Plasmon-mediated syntheses of metallic nanostructures.

The ability to prepare noble metal nanostructures of a desired composition, size, and shape enables their resulting properties to be exquisitely tailored, which has led to the use of these structures in numerous applications, ranging from medicine to electronics. The prospect of using light to guide nanoparticle reactions is extremely attractive since one can, in principle, regulate particle growth based on the ability of the nanostructures to absorb a specific excitation wavelength. Therefore, using the nature of light, one can generate a homogenous population of product nanoparticles from a heterogeneous starting population. The best example of this is afforded by plasmon-mediated syntheses of metal nanoparticles, which use visible light irradiation and plasmon excitation to drive the chemical reduction of Ag(+) by citrate. Since the initial discovery that Ag triangular prisms could be prepared by the photo-induced conversion of Ag spherical nanoparticles, plasmon-mediated synthesis has become a highly controllable technique for preparing a number of different Ag particles with tight control over shape, as well as a wide variety of Au-Ag bimetallic nanostructures. We discuss the underlying physical and chemical factors that drive structural selection and conclude by outlining some of the important design considerations for controlling particle shape as learned through studies of plasmon-mediated reactions, but applicable to all methods of noble metal nanocrystal synthesis.

Synthesis of gold hexagonal bipyramids directed by planar-twinned silver triangular nanoprisms.

The direct growth of planar-twinned Au nanoparticles (NPs) in high yield remains a challenge in shape-controlled NP synthesis largely because suitable planar-twinned seeds for Au NP growth have not been identified to date. Herein we describe the use of planar-twinned Ag triangular nanoprisms as a means to dictate Au NP twin structure. In a one-pot process, the Ag triangular nanoprisms first undergo oxidative Au replacement, forming Ag-Au alloy nanoframes and concomitantly releasing Ag(+) into solution, which then directs subsequent Au NP growth through an underpotential deposition process. The planar-twinned structure of the initial Ag nanoprism is maintained throughout particle growth. Using this method, we have successfully synthesized Au hexagonal bipyramids in high yield for the first time.

Plasmon-mediated synthesis of silver cubes with unusual twinning structures using short wavelength excitation.

The plasmon-mediated synthesis of silver nanoparticles is a versatile synthetic method which leverages the localized surface plasmon resonance (LSPR) of nanoscale silver to generate particles with non-spherical shapes and control over dimensions. Herein, a method is reported for controlling the twinning structure of silver nanoparticles, and consequently their shape, via the plasmon-mediated synthesis, solely by varying the excitation wavelength between 400, 450, and 500 nm, which modulates the rate of Ag⁺ reduction. Shorter, higher energy excitation wavelengths lead to faster rates of reaction, which in turn yield structures containing a greater number of twin boundaries. With this method, silver cubes can be synthesized using 450 nm excitation, which represents the first time this shape has been realized by a plasmon-mediated synthetic approach. In addition, these cubes contain an unusual twinning structure composed of two intersecting twin boundaries or multiple parallel twin boundaries. With respect to their twinning structure, these cubes fall between planar-twinned and multiply twinned nanoparticles, which are synthesized using 500 and 400 nm excitation, respectively.

Chemically isolating hot spots on concave nanocubes.

We report a simple and general strategy for selectively exposing and functionalizing the sharp corners of concave nanocubes, which are the SERS hot spots for such structures. This strategy takes advantage of the unique shape of the concave cubes by coating the particles with silica and then etching it away to expose only the corner regions, while maintaining the silica coating in the concave faces. These corner regions can then be selectively modified for improved enhancement and signal response with SERS.

Correlating the structure and localized surface plasmon resonance of single silver right bipyramids.

Localized surface plasmon resonances (LSPRs), collective electron oscillations in metal nanoparticles, are being heavily scrutinized for applications in prototype devices and circuits, as well as for chemical and biological sensing. Both the plasmon frequency and linewidth of a LSPR are critical factors for application optimization, for which their dependence on structural factors has been qualitatively unraveled over the past decade. However, quantitative knowledge based on systematic single particle studies has only recently become available for a few particle shapes. We show here that to understand the effect of structure (both size and shape) on plasmonic properties, one must take multiple parameters into account. We have successfully done so for a large data set on silver right bipyramids. By correlating plasmon energy and linewidth with edge length and corner rounding for individual bipyramids, we have found that the corner rounding has a significant effect on the plasmon energy for particles of the same size, and thus corner rounding must be taken into account to accurately describe the dependence of a LSPR on nanoparticle size. A detailed explanation of the phenomena responsible for the observed effects and their relationship to each other is presented.

