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• Vol. 3, Issue 4, 044002 (2021)
Yan Jin1, Lin Zhou1、2、*, Jie Liang1, and Jia Zhu1、*
Author Affiliations
• 1Nanjing University, College of Engineering and Applied Sciences, National Laboratory of Solid State Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, Nanjing, China
• 2Nanjing University, Key Laboratory of Intelligent Optical Sensing and Manipulation, Ministry of Education, Nanjing, China
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Fig. 1. Overview of electrochemistry enabled dynamic plasmonics: (a)–(c) approaches to realize dynamic plasmonics and (d)–(f) applications of dynamic plasmonics. (a) Reproduced with permission from Ref. 32, Copyright 2016, American Chemical Society. (b), (d) Reproduced with permission from Ref. 56, Copyright 2015, American Chemical Society. (c), (e) Reproduced with permission from Ref. 57, Copyright 2019, American Association for the Advancement of Science. (f) Reproduced with permission from Ref. 58, Copyright 2018, National Academy of Sciences.
Fig. 2. Structural transformation for dynamic plasmonics. (a) Schematic of Au/Ag nanodome arrays. (b) Simulation of two-dimensional reflection spectra as a function of Ag shell thickness. (c) Measured reflection spectra of the device after different electrodeposition times. (d) Schematic of the morphology evolution during lithium deposition at different applied currents: lithium particle growth and disorder lithium dendrite formation. (e) Simulation reflectance of two lithium morphologies: shifts of reflectance dip and suppressed reflectance intensity. (f) The scanning electron microscope (SEM) image of lithium particles. (g) The SEM image of lithium dendrites. (h) Schematic of selective lithium deposition transferring metal–insulator–metal to the semi-infinite metallic grating. (i) The corresponding calculated reflection spectra switching between MPR and SPP. (a)–(c) Reproduced with permission from Ref. 32, Copyright 2016, American Chemical Society. (d)–(g) Reproduced with permission from Ref. 58, Copyright 2018, National Academy of Sciences. (h), (i) Reproduced with permission from Ref. 59, Copyright 2020, Wiley-VCH GmbH.
Fig. 3. Carrier-density modulation for dynamic plasmonics. (a) The SEM image of the colloidal silver particles. Inset is the transmission electron microscopy (TEM) image. (b) Absorption spectra of the silver solution at the open circuit potential of (a) $+0.15 V$, (b) $−0.6 V$, and (c) $+0.15 V$ versus Ag/AgCl. (c) The position of the plasmon peak and number of electrons transferred of the colloidal silver surface as a function of potential. TEM images of (d) AZO and (e) ITO nanocrystals. The transmittance of (f) AZO and (g) ITO nanocrystals before (orange, dashed) and after 20,000 cycles (purple, solid) with voltage modulation. (h) The TEM image of 5% Nb-doped $TiO2$ nanocrystals. (i) In situ spectroelectrochemistry of 5% Nb-doped $TiO2$ films with four distinct optical states, with different transmittance of visible (yellow arrow) and infrared (red arrow) light. (a)–(c) Reproduced with permission from Ref. 81, Copyright 1997, American Chemical Society. (d)–(g) Reproduced with permission from Ref. 82, Copyright 2013, Wiley-VCH Verlag GmbH & Co. (h), (i) Reproduced with permission from Ref. 56, Copyright 2015, American Chemical Society.
Fig. 4. Electrochemically active surrounding-media manipulation for dynamic plasmonics. (a)–(d) Schematic, experimentally obtained reflectance spectra and FDTD simulated reflectance spectra of plasmochromic nanocavities based on a $WO3$ insulator layer with lithium insertion. (e) Schematic of a PANI-coated Au nanoparticle on a metallic Au mirror and redox reaction of PANI ($PANI0$, fully reduced; $PANI1+$, half oxidized; $PANI2+$, fully oxidized). (f) Scattering spectra and inset SEM image of a single PANI-coated Au nanoparticle ($c0$, $PANI0$; $c2+$, $PANI2+$). (g) Reversible switching of coupled plasmon resonance wavelength versus the applied voltage. (a)–(d) Reproduced with permission from Ref. 37, Copyright 2020, American Chemical Society. (e)–(g) Reproduced with permission from Ref. 57, Copyright 2019, American Association for the Advancement of Science.
