Jesse Theiss

Plasmonic nanoparticle arrays with nanometer separation for high-performance SERS substrates.

We demonstrate a method for fabricating arrays of plasmonic nanoparticles with separations on the order of 1 nm using an angle evaporation technique. Samples fabricated on thin SiN membranes are imaged with high-resolution transmission electron microscopy (HRTEM) to resolve the small separations achieved between nanoparticles. When irradiated with laser light, these nearly touching metal nanoparticles produce extremely high electric field intensities, which result in surface-enhanced Raman spectroscopy (SERS) signals. We quantify these enhancements by depositing a p-aminothiophenol dye molecule on the nanoparticle arrays and spatially mapping their Raman intensities using confocal micro-Raman spectroscopy. Our results show significant enhancement when the incident laser is polarized parallel to the axis of the nanoparticle pairs, whereas no enhancement is observed for the perpendicular polarization. These results demonstrate proof-of-principle of this fabrication technique. Finite difference time domain simulations based on HRTEM images predict an electric field intensity enhancement of 82400 at the center of the nanoparticle pair and an electromagnetic SERS enhancement factor of 10(9)-10(10).

Electrical and Optical Characterization of Surface Passivation in GaAs Nanowires

We report a systematic study of carrier dynamics in Al(x)Ga(1-x)As-passivated GaAs nanowires. With passivation, the minority carrier diffusion length (L(diff)) increases from 30 to 180 nm, as measured by electron beam induced current (EBIC) mapping, and the photoluminescence (PL) lifetime increases from sub-60 ps to 1.3 ns. A 48-fold enhancement in the continuous-wave PL intensity is observed on the same individual nanowire with and without the Al(x)Ga(1-x)As passivation layer, indicating a significant reduction in surface recombination. These results indicate that, in passivated nanowires, the minority carrier lifetime is not limited by twin stacking faults. From the PL lifetime and minority carrier diffusion length, we estimate the surface recombination velocity (SRV) to range from 1.7 × 10(3) to 1.1 × 10(4) cm·s(-1), and the minority carrier mobility μ is estimated to lie in the range from 10.3 to 67.5 cm(2) V(-1) s(-1) for the passivated nanowires.

Raman spectroscopy of ripple formation in suspended graphene.

Using Raman spectroscopy, we measure the optical phonon energies of suspended graphene before, during, and after thermal cycling between 300 and 700 K. After cycling, we observe large upshifts ( approximately 25 cm(-1)) of the G band frequency in the graphene on the substrate region due to compression induced by the thermal contraction of the underlying substrate, while the G band in the suspended region remains unchanged. From these large upshifts, we estimate the compression in the substrate region to be approximately 0.4%. The large mismatch in compression between the substrate and suspended regions causes a rippling of the suspended graphene, which compensates for the change in lattice constant due to the compression. The amplitude (A) and wavelength (lambda) of the ripples, as measured by atomic force microscopy, correspond to an effective change in length Deltal/l that is consistent with the compression values determined from the Raman data.

Plasmon resonant enhancement of dye sensitized solar cells

We report an improvement in the efficiency of dye sensitized solar cells (DSSCs) by exploiting the plasmonic resonance of Au nanoparticles. By comparing the performance of DSSCs with and without Au nanoparticles, we demonstrate a 2.4-fold enhancement in the photoconversion efficiency. Enhancement in the photocurrent extends over the wavelength range from 460 nm to 730 nm. The underlying mechanism of enhancement is investigated by comparing samples with different geometries, including nanoparticles deposited on top of and embedded in the TiO2 electrode, as well as samples with the light absorbing dye molecule deposited on top of and underneath the Au nanoparticles. The mechanism of enhancement is attributed to the local electromagnetic response of the plasmonic nanoparticles, which couples light very effectively from the far field to the near field at the absorbing dye molecule monolayer, thereby increasing the local electron–hole pair (or exciton) generation rate significantly. The UV-vis absorption spectra and photocurrent spectra provide further information regarding the energy transfer between the plasmonic nanoparticles and the light absorbing dye molecules. Based on scanning electron microscope images, we perform electromagnetic simulations of these different Au nanoparticle/dye/TiO2 configurations, which corroborate the enhancement observed experimentally.

A microscopic study of strongly plasmonic Au and Ag island thin films

Thin Au and Ag evaporated films (∼5 nm) are known to form island-like growth, which exhibit a strong plasmonic response under visible illumination. In this work, evaporated thin films are imaged with high resolution transmission electron microscopy, to reveal the structure of the semicontinuous metal island film with sub-nm resolution. The electric field distributions and the absorption spectra of these semicontinuous island film geometries are then simulated numerically using the finite difference time domain method and compared with the experimentally measured absorption spectra. We find surface enhanced Raman scattering (SERS) enhancement factors as high as 108 in the regions of small gaps (≤2 nm), which dominate the electromagnetic response of these films. The small gap enhancement is further substantiated by a statistical analysis of the electric field intensity as a function of the nanogap size. Areal SERS enhancement factors of 4.2 × 104 are obtained for these films. These plasmonic films can also ...

