Kevin L. Shuford

Multipolar excitation in triangular nanoprisms

Theoretical studies on the optical properties of gold triangular prisms in solution are presented to determine how structural modifications affect the extinction spectrum. Well-defined trends in the particle extinction are found to depend on the triangular edge length and the prism thickness. Calculations performed on large, thin triangular prisms indicate multipolar excitation and display numerous peaks in the extinction spectrum. The dominant peaks are assigned to different in-plane modes corresponding to the lowest three orders of a multipole expansion. Vector polarization plots are presented to support the peak assignments. Altering the prisms by snipping off the points of the triangular cross section significantly blueshifts the dipole peak, but the higher-order modes are only slightly affected. Snipping off large volumes can lead to the suppression of high-order multipoles in the extinction spectrum.

A Facile Polyol Route to Uniform Gold Octahedra with Tailorable Size and Their Optical Properties

A straightforward and effective polyol route for the controllable synthesis of high-quality gold (Au) octahedra with uniform size is presented in an ethylene glycol solution. Large-scale Au octahedra with the size ranging from tens to hundreds of nanometers were selectively synthesized in high-yield. The surfaces of octahedral Au nanocrystals are smooth and correspond to {111} planes. Formation of Au nanooctahedra was attributed to the preferential adsorption of cationic surfactant poly(diallyldimethylammonium) chloride (PDDA) molecules on the {111} planes of Au nuclei that inhibited the growth rate along the <111> direction. The reduction rate of gold ions in the synthesis process can be rationally manipulated by acidic and basic solutions. This provides a facile and effective route to harvest Au octahedra with different dimensions. The synthetic strategy has the advantage of one-pot and requires no seeds, no foreign metal ions, and no pretreatment of the precursor, so that this is a practical method for controllable synthesis of Au octahedra. Size-dependent optical properties of Au octahedra were numerically and experimentally analyzed. The analysis shows that Au octahedra with sharp edges possess attractive optical properties, promising their applications to surface-enhancement spectroscopy, chemical or biological sensing, and the fabrication of nanodevices.

Multiple surface plasmon modes for a colloidal solution of nanoporous gold nanorods and their comparison to smooth gold nanorods.

The paper represents a novel approach to investigating localized surface plasmon (LSP) resonance modes of nanoporous Au nanorods (NRs) in a solution phase with control over surface morphology. Au NRs, which have distinctive features such as nanopores and ligaments, showed interesting LSP resonance modes depending on the surface morphology and the total length of the structure. Compared with the analogous smooth surface NRs, the LSP modes of nanoporous NRs are red-shifted, which can be interpreted as a longer effective rod length and larger amplitude of plasmon oscillation.

Understanding controls on interfacial wetting at epitaxial graphene: Experiment and Theory

The interaction of interfacial water with graphitic carbon at the atomic scale is studied as a function of the hydrophobicity of epitaxial graphene. High resolution x-ray reflectivity shows that the graphene-water contact angle is controlled by the average graphene thickness, due to the fraction of the film surface expressed as the epitaxial buffer layer whose contact angle (contact angle {Theta}{sub c} = 73{sup o}) is substantially smaller than that of multilayer graphene ({Theta}{sub c} = 93{sup o}). Classical and ab initio molecular dynamics simulations show that the reduced contact angle of the buffer layer is due to both its epitaxy with the SiC substrate and the presence of interfacial defects. This insight clarifies the relationship between interfacial water structure and hydrophobicity, in general, and suggests new routes to control interface properties of epitaxial graphene.

Intraparticle surface plasmon coupling in quasi-one-dimensional nanostructures.

The optical properties of two-component quasi-one-dimensional nanostructures consisting of Au and Ni blocks have been investigated. The optically inactive component Ni plays a relaying role in the surface plasmon coupling both for the dipole mode and for the higher-order modes of gold blocks. The experimental results exhibit that the free electrons in Ni participate in the optical coupling phenomenon and that plasmon excitations in the Au blocks induce the free electrons in Ni to oscillate.

Fabrication of 2D Au Nanorings with Pt Framework

Surface plasmonics of nanomaterials has been one of the main research themes in nanoscience. Spherical and elongated nanoparticles show their corresponding unique optical features mainly depending on the physical dimensions. Here we successfully synthesized Au nanorings having Pt framework (Pt@Au nanorings) with high uniformity through wet-chemistry. The synthetic strategy consisted of serial reactions involving site-selective growth of Pt on the rim of Au nanoplates, subsequent etching of Au nanoplates, followed by regrowth of Au on the Pt rim. In this synthetic method, Au(3+) ions exhibited dual functionality as an etchant and a metal precursor. The resultant product, Pt@Au nanorings, exhibited unique localized surface plasmon resonance (LSPR) bands originating from the Au shell. The inner Pt skeleton turns out to be important to hold structural stability.

Multiple surface plasmon modes for gold/silver alloy nanorods.

Alloy nanorods consisting of bimetallic gold and silver are synthesized by employing the electrochemical codeposition of Au/Ag alloy materials into the pores of anodized aluminum oxide templates. This paper presents the variation of localized surface plasmon resonance (LSPR) modes of the Au(x)/Ag(1-x) alloy nanorods as a function of relative compositions of Au and Ag. Transverse and multiple longitudinal modes were observed when the length was longer than ca. 300 nm. For a given length, the transverse LSPR mode systematically blue-shifted as the Ag portion increased, while there was little variation in peak positions of the longitudinal LSPR modes. The optical properties of the Au(x)/Ag(1-x) alloy nanorods were calculated using the discrete dipole approximation and showed a good agreement with the experimental measurements.

1,2‐Phosphaborines: Hybrid Inorganic/Organic P–B Analogues of Benzene

Photolysis of the cyclic phosphine oligomer [PPh]5 in the presence of pentaarylboroles leads to the formation of 1,2-phosphaborines by the formal insertion of a phenylphosphinidene fragment into the endocyclic CB bond. The solid-state structure features a virtually planar central ring with bond lengths indicating significant delocalization. Appreciable ring current in the 1,2-phosphaborine core, detected in nuclear independent chemical shift (NICS) calculations, are consistent with aromatic character. These products are the first reported 1,2-BPC4 conjugated heterocycles and open a new avenue for BP as a valence isoelectronic substitute for CC in arene systems.

Efficient disc on pillar substrates for surface enhanced Raman spectroscopy

In this work, geometrical optimizations of Ag disc on pillar (DOP) hybrid plasmonic nanostructures were conducted and allowed us to achieve reproducible average enhancement factors of 1 × 10(9) and greater.

Octahedral and Cubic Gold Nanoframes with Platinum Framework.

Herein, we report a general synthetic pathway to various shapes of three-dimensional (3D) gold nanoframes (NFs) embedded with a Pt skeleton for structural rigidity. The synthetic route comprises three steps: site-specific (edge and vertex) deposition of Pt, etching of inner Au, and regrowth of Au on the Pt framework. Site-specific reduction of Pt on Au nanoparticles (NPs) led to the high-quality of 3D Au NFs with good structural rigidity, which allowed the detailed characterization of the corresponding 3D metal NFs. The synthetic method described here will open new avenues toward many new kinds of 3D metal NFs.