Fig. 5. Applications of dynamic plasmonics: structural color displays. (a) Schematic of PANI-coated Au nanoparticles-based displays integrated with an electrochemical cell for scalable color generation. (b) Dark field images of Au nanoparticles with 20-, 40-, and 60-nm diameters during PANI redox reactions. (c) Color gamut (CIE 1931 chromaticity) of PANI-coated Au nanoparticles with 20-, 40-, and 60-nm diameters during PANI redox. (d) Device photo of PANI-coated Au nanoparticles before and after 3 months. Switching times of various plasmonic nanomaterials versus (e) the wavelength and (f) pixel areas. (a)–(f) Reproduced with permission from Ref. 57, Copyright 2019, American Association for the Advancement of Science.
Fig. 6. Applications of dynamic plasmonics: chemical sensors. (a)–(d) Electrocatalysis reaction sensors: (a) schematic of dark-field microscopy integrated with an electrochemical workstation for chemical reaction sensors; (b) schematic of the electrocatalytic oxidation reaction mechanism of $H2O2$ on a single gold nanoparticle surface; (c) scattering spectra of a single gold nanoparticle ($∼40 nm×65 nm$) during the cyclic scanning; (d) scattering peak shift of $40 nm×65 nm$ (I, III) and $40 nm×84 nm$ (II, IV) single gold nanoparticle with (I, II) and without (III, IV) 1 mM $H2O2$ in 0.10 M $KNO3$ solution under the applied potential from $−0.10$ to 1.00 V. (e)–(j) Battery sensors: (e)–(h) in operando reflectance during lithium metal (e), (g) deposition and (f), (h) stripping at two applied current densities: (e), (f) 0.03 mA and (g), (h) 1 mA. In situ lithium dendrite detection with (i) applied current and (j) in situ reflectance. (a)–(d) Reproduced with permission from Ref. 110, Copyright 2014, American Chemical Society. (e)–(j) Reproduced with permission from Ref. 58, Copyright 2018, National Academy of Sciences.
 Material $WO3$102 Cu-Ag34 Cu-Bi, NiO35 ITO82 AZO82 Approach Ion insertion Electrochemical deposition Electrochemical deposition and ion insertion Capacitive charging Capacitive charging Mechanism Polaronic absorption Structural transformation Structural transformation Carrier-density change Carrier-density change Device area — $25 cm2$ $100 cm2$ $4 cm2$ $4 cm2$ Spectral range VIS 400 to 1000 nm VIS NIR NIR $ΔT$ 97.7% (633 nm) 75% (600 nm) 65% (600 nm) 25% (solar NIR) 40% (solar NIR) Switch speed coloration/bleaching 6 s/2.7 s $<3 min$ 60 s 3.06 s/6.8 s 0.1 M $LiCO4/PC$ 1 s/1.8 s 0.1 M $LiCO4/PC$ Coloration efficiency ($cm2 C−1$) (for contrast ratio at a specific wavelength) 118.3 (for 97.7% at 633 nm) 90 (for 60% at 600 nm) — 400 (for $∼60%$ at 1800 nm) 450 (for $∼57%$ at 2000 nm) Cycling 300 5500 4000 20,000, 45% capacity decay 20,000, 11% capacity decay
Table 1. Summary of smart windows of various approaches.
 Structure Au/Ag core shell nanodome32 Au-$WO3$-Au nanohole cavities37 PANI-coated Au nanoparticle on Au mirror57 LC on Al nanowell26 Approach Electrochemical deposition Li ion insertion into $WO3$ Redox reaction of polymer LCs orientation change Mechanism Structural transformation Surrounding refractive index change Surrounding refractive index change Surrounding refractive index change Spectral range/tunability 220-nm shift 64-nm shift $>100-nm$ shift 95-nm shift Reflectivity 60% 35% $>50%$ 50% to 80% Speed $<1 s$ 4 s 30 ms Millisecond-scale Resolution — $5×104 pixels/inch$ $>109 pixels/inch$ High Angle independence — — Yes 20 deg Stability, retention — 100 cycles, 88% $>3$ months — Energy consumption — $5.6 mW cm−2$ $0.3 mW cm−2$ —
Table 2. Summary of structural color displays of various approaches.