The Effect of Surface Chemistry on the Glass Transition of Polycarbonate Inside Cylindrical Nanopores.

The effect of surface chemistry on the glass transition of polycarbonate (PC) inside cylindrical nanopores is studied. Polycarbonate is melt-wetted into nanoporous anodic aluminum oxide (AAO) treated with hydrophobic alkyl- and fluorosilanes of varying length. The curvature observed at the nanowire tips is consistent with a contact angle descriptive of polycarbonate-AAO surface interactions. Differential scanning calorimetry (DSC) thermograms reveal a distinct broadening of the Tg that is related to the motion of polymer chains at the nanopore wall as well as at the core. DSC and thermal gravimetric analysis (TGA) show that polycarbonate infiltrated into a naked AAO template (without silane treatment) degrades upon heating, suggestive of a surface-catalyzed degradation mechanism. It is further shown that silane treatment largely prevents PC thermal degradation.

The effect of nanoparticle location and shape on thermal transitions observed in hydrated layer-by-layer assemblies.

Nanoparticles can have a profound effect on thermal transitions observed in polymer nanocomposites. Many layer-by-layer (LbL) assemblies contain nanoparticles for added functionality, but the resulting effects of nanoparticles on an LbL film's thermal properties are not known. Previously, we have shown that a nanoparticle-free LbL film containing strong polyelectrolytes, poly(diallyldimethylammonium chloride)/poly(styrene sulfonate) (PDAC/PSS), exhibited a single reversible thermal transition much like a glass-melt transition. In the work presented here, nanoparticles of either spherical (SiO2) or platelet (Laponite clay) shape are inserted at varying vertical locations throughout PDAC/PSS LbL films. Temperature-controlled quartz crystal microbalance (QCM-D) and modulated differential scanning calorimetry (MDSC) are applied, for which QCM-D proved to be more sensitive to the transition. All Laponite-containing films possess two thermal transitions. During growth, Laponite-containing films exhibit steady increases in dissipation, which is proposed to arise from mechanically decoupled regions separated by the Laponite nanoparticles. For SiO2-containing films, three transitions are detectable only when the SiO2 nanoparticles are placed in the middle of the film; no transitions are observed for SiO2 placed at the bottom or top, perhaps because of a weakening of the transition. The lowest transition is close in value to that of neat PDAC/PSS LbL films, and was assigned to a "bulk" response. The higher transition(s) is attributed to polymer chains in an interfacial region near the nanoparticle. We propose that nanoparticles restrict segmental mobility, thus elevating the transition temperature in the interfacial region.

In vivo whole animal fluorescence imaging of a microparticle-based oral vaccine containing (CuInSe(x)S(2-x))/ZnS core/shell quantum dots.

Zinc sulfide-coated copper indium sulfur selenide (CuInSexS2-x/ZnS core/shell) nanocrystals were synthesized with size-tunable red to near-infrared (NIR) fluorescence with high quantum yield (40%) in water. These nanocrystals were tested as an imaging agent to track a microparticle-based oral vaccine administered to mice. Poly(lactic-co-glycolic acid) (PLGA) microparticle-encapsulated CuInSexSe2-x/ZnS quantum dots were orally administered to mice and were found to provide a distinct visible fluorescent marker in the gastrointestinal tract of living mice.

A comparison of thermal transitions in dip- and spray-assisted layer-by-layer assemblies.

Spray-assisted layer-by-layer (LbL) assembly is far more rapid than conventional dip-assisted assembly methods and has gained widespread interest recently. Even so, it has remained unclear as to how the structure and properties of the resulting LbL film vary with processing method. Here, we compared the thermal properties of poly(ethylene oxide) (PEO)/poly(acrylic acid) (PAA) and PEO/poly(methacrylic acid) (PMAA) hydrogen-bonded LbL assemblies prepared using both dip-assisted and spray-assisted deposition methods. While the surface morphologies of PEO/PAA LbL assemblies were similar, those of PEO/PMAA LbL assemblies were greatly influenced by deposition method. In both PEO/PAA and PEO/PMAA LbL assemblies, glass transition temperatures were not influenced by deposition method, but the transition's breadth was consistently larger for the spray-assisted LbL films. These results indicate that the internal structure of spray-assisted LbL films is slightly more heterogeneous, possibly arising from the shorter time scale of deposition.

Influence of composition on the performance of sintered Cu(In,Ga)Se2 nanocrystal thin-film photovoltaic devices.

Thin-film photovoltaic devices (PVs) were prepared by selenization using oleylamine-capped Cu(In,Ga)Se2 (CIGS) nanocrystals sintered at a high temperature (>500 °C) under Se vapor. The device performance varied significantly with [Ga]/[In+Ga] content in the nanocrystals. The highest power conversion efficiency (PCE) observed in the devices studied was 5.1 % under air mass 1.5 global (AM 1.5 G) illumination, obtained with [Ga]/[In+Ga]=0.32. The variation in PCE with composition is partly a result of bandgap tuning and optimization, but the main influence of nanocrystal composition appeared to be on the quality of the sintered films. The [Cu]/[In+Ga] content was found to be strongly influenced by the [Ga]/[In+Ga] concentration, which appears to be correlated with the morphology of the sintered film. For this reason, only small changes in the [Ga]/[In+Ga] content resulted in significant variations in device efficiency.

CuInSe2 Quantum Dot Solar Cells with High Open-Circuit Voltage.

CuInSe2 (CISe) quantum dots (QDs) were synthesized with tunable size from less than 2 to 7 nm diameter. Nanocrystals were made using a secondary phosphine selenide as the Se source, which, compared to tertiary phosphine selenide precursors, was found to provide higher product yields and smaller nanocrystals that elicit quantum confinement with a size-dependent optical gap. Photovoltaic devices fabricated from spray-cast CISe QD films exhibited large, size-dependent, open-circuit voltages, up to 849 mV for absorber films with a 1.46 eV optical gap, suggesting that midgap trapping does not dominate the performance of these CISe QD solar cells.

Raman Spectroscopy of Oxide-Embedded and Ligand-Stabilized Silicon Nanocrystals.

Oxide-embedded and oxide-free alkyl-terminated silicon (Si) nanocrystals with diameters ranging from 3 nm to greater than 10 nm were studied by Raman spectroscopy. For ligand-passivated nanocrystals, the zone center Raman-active mode of diamond cubic Si shifted to lower frequency with decreasing size, accompanied by asymmetric peak broadening, as extensively reported in the literature. The size dependence of the Raman peak shifts, however, was significantly more pronounced than previously reported or predicted by the RWL (Richter, Wang, and Ley) and bond polarizability models. In contrast, Raman peak shifts for oxide-embedded nanocrystals were significantly less pronounced as a result of the stress induced by the matrix.

Thickness-limited performance of CuInSe2 nanocrystal photovoltaic devices.

This paper reports our latest results using colloidal CuInSe2 nanocrystal inks to prepare photovoltaic (PV) devices. Thus far, devices with nanocrystal layers processed under ambient conditions with no post-deposition treatment have achieved power conversion efficiencies of up to 3.1%. Device efficiency is largely limited by charge carrier trapping in the nanocrystal layer, and the highest device efficiencies are obtained with very thin layers-less than 150 nm-absorbing only a fraction of the incident light. Devices with thicker nanocrystal layers had lower power conversion efficiency, despite the increased photon absorption, because the internal quantum efficiency of the devices decreased significantly. The thin, most efficient devices exhibited internal quantum efficiencies as high as 40%, across a wide spectrum. Mott-Schottky measurements revealed that the active region thickness in the devices is approximately 50 nm.