Michael D. Barnes

Probing the chiroptical response of a single molecule.

Chirally sensitive measurement techniques have generally been restricted to bulk samples. Here, we report the observation of fluorescence-detected circular dichroism (FDCD) from single (bridgedtriarylamine) helicene molecules by using an excitation wavelength (457 nanometers) in the vicinity of an electronic transition that shows circular dichroism in bulk samples. The distributions of dissymmetry (g) parameters by analysis of signals from pure M- and P-type diastereomers are almost perfect mirror images of one another, each spanning a range of both positive and negative values. In addition, we observe a well-defined structure in the histogram of dissymmetry parameters suggestive of specific molecular orientations at the polymer interface. These single-molecule results highlight strong intrinsic circular dichroism responses that can be obscured by cancellation effects in ensemble measurements of a randomly oriented bulk sample.

Observation of dipolar emission patterns from isolated Eu3+:Y2O3 doped nanocrystals: new evidence for single ion luminescence

Abstract We report results of emission pattern imaging experiments from single Eu3+:Y2O3 nanocrystals (3–12 nm size) designed to provide new insight on the luminescence dynamics of isolated rare-earth doped nano-phosphors. We observe dipolar emission patterns that are characteristic of single quantum emitters whose orientation appears fixed on the measurement time scale. We also show that the luminescence from single nanoparticles is linearly polarized, also characteristic of single quantum system behavior. Taken in combination with dynamical observations of blinking and discrete photobleaching, these experiments provide strong evidence for single ion luminescence, and confirm the dipolar nature of the optical transitions of Eu3+ in inorganic crystals.

Tuning aggregation of poly(3-hexylthiophene) within nanoparticles.

Nanoparticles derived from π-conjugated polymers have gained widespread attention as active layer materials in various organic electronics applications. The optoelectronic, charge transfer, and charge transport properties of π-conjugated polymers are intimately connected to the polymer aggregate structure. Herein we show that the internal aggregate structure of regioregular poly(3-hexylthiophene) (P3HT) within polymer nanoparticles can be tuned by solvent composition during nanoparticle fabrication through the miniemulsion process. Using absorption spectra and single-NP photoluminescence decay properties, we show that a solvent mixture consisting of a low boiling good solvent and a high boiling marginal solvent results in polymer aggregate structure with a higher degree of uniformity and structural order. We find that the impact of solvent on the nature of P3HT aggregation within nanoparticles is different from what has been reported in thin films.

Quantum dots coordinated with conjugated organic ligands: new nanomaterials with novel photophysics

CdSe quantum dots functionalized with oligo-(phenylene vinylene) (OPV) ligands (CdSe-OPV nanostructures) represent a new class of composite nanomaterials with significantly modified photophysics relative to bulk blends or isolated components. Single-molecule spectroscopy on these species have revealed novel photophysics such as enhanced energy transfer, spectral stability, and strongly modified excited state lifetimes and blinking statistics. Here, we review the role of ligands in quantum dot applications and summarize some of our recent efforts probing energy and charge transfer in hybrid CdSe-OPV composite nanostructures.

Homogeneous linewidths of Rhodamine 6G at room temperature from cavity-enhanced spontaneous emission rates

Fluorescence lifetimes of Rhodamine 6G in levitated micron‐sized droplets have been measured using a time‐correlated photon counting technique. The coupling of emission into spherical cavity modes of the droplet results in significant emission rate enhancements which allow estimation of the homogeneous linewidth at room temperature.

Probing Inter- and Intrachain Exciton Coupling in Isolated Poly(3-hexylthiophene) Nanofibers: Effect of Solvation and Regioregularity.

We report wavelength and time-resolved photoluminescence studies of isolated extended (1-10 μm length) poly(3-hexylthiophene) (P3HT) nanofibers (xNFs) cast on glass from suspension. The PL spectra of xNFs show multiple vibronic replicas that appear to be associated with the existence of both H- and J-type aggregates. The PL spectra of xNFs made from regioregular (rr)- (93%) and highly regioregular (hrr)-P3HT (98%) both show similarities in PL spectra suggestive of common chain packing features, as well as subtle differences that can be attributed to higher long-range order in the hrr-xNFs. Specifically, PL spectral measurements on isolated xNFs made from highly regioregular (>98%) P3HT showed a red-shifted electronic origin (≈30 meV) and increased 0-0/0-1 PL intensity ratio for the J-type species, suggestive of enhanced structural coherence length and intrachain order.

