Site-Selective Plasmonic Etching of Silver Nanocubes - American

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Site-Selective Plasmonic Etching of Silver Nanocubes Koichiro Saito, Ichiro Tanabe, and Tetsu Tatsuma J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.6b02393 • Publication Date (Web): 21 Oct 2016 Downloaded from http://pubs.acs.org on October 21, 2016

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The Journal of Physical Chemistry Letters

Site-Selective Plasmonic Etching of Silver Nanocubes Koichiro Saito, Ichiro Tanabe,† and Tetsu Tatsuma* Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 1538505, Japan

†

Present address: Department of Materials Engineering Science, Graduate School of Engineering

Science, Osaka University, Toyonaka, Osaka 560-8531, Japan Corresponding Author: [email protected]

ACS Paragon Plus Environment

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ABSTRACT

Plasmon-induced charge separation (PICS) at the interface between a plasmonic nanoparticle and semiconductor is now widely used for photovoltaics and photocatalysis. Here we take advantage of PICS for site-selective nanoetching of silver nanocubes on TiO2 beyond the diffraction limit. A silver nanocube exhibits two resonance modes localized at the top and bottom of the nanocube (distal and proximal modes, respectively) when it is placed on TiO2. We achieved selective etching at the top and the bottom of the nanocubes by PICS based on the distal and proximal modes, respectively. The site-selective nanophotonic etching reveals that the anodic reaction involved in PICS is induced by the plasmonic near field, which causes an external photoelectric effect. In particular, the distal mode etching at the top edges is explained in terms of ejection of energetic electrons (or hot electrons) from the distal site to TiO2 across the nanocube.

TOC GRAPHICS

KEYWORDS: localized surface plasmon resonance, plasmon-induced charge separation, silver nanocube, nanoparticle morphology control.


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Plasmonic nanomaterials, which exhibit localized surface plasmon resonance (LSPR), attract much attention recently. LSPR is resonance of electron oscillation in the nanomaterial with electric field oscillation of incident light. Plasmon has a certain lifetime, and it finally decays via (i) nonradiative transition, which is observed as light absorption,1,2 (ii) radiative transition, which is observed as light scattering,1,2 (iii) transfer of energy to an excitable matter through near-field excitation3,4 or resonance energy transfer,5 and (iv) uphill electron transfer to semiconductor in contact.6-8 We have reported the last one, i.e. plasmon-induced charge separation (PICS) for the first time.6 PICS can be applied not only to photovoltaics,6,9-12 photocatalysis,6,13-15 chemical sensing,16 and photoactuation,17 but also to recording of images and information18-21 on the basis of photoinduced oxidation of the nanoparticles. It has been reported that PICS involves electron transfer from plasmonic nanoparticle to semiconductor in direct contact.7,22-25 The anodic and cathodic sites are therefore located on the plasmonic nanoparticles20,21,26-31 and semiconductor,27,28 respectively. The electron transfer could be due to external photoelectric effect including hot electron injection (Figure 1a, b)8,32,33 or interfacial electron transition (Figure 1c). 34,35 Also, it has been revealed by using Ag nanorods on TiO2 that PICS proceeds preferentially at localized sites of optical near field.28 However, further details have not yet been elucidated. In the present study, we use Ag nanocubes to give deeper insights into the mechanisms of Ag oxidation by PICS. Van Duyne et al. demonstrated that a plasmon resonance mode of a Ag nanocube is divided when it is placed on a glass plate into “distal mode” and “proximal mode”, which are the resonance modes localized at the top and bottom of the nanocube, respectively,36,37 at different wavelengths. If the glass substrate is coated with TiO2, which has much higher refractive index, the separation of those modes is more significant.38 Here we used Ag nanocubes on TiO2, and


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found that selective excitation of one of those modes gave rise to site-selective nanoetching based on PICS, beyond the diffraction limit. The nanoetching leads to a conclusion that the anodic reaction of PICS is induced by the near field. In particular, the distal mode etching is cause by a distal photoelectric effect (Figure 1a).

Figure 1. Schematic images of (a-c) plasmon-induced charge separation (PICS) based on (a) distal and (b) interfacial photoelectric effects and (c) photo-induced interfacial electron transition and (d, e) site-selective etching based on PICS (d) at the bottom and (e) at the top of the nanocube.


