The volume phase transition (VPT) behavior of individual thermally responsive poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) hydrogel microparticles was studied by in-situ dynamic mode atomic force microscopy (AFM) and force spectroscopy during heating and cooling cycles. Hydrogel samples were prepared by electrostatic immobilization of microparticles to amine-modified gold surfaces. The AFM studies of particle deswelling were performed by varying the force applied on the particles during imaging as a function of the geometry and material of the AFM probe. Aluminum-coated silicon cantilevers were found to influence substantially the behavior of the particles during the VPT, leading to a significant shape change. Low force impact magnetic excitation of the AFM probe (MAC mode) during dynamic mode measurements resulted in an undisturbed deswelling behavior enabling observation of the expected volume changes of the particles without significant tip-sample interaction. Hence, MAC-mode AFM was determined to be the most suitable technique for in-situ AFM studies on volume and shape changes at single hydrogel particles during VPT. Elasticity measurements performed at single particles at temperatures below and above the VPT revealed a 15-fold increase in the Young's modulus after passing the VPT, indicating the transition from a soft, swollen network to a stiffer, deswollen state.
We report a new top-down nanofabrication technology to realize large area metal nanowire (m-NW) arrays with tunable sub-20 nm separation nanogaps without the use of chemical etching or milling of the metal layer. The m-NW array nanofabrication technology is based on a self-regulating metal deposition process that is facilitated by closely spaced and isolated heterogeneous template surfaces that confine the metal deposition into two dimensions, and therefore, electrically isolated parallel arrays of m-NW can be realized with uniform and controllable nanogaps. Au-NW and Ag-NW arrays are presented with high-density ~10(5) NWs cm(-1), variable NW diameters down to ~50 nm, variable nanogaps down to ~5 nm, and very large nanogap length density ~1 km cm(-2). The m-NW arrays are designed and implemented as interdigitated nanoelectrodes for electrochemical applications and as plasmonic substrates where the coupled-mode localized surface plasmon resonance (LSPR) wavelength in the nanogaps between adjacent m-NW dimers can be precisely tuned to match any excitation source in the range from 500 to 1000 nm, thus providing optimal local electromagnetic field enhancement. A spatially averaged (n = 2500) surface-enhanced Raman scattering (SERS) analytical enhancement factor of (1.2 ± 0.1) × 10(7) is demonstrated from a benzenethiol monolayer chemisorbed on a Au-NW array substrate with LSPR wavelength matched to a He-Ne laser source.
Two distinct single-photon plasmon-modulated photo-luminescence processes are generated from nanostructured gold surfaces by tuning the spectral overlap of the incident laser source, localized surface plasmon resonance band, and the interband transitions between the d and sp bands, near the X- and L-symmetry points of the electronic band structure of gold. In the main section of the article, the characteristics of these photoluminescence processes are described and discussed. In the last section, the background continuum accompanying surface-enhanced Raman scattering (SERS) spectra from benzenethiol and 4-mercaptopyridine self-assembled monolayers chemisorbed on nanostructured gold surfaces is shown to originate from plasmon-modulated photoluminescence.
Pinhole-free insulation of micro- and nanoelectrodes is the key to successful microelectrochemical experiments performed in vivo or in combination with scanning probe experiments. A novel insulation technique based on fluorocarbon insulation layers deposited from pentafluoroethane (PFE, CF3CHF2) plasmas is presented as a promising electrical insulation approach for microelectrodes and combined atomic force microscopy-scanning electrochemical microscopy (AFM-SECM) probes. The deposition allows reproducible and uniform coating, which is essential for many analytical applications of micro- and nanoelectrodes such as, e.g., in vivo experiments and SECM experiments. Disk-shaped microelectrodes and frame-shaped AFM tip-integrated electrodes have been fabricated by postinsulation focused ion beam (FIB) milling. The thin insulation layer for combined AFM-SECM probes renders this fabrication technique particularly useful for submicro insulation providing radius ratios of the outer insulation versus the disk electrode (RG values) suitable for SECM experiments. Characterization of PFE-insulated AFM-SECM probes will be presented along with combined AFM-SECM approach curves and imaging.
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