SINGLE-MOLECULE ANALYSIS OF ULTRADILUTE SOLUTIONS WITH GUIDED STREAMS OF 1-MU M WATER DROPLETS

We describe instrumentation for real-time detection of single-molecule fluorescence in guided streams of 1-µm (nominal) water droplets. In this technique, target molecules were confined to droplets whose volumes were comparable with illumination volumes in diffraction-limited fluorescence microscopy and guided to the waist of a cw probe laser with an electrostatic potential. Concentration detection limits for Rhodamine 6G in water were determined to be ∼1 fM, roughly 3 orders of magnitude lower than corresponding limits determined recently with diffraction-limited microscopy techniques for a chemical separation of similar dyes. In addition to its utility as a vehicle for probing single molecules, instrumentation for producing and focusing stable streams of 1–2-µm-diameter droplets may have other important analytical applications as well.

Confinement and manipulation of individual molecules in attoliter volumes.

We report observation of fluorescence from individual rhodamine 6G molecules in streams of charged 1-μm-diameter water droplets. With this approach, illumination volumes comparable to diffraction-limited fluorescence microscopy techniques (≤500 aL) are achieved, resulting in similarly high contrast between single-molecule fluorescence signals and nonfluorescent background. However, since the fluorescent molecules are confined to electrically charged droplets, in situ electrodynamic manipulation (e.g., focusing, switching, or merging) can be accomplished in a straightforward manner, allowing experimental control over both the delivery of molecules of interest to the observation region and the laser-molecule interaction time. As illustrated by photocount statistics that are independent of molecular diffusion and spatial characteristics of the excitation field, individual rhodamine 6G molecules in 1-μm droplets are reproducibly delivered to a target a few micrometers in diameter at a rate of between 10 and 100 Hz, with laser beam transit times more than 1 order of magnitude longer than diffusion-limited laser-molecule interaction times in equivalent volumes of free solution.

Azulene Methacrylate Polymers: Synthesis, Electronic Properties, and Solar Cell Fabrication

We report the synthesis of novel azulene-substituted methacrylate polymers by free radical polymerization, in which the azulene moieties represent hydrophobic dipoles strung pendant to the polymer backbone and impart unique electronic properties to the polymers. Tunable optoelectronic properties were realized by adjusting the azulene density, ranging from homopolymers (having one azulene group per repeat unit) to copolymers in which the azulene density was diluted with other pendant groups. Treating these polymers with organic acids revealed optical and excitonic behavior that depended critically on the azulene density along the polymer chain. Copolymers of azulene with zwitterionic methacrylates proved useful as cathode modification layers in bulk-heterojunction solar cells, where the relative azulene content affected the device metrics and the power conversion efficiency reached 7.9%.

A CCD based approach to high-precision size and refractive index determination of levitated microdroplets using Fraunhofer diffraction

We describe a fast and convenient method of high precision size and refractive index determination of electrodynamically levitated microdroplets using Fraunhofer diffraction. The diffraction data were obtained with a 16-bit, unintensified charge coupled device (CCD) camera, and converted into angle-resolved elastic scattering intensity patterns by means of a carefully determined set of transformation parameters. The angular scattering patterns were analyzed without any a priori estimate of the droplet size and only a nominal estimate (≈2%) of the refractive index. Experimental angular scattering patterns were fit to calculated patterns from Mie theory using a graded step-size and scaling algorithm and optimized with respect to both droplet diameter and refractive index (real part only) with a precision of ⩽3 parts in 104 and 1 part in 103, respectively. Potential application to quantitative fluorescence and Raman spectroscopy, as well as mixture analysis in microdroplets is discussed.