Nanohole arrays exhibit unique surface plasmon resonance (SPR) characteristics according to hole periodicity, diameter, and excitation wavelength (λ(SPR)). This contribution investigates the SPR characteristics and surface sensitivity of various nanohole arrays with the aim of tuning the parameters for optimal sensing capability. Both the Bragg surface plasmons (SPs) arising from diffraction by the periodic holes and the traditional propagating SPs are characterized with emphasis on sensing capability of the propagating SPs. Several trends in bulk sensitivity and penetration depth were established, and the surface sensitivity was calculated from bulk sensitivity and penetration depth of the SPs for different analyte thicknesses. Increased accuracy and precision in penetration depth values were achieved by incorporating adsorbate effects on substrate permittivity. The optimal nanohole array conditions for highest surface sensitivity were determined (820 nm periodicity, 0.27 diameter/periodicity, and λ(SPR) = 1550 nm), which demonstrated an increase in surface sensitivity for the 10 nm analyte over continuous gold films at their optimal λ(SPR) (1300 nm) and conventional visible λ(SPR) (700 nm).
Thin films of conducting polymers exhibit unique chemical and physical properties that render them integral parts in microelectronics, energy storage devices, and chemical sensors. Overall, polyaniline (PAni) doped in acidic media has shown metal-like electronic conductivity, though exact physical and chemical properties are dependent on the polymer structure and dopant type. Difficulties arising from poor processability render production of doped PAni thin films particularly challenging. In this contribution, DC magnetron sputtering, a physical vapor deposition technique, is applied to the preparation of conductive thin films of PAni doped with hydrochloric acid (PAni-HCl) in an effort to circumvent issues associated with conventional thin film preparation methods. Samples manufactured by the sputtering method are analyzed along with samples prepared by conventional drop-casting. Physical characterization (atomic force microscopy, AFM) confirm the presence of PAni-HCl and show that films exhibit a reduced roughness and potentially pinhole-free coverage of the substrate. Spectroscopic evidence (UV-vis, FT-IR, and X-ray photoelectron spectroscopy (XPS)) suggests that structural changes and loss of conductivity, not uncommon during PAni processing, does occur during the preparation process. Finally, the applicability of sputtered films to gas-phase sensing of NH(3) was investigated with surface plasmon resonance (SPR) spectroscopy and compared to previous contributions. In summary, sputtered PAni-HCl films exhibit quantifiable, reversible behavior upon exposure to NH(3) with a calculated LOD (by method) approaching 0.4 ppm NH(3) in dry air.
Manipulation of the electronic and optical properties of plasmonic nanomaterials offers unique and exciting opportunities for several fields including opto-electronics, bio-medical engineering and photovoltaics. In particular, gold nanorods (GNR) represent a class of plasmonic nanomaterials that provide tunable optical properties from the visible to the near infrared regime. Herein, we have developed a highly effective method to prepare polymer nanocomposites (PNCs) doped with GNR additives utilizing extrusion and injection molding. A key outcome is that the process is amenable to scalable manufacturing and can produce highly reproducible PNCs with excellent optical properties. The resultant PNCs display good particle dispersion, minimal aggregation and a high retention of the optical properties as confirmed by UV-Vis spectroscopy and transmission electron microscopy. The nano-additives are incorporated into different thermoplastics to demonstrate the versatility of this method for different matrices and to
Intrinsically conducting polymers belong to a class of organic polymers with intriguing electronic and physical properties specifically for electro-optical applications. Significant interest into doped polyaniline (PAni) can be attributed to its high conductivity and environmental stability. Poor dissolution in most solvents has thus far hindered the successful integration of PAni into commercial applications, which in turn, has led to the investigations of various deposition and acidic doping methods. Physical vapor deposition methods, including D.C. magnetron sputtering and vacuum thermal evaporation, have shown exceptional control over physical film properties (thickness and morphology). However, resulting films are less conductive than films deposited by conventional methods (i.e., spin and drop casting) due to interruption of the hyperconjugation of polymer chains. Specifically, vacuum thermal evaporation requires a postdoping process, which results in incorporation of impurities and oxidation of surface moieties. In this contribution, thermally evaporated films, sequentially doped by vacuum evaporation of an organic acid (camphorsulfonic acid, CSA) is explored. Spectroscopic evidence confirms the successful doping of PAni with CSA while physical characterization (atomic force microscopy) suggests films retain good morphology and are not damaged by the doping process. The procedure presented herein also combines other postpreparation methods in an attempt to improve conductivity and/or substrate adhesion.
Nanoscale engineering of noble metal particles has provided numerous material configurations to selectively confine and manipulate light across the electromagnetic spectrum. Transitioning these materials to a composite form while maintaining the desired resonance properties has proven challenging. In this work, the successful integration of plasmon-focusing gold nanostars (GNSs) into polymer nanocomposites (PNCs) is demonstrated. Tailored GNSs are produced with over a 90% yield and methods to control the branching structures are shown. A protective silica capping shell is employed on the nanomaterials to facilitate survivability in the high temperate/high shear processing parameters to create optically-tuned injection molded PNCs. The developed GNS PNCs possess dichroic scattering and absorption behavior, opening up potential applications in the fields of holographic imaging, optical filtering and photovoltaics.
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