Stepwise evolution of spherical seeds into 20-fold twinned icosahedra.

Understanding the factors that influence the growth and final shape of noble metal nanostructures is important for controlling their properties. However, relative to their single-crystalline counterparts, the growth of nanoparticles that contain twin defects can be difficult to control because multiple competitive growth pathways can yield such structures. We used spherical, cubic, and octahedral single-crystalline gold nanoparticles as dual electron microscopy labels and plasmonic seeds to track the growth of multiply twinned silver nanostructures. As the bimetallic nanostructures grew, they successively developed twin planes to ultimately form multiply twinned nanoparticles from single-crystalline seeds. Collectively, these data demonstrate how a series of nanoparticles of different shapes and internal crystal structures are interrelated and develop from one another.

Defining rules for the shape evolution of gold nanoparticles.

The roles of silver ions and halides (chloride, bromide, and iodide) in the seed-mediated synthesis of gold nanostructures have been investigated, and their influence on the growth of 10 classes of nanoparticles that differ in shape has been determined. We systematically studied the effects that each chemical component has on the particle shape, on the rate of particle formation, and on the chemical composition of the particle surface. We demonstrate that halides can be used to (1) adjust the reduction potential of the gold ion species in solution and (2) passivate the gold nanoparticle surface, both of which control the reaction kinetics and thus enable the selective synthesis of a series of different particle shapes. We also show that silver ions can be used as an underpotential deposition agent to access a different set of particle shapes by controlling growth of the resulting gold nanoparticles through surface passivation (more so than kinetic effects). Importantly, we show that the density of silver coverage can be controlled by the amount and type of halide present in solution. This behavior arises from the decreasing stability of the underpotentially deposited silver layer in the presence of larger halides due to the relative strengths of the Ag(+)/Ag(0)-halide and Au(+)/Au(0)-halide interactions, as well as the passivation effects of the halides on the gold particle surface. We summarize this work by proposing a set of design considerations for controlling the growth and final shape of gold nanoparticles prepared by seed-mediated syntheses through the judicious use of halides and silver ions.

Dispersible gold nanorod dimers with sub-5 nm gaps as local amplifiers for surface-enhanced Raman scattering.

We report the synthesis of solution-dispersible, 35 nm diameter gold nanorod dimers with gaps as small as ∼2 nm for surface-enhanced Raman scattering (SERS). Using on-wire lithography (OWL), we prepared tailorable dimers in high yield and high monodispersity (∼96% dimers) that produce both large and reproducible SERS signals with enhancement factors of (6.8 ± 0.7) × 10(8) for single dimers in air and 1.2 × 10(6) for ensemble-averaged solution measurements. Furthermore, we show that these structures, which are the smallest ever made by OWL, can be used to detect molecules on flat surfaces and in aqueous solutions. When combined, these attributes with respect to sensitivity, reproducibility, and tailorability lead to a novel and powerful local amplification system for SERS applications.

Plasmon Length: A Universal Parameter to Describe Size Effects in Gold Nanoparticles.

Localized surface plasmon resonances are central to many sensing and signal transmission applications. Tuning of the plasmon energy and line width through particle size and shape is critical to the design of such devices. To gain quantitative information on the size dependence of plasmonic properties, mainly due to retardation effects, we correlated optical spectra and structures for 500 individual gold particles of five different shapes. We show that the effects of size on the dipolar plasmon frequency and line width are shape-independent when size is described by the plasmon length, the length over which the oscillations take place. This result suggests that edge effects are rather unimportant for dipolar modes in a large size range between 50 and 350 nm. Therefore, in describing the size-dependent plasmonic properties of nanoparticles, one should focus on the distance along which the oscillation occurs rather than its intrinsic shape.

Shape control of gold nanoparticles by silver underpotential deposition.

