In this work, we use dark-field microscopy to observe a new plasmon resonance effect for a single silver nanocube in which the plasmon line shape has two distinct peaks when the particles are located on a glass substrate. The dependence of the resonance on nanocube size and shape is characterized, and it is found that the bluer peak has a higher figure of merit for chemical sensing applications than that for other particle shapes that have been studied previously. Comparison of the measured results with finite difference time domain (FDTD) electrodynamics calculations enables us to confirm the accuracy of our spectral assignments.

The plasmonic properties of single silver triangular nanoprisms are investigated using dark-field optical microscopy and spectroscopy. Two distinct localized surface plasmon resonances (LSPR) are observed. These are assigned as in-plane dipolar and quadrupolar plasmon excitations using electrodynamic modeling based on the discrete dipole approximation (DDA). The dipole resonance is found to be very intense, and its peak wavelength is extremely sensitive to the height, edge length, and tip sharpness of the triangular nanoprism. In contrast, the intensity of the quadrupole resonance is much weaker relative to the dipole resonance in the single particle spectra than in the ensemble averaged spectrum. Several parameters relevant to the chemical sensing properties of these nanoprisms have been measured. The dependence of the dipole plasmon resonance on the refractive index of the external medium is found to be as high as 205 nm RIU(-1) and the plasmon line width as narrow as approximately 0.17 eV. These data lead to a sensing figure of merit (FOM), the slope of refractive index sensitivity in eV RIU(-1)/line width (eV), as high as 3.3. In addition, the LSPR shift response to alkanethiol chain length was found to be linear with a slope of 4.4 nm per CH2 unit. This is the highest short-range refractive index sensitivity yet measured for a nanoparticle.

The plasmonic properties of noble metal nanoparticles have potential uses in a wide variety of technologies, particularly sensing devices, based on their optical response. To better understand how nanoparticles can be incorporated in such devices, the detailed relationship between the optical response and structural properties of single nanoparticles is needed. Here we demonstrate that correlated localized surface plasmon resonance (LSPR) spectroscopy and high-resolution transmission electron microscopy (HRTEM) measurements can be used to obtain the optical response and detailed structural information for a single nanoparticle, using a silver (Ag) nanocube as the example. By carefully incorporating the HRTEM structural details into finite-difference time-domain (FDTD) electrodynamics calculations, excellent agreement with the LSPR measurements is obtained. The FDTD calculations show strong sensitivity between the nanocube optical response and the face-to-face width, corner and side rounding, and substrate of each cube, so careful determination of these parameters (1 nm resolution) is needed if theory and experiment are to match. In addition, the comparison of theory and experiment enables us to study the relative merits of the Johnson and Christy and Lynch and Hunter Ag dielectric data for describing perfect crystalline nanoparticles.

Eleven new quaternary rare-earth tellurides, CsLnZnTe3 (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Y), were prepared from solid-state reactions at 1123 K. These isostructural materials crystallize in the layered KZrCuS3 structure type in the orthorhombic space group Cmcm. The structure is composed of LnTe6 octahedra and ZnTe4 tetrahedra that share edges to form [LnZnTe3] layers. These layers stack perpendicular to [010] and are separated by layers of face- and edge-sharing CsTe8 bicapped trigonal prisms. There are no Te-Te bonds in the structure of these CsLnZnTe3 compounds so the formal oxidation states of Cs/Ln/Zn/Te are 1+/3+/2+/2-. Optical band gaps of 2.13 eV for CsGdZnTe3 and 2.12 eV for CsTbZnTe3 were deduced from single-crystal optical absorption measurements. A first-principles calculation of the density of states and the frequency-dependent optical properties was performed on CsGdZnTe3. The calculated band gap of 2.1 eV is in good agreement with the experimental value. A quadratic fit for the lanthanide contraction of the Ln-Te distance is superior to a linear one if the closed-shell atom is included.