We investigated the effect of substrate-induced strain on the metal-insulator transition (MIT) in single-crystalline VO(2) nanobeams. A simple nanobeam-substrate adhesion leads to uniaxial strain along the nanobeam length because of the nanobeam's unique morphology. The strain changes the relative stability of the metal (M) and insulator (I) phases and leads to spontaneous formation of periodic, alternating M-I domain patterns during the MIT. The spatial periodicity of the M-I domains can be modified by changing the nanobeam thickness and the Young's modulus of the substrate.

We report the synthesis of single-crystalline VO2 nanowires with rectangular cross sections using a vapor transport method. These nanowires have typical diameters of 60 (+/-30) nm and lengths up to >10 mum. Electron microscopy and diffraction measurements show that the VO2 nanowires are single crystalline and exhibit a monoclinic structure. Moreover, they preferentially grow along the [100] direction and are bounded by the (01) and (011) facets. These VO2 nanowires should provide promising materials for fundamental investigations of nanoscale metal-insulator transitions.

Plasmonics is a rapidly growing field, yet imaging of the plasmonic modes in complex nanoscale architectures is extremely challenging. Here we obtain spatial maps of the localized surface plasmon modes of high-aspect-ratio silver nanorods using electron energy loss spectroscopy (EELS) and correlate to optical data and classical electrodynamics calculations from the exact same particles. EELS mapping is thus demonstrated to be an invaluable technique for elucidating complex and overlapping plasmon modes.

The use of bottom-up fabrication of nanostructures for nanotechnology inherently requires two-dimensional control of the nanostructures at a particular surface. This could in theory be achieved crystallographically with a structure whose three-dimensional unit cell has two or more--tuneable--dimensions on the nanometre scale. Here, we present what is to our knowledge the first example of a truly periodic two-dimensional nanometre-scale phase separation in any inorganic material, and demonstrate our ability to tune the unit-cell dimensions. As such, it represents great potential for the use of standard ceramic processing methods for nanotechnology. The phase separation occurs spontaneously in the homologous series of the perovskite-based Li-ion conductor, (Nd(2/3-x)Li(3x))TiO3, to give two phases whose dimensions both extend into the nanometre scale. This unique feature could lead to its application as a template for the assembly of nanostructures or molecular monolayers.

Electromigrated nanogaps have shown great promise for use in molecular scale electronics. We have fabricated nanogaps on free-standing transparent SiN(x) membranes which permit the use of transmission electron microscopy (TEM) to image the gaps. The electrodes are formed by extending a recently developed controlled electromigration procedure and yield a nanogap with approximately 5 nm separation clear of any apparent debris. The gaps are stable, on the order of hours as measured by TEM, but over time (months) relax to about 20 nm separation determined by the surface energy of the Au electrodes. A major benefit of electromigrated nanogaps on SiN(x) membranes is that the junction pinches in away from residual metal left from the Au deposition which could act as a parasitic conductance path. This work has implications to the design of clean metallic electrodes for use in nanoscale devices where the precise geometry of the electrode is important.

Transitioning energy-intensive and environmentally intensive processes toward sustainable conditions is necessary in light of the current global condition. To this end, photocatalytic processes represent new approaches for H2 generation; however, their application toward tandem catalytic reactivity remains challenging. Here, we demonstrate that metal oxide materials decorated with noble metal nanoparticles advance visible light photocatalytic activity toward new reactions not typically driven by light. For this, Pd nanoparticles were deposited onto Cu2O cubes to generate a composite structure. Once characterized, their hydrodehalogenation activity was studied via the reductive dechlorination of polychlorinated biphenyls. To this end, tandem catalytic reactivity was observed with H2 generation via H2O reduction at the Cu2O surface, followed by dehalogenation at the Pd using the in situ generated H2. Such results present methods to achieve sustainable catalytic technologies by advancing photocatalytic approaches toward new reaction systems.

Since the observation of single-molecule surface-enhanced Raman scattering (SMSERS) in 1997, questions regarding the nature of the electromagnetic hot spots responsible for such observations still persist. For the first time, we employ electron-energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) to obtain maps of the localized surface plasmon modes of SMSERS-active nanostructures, which are resolved in both space and energy. Single-molecule character is confirmed by the bianalyte approach using two isotopologues of Rhodamine 6G. Surprisingly, the STEM/EELS plasmon maps do not show any direct signature of an electromagnetic hot spot in the gaps between the nanoparticles. The origins of this observation are explored using a fully three-dimensional electrodynamics simulation of both the electron-energy-loss probability and the near-electric field enhancements. The calculations suggest that electron beam excitation of the hot spot is possible, but only when the electron beam is located outside of the junction region.

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