David A. Rider

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.

Indium tin oxide nanopillar electrodes in polymer/fullerene solar cells

Using high surface area nanostructured electrodes in organic photovoltaic (OPV) devices is a route to enhanced power conversion efficiency. In this paper, indium tin oxide (ITO) and hybrid ITO/SiO(2) nanopillars are employed as three-dimensional high surface area transparent electrodes in OPVs. The nanopillar arrays are fabricated via glancing angle deposition (GLAD) and electrochemically modified with nanofibrous PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(p-styrenesulfonate)). The structures are found to have increased surface area as characterized by porosimetry. When applied as anodes in polymer/fullerene OPVs (architecture: commercial ITO/GLAD ITO/PEDOT:PSS/P3HT:PCBM/Al, where P3HT is 2,5-diyl-poly(3-hexylthiophene) and PCBM is [6,6]-phenyl-C(61)-butyric acid methyl ester), the air-processed solar cells incorporating high surface area, PEDOT:PSS-modified ITO nanoelectrode arrays operate with improved performance relative to devices processed identically on unstructured, commercial ITO substrates. The resulting power conversion efficiency is 2.2% which is a third greater than for devices prepared on commercial ITO. To further refine the structure, insulating SiO(2) caps are added above the GLAD ITO nanopillars to produce a hybrid ITO/SiO(2) nanoelectrode. OPV devices based on this system show reduced electrical shorting and series resistance, and as a consequence, a further improved power conversion efficiency of 2.5% is recorded.

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.

C60 Fullerene Nanocolumns–Polythiophene Heterojunctions for Inverted Organic Photovoltaic Cells

Inverted organic photovoltaic cells have been fabricated based on vertical C(60) nanocolumns filled with spin-coated poly[3-(4-carboxybutyl)thiophene-2,5-diyl] (P3CBT). These C(60) nanocolumns were prepared via glancing angle deposition (GLAD), an efficient synthetic approach that controls the morphology of the resulting film, including intercolumn spacing, nanostructure shapes, and overall film thickness, among others. Intercolumn spacing was tuned to better match the expected P3CBT exciton diffusion length while simultaneously increasing heterointerface area. Due to observed in situ dissolution of the C(60) nanocolumns in solvents typically used to spin-coat polythiophene-based polymers (i.e., chloroform and chlorobenzene), the carboxylic acid-substituted polythiophene, P3CBT, was used as it is soluble in dimethyl sulfoxide (DMSO), a solvent that did not affect the structure of the GLAD-produced C(60) nanostructures. Preservation of the C(60) nanocolumnar structure in the presence of DMSO, with and without P3CBT, was verified by absorbance spectroscopy and SEM imaging. Incorporating these nanostructured C(60)/P3CBT films into photovoltaic devices on indium tin oxide (ITO) showed that the engineered nanomorphology yielded a 5-fold increase in short-circuit current and a power conversion efficiency (PCE) increase from (0.2 ± 0.03)% to (0.8 ± 0.2)% when compared to a planar device. When compared to a standard bulk heterojunction (BHJ) device based upon the same materials, the C(60)-GLAD device outperformed fully solution-processed bulk heterojunctions, which were observed to have PCEs of (0.49 ± 0.03)%.

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.

Layer-by-Layer Assembled Multilayers of Polyethylenimine-Stabilized Platinum Nanoparticles and PEDOT:PSS as Anodes for the Methanol Oxidation Reaction

Polyethylenimine-capped platinum nanoparticles (PEI-capped Pt NPs) are synthesized by photoreduction and qualified as a component for electrostatic layer-by-layer assembly and subsequent electrocatalysis. The PEI-capped Pt NPs are characterized for size and charge using scanning force microscopy, transmission electron microscopy, dynamic light scattering and zetapotential. Well-defined multilayers are produced via thin film electrostatic assembly of PEI-capped Pt NPs with the conducting polymer: poly(3,4-ethylenedioxythiophene):poly(p-styrenesulfonate) [(PEDOT:PSS)(-)Na(+)]. The composite thin films are subsequently characterized by ultraviolet-visible spectroscopy, scanning force microscopy, inductively coupled plasma mass spectroscopy and thermogravimetric analysis. The layer-by-layer deposition process was found to proceed in a controlled manner which permits the fabrication of stable and uniform multilayer thin films. [PEI-capped Pt NPs/(PEDOT:PSS)] multilayers were found to be an active catalyst coating for the oxidation of methanol and a 20 bilayer film proceeds with a stable level of catalyst activity for over 1000 oxidation cycles.

Block copolymer templated synthesis of PtIr bimetallic nanocatalysts for the formic acid oxidation reaction

Arrays of PtIr alloy nanoparticle (NP) clusters are synthesized from a method using block copolymer templates, which allows for relatively narrow NP diameter distributions (∼4–13 nm) and uniform intercluster spacing (∼60 or ∼100 nm). Polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer micelles were used to create thin film templates of NPs with periodic pyridinium-rich domains that are capable of electrostatically loading PtCl62− and IrCl62− anion precursors for the preparation of NP arrays. The composition of PtIr NPs was specified by the ratio of metal anions in a low-pH immersion bath. Formic acid oxidation, studied by cyclic voltammetry, shows that the arrays of clusters of PtIr alloy NPs are highly active catalysts, with mass activity values on par or exceeding current industrial standard catalysts. The uniformity in the NP population in a cluster and the small diameter range established by the block copolymer template permit an estimate of the optimal Pt : Ir ratio for the direct oxidation of formic acid, where, ∼10 nm Pt16Ir84 alloy NPs were the most active with a mass activity of 37 A g−1.

Synthesis and Characterization of Tunable, pH-Responsive Nanoparticle–Microgel Composites for Surface-Enhanced Raman Scattering Detection

The synthesis of microgels with pH-tunable swelling leads to adjustable and pH-responsive substrates for surface-enhanced Raman scattering (SERS)-active nanoparticles (NPs). Sterically stabilized and cross-linked latexes were synthesized from random copolymers of styrene (S) and 2-vinylpyridine (2VP). The pH-dependent latex-to-microgel transition and swellability were tuned based on their hydrophobic-to-hydrophilic content established by the S/2VP ratio. The electrostatic loading of polystyrene/poly(2-vinylpyridine) microgels [PSxP2VPy (M)] with anions such as tetrachloroaurate (AuCl4–) and borate-capped Ag NPs was quantified. The PSxP2VPy (M) can load ∼0.3 equiv of AuCl4– and the subsequent photoreduction results in Au NP-loaded PSxP2VPy (M) with NPs located throughout the structure. Loading PSxP2VPy (M) with borate-capped Ag NPs produces PSxP2VPy (M) with NPs located on the surface of the microgels, where the Ag content is set by S/2VP. The pH-responsive SERS activity is also reported for these Ag NP-loaded microgels. Analytical enhancement factors for dissolved crystal violet are high (i.e., 109 to 1010) and are set by S/2VP. The Ag NP-loaded microgels with ∼80 wt % 2VP exhibited the most stable pH dependent response.

Inorganic and organometallic polymers

This article provides an inexhaustive overview of research selected from the 2012 scientific literature involving polymers with inorganic elements as a key part of their structure.