Kent A. Meyer

Combined chemical and topographic imaging at atmospheric pressure via microprobe laser desorption/ionization mass spectrometry–atomic force microscopy

The operational characteristics and imaging performance are described for a new instrument comprising an atomic force microscope coupled with a pulsed laser and a linear ion trap mass spectrometer. The operating mode of the atomic force microscope is used to produce topographic surface images having sub-micrometer spatial and height resolution. Spatially resolved mass spectra of ions, produced from the same surface via microprobe-mode laser desorption/ionization at atmospheric pressure, are also used to create a 100 x 100 microm chemical image. The effective spatial resolution of the image (approximately 2 microm) was constrained by the limit of detection (estimated to be 10(9)-10(10) molecules) rather than by the diameter of the focused laser spot or the step size of the sample stage. The instrument has the potential to be particularly useful for surface analysis scenarios in which chemical analysis of targeted topographic features is desired; consequently, it should have extensive application in a number of scientific areas. Because the number density of desorbed neutral species in laser desorption/ionization is known to be orders-of-magnitude greater than that of ions, it is expected that improvements in imaging performance can be realized by implementation of post-ionization methods.

Highly efficient solid-state neutron scintillators based on hybrid sol-gel nanocomposite materials

This research highlights opportunities in the formulation of neutron scintillators that not only have high scintillation efficiencies but also can be readily cast into two-dimensional detectors. Series of transparent, crack-free monoliths were prepared from hybrid polystyrene-silica nanocomposites in the presence of arene-containing alkoxide precursor through room temperature sol-gel processing. The monoliths also contain lithium-6 salicylate as a target material for neutron-capture reactions and amphiphilic scintillator solution as a fluorescent sensitizer. Polystyrene was functionalized by trimethoxysilyl group in order to enable the covalent incorporation of aromatic functional groups into the inorganic sol-gel matrices for minimizing macroscopic phase segregation and facilitating lithium-6 doping in the sol-gel samples. Neutron and alpha responses of these hybrid polystyrene-silica monoliths were explored.

Development of a scanning surface probe for nanoscale tip-enhanced desorption/ablation

We report on the development of a versatile scanning apparatus for nanoscale surface sampling that utilizes the interaction of laser radiation at a sharp probe tip to effect desorption/ablation on opaque substrates. The process, which currently yields surface craters as small as approximately 50 nm diameterx5 nm deep, has been demonstrated with both metal-coated and bare silicon tips. Desorption/ablation under the tip occurs at illumination intensities below the corresponding optical far-field threshold, suggesting that the latter process should not degrade the spatial resolution attainable for proposed chemical imaging methods based on the scanning surface probe.

Combined Apertureless Near-Field Optical Second-Harmonic Generation/Atomic Force Microscopy Imaging and Nanoscale Limit of Detection

A dual function atomic force/near-field scanning optical microscope (AFM/NSOM) with an ultrafast laser excitation source was used to investigate apertureless, tip enhanced second-harmonic generation (SHG) of ZnO nanowires with spatial resolution below the optical diffraction limit. Single-wire SHG spectra show little to no contribution from bandgap or other emission. Polarization data established values for X33/X31 close to previous estimates and confirm the SHG process. Experimental results indicate that the SHG signal was reduced for nanowires after exposure to an atmosphere of carbon dioxide and water vapor. An equation was derived for estimating the minimum X(2) detectable using apertureless SHG NSOM.

Computational and Experimental Evaluation of Nanoparticle Coupling

We present theoretical and experimental studies on the optical properties of dimers composed of octahedron-shaped, gold nanoparticles. The experimental measurements show that the photoluminescence varies quite dramatically as two octahedra are brought into close proximity. AFM images and optical emission have been recorded for dimers in uncoupled and strongly coupled configurations. The former displays a single emission peak, while the latter shows two peaks with the new feature at longer wavelengths. Calculations indicate that the red-shifted peak originates from a strongly coupled plasmon state that oscillates along the extended axis of the dimer. Theoretically, we investigate the distances over which the dimers couple and find this to be particularly plasmon mode dependent. The anisotropic morphology and sharp apexes contribute significantly to the orientational dependence of the interparticle couplings and field properties.

Surface coating effects on the assembly of gold nanospheres

Optical spectra and atomic force microscopy (AFM) images of individually selected spheres and mechanically assembled silica-coated gold nanosphere pairs were recorded. The shell served as a means of rigid control of the minimum spacing between the metal cores. The spectra of the assembled spheres were simulated using classical electrodynamics. The observed spectra resulted in superior characterization of the particle assembly geometry, relative to the AFM data. Experimental investigations regarding less-rigid polyvinylpyrrolidone (PVP) sphere coatings were also performed and some comparisons were made.

Optical Absorption Measurements with Parametric Down-Converted Photons

It has been known for some time that correlated detection of pairs of photons generated by parametric down-conversion can eliminate several sources of error that occur in single-beam measurements. In the correlated photon measurements, the down-converted photons are separated into two beams with one photon of a pair in each beam. The absolute detection efficiency of a detector in one beam can be determined from the count rate of a detector in the other beam and the coincidence rate for the two detectors. These ideas can be used to measure the optical absorbance of a sample placed in front of one of the detectors. Errors due to stray light and dark counts are substantially reduced and fluctuations in pump intensity largely eliminated.

Nanoscale coupling effects on single particle microscopy

We present theoretical studies and experimental results on the optical properties of gold, octahedra-shaped nanoparticles. We show that the optical spectrum varies quite dramatically as two nanoparticles are brought into close proximity. AFM images and optical spectra have been obtained for nanooctahedra dimers in uncoupled and strongly coupled configurations. The former displays a single peak in the optical spectrum, while the latter shows an additional peak at longer wavelengths. Calculations indicate that the additional spectral feature originates from a strongly coupled plasmon state that oscillates along the extended axis of the dimer. We investigate theoretically the distances over which the dimers couple and find these results to be particularly orientation dependent. The anisotropic particle shape and sharp apices contribute significantly to the orientational dependence of the interparticle couplings.