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An indium-tin oxide (ITO; 150 nm thick) coated glass plate was coated further with TiO2 (120 nm thick) and Ag nanocubes39 (average size ~ 100 nm) were deposited on it (2 × 107 particles cm-2). When the sample is irradiated from the front side, the backward scattering spectrum of the nanocubes is peaked at 410 nm and 617 nm (Figure 2a). Those blue and red scattering peaks are attributed to the distal and proximal modes, respectively, on the basis of finite-difference time-domain (FDTD) calculations (Figure 2b). The calculation model is basically the same as the sample used for experiments; a Ag nanocube with 100 nm edge length is located 2 nm away from the TiO2 surface of glass/ITO (150 nm)/TiO2 (120 nm) substrate considering the thickness of the protecting agent.37 The curvature radius of the edges is 10 nm. Figure 3a shows a typical dark filed image of the Ag nanocubes on TiO2, in which the blue scattering light overlaps with the red scattering light. We observed morphology of exactly the same particles (particle a1, a2, a3) by scanning electron microscopy (SEM) (Figure 3a). The particle a2, which is smaller than the others (a1, a3), exhibits lower scattering. These results are reasonable considering the scattering intensity increases with the volume of the nanoparticle.40


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Figure 2. (a) Experimentally observed and (b) calculated backward scattering spectra of the Ag nanocubes on the TiO2 irradiated from the front side. (c) Backward scattering spectrum of a Ag nanocube selectively etched at the bottom and (d) that at the top (solid curves. The dotted curves shows the spectrum before etching).


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Figure 3. Dark filed (left) and SEM (right) images of Ag nanocubes on TiO2 (120 nm thick) (a) before light irradiation, (b) after proximal mode excitation and (c) distal mode excitation. Ag nanocubes placed on TiO2 were irradiated with light of wavelength ranging from 620 to 700 nm (15 mW cm-2) for 1 h for selective excitation of the proximal mode, which has a broad resonance peak. The irradiation was carried out in nitrogen in order to avoid direct oxidation of the nanocubes by ambient O2. Relative humidity (RH) was controlled to be >80% because adsorbed water works as an electrolyte for PICS in the gas phase (see below for further details).27


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As shown in Figure 3b, the red scattering based on the proximal mode decreased and the blue scattering light was left after the light irradiation. The same nanocubes were observed by SEM, and we found that the bottom part was etched for each nanocube (particle b1, b2). Most of the other particles showed the same trend. The results suggest that the bottom of the nanocube is preferentially oxidized and dissolved by the excitation of the proximal mode, resulting in the decrease in the red scattering based on the proximal mode and remaining of the blue scattering based on the distal mode (Figure 1d). We also carried out calculations for simulating the scattering spectra by means of the FDTD method. The site-selective etching was simulated by increasing the curvature radius from 10 to 30 nm only at the bottom edges. As a result, the scattering peak of the proximal mode exhibited a large blueshift whereas the shift of the distal mode peak was much smaller (Figure 2c). These results correspond to the color changes observed by the dark field microscopy. The proximal mode peak is initially separated from the distal mode chiefly because of the high refractive index of the TiO2 film. The separation is mitigated by the site-selective etching at the bottom and the decrease in the contact area of the nanocube with TiO2. Next, the distal mode of Ag nanocubes on TiO2 was selectively excited by 420 nm light (5 mW cm-2) for 12 h under nitrogen atmosphere (>80% RH). Narrow band light (full width at half maximum = 10 nm) was used because of the sharp distal mode peak. Since the light intensity was accordingly low, the illumination time for the distal mode was extended in order to compensate for shortage of the number of absorbed photons. The results are shown in Figure 3c. A number of Ag nanocubes lost blue scattering of the distal mode and red scattering of the proximal mode remained. Such particles that showed the color change were beveled at the top edges. The site-selective etching must be responsible for the selective removal of the distal mode


