Electrostatic layer-by-layer assembly of CdSe nanorod/polymer nanocomposite thin films.

Electrostatic layer-by-layer assembly was the basis for the synthesis of multilayer nanorod/polymer composite films. Cationic and water-soluble CdSe nanorods (NRs) were synthesized and partnered with anionic polymers including poly(sodium 4-styrenesulfonate) (PSS) and two polythiophene-based photoactive polymers, sodium poly[2-(3-thienyl)-ethoxy-4-butylsulfonate (PTEBS) and poly[3-(potassium-6-hexanoate)thiophene-2,5-diyl] (P3KHT). Controlled multilayer growth is shown through UV-vis spectroscopy, cross-sectional SEM and surface analytical techniques including atomic force microscopy. The formation of an intimate nanorod/conducting polymer bulk heterojunction is confirmed through cross-sectional SEM, TEM, and scanning Auger analysis. A series of photovoltaic devices was fabricated on ITO electrodes using CdSe NRs in combination with PTEBS or P3KHT. A thorough device analysis showed that performance was limited by low short circuit current although charge transfer was confirmed in the ELBL nanocomposite thin films.

Surface area characterization of obliquely deposited metal oxide nanostructured thin films.

The glancing angle deposition (GLAD) technique is used to fabricate nanostructured thin films with high surface area. Quantifying this property is important for optimizing GLAD-based device performance. Our group has used high-sensitivity krypton gas adsorption and the complementary technique of cyclic voltammetry to measure surface area as a function of deposition angle, thickness, and morphological characteristics for several metal oxide thin films. In this work, we studied amorphous titanium dioxide (TiO(2)), amorphous silicon dioxide (SiO(2)), and polycrystalline indium tin oxide (ITO) nanostructures with vertical and helical post morphologies over a range of oblique deposition angles from 0 to 86 degrees. Krypton gas sorption isotherms, evaluated using the Brunauer-Emmettt-Teller (BET) method, revealed maximum surface area enhancements of 880 +/- 110, 980 +/- 125, and 210 +/- 30 times the footprint area (equivalently 300 +/- 40, 570 +/- 70, and 50 +/- 6 m(2) g(-1)) for vertical posts TiO(2), SiO(2), and ITO. We also applied the cyclic voltammetry technique to these ITO films and observed the same overall trends as seen with the BET method. In addition, we applied the BET method to the measurement of helical films and found that the surface area trend was shifted with respect to that of vertical post films. This revealed the important influence of the substrate rotation rate and film morphology on surface properties. Finally, we showed that the surface area scales linearly with film thickness, with slopes of 730 +/- 35 to 235 +/- 10 m(2) m(-2) microm(-1) found for titania vertical post films deposited at angles from 70 to 85 degrees. This characterization effort will allow for the optimization of solar, photonic, and sensing devices fabricated from thin metal oxide films using GLAD.

Optical interference effects in the design of substrates for surface-enhanced Raman spectroscopy.

This paper presents results showing that the design of substrates used for surface-enhanced Raman spectroscopy (SERS) can impact the apparent enhancement factors (EFs) obtained due to optical interference effects that are distinct from SERS, providing additional enhancement of the Raman intensity. Thus, a combination of SERS and a substrate designed to maximize interference-based enhancement is demonstrated to give additional Raman intensity above that observed for SERS alone. The system explored is 4-nitroazobenzene (NAB) and biphenyl (BP) chemisorbed on a nanostructured silver film obtained by vacuum deposition of Ag on thermally oxidized silicon wafers. The enhancing silver layer is partially transparent, enabling a standing wave to form as a result of the combination of the incident light and light reflected from the underlying Si substrate (i.e., light that passes through the Ag and the intervening dielectric layer of SiO(x)). The Raman intensity is measured as a function of the thickness of the thermal oxide layer in the range from approximately 150 to approximately 400 nm, and despite a lack of morphological variation in the silver films, there is a strong dependence of the Raman intensity on the oxide thickness. The Raman signal for the optimal SiO(x) interlayer thickness is 38 times higher than the intensity obtained when the Ag particles are deposited directly onto Si (with native oxide). To account for the trends observed in the Raman intensity versus thickness data, calculations of the relative mean square electric field (MSEF) at the surface of the SiO(x) are carried out. These calculations are also used to further optimize the experimental setup.

Thienylsilane-modified indium tin oxide as an anodic interface in polymer/fullerene solar cells.

The generation and characterization of a robust thienylsilane molecular layer on indium tin oxide substrates was investigated. The molecular layer was found to reduce the oxidation potential required for the electrochemical polymerization of 3,4-ethylenedioxythiophene. The resulting electrochemically prepared poly(3,4-ethylenedioxythiophene):poly(p-styrenesulfonate) (ePEDOT:PSS) films were found to be more uniform in coverage with lower roughness and higher conductivity than analogous films fabricated with bare ITO. A relative improvement in the efficiency of 2,5-diyl-poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) bulk heterojunction solar cells was observed when devices were formed on thienylsilane-modified ITO electrodes, rather than unmodified ITO control electrodes.