Lisa V. Brown

Hot Electrons Do the Impossible: Plasmon-Induced Dissociation of H2 on Au

Heterogeneous catalysis is of paramount importance in chemistry and energy applications. Catalysts that couple light energy into chemical reactions in a directed, orbital-specific manner would greatly reduce the energy input requirements of chemical transformations, revolutionizing catalysis-driven chemistry. Here we report the room temperature dissociation of H(2) on gold nanoparticles using visible light. Surface plasmons excited in the Au nanoparticle decay into hot electrons with energies between the vacuum level and the work function of the metal. In this transient state, hot electrons can transfer into a Feshbach resonance of an H(2) molecule adsorbed on the Au nanoparticle surface, triggering dissociation. We probe this process by detecting the formation of HD molecules from the dissociations of H(2) and D(2) and investigate the effect of Au nanoparticle size and wavelength of incident light on the rate of HD formation. This work opens a new pathway for controlling chemical reactions on metallic catalysts.

Aluminum Plasmonic Nanoantennas

The use of aluminum for plasmonic nanostructures opens up new possibilities, such as access to short-wavelength regions of the spectrum, complementary metal-oxide-semiconductor (CMOS) compatibility, and the possibility of low-cost, sustainable, mass-producible plasmonic materials. Here we examine the properties of individual Al nanorod antennas with cathodoluminescence (CL). This approach allows us to image the local density of optical states (LDOS) of Al nanorod antennas with a spatial resolution less than 20 nm and to identify the radiative modes of these nanostructures across the visible and into the UV spectral range. The results, which agree well with finite difference time domain (FDTD) simulations, lay the groundwork for precise Al plasmonic nanostructure design for a variety of applications.

Light-Induced Release of DNA from Gold Nanoparticles: Nanoshells and Nanorods

Plasmon-resonant nanoparticle complexes show highly promising potential for light-triggered, remote-controlled delivery of oligonucleotides on demand, for research and therapeutic purposes. Here we investigate the light-triggered release of DNA from two types of nanoparticle substrates: Au nanoshells and Au nanorods. Both light-triggered and thermally induced release are distinctly observable from nanoshell-based complexes, with light-triggered release occurring at an ambient solution temperature well below the DNA melting temperature. Surprisingly, no analogous measurable release was observable from nanorod-based complexes below the DNA melting temperature. These results suggest that a nonthermal mechanism may play a role in plasmon resonant, light-triggered DNA release.

Narrowband photodetection in the near-infrared with a plasmon-induced hot electron device

In gratings, incident light can couple strongly to plasmons propagating through periodically spaced slits in a metal film, resulting in a strong, resonant absorption whose frequency is determined by the nanostructure periodicity. When a grating is patterned on a silicon substrate, the absorption response can be combined with plasmon-induced hot electron photocurrent generation. This yields a photodetector with a strongly resonant, narrowband photocurrent response in the infrared, limited at low frequencies by the Schottky barrier, not the bandgap of silicon. Here we report a grating-based hot electron device with significantly larger photocurrent responsivity than previously reported antenna-based geometries. The grating geometry also enables more than three times narrower spectral response than observed for nanoantenna-based devices. This approach opens up the possibility of plasmonic sensors with direct electrical readout, such as an on-chip surface plasmon resonance detector driven at a single wavelength.

Surface-Enhanced Infrared Absorption Using Individual Cross Antennas Tailored to Chemical Moieties

The development of antenna structures for surface-enhanced infrared absorption spectroscopy (SEIRA) is a topic of intense and growing interest for extending IR spectroscopy to zeptomolar quantities and ultimately to the single-molecule level. Here we show that strong infrared spectroscopic enhancements can be obtained from individual gold nanoantennas using conventional IR spectrometric sources. The antenna structure dimensions can be tuned to enhance the IR modes of specific chemical moieties. Simulations of the electric field intensity in the antenna junction region reveal a maximum SEIRA enhancement factor of more than 12,000. These findings open new opportunities for analyzing IR vibrations of exceptionally small quantities of molecules using widely accessible light sources.

