Computational study of the structure, dynamics, and photophysical properties of conjugated polymers and oligomers under nanoscale confinement.

Computational simulations were used to investigate the dynamics and resulting structures of several para-phenylenevinylene (PPV) based polymers and oligomers (PPV, 2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylenevinylene --> MEH-PPV and 2,5,2',5'-tetrahexyloxy-7,8'-dicyano-p-phenylenevinylene --> CN-PPV). The results show how the morphology and structure are controlled to a large extent by the nature of the solute-solvent interactions in the initial solution-phase preparation. Secondary structural organization is induced by using the solution-phase structures to generate solvent-free single molecule nanoparticles. Isolation of these single molecule nanostructures from microdroplets of dilute solution results in the formation of electrostatically oriented nanostructures at a glass surface. Our structural modeling suggests that these oriented nanostructures consist of folded PPV conjugated segments with folds occurring at tetrahedral defects (sp3 C-C bonds) within the polymer chain. This picture is supported by detailed experimental fluorescence and scanning probe microscopy studies. We also present results from a fully quantum theoretical treatment of these systems which support the general conclusion of structure-mediated photophysical properties.

Photon antibunching from oriented semiconducting polymer nanostructures.

Fluorescence intensity correlation measurements reveal that z-oriented nanostructures from single chains of a cyano-substituted polyphenylene vinylene (CN-PPV) polymer act as single-quantum emitters. Photon antibunching is observed for the first time on individual polymer nanostructures with a modulation depth exceeding 90%, providing definitive proof that radiative recombination of molecular excitons occurs at a single localized site within the folded polymer chain.

Size-correlated spectroscopy and imaging of rare-earth-doped nanocrystals.

Isolated europium-doped metal-oxide nanoparticles were probed by size-correlated high-numerical-aperture (far-field) imaging techniques. A modified Digital Instruments Bioscope atomic force microscope mounted upon a Nikon TE300 inverted microscope was used to interrogate (dry) particles ranging in size from 2 to 150 nm on the surface of a glass or quartz coverslip. These experiments revealed several interesting features of doped-nanoparticle luminescence such as Poissonian occupation statistics, size-dependent luminescence efficiency enhancement for particle sizes of <10 nm, and correlation of interesting transient behavior at particle sizes of <5 nm.