Directed branch growth in aligned nanowire arrays.

Branch growth is directed along two, three, or four in-plane directions in vertically aligned nanowire arrays using vapor-liquid-solid glancing angle deposition (VLS-GLAD) flux engineering. In this work, a dynamically controlled collimated vapor flux guides branch placement during the self-catalyzed epitaxial growth of branched indium tin oxide nanowire arrays. The flux is positioned to grow branches on select nanowire facets, enabling fabrication of aligned nanotree arrays with L-, T-, or X-branching. In addition, a flux motion algorithm is designed to selectively elongate branches along one in-plane axis. Nanotrees are found to be aligned across large areas by X-ray diffraction pole figure analysis and through branch length and orientation measurements collected over 140 µm(2) from scanning electron microscopy images for each array. The pathway to guided assembly of nanowire architectures with controlled interconnectivity in three-dimensions using VLS-GLAD is discussed.

Ultrathin-layer chromatography on SiO(2), Al(2)O(3), TiO(2), and ZrO(2) nanostructured thin films.

We explored four different inorganic oxides and determined their merits in miniaturized planar chromatography. Despite progression of chromatographic techniques over several decades, such alternatives to traditional planar silica gel stationary phases have not been fully evaluated. Glancing angle deposition(GLAD) provided an excellent platform for engineering nanostructured thin films in these materials for ultrathin-layer chromatography (UTLC). Separations of carotenoids and synthetic food dyes were used to investigate the attributes of SiO(2), Al(2)O(3), TiO(2), and ZrO(2)GLAD UTLC media. These anisotropic high surface area thin films possessed similar channel-like features but different chromatographic properties.TiO(2)and ZrO(2)media were especially interesting since analyte retention could be modified through sim-ple oxidation heat treatments and UV irradiation. Generally, oxidation reduced analyte retention while UV exposure increased retention. Changes in retention factor as large as ΔhRF∼ 40 (for Acid Red 14 on titanium oxide) were achieved. Food dye mixtures were applied using consumer inkjet printers as per the Office Chromatography concept and separation performance was quantified using advanced video instrumentation designed for miniaturized plates. Enhanced time-resolved UTLC methods were used to calculate figures of merit from recorded dye separation videos. Small theoretical plate heights (<4 µm)and low limits of detection (<2 ng per zone for the food dye tartrazine) were measured. The combination of engineered GLAD UTLC plates, inkjet application of analyte spots, time-resolved UTLC, and custom analysis algorithms enabled some of the best performance achieved on GLAD UTLC layers. Separations on the inorganic oxide thin films were also successfully hyphenated with electrospray ionization mass spectrometry for the first time. This investigation demonstrates the utility of alternative inorganic oxide GLADUTLC media and probes avenues of expanding the capabilities of miniaturized planar chromatography.

Inkjet application, chromatography, and mass spectrometry of sugars on nanostructured thin films.

Ultrathin-layer chromatography (UTLC) potentially offers faster analysis, reduced solvent and sample volumes, and lower costs. One novel technique for producing UTLC plates has been glancing angle deposition (GLAD), a physical vapor deposition technique capable of aligning macropores to produce interesting separation properties. To date, however, GLAD-UTLC plates have been restricted to model dye systems, rather than realistic analytes. This study demonstrates the transfer of high-performance thin-layer chromatography (HPTLC) sugar analysis methods to GLAD-UTLC plates using the office chromatography framework. A consumer inkjet printer was used to apply very sharp low volume (3-30 nL) bands of water-soluble analytes (lactose, sucrose, and fructose). Analytic performance measurements extrapolated the limits of detection to be 3-5 ng/zone, which was experimentally proven down to 60-70 ng/band, depending on the sugar. This qualitative analysis of sugars in a commercially available chocolate sample is the first reported application of GLAD-UTLC to food samples. The potential utility of GLAD-UTLC is further exemplified by successful coupling with electrospray ionization mass spectrometry for the first time to characterize underivatized sugars.

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)%.

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.

Photoluminescence emission profiles of Y(2)O(3) : Eu films composed of high-low density stacks produced by glancing angle deposition.

Periodic high-/low-index film stacks composed of Y(2)O(3) : Eu were grown by glancing angle deposition on silicon and fused silica substrates. Postdeposition annealing at temperatures from 600 to 1000 degrees C for 1 h in air was performed to activate photoluminescence. Absolute photoluminescence spectra were obtained as a function of observation angle. The angular emission distribution was non-Lambertian, with peak emission at angles of 50 to 60 degrees with respect to substrate normal. Spectroscopic transmittance and ellipsometry measurements were performed to characterize the films. Using this description, we were able to reproduce the angular photoluminescence patterns of the films.

Detection of lead in water using laser-induced breakdown spectroscopy and laser-induced fluorescence.

Laser-induced breakdown spectroscopy (LIBS) is a well-known technique for fast, stand-off, and nondestructive analysis of the elemental composition of a sample. We have been investigating micro-LIBS for the past few years and demonstrating its application to microanalysis of surfaces. Recently, we have integrated micro-LIBS with laser-induced fluorescence (LIF), and this combination, laser ablation laser-induced fluorescence (LA-LIF), allows one to achieve much higher sensitivity than traditional LIBS. In this study, we use a 170 microJ laser pulse to ablate a liquid sample in order to measure the lead content. The plasma created was re-excited by a 10 microJ laser pulse tuned to one of the lead resonant lines. Upon optimization, the 3sigma limit of detection was found to be 35 +/- 7 ppb, which is close to the EPA standard for the level of lead allowed in drinking water.