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scattering (Figure 1e). In FDTD simulation, an increase in the curvature radius to 30 nm at the top edges of the nanocube almost selectively blueshifted and weakened the distal mode scattering (Figure 2d); the simulated result corresponds well to the color change observed in the dark field microscopy. In the meantime, nanoparticles which are etched not only at the top but also at the bottom are also observed, likely because the optical near field localized at the bottom of the nanocube, which is less intense than that localized at the top, is not negligible (Figure 2b). The site-selective etching of Ag nanocubes can be explained in terms of PICS. PICS drives the electron transfer6,22-25 from the Ag nanocube in resonance state to the TiO2 conduction band. As a result, Ag is oxidized to Ag+ ions and are dissolved into the adsorbed water layer.27,28 The electrons injected into TiO2 are accepted by pre-adsorbed O2 or the released Ag+ ions to deposit small Ag nanoparticles in the latter case (Figure 1d and e).27,28 Actually some small redeposited particles are observed around the nanocube (Figure 2b, indicated by yellow circles). The redeposition occurs both in the vicinity of and away from the nanocube because the sufficiently thick adsorbed water layer allows ion migration by a few micrometers.27 The nanoetching cannot be explained in terms of a thermal effect, because it is known that the maximum temperature increase for 100 nm nanoparticles is lower than 0.5 °C even under 100 W cm-2 light,41 which is 4 orders of magnitude stronger than the present case (5−15 mW cm2

). Actually, no significant spectral change was observed for Ag nanocubes on a glass plate under

100 mW cm-2 light (λ > 420 nm) for 24 h, whereas an obvious spectral change was observed for nanocubes on TiO2 even at 1 h under the identical conditions. In addition, the spectral changes observed on TiO2 were decelerated in a dry atmosphere. This can be explained if the observed processes are electrochemical ones as reported for other


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Ag nanoparticles on TiO2.20,27,28 The overall electrochemical process involves the charge separation, anodic reactions (i.e. oxidation) at a plasmonic nanoparticle, cathodic reactions (i.e. reduction) at TiO2, transport of electrons from the anodic to cathodic sites in the solid phase, and migration of ions between the anodic and cathodic sites through the adsorbed water layer. The ion migration is necessary for charge compensation for continuous reactions otherwise positive and negative charges will be excess at around the anodic and cathodic sites, respectively. This is analogous to metal corrosion and photocatalysis, which are also electrochemical systems and slow down in dry air. Under dry conditions, the adsorbed water layer is almost removed, and the ion transport and thereby the overall process are retarded largely. In contrast, a thermal effect should be decelerated by an adsorbed water layer, which promotes heat dissipation through vaporization of water. As Figure 3 shows, the oxidation of Ag nanocubes occurs at the sites where the optical near field is localized. This behavior is similar to that of Ag nanorods on TiO2,28 but the present results give deeper mechanistic insights. In the case of the nanorods used in the previous work, the anodic sites are always in close proximity to the TiO2 surface. Therefore, both of the volume (Figure 1a) and interfacial (Figure 1b) photoelectric effects33 as well as photo-induced interfacial electron transition (Figure 1c)34,35 can occur. However, in the case of the nanocube, the anodic site is 80−100 nm away from the TiO2 surface in the case of the selective oxidation at the top edges (Figure 1e). This is difficult to explain in terms of the interfacial photoelectric effect or the interfacial electron transition, which should cause etching at the interfacial region or nonselective etching overall the nanocube. The ballistic mean free path length in Ag for electrons with energy above the Fermi level by 0.84 eV, which is the ideal height of the Schottky barrier between Ag42 and TiO2,43 is estimated to be ~56 nm,44 which is close to the distance between the


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distal mode site and the TiO2 surface (80−100 nm). Since the distal mode resonance wavelength corresponds to the photon energy of 3.0 eV, the energetic electron should travel for distance longer than 56 nm losing some energy.33 Therefore, we conclude that the distal photoelectric effect (or distal hot electron injection) shown in Figure 1a can occur even at a relatively low efficiency, at least for this specific case, in which a hole generated at the distal mode site can be ejected instantaneously to the solution without any complex reaction. In summary, we achieved site-selective photoetching of Ag nanocubes on TiO2 beyond the diffraction limit taking advantage of PICS. The site-selective oxidation based on PICS can be explained in terms of photoelectric effect. In particular, the distal mode etching at the top of the nanocube is caused by ejection of Ag+ ions to the adsorbed water layer and ejection of energetic electrons to TiO2 across the nanocube both from the distal mode site (i.e. top edges). The siteselective nanophotonic etching is expected to contribute to design of novel plasmonic materials and devices.

Experimental Methods A TiO2 film (~120 nm thick) was prepared on a Pyrex glass or ITO-coated (~150 nm thick) glass sheet from a titaniumalkoxide ethanol solution (NDH-510C, Nippon Soda) by a solgel dip-coating method. The withdrawal rate was 3 mm s-1. The precursor was dried at 120 °C for 40 min and calcined at 500 °C for 1 h. Ag nanocubes were synthesized by the method developed by Xia et al.39 with slight modifications.38 Briefly, ethylene glycol (EG, 5mL) was stirred at 145−150 °C in a 20 mL capped vial for 1 h, followed by addition of 3 mM HCl in EG (1 mL). After stirring in the capped vial for 10 min, 94 mM AgNO3 in EG (3 mL) and 147 mM


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poly(vinylpyrrolidone) (PVP) (monomer unit, Mr ~ 55000) in EG (3 mL) were added simultaneously to the stirred solution at 0.75 mL min-1, followed by stirring in the capped vial at 145-150 °C for about 2 h. The nanocubes were precipitated by addition of excess acetone, separated by centrifugation at 2000g and resuspended in ethanol. The nanocube suspension was applied to a substrate and ethanol was evaporated in dark. Then, the substrate was rinsed with ethanol. The casting and rinsing were repeated several times. A spectrophotometer V-670 (Jasco; equipped with an integrating sphere for backward scattering spectra) and an optical microscope (BX-51, Olympus) with a 100× field lens and a CCD camera (C7780-20, Hamamatsu Photonics) were used for optical characterization. The light source was a Xe lamp (LA-251Xe, Hayashi Watch Works). Samples were irradiated with 420 nm light through a band-pass filter (MX0420, Asahi Spectra; full width at half maximum = 10 nm) or 620-700 nm light through a long-pass (SCF-50S-62R, Sigma Koki) and short-pass filter (CLDF-50S, Sigma Koki). For FDTD simulations via FDTD Solutions (Lumerical Solutions), the simulation domain (750 × 750 × 750 nm) consisted of 4 nm cubic cells and the region (200 × 200 × 200 nm) around a nanocube was further meshed with a three-dimensional grid of 2 nm spacing. Backward scattering from the nanocube was monitored by a 700 × 700 nm square screen set 270 nm apart from the air-TiO2 interface. The dielectric functions of Ag,45 TiO2,46 and ITO47 were extracted from the literature data.

AUTHOR INFORMATION


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Corresponding Author *E-mail: [email protected]. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported in part by Grants-in-Aid for Scientific Research (No. 16H02082) from the Japan Society for the Promotion of Science (JSPS). K.S. thanks a JSPS Research Fellowship for Young Scientists.

REFERENCES (1) Hartland, G. V. Optical Studies of Dynamics in Noble Metal Nanostructures. Chem. Rev. 2011, 111, 3858–3887. (2) Sönnichsen, C.; Franzl, T.; Wilk, T.; von Plessen, G.; Feldmann, J.; Wilson, O.; Mulvaney, P. Drastic Reduction of Plasmon Damping in Gold Nanorods. Phys. Rev. Lett. 2002, 88, 077402. (3) Lakowicz, J. R. Radiative Decay Engineering 5: Metal-Enhanced Fluorescence and Plasmon Emission. Anal. Biochem. 2005, 337, 171–194. (4) Atwater, H.A.; Polman, A. Plasmonics for Improved Photovoltaic Devices. Nat. Mater. 2010, 9, 205–213. (5) Cushing, S. K.; Li, J. T.; Meng, F. K.; Senty, T. R.; Suri, S.; Zhi, M. J.; Li, M.; Bristow, A. D.; Wu, N. Q. Photocatalytic Activity Enhanced by Plasmonic Resonant Energy Transfer from Metal to Semiconductor. J. Am. Chem. Soc. 2012, 134, 15033–15041.


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(6) Tian, Y.; Tatsuma, T. Mechanisms and Applications of Plasmon-Induced Charge Separation at TiO2 Films Loaded with Gold Nanoparticles. J. Am. Chem. Soc. 2005, 127, 7632–7637. (7) Tatsuma, T. Plasmonic Photoelectrochemistry: Functional Materials Based on Photoinduced Reversible Redox Reactions of Metal Nanoparticles. Bull. Chem. Soc. Jpn. 2013, 86, 1–9. (8) Clavero, C. Plasmon-Induced Hot-Electron Generation at Nanoparticle/Metal-Oxide Interfaces for Photovoltaic and Photocatalytic Devices. Nat. Photonics 2014, 8, 95−103 (9) Takahashi, Y.; Tatsuma, T. Solid State Photovoltaic Cells Based on Localized Surface Plasmon-Induced Charge Separation. Appl. Phys. Lett. 2011, 99, 182110. (10) Lee, Y. K.; Jung, C. H.; Park, J.; Seo, H.; Somorjai, G. A.; Park, J. Y. Surface PlasmonDriven Hot Electron Flow Probed with Metal-Semiconductor Nanodiodes. Nano Lett. 2011, 11, 4251–4255. (11) Reineck, P.; Lee, G. P.; Brick, D.; Karg, M.; Mulvaney, P.; Bach, U. A Solid-State Plasmonic Solar Cell via Metal Nanoparticle Self-Assembly. Adv. Mater. 2012, 24, 4750–4755. (12) Mubeen, S.; Lee, J.; Lee, W. R.; Singh, N.; Stucky, G. D.; Moskovits, M. On the Plasmonic Photovoltaic. ACS Nano 2014, 8, 6066−6073. (13) Kowalska, E.; Abe, R.; Ohtani, B. Visible Light-Induced Photocatalytic Reaction of Gold-Modified Titanium(IV) Oxide Particles: Action Spectrum Analysis. Chem. Commun. 2009, 241–243.


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(14) Kominami, H.; Tanaka, A.; Hashimoto, K. Mineralization of Organic Acids in Aqueous Suspensions of Gold Nanoparticles Supported on Cerium(IV) Oxide Powder Under Visible Light Irradiation. Chem. Commun. 2010, 46, 1287–1289. (15) Gomes S. C.; Juárez, R.; Marino, T.; Molinari, R.; García, H. Influence of Excitation Wavelength (UV or Visible Light) on the Photocatalytic Activity of Titania Containing Gold Nanoparticles for the Generation of Hydrogen or Oxygen from Water. J. Am. Chem. Soc. 2010, 133, 595–602. (16) Tatsuma, T.; Katagi, Y.; Watanabe, S.; Akiyoshi, K.; Kawawaki, T.; Nishi, H.; Kazuma, E. Direct Output of Electrical Signals from LSPR Sensors on the Basis of PlasmonInduced Charge Separation. Chem. Commun. 2015, 51, 6100–6103. (17) Tatsuma, T.; Takada, K.; Miyazaki, T. UV Light-Induced Swelling and Visible LightInduced Shrinking of a TiO2-Containing Redox Gel. Adv. Mater. 2007, 19, 1249–1251. (18) Ohko, Y.; Tatsuma, T.; Fujii, T.; Naoi, K.; Niwa, C.; Kubota, Y.; Fujishima, A. Multicolour Photochromism of TiO2 Films Loaded with Silver Nanoparticles. Nat. Mater. 2003, 2, 29–31. (19) Kazuma, E.; Tatsuma, T. Photoinduced Reversible Changes in Morphology of Plasmonic Ag Nanorods on TiO2 and Application yo Versatile Photochromism. Chem. Commun. 2012, 48, 1733–1735. (20) Tanabe, I.; Tatsuma, T. Plasmonic Manipulation of Color and Morphology of Single Silver Nanospheres. Nano Lett. 2012, 12, 5418–5421. (21) Konishi, Y.; Tanabe, I.; Tatsuma, T. Stable Spectral Dip Formation and Multicolour Changes of Plasmonic Gold Nanoparticles on TiO2. Chem. Commun. 2013, 49, 606–608.


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(22) Tian, Y.; Tatsuma, T. Plasmon-Induced Photoelectrochemistry at Metal Nanoparticles Supported on Nanoporous TiO2. Chem. Commun. 2004, 1810–1811. (23) Sakai, N.; Fujiwara, Y.; Takahashi, Y.; Tatsuma, T. Plasmon Resonance-Based Generation of Cathodic Photocurrent at Electrodeposited Gold Nanoparticles Coated with TiO2 Films. ChemPhysChem 2009, 10, 766–769. (24) Takahashi, Y.; Tatsuma, T. Electrodeposition of Thermally Stable Gold and Silver Nanoparticle Ensembles through a Thin Alumina Nanomask. Nanoