectures where partially oxidized 200–300 nm Mg nanoplates and nanorods support many smaller Au, Ag, Pd, or Fe nanoparticles, with potential for a stepwise process introducing multiple decoration compositions on a single Mg particle. We investigated this mechanism by electron-beam imaging and local composition mapping with energy-dispersive X-ray spectroscopy as well as, at the ensemble level, by inductively coupled plasma mass spectrometry. High-resolution scanning transmission electron microscopy further supported the bimetallic nature of the particles and provided details of the interface geometry, which includes a Mg oxide separation layer between Mg and the other metal. Depending on the composition of the metallic decorations, strong plasmonic optical signals characteristic of plasmon resonances were observed in the bulk with ultraviolet-visible spectrometry and at the single particle level with darkfield scattering. These novel bimetallic and multimetallic designs open up an exciting array of applications where one or multiple plasmonic structures could interact in the near-field of earth-abundant Mg and couple with catalytic nanoparticles for applications in sensing and plasmon-assisted catalysis.

Recently, aluminum has been established as an earth-abundant alternative to gold and silver for plasmonic applications. Particularly, aluminum nanocrystals have shown to be promising plasmonic photocatalysts, especially when coupled with catalytic metals or oxides into “antenna-reactor” heterostructures. Here, a simple polyol synthesis is presented as a flexible route to produce aluminum nanocrystals decorated with eight varieties of size-tunable transition-metal nanoparticle islands, many of which have precedence as heterogeneous catalysts. High-resolution and three-dimensional structural analysis using scanning transmission electron microscopy and electron tomography shows that abundant nanoparticle island decoration in the catalytically relevant few-nanometer size range can be achieved, with many islands spaced closely to their neighbors. When coupled with the Al nanocrystal plasmonic antenna, these small decorating islands will experience increased light absorption and strong hot-spot generation. This combination makes transition-metal decorated aluminum nanocrystals a promising material platform to develop plasmonic photocatalysis, surface-enhanced spectroscopies, and quantum plasmonics., This research was financially supported by the National Science Foundation (NSF) grant ECCS-1610229, the Air Force Office of Scientific Research Multidisciplinary Research Program of the University Research Initiative (AFOSR MURI FA9550-15- 1-0022), the Army Research Office (MURI W911NF-12-1- 0407), Defense Threat Reduction Agency (HDTRA 1-16-1- 0042), the Welch Foundation under grants C-1220 (N.H.) and C-1222 (P.N.) and by the American Chemical Society Petroleum Research Fund under grant no. 56256 DNI5 (E.R.). D.S. acknowledges the National Science Foundation for a Graduate Research Fellowship under grant no. 1450681. D.R. acknowledges support by the Department of Defense (DoD) through the National Defense Science and Engineering Graduate Fellowship (NDSEG) Program. R.L. acknowledges a Junior Research Fellowship at Clare College, Cambridge. The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement 291522-3DIMAGE as well as from the European Union Seventh Framework Programme under grant agreement 312483-ESTEEM2 (Integrated Infrastructure Initiative − I3).

Of the 6.7 million individuals in the United States who are visually impaired, 63% are unemployed, and 59% have not attained an education beyond a high school diploma. Providing a basic science education to children and adults with visual disabilities can be challenging because most scientific learning relies on visual demonstrations. Creating resources to help teachers and service organizations better communicate science is thus critical both to the education of sighted students as well as to the continuing education of individuals with blindness or low vision (BLV). Here, 4 new scientific learning activities that last 5–15 min each are described. These simple exercises are designed to educate the general public, including both those who are sighted and those with BLV. The modules use tactile and auditory approaches to convey basic concepts including the metric system, material strength and deformation, transparency, and the electromagnetic spectrum. These modules were tested on 20 adults with BLV during a science outreach event. Answers to learning assessment questions indicate that the modules conveyed information about the scientific concepts presented and increased an interest in science for most participants.

The internal structure of hollow AgAu nanorods created by partial galvanic replacement was manipulated reversibly, and its effect on optical properties was mapped with nanometer resolution. Using the electron beam in a scanning transmission electron microscope to create solvated electrons and reactive radicals in an encapsulated solution-filled cavity in the nanorods, Ag ions were reduced nearby the electron beam, reshaping the core of the nanoparticles without affecting the external shape. The changes in plasmon-induced near-field properties were then mapped with electron energy-loss spectroscopy without disturbing the internal structure, and the results are supported by finite-difference time-domain calculations. This reversible shape and near-field control in a hollow nanoparticle actuated by an external stimulus introduces possibilities for applications in reprogrammable sensors, responsive materials, and optical memory units. Moreover, the liquid-filled nanorod cavity offers new opportunities for in situ microscopy of chemical reactions.