Fan-Shaped Gold Nanoantennas above Reflective Substrates for Surface-Enhanced Infrared Absorption (SEIRA)

Here, we report a new nanoantenna for surface-enhanced infrared absorption (SEIRA) detection, consisting of a fan-shaped Au structure positioned at a well-specified distance above a reflective plane with an intervening silica spacer layer. We examine how to optimize both the antenna dimensions and the spacer layer for optimal SEIRA enhancement of the C-H stretching mode. This tunable 3D geometry yields a theoretical SEIRA enhancement factor of 10(5), corresponding to the experimental detection of 20-200 zeptomoles of octadecanethiol, using a standard commercial FTIR spectrometer. Experimental studies illustrate the sensitivity of the observed SEIRA signal to the gap dimensions. The optimized antenna structure exhibits an order of magnitude greater SEIRA sensitivity than previous record-setting designs.

Manipulating magnetic plasmon propagation in metallic nanocluster networks.

Neighboring fused heptamers can support magnetic plasmons due to the generation of antiphase ring currents in the metallic nanoclusters. In this paper, we use such artificial plasmonic molecules as basic elements to construct low-loss plasmonic waveguides and devices. These magnetic plasmon-based complexes exhibit waveguiding functionalities including plasmon steering over large-angle bends, splitting at intersections, and Mach-Zehnder interference between consecutive Y-splitters. Our findings provide a strategy for circumventing significant challenges in the miniaturization and high-density integration of optical circuits in integrated optics, allowing for the development of ultracompact plasmonic networks for practical applications.

Targeting pancreatic cancer with magneto-fluorescent theranostic gold nanoshells

AIM We report a magneto-fluorescent theranostic nanocomplex targeted to neutrophil gelatinase-associated lipocalin (NGAL) for imaging and therapy of pancreatic cancer. MATERIALS & METHODS Gold nanoshells resonant at 810 nm were encapsulated in silica epilayers doped with iron oxide and the near-infrared (NIR) dye indocyanine green, resulting in theranostic gold nanoshells (TGNS), which were subsequently conjugated with antibodies targeting NGAL in AsPC-1-derived xenografts in nude mice. RESULTS Anti-NGAL-conjugated TGNS specifically targeted pancreatic cancer cells in vitro and in vivo providing contrast for both NIR fluorescence and T2-weighted MRI with higher tumor contrast than can be obtained using long-circulating, but nontargeted, PEGylated nanoparticles. The nanocomplexes also enabled highly specific cancer cell death via NIR photothermal therapy in vitro. CONCLUSION TGNS with embedded NIR and magnetic resonance contrasts can be specifically targeted to pancreatic cancer cells with expression of early disease marker NGAL, and enable molecularly targeted imaging and photothermal therapy.

Fan-shaped gold nanoantennas above reflective substrates for surface-enhanced infrared absorption (SEIRA) (Presentation Recording)

Surface-enhanced infrared absorption (SEIRA) has been gaining substantial attention by using plasmonic nanoantennas to amplify near-field intensities so that it can extend IR spectroscopy to zeptomolar quantities and ultimately to the sigle-molecule level. Here we report a new nanoantenna for SEIRA detection, consisting of a fan-shaped Au structure positioned at a well-specified distance above a reflective plane with an intervening silica spacer layer. This antenna can be easily tuned to overlap vibrational modes within a broad spectral range from the near-IR into terahertz regimes. Our finite difference time domain (FDTD) simulations reveal a maximum SEIRA enhancement factor of 105 in the antenna junction area, which is corresponding to the experimental detection of 20-200 zeptomoles of octadecanethiol, using a standard commercial FTIR spectrometer. Our optimized antenna exhibits an order of magnitude greater SEIRA sensitivity than previous record-setting designs, which opens new opportunities for using infrared spectroscopy to analyze exceptionally small quantities of molecules.