Four different gold nanostructures: octahedra, rhombic dodecahedra, truncated ditetragonal prisms, and concave cubes, have been synthesized using a seed-mediated growth method by strategically varying the Ag(+) concentration in the reaction solution. Using X-ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy, we provide quantitative evidence that Ag underpotential deposition is responsible for stabilizing the various surface facets that enclose the above nanoparticles. Increasing concentrations of Ag(+) in the growth solution stabilize more open surface facets, and experimental values for Ag coverage on the surface of the particles fit well with a calculated monolayer coverage of Ag, as expected via underpotential deposition.

Bottom-up synthesis of gold octahedra with tailorable hollow features.

Gold octahedra with hollow features have been synthesized in high yield via the controlled overgrowth of preformed concave cube seeds. This Ag(+)-assisted, seed-mediated synthesis allows for the average edge length of the octahedra and the size of the hollow features to be independently controlled. We propose that a high concentration of Ag(+) stabilizes the {111} facets of the octahedra through underpotential deposition while the rate of Au(+) reduction controls the dimensions of the hollow features. This synthesis represents a highly controllable bottom-up approach for the preparation of hollow gold nanostructures.

Synthesis of silver nanorods by low energy excitation of spherical plasmonic seeds.

Plasmon excitation of Ag seed particles with 600-750 nm light in the presence of Ag(+) and trisodium citrate was used to synthesize penta-twinned nanorods. Importantly, the excitation wavelength can be used to control the reaction rate and, consequently, the aspect ratio of the nanorods. When the excitation wavelength is red-shifted from the surface plasmon resonance of the spherical seed particles, the rate of Ag(+) reduction becomes slower and more kinetically controlled. Such conditions favor the deposition of silver onto the tips of the growing nanorods as compared to their sides, resulting in the generation of higher aspect ratio rods. However, control experiments reveal that there is only a range of low energy excitation wavelengths (between 600 and 750 nm) that yields monodisperse nanorods. This study further highlights the utility of using wavelength to control the size and shape of growing nanoparticles using plasmon-mediated methods.

Synthesis and isolation of {110}-faceted gold bipyramids and rhombic dodecahedra.

Two {110}-faceted gold nanostructures--rhombic dodecahedra and obtuse triangular bipyramids--have been synthesized via a Ag-assisted, seed-mediated growth method. The combination of a Cl(-)-containing surfactant with a low concentration of Ag(+) plays a role in the stabilization of the {110} facets. To the best of our knowledge, this is the first reported synthesis of a {110}-faceted bipyramid structure.

Concave cubic gold nanocrystals with high-index facets.

A new class of gold nanostructures, concave nanocubes, enclosed by 24 high-index {720} facets, have been prepared in a monodisperse fashion by a modified seed-mediated synthetic method. The Cl(-) counterion in the surfactant plays an essential role in controlling the concave morphology of the final product. The concave nanocubes exhibit higher chemical activities compared with low-index {111}-faceted octahedra.

Photomediated synthesis of silver triangular bipyramids and prisms: the effect of pH and BSPP.

The photomediated synthesis of silver right triangular bipyramids and prisms has been studied, and we have determined that pH and [BSPP]/[Ag(+)] ratio (bis(p-sulfonatophenyl)phenylphosphine, BSPP) finely control the reaction rate and, consequently, the crystal growth pathway and morphology of final products. A fast reaction rate, realized at a high pH such as 10 or 11 and a [BSPP]/[Ag(+)] ratio close to 1.0, is necessary to synthesize (100)-faceted right triangular bipyramids in high yield by preferential deposition on (111) facets of planar-twinned seeds. A slower reaction rate, which occurs at lower pH or higher [BSPP]/[Ag(+)] ratios, results in preferential deposition on (100) facets of planar-twinned seeds and the formation of nanoparticles possessing a larger surface area defined by (111) facets, such as truncated triangular bipyramids or prisms. BSPP further influences the reaction rate by ensuring a relatively constant concentration of aqueous Ag(+). In the absence of BSPP, the aqueous [Ag(+)] steadily decreases as it is consumed and results in a continuously decreasing reaction rate, which changes the preferred facet for silver deposition. At the beginning of the reaction, growth on (111) facets almost exclusively occurs and results in the formation of right triangular bipyramids, which only have (100) facets. When the reaction rate is decreased due to the consumption of Ag(+) through the course of the reaction, the facet deposition preference changes from (111) to (100) and results in the formation of truncated bitetrahedra, with (111) facets, as the predominant product.