Crystal aggregates in igneous rocks have been variously ascribed to growth processes (e.g., twinning, heterogeneous nucleation, epitaxial growth, dendritic growth), or dynamical processes (e.g., synneusis, accumulation during settling). We tested these hypotheses by quantifying the relative orientation of adjacent crystals using electron backscatter diffraction. Both olivine aggregates from Kīlauea volcano (Hawaiʻi, USA) and chromite aggregates from the Bushveld Complex (South Africa) show diverse attachment geometries inconsistent with growth processes. Near-random attachments in chromite aggregates are consistent with accumulation by settling of individual crystals. Attachment geometries and prominent geochemical differences across grain boundaries in olivine aggregates are indicative of synneusis.

The growing interest in plasmonic nanoparticles and their increasingly diverse applications is fuelled by the ability to tune properties via shape control, promoting intense experimental and theoretical research. Such shapes are dominated by geometries that can be described by the kinetic Wulff construction such as octahedra, thin triangular platelets, bipyramids, and decahedra, to name a few. Shape is critical in dictating the optical properties of these nanoparticles, in particular their localized surface plasmon resonance behavior, which can be modeled numerically. One challenge of the various available computational techniques is the representation of the nanoparticle shape. Specifically, in the discrete dipole approximation, a particle is represented by discretizing space via an array of uniformly distributed points-dipoles; this can be difficult to construct for complex shapes including those with multiple crystallographic facets, twins, and core-shell particles. Here, we describe a standalone user-friendly graphical user interface (GUI) that uses both kinetic and thermodynamic Wulff constructions to generate a dipole array for complex shapes, as well as the necessary input files for DDSCAT-based numerical approaches. Examples of the use of this GUI are described through three case studies spanning different shapes, compositions, and shell thicknesses. Key advances offered by this approach, in addition to simplicity, are the ability to create crystallographically correct structures and the addition of a conformal shell on complex shapes.

Metal–semiconductor contact has been a critical topic in the semiconductor industry because it influences device performance remarkably. Conventional metals have served as the major contact material in electronic and optoelectronic devices, but such a selection becomes increasingly inadequate for emerging novel materials such as two-dimensional (2D) materials. Deposited metals on semiconducting 2D channels usually form large resistance contacts due to the high Schottky barrier. A few approaches have been reported to reduce the contact resistance but they are not suitable for large-scale application or they cannot create a clean and sharp interface. In this study, a chemical vapor deposition (CVD) technique is introduced to produce large-area semiconducting 2D material (2H MoTe2) planarly contacted by its metallic phase (1T′ MoTe2). We demonstrate the phase-controllable synthesis and systematic characterization of large-area MoTe2 films, including pure 2H phase or 1T′ phase, and 2H/1T′ in-plane heterostructure. Theoretical simulation shows a lower Schottky barrier in 2H/1T′ junction than in Ti/2H contact, which is confirmed by electrical measurement. This one-step CVD method to synthesize large-area, seamless-bonding 2D lateral metal–semiconductor junction can improve the performance of 2D electronic and optoelectronic devices, paving the way for large-scale 2D integrated circuits.

Plasmonic nanoparticle (NP) dimer structures, forming highly intense areas of field enhancement called hotspots, have been the focus of extensive investigations due to their phenomenal light manipulating abilities. However, the actual morphology of the NP hotspot is usually distinct from the ideal nanosphere dimer model. In this study, we demonstrate numerically that small morphology variations in the presence of nanobridge, nanocrevice, nanofacet or nanoroughness, can have a major impact on the plasmonic properties of the whole system. The resonance wavelength and magnitude of the near-field enhancement are found to acutely depend on the interparticle gap geometry. The hotspot may become degenerated or regenerated. We also observe that the hybridized modes excited under longitudinal polarizations, including the bonding dipole plasmon (BDP) and charge transfer plasmon (CTP) modes, can be assigned to the bonding longitudinal antenna plasmon (LAP) modes for all gap geometries. These results provide means to understand and justify the ongoing poor reproducibility of surface enhanced Raman scattering (SERS) substrates, stressing the importance of precision plasmonics.

Hollow AgAu nanostructures have a myriad of potential applications related to their strong and tunable localized surface plasmon resonances. Here, we describe how the hydrolysis of the Au precursor, AuCl4–, produces AuCl4–x(OH)x–, where x is both time and pH-dependent, and how this can be used to control the morphology of hollow nanoshells in the co-reduction-assisted galvanic replacement of Ag by Au. Controlling the degree of hydrolysis is the key to obtain smooth shells: too small values of x (low hydrolysis) yield inhomogeneously replaced rough shells whereas too large values of x lead to the dominance of Au nucleation over galvanic replacement. Kinetic studies reveal two time constants for the galvanic replacement varying with temperature and composition; a short (100 min) half-life component associated with the continuous reduction and replacement of Ag. By optimizing the reaction’s pH and Au speciation, we obtained smooth alloy shells with fine control of composition, size, and shape over a broad range, thereby tuning the optical properties. This framework for understanding and controlling reaction kinetics and nanoshell morphology is applicable to other metallic systems and precursors, providing new ways to rationally design nanostructure syntheses.

Metallic nanoparticles with strong optically resonant properties behave as nanoscale optical antennas, and have recently shown extraordinary promise as light-driven catalysts. Traditionally, however, heterogeneous catalysis has relied upon weakly light-absorbing metals such as Pd, Pt, Ru, or Rh to lower the activation energy for chemical reactions. Here we show that coupling a plasmonic nanoantenna directly to catalytic nanoparticles enables the light-induced generation of hot carriers within the catalyst nanoparticles, transforming the entire complex into an efficient light-controlled reactive catalyst. In Pd-decorated Al nanocrystals, photocatalytic hydrogen desorption closely follows the antenna-induced local absorption cross-section of the Pd islands, and a supralinear power dependence strongly suggests that hot-carrier-induced desorption occurs at the Pd island surface. When acetylene is present along with hydrogen, the selectivity for photocatalytic ethylene production relative to ethane is strongly enhanced, approaching 40:1. These observations indicate that antenna-reactor complexes may greatly expand possibilities for developing designer photocatalytic substrates.

Catalytic and optical properties can be coupled by combining different metals into nanoscale architectures in which both the shape and the composition provide fine-tuning of functionality. Here, discrete, small Pt nanoparticles (diameter = 3-6 nm) were grown in linear arrays on Au nanoprisms, and the resulting structures are shown to retain strong localized surface plasmon resonances. Multidimensional electron microscopy and spectroscopy techniques (energy-dispersive X-ray spectroscopy, electron tomography, and electron energy-loss spectroscopy) were used to unravel their local composition, three-dimensional morphology, growth patterns, and optical properties. The composition and tomographic analyses disclose otherwise ambiguous details of the Pt-decorated Au nanoprisms, revealing that both pseudospherical protrusions and dendritic Pt nanoparticles grow on all faces of the nanoprisms (the faceted or occasionally twisted morphologies of which are also revealed), and shed light on the alignment of the Pt nanoparticles. The electron energy-loss spectroscopy investigations show that the Au nanoprisms support multiple localized surface plasmon resonances despite the presence of pendant Pt nanoparticles. The plasmonic fields at the surface of the nanoprisms indeed extend into the Pt nanoparticles, opening possibilities for combined optical and catalytic applications. These insights pave the way toward comprehensive nanoengineering of multifunctional bimetallic nanostructures, with potential applications in plasmon-enhanced catalysis and in situ monitoring of chemical processes via surface-enhanced spectroscopy.

Plasmonic devices designed in three dimensions enable careful tuning of optical responses for control of complex electromagnetic interactions on the nanoscale. Probing the fundamental characteristics of the constituent nanoparticle building blocks is, however, often constrained by diffraction-limited spatial resolution in optical spectroscopy. Electron microscopy techniques, including electron energy loss spectroscopy (EELS), have recently been developed to image surface plasmon resonances qualitatively at the nanoscale in three dimensions using tomographic reconstruction techniques. Here, we present an experimental realization of a distinct method that uses direct analysis of modal surface charge distributions to reconstruct quantitatively the three-dimensional eigenmodes of a silver right bipyramid on a metal oxide substrate. This eigenmode tomography removes ambiguity in two-dimensional imaging of spatially localized plasmonic resonances, reveals substrate-induced mode degeneracy breaking in the bipyramid, and enables EELS for the analysis not of a particular electron-induced response but of the underlying geometric modes characteristic of particle surface plasmons.

Nanoparticles of some metals (Cu/Ag/Au) sustain oscillations of their electron cloud called localized surface plasmon resonances (LSPRs). These resonances can occur at optical frequencies and be driven by light, generating enhanced electric fields and spectacular photon scattering. However, current plasmonic metals are rare, expensive, and have a limited resonant frequency range. Recently, much attention has been focused on earth-abundant Al, but Al nanoparticles cannot resonate in the IR. The earth-abundant Mg nanoparticles reported here surmount this limitation. A colloidal synthesis forms hexagonal nanoplates, reflecting Mg's simple hexagonal lattice. The NPs form a thin self-limiting oxide layer that renders them stable suspended in 2-propanol solution for months and dry in air for at least two week. They sustain LSPRs observable in the far-field by optical scattering spectroscopy. Electron energy loss spectroscopy experiments and simulations reveal multiple size-dependent resonances with energies across the UV, visible, and IR. The symmetry of the modes and their interaction with the underlying substrate are studied using numerical methods. Colloidally synthesized Mg thus offers a route to inexpensive, stable nanoparticles with novel shapes and resonances spanning the entire UV-vis-NIR spectrum, making them a flexible addition to the nanoplasmonics toolbox.

© 2018 Elsevier Inc. The “alchemy of water,” i.e., turning water into fuel (such as hydrogen) with sunlight, is an exciting prospect for sustainable energy. In a recent Chem issue, Atta et al. (2018) developed plasmonic-TiO2nanostructures that bring photocatalytic water splitting one step closer to reality. The “alchemy of water,” i.e., turning water into fuel (such as hydrogen) with sunlight, is an exciting prospect for sustainable energy. In a recent Chem issue, Atta et al. (2018) developed plasmonic-TiO2nanostructures that bring photocatalytic water splitting one step closer to reality.

Lipid membranes and membrane proteins are important biosensing targets, motivating the development of label-free methods with improved sensitivity. Silica-coated metal nanoparticles allow these systems to be combined with supported lipid bilayers for sensing membrane proteins through localized surface plasmon resonance (LSPR). However, the small sensing volume of LSPR makes the thickness of the silica layer critical for performance. Here, we develop a simple, inexpensive, and rapid sol-gel method for preparing thin conformal, continuous silica films and demonstrate its applicability using gold nanodisk arrays with LSPRs in the near-infrared range. Silica layers as thin as ∼5 nm are observed using cross-sectional scanning transmission electron microscopy. The loss in sensitivity due to the thin silica coating was found to be only 16%, and the biosensing capabilities of the substrates were assessed through the binding of cholera toxin B to GM1 lipids. This sensor platform should prove useful in the rapid, multiplexed detection and screening of membrane-associated biological targets.

Metal halide perovskites have emerged as exceptional semiconductors for optoelectronic applications. Substitution of the monovalent cations has advanced luminescence yields and device efficiencies. Here, we control the cation alloying to enhance optoelectronic performance through alteration of the charge carrier dynamics in mixed-halide perovskites. In contrast to single-halide perovskites, we find high luminescence yields for photoexcited carrier densities far below solar illumination conditions. Using time-resolved spectroscopy we show that the charge carrier recombination regime changes from second to first order within the first tens of nanoseconds after excitation. Supported by microscale mapping of the optical bandgap, electrically gated transport measurements and first-principles calculations, we demonstrate that spatially varying energetic disorder in the electronic states causes local charge accumulation, creating p- and n-type photodoped regions, which unearths a strategy for efficient light emission at low charge-injection in solar cells and light-emitting diodes. Localized photodoping in mixed-cation perovskites is shown to modify charge-carrier recombination and thus offer a route for more efficient light emission.

Indium-decorated palladium nanoparticles (In-on-PdNPs) are active for room-temperature catalytic reduction of aqueous nitrate, where the active sites are metallic In atoms on the Pd surface. The PdNPs are pseudo-spherical in shape, and it is unclear if their faceted nature plays a role in nitrate reduction. We synthesized different-sized, cube-shaped NPs with differing In coverages (sc%), and studied the resultant In-on-Pd-nanocubes (NCs) for nitrate reduction. The NCs exhibited volcano-shape activity dependence on In sc%, with peak activity around 65–75 sc%. When rate constants were normalized to undercoordinated atoms (at edge + corners), the NCs exhibited near-identical maximum activity (20×-higher than In-on-PdNPs) at ρIn/Pd edge+corner ∼0.5 (∼5 In atoms per 10 edge and corner atoms). NCs with a higher In edge + corner density (ρIn/Pd edge+corner ∼1.5) were less active but did not generate NH4+ at nitrate conversions tested up to 36 %. Edge-decorated cubes may be the structural basis of improved bimetallic catalytic denitrification of water.

Two-dimensional (2D) transition-metal dichalcogenides (TMDs) are a unique class of 2D materials possessing unique optoelectronic properties when exfoliated into mono- and few-layer sheets. Recently, electroablation (EA) has become of interest as a promising synthesis method for single-layer sheets of TMDs. Here, we introduce spectroelectrochemical micro-extinction spectroscopy (SE-MExS) as a high-throughput technique to study electrochemical thinning of TMDs as it occurs. This approach enables the parallel use of spectroscopy and imaging to nondestructively characterize 2D materials in situ. We unravel optoelectronics of the TMDs by observing changes in optical properties during EA. We find that the EA process for MoS2, WS2, MoSe2, and WSe2 occurs edge first, generating high density of edge sites. Our results show that stable monolayers of MoS2, WS2, and MoSe2 can be synthesized from bulk precursors by the EA process, while conversely, no WSe2 remains postablation.

Depending on the experimental conditions and plasmonic systems, the correlations between near-field\ud surface enhanced Raman scattering (SERS) behaviors and far-field localized surface plasmon resonance\ud (LSPR) responses have sometimes been accepted directly or argued or explored. In this work, we focus\ud on the attractive subwavelength closely spaced metallic nanorod arrays and investigate in detail the\ud complex relationship between their SERS behaviors and plasmon resonances. This is achieved utilizing a\ud combination of array fabrication, conventional LSPR spectra, SERS measurements, electron microscopy\ud and numerical modeling. Three key factors that may impact the correlations have been comprehensively\ud analyzed: the intrinsic near-field to far-field red-shift is found to be rather small in the lattice; the surface\ud roughness has actually little impact on the spectral alignment of the near- and far-field responses; the\ud continuous dependence of individual SERS peak heights on the Stokes Raman shift has been visualized\ud and further clarified. By 3D finite element method (FEM) plasmon mapping, the physical origin of the collective\ud resonances in the lattice is verified directly to be the Fabry–Perot-like cavity mode. The strong\ud near-field enhancement results from the coupling of surface plasmon polaritons (SPPs) propagating at\ud the two sidewalls of neighbouring nanorods forming the resonant cavity. The physical principles demonstrated\ud here benefit significantly the optimization of nano-optic devices based on closely spaced metallic\ud nanorod arrays, as well as the fundamental understanding of the near- and far-field relationship.

Anisotropy in a crystal structure can lead to large orientation-dependent variations of mechanical, optical, and electronic properties. Material orientation control can thus provide a handle to manipulate properties. Here, a novel sputtering approach for 2D materials enables growth of ultrathin (2.5-10 nm) tellurium films with rational control of the crystalline orientation templated by the substrate. The anisotropic Te 〈0001〉 helical chains align in the plane of the substrate on highly oriented pyrolytic graphite (HOPG) and orthogonally to MgO(100) substrates, as shown by polarized Raman spectroscopy and high-resolution electron microscopy. Furthermore, the films are shown to grow in a textured fashion on HOPG, in contrast with previous reports. These ultrathin Te films cover exceptionally large areas (>1 cm2) and are grown at low temperature (25 °C) affording the ability to accommodate a variety of substrates including flexible electronics. They are robust toward oxidation over a period of days and exhibit the non-centrosymmetric P3121 Te structure. Raman signals are acutely dependent on film thickness, suggesting that optical anisotropy persists and is even enhanced at the ultrathin limit. Hall effect measurements indicate orientation-dependent carrier mobility up to 19 cm2 V-1 s-1. These large-area, ultrathin Te films grown by a truly scalable, physical vapor deposition technique with rational control of orientation/thickness open avenues for controlled orientation-dependent properties in semiconducting thin films for applications in electronic and optoelectronic devices.