Direct observation of heat dissipation in individual suspended carbon nanotubes using a two-laser technique

A two-laser technique is used to investigate heat spreading along individual single walled carbon nanotube (SWCNT) bundles in vacuum and air environments. A 532 nm laser focused on the center of a suspended SWCNT bundle is used as a local heat source, and a 633 nm laser is used to measure the spatial temperature profile along the SWCNT bundle by monitoring the G band downshifts in the Raman spectra. A constant temperature gradient is observed when the SWCNT bundle is irradiated in vacuum, giving direct evidence of diffusive transport of the phonons probed by the Raman laser. In air, however, we observe an exponentially decaying temperature profile with a decay length of about 7 μm, due to heat dissipation from the SWCNT bundle to the surrounding gas molecules. The thermal conductivity of the suspended carbon nanotube (CNT) is determined from its electrical heating temperature profile as measured in vacuum and the nanotube bundle diameter measured via transmission electron microscopy. Based on the exponent...

Laser directed growth of carbon-based nanostructures by plasmon resonant chemical vapor deposition.

We exploit the strong plasmon resonance of gold nanoparticles in the catalytic decomposition of CO to grow various forms of carbonaceous materials. Irradiating gold nanoparticles in a CO environment at their plasmon resonant frequency generates high temperatures and strong electric fields required to break the CO bond. By varying the laser power, exposure time, and gas flow rate, we deposit amorphous carbon, graphitic carbon, and carbon nanotubes. The formation of iron oxide nanocrystals catalyzes the growth of carbon nanotubes. Predefined microstructure geometries are patterned by moving the focused laser spot during the growth process, forming suspended single-walled carbon nanotube structures. Raman spectroscopy, energy dispersive X-ray spectroscopy, and transmission electron microscopy are used to characterize the resulting material. The localized nature of the plasmonic heating enables growth of these materials, while the underlying substrate remains at room temperature.

Photocurrent spectroscopy of exciton and free particle optical transitions in suspended carbon nanotube pn-junctions

We study photocurrent generation in individual, suspended carbon nanotube pn-junction diodes formed by electrostatic doping using two gate electrodes. Photocurrent spectra collected under various electrostatic doping concentrations reveal distinctive behaviors for free particle optical transitions and excitonic transitions. In particular, the photocurrent generated by excitonic transitions exhibits a strong gate doping dependence, while that of the free particle transitions is gate independent. Here, the built-in potential of the pn-junction is required to separate the strongly bound electron-hole pairs of the excitons, while free particle excitations do not require this field-assisted charge separation. We observe a sharp, well defined E11 free particle interband transition in contrast with previous photocurrent studies. Several steps are taken to ensure that the active charge separating region of these pn-junctions is suspended off the substrate in a suspended region that is substantially longer than th...

Tailoring the crystal structure of individual silicon nanowires by polarized laser annealing

We study the effect of polarized laser annealing on the crystalline structure of individual crystalline-amorphous core-shell silicon nanowires (NWs) using Raman spectroscopy. The crystalline fraction of the annealed spot increases dramatically from 0 to 0.93 with increasing incident laser power. We observe Raman lineshape narrowing and frequency hardening upon laser annealing due to the growth of the crystalline core, which is confirmed by high resolution transmission electron microscopy (HRTEM). The anti-Stokes:Stokes Raman intensity ratio is used to determine the local heating temperature caused by the intense focused laser, which exhibits a strong polarization dependence in Si NWs. The most efficient annealing occurs when the laser polarization is aligned along the axis of the NWs, which results in an amorphous-crystalline interface less than 0.5 µm in length. This paper demonstrates a new approach to control the crystal structure of NWs on the sub-micron length scale.

Plasmonic mode mixing in nanoparticle dimers with nm-separations via substrate-mediated coupling

We fabricate arrays of metallic nanoparticle dimers with nanometer separation using electron beam lithography and angle evaporation. These “nanogap” dimers are fabricated on thin silicon nitride membranes to enable high resolution transmission electron microscope imaging of the specific nanoparticle geometries. Plasmonic resonances of the pairs are characterized by dark-field scattering micro-spectroscopy, which enables the optical scattering from individual nanostructures to be measured by using a spatially-filtered light source to illuminate a small area. Scattering spectra from individual dimers are correlated with transmission electron microscope images and finite-difference time-domain simulations of their electromagnetic response, with excellent agreement between simulation and experiment. We observe a strong polarization dependence with two dominant scattering peaks in spectra taken with the polarization aligned along the dimer axis. This response arises from a unique Fano interference, in which the bright hybridized modes of an asymmetric dimer are able to couple to the dark higherorder hybridized modes through substrate-mediated coupling. The presence of this interference is strongly dependent on the nanoparticle geometry that defines the plasmon energy profile but also on the intense localization of charge at the dielectric surface in the nanogap region for separations smaller than 6 nm.