Red to Blue High Electrochromic Contrast and Rapid Switching Poly(3,4-ethylenedioxypyrrole)-Au/Ag Nanocomposite Devices for Smart Windows

Abstract

Poly(3,4-ethylenedioxypyrrole) (PEDOP)-Ag and PEDOP-Au nanocomposite films have been synthesized for the first time by electropolymerization of the conducting-polymer precursor in a waterproof ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, followed by Ag/Au nanoparticle incorporation. That the Ag/Au nanoparticles are not adventitious entities in the film is confirmed by a) X-ray photoelectron spectroscopy, which provides evidence of Ag/Au-PEDOP interactions through chemical shifts of the Ag/Au core levels and new signals due to Ag-N(H) and Au-N(H) components, and b) electron microscopy, which reveals Au nanoparticles with a face-centered-cubic crystalline structure associated with the amorphous polymer. Spectroelectrochemistry of electrochromic devices based on PEDOP-Au show a large coloring efficiency (η(max) =270 cm(2) C(-1), λ=458 nm) in the visible region, for an orange/red to blue reversible transition, followed by a second, remarkably high η(max) of 490 cm(2) C(-1) (λ=1000 nm) in the near-infrared region as compared to the much lower values achieved for the neat PEDOP analogue. Electrochemical impedance spectroscopy studies reveal that the metal nanoparticles lower charge-transfer resistance and facilitate ion intercalation-deintercalation, which manifests in enhanced performance characteristics. In addition, significantly faster color-bleach kinetics (five times of that of neat PEDOP!) and a larger electrochemical ion insertion capacity unambiguously demonstrate the potential such conducting-polymer nanocomposites have for smart window applications.

Plasmonic/Nonlinear Optical Material Core/Shell Nanorods as Nanoscale Plasmon Modulators and Optical Voltage Sensors

“…[12][13][14] Thec omposition, size,a nd morphology of ag iven plasmonic nanostructure are fixed and cannot be varied in ad ynamic way after the initial synthesis or fabrication. [12][13][14] Therefore,t he integration of plasmonic nanostructures with active dielectric materials can enable the active modulation of the plasmonic resonance by using an external trigger (for example,l ight, heat, electric potential) and may open up ap athway to advanced nanodevices,i ncluding active metamaterials, [28] smart windows, [29] and displays, [30] as well as an ew generation of nanoscale sensors that can sensitively monitor local environmental changes.Herein, we explore the interaction between plasmonic nanostructures and NLO materials to enable active modulation of the dielectric environment and thus plasmonic properties by an external electrical field. [15][16][17][18][19][20][21][22][23][24] Considerable efforts have been devoted to investigating the interaction between plasmonic nanostructures and the surrounding environments,s uch as electro-and photo-chromic molecules, [15,16] inorganic materials, [17,18] polymers, [19][20][21] and liquid crystals.…”

“…[22][23][24] On one hand, the plasmonic resonance can substantially modify the optical properties of the nearby materials,f or example,t oenhance the absorption or accelerate the radiative decay rate. [12][13][14] Therefore,t he integration of plasmonic nanostructures with active dielectric materials can enable the active modulation of the plasmonic resonance by using an external trigger (for example,l ight, heat, electric potential) and may open up ap athway to advanced nanodevices,i ncluding active metamaterials, [28] smart windows, [29] and displays, [30] as well as an ew generation of nanoscale sensors that can sensitively monitor local environmental changes. [12][13][14] Therefore,t he integration of plasmonic nanostructures with active dielectric materials can enable the active modulation of the plasmonic resonance by using an external trigger (for example,l ight, heat, electric potential) and may open up ap athway to advanced nanodevices,i ncluding active metamaterials, [28] smart windows, [29] and displays, [30] as well as an ew generation of nanoscale sensors that can sensitively monitor local environmental changes.…”

Conducting Polymers

“…Au nanoparticlepolyaniline nanocomposite layers obtained through layer-by-layer adsorption were applied for the simultaneous determination of dopamine and uric acid [1040]. Poly(3,4-ethylenedioxypyrrole) (PEDOP)-Ag and PEDOP-Au nanocomposites were synthesized by electropolymerization in a waterproof ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide, followed by Ag/Au nanoparticle incorporation, for the utilization in electrochromic devices [993]. Poly(3,4-ethylenedioxythiophene) was used to immobilize metal particles and borohydride reagent, and the composite was applied for hydrogenation of nitrophenol as well as for electrooxidation of methanol, formic acid, and borohydride [1036].…”

(Gold Nanorod Core)/(Polyaniline Shell) Plasmonic Switches with Large Plasmon Shifts and Modulation Depths

“…[ 43 ] PANI coating enables an unprecedented switching performance on the longitudinal plasmon resonance of Au nanorods, with the modulation depth in the scattering intensity and the plasmonic spectral shift reaching up to 10 dB and 100 nm, respectively. Integration of plasmonic metal nanostructures with active dielectric materials therefore enables the development and creation of advanced devices, such as metamaterials for terahertz phase modulation, [ 35 ] smart windows, [ 36 ] and displays. Such a large modulation depth has not been achieved before with PANI as the controlling medium.…”

“…The use of a much smaller amount of the material for the core/ shell nanostructures is brought by the large extinction crosssections of plasmonic Au nanorods. Integration of plasmonic metal nanostructures with active dielectric materials therefore enables the development and creation of advanced devices, such as metamaterials for terahertz phase modulation, [ 35 ] smart windows, [ 36 ] and displays. Our Plasmonic metal nanostructures possess extraordinary capabilities of manipulating light at nanoscale.…”