Single-molecule fluorescence microscopy is used to follow dynamic ligand reorganization on the surface of single plasmonic gold nanorods. Fluorescently labeled DNA is attached to gold nanorods via a gold−thiol bond using a low-pH loading method. No fluorescence activity is initially observed from the fluorescent labels on the nanorod surface, which we attribute to a collapsed geometry of DNA on the metal. Upon several minutes of laser illumination, a marked increase in fluorescence activity is observed, suggesting that the ligand shell reorganizes from a collapsed, quenched geometry to an upright, ordered geometry. The ligand reorganization is facilitated by plasmon-mediated photothermal heating, as verified by controls using an external heat source and simulated by coupled optical and heat diffusion modeling. Using super-resolution image reconstruction, we observe spatial variations in which ligand reorganization occurs at the singleparticle level. The results suggest the possibility of nonuniform plasmonic heating, which would be hidden with traditional ensemble-averaged measurements.
A new plasma processing-based methodology for enhancing the streaming potential (V s ) that may be obtained in electrokinetic flows for a given pressure gradient over a silicon surface-based microchannel is indicated. The dependence of the V s on both the surface zeta potential and the electrolyte slip length was carefully determined through a series of experiments involving the variation of CF 4 -and Ar-based plasma parameters, incorporating pressure, exposure time, and power. It was determined through analytical estimates that, while the zeta potential is always increased, the slip length may be diminished under certain conditions. A record value of ∼0.1 mV/Pa was obtained using CF 4 plasma at 500 W, 10 mTorr, and 300 s of exposure. The implications of the work extend to the investigation of whether smooth surfaces may be effective for generating large V s 's for new modalities of electrical voltage sources in microfluidics-based applications.
The resistivity of halogen-free atomic layer deposition (ALD) TiN thin films was decreased to 220 μΩ cm by combining the use of a high-thermal stability nonhalogenated Ti precursor with a highly reactive nitrogen source, anhydrous hydrazine (N 2 H 4 ). TDMAT [tetrakis (dimethyl-amino)titanium], TDEAT [tetrakis(diethylamido)titanium], and TEMATi [tetrakis (ethylmethyl-amido)titanium] were compared to TiCl 4 as precursors for ALD TiN using N 2 H 4 as a coreactant. By minimizing the pulse length of the Ti-source precursor and optimizing the deposition temperature, the resistivity of TiN thin films deposited using these precursors was reduced to 400 μΩ cm for TDMAT (at 350 °C), 300 μΩ cm TDEAT (at 400 °C), and 220 μΩ cm for TEMATi (at 425 °C) compared to 80 μΩ cm for TiCl 4 (at 500 °C). The data are consistent with the lowest resistivity for halogen-free ALD corresponding to the organic precursor with the highest thermal stability, thereby allowing maximum ALD temperature. After optimization, TiN thin films were grown in horizontal vias, illustrating conformal and uniform TiN using both TiCl 4 and TEMATi in horizontal vias in patterned substrates.
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