Electrically Tunable Plasmonic Behavior of Nanocube–Polymer Nanomaterials Induced by a Redox-Active Electrochromic Polymer

König, Tobias; Ledin, Petr A.; Kerszulis, Justin A.; Mahmoud, Mahmoud; El‐Sayed, Mostafa A.; Reynolds, John R.; Tsukruk, Vladimir V.

doi:10.1021/nn501601e

Cited by 364 publications

(268 citation statements)

References 59 publications

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“…Previous attempts to realize such a dynamic and reversible tuning used liquid crystals, [ 4,5 ] phase-change materials, DNA origami, [6][7][8] mechanical stretching, [ 9,10 ] stimuli-responsive polymers, [11][12][13][14] and electric fi elds. [ 15,16 ] However, either the tuning range was very small (<50 nm) or the plasmonic nanostructures were poorly defi ned (random aggregates), which hinders in-depth understanding and practical applications. In addition, tuning rates have been rather slow, on the timescale of seconds.…”

Section: Doi: 101002/adom201600094mentioning

confidence: 99%

Fast Dynamic Color Switching in Temperature‐Responsive Plasmonic Films

Ding

Rüttiger

Zheng

et al. 2016

Advanced Optical Materials

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COMMUNICATIONmembranes, biosensing, tissue engineering, and drug delivery. [ 19,20 ] Due to its strong volume shrinkage (up to 90%) when the temperature rises above a critical hydration temperature ( T c ) and its full reversibility across this phase transition, pNIPAM has been utilized to tune plasmons in Au/Ag nanoparticles (NPs) and nanorods. [21][22][23][24][25][26][27] However, because these plasmonic assemblies are either randomly decorated around the surface of pNIPAM microgels or aggregates with undefi ned number of particles and confi gurations, it is hard to understand the physics of the mixture of different plasmonic constructs properly. Moreover, it takes time for water to diffuse inside the microgels to fully swell them, thus the speed of volume changes has been relatively slow (typically a few seconds).Here, we graft pNIPAM layers ( d = 70 nm thick) onto Au mirror by applying surface-initiated atom transfer radical polymerization (SI-ATRP) protocols, and place scattering Au NPs on top. By utilizing the phase transition of the pNIPAM, the separation between Au NP and Au fi lm is widely tunable, thereby leading to a dynamic and reversible plasmon tuning system based on modulating the resonant modes. The resulting fi lms exhibit strong color changes, are simple to fabricate, can be fl exible, are low cost, can easily scale to large areas, and respond faster than video rates. In addition, the plasmonic nanoparticles can also be optically irradiated to locally switch the surrounding pNIPAM layers, creating video-rate all-optical switching over large areas.The Au mirrors are deposited via electron beam evaporation with roughness controlled below 1.5 ± 0.5 nm. [ 28 ] The pNIPAM fi lms are then prepared on these Au fi lms by SI-ATRP ( Figure 1 , Experimental Section). [ 29 ] The thickness of the as-grown dry pNIPAM fi lms is determined to be 67 ± 1 nm via ellipsometry ( Figure S1, Supporting Information). The molecular weight estimated from the free pNIPAM synthesized under the same condition is 26.3 kDa as determined by size-exclusion chromatography. The transition temperature of this pNIPAM fi lm determined through contact angle measurement is around 30 °C ( Figure S2, Supporting Information). This value is slightly lower than the normal lower critical solution temperature (LCST) (32 °C) of pNIPAM mainly because of the residue Cu 2+ salts and polar end groups introduced during the ATRP process. The D = 100 nm diameter Au NPs (from BBI Solutions with 10% monodispersity, Figure S3, Supporting Information) deposited on the fi lms from solution appear slightly embedded inside the pNIPAM brushes as seen in scanning electron microscopy (SEM) images (inset Figure 1 ). Nanoparticle densities are varied up to 1 nanoparticle µm -2 to ensure that there is minimal coupling between nanoparticles, while the total scattering is maximized. Though this Au NP on mirror (NPoM) is related to the recent advances in small-gap constructs, [ 22 ] here the gap remains larger than the radius, reducing the plasmonic This is an ope...

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Section: Doi: 101002/adom201600094mentioning

confidence: 99%

Fast Dynamic Color Switching in Temperature‐Responsive Plasmonic Films

Ding

Rüttiger

Zheng

et al. 2016

Advanced Optical Materials

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“…Percentage interaction values were based on analytic weighting factors characteristic of 1/e plasmon interaction distance from the nanoantenna surface [17]. Dielectric data for soda lime glass and ITO reported by Rubin and König et al, respectively, were used [49,50].…”

Section: Numerical Modelingmentioning

confidence: 99%

Coupled dipole plasmonics of nanoantennas in discontinuous, complex dielectric environments

Forcherio

Blake

Seeram

et al. 2015

Journal of Quantitative Spectroscopy and Radiative Transfer

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a b s t r a c tTwo-dimensional metamaterials support both plasmonic and coupled lattice (Fano) resonant modes that together could enhance optoelectronics. Descriptions for plasmon excitation in Fano resonant lattices in non-vacuum environments typically use idealized, homogeneous matrices due to computational expense and limitations of common approaches. This work described both localized and coupled resonance activity of twodimensional, square lattices of gold (Au) nanospheres (NS) in discontinuous, complex dielectric media using compact synthesis of discrete and coupled dipole approximations. This multi-scale approach supported attribution of experimentally observed spectral resonance energy and bandwidth to interactions between metal and dielectric substrate (s) supporting the lattices. Effective polarizabilities of single AuNS, either in vacuo or supported by glass and/or indium tin oxide (ITO) substrates, were obtained with discrete dipole approximation (DDA). This showed plasmon energy transport varied with type of substrate: glass increased scattering, while ITO increased absorption and energy confinement. Far-field lattice interactions between AuNS with/without substrates were computed by coupled dipole approximation (CDA) using effective polarizabilities. This showed glass enhanced diffractive features (e.g., coupled lattice resonance), while ITO supported plasmon modes. This compact, multiscale approach to describe metasurfaces in complex environments could accelerate their development and application.

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“…1,2 If the hybrid system is made of gold or silver nanostructures coated with polymeric shells, their optical properties can be dynamically modified or switched provided that an external stimulus (pH, temperature, electrical conductivity, light...) impacts the physical or chemical properties of the polymer. [3][4][5][6][7] These optical properties are governed by the excitation of localized surface plasmon (LSP) modes, corresponding to a collective oscillation of the conduction electrons at the particle surface. 8 As a result, a large extinction cross-section emerges at the resonance, in the visible or near-infrared region (mainly for gold, silver and copper).…”

mentioning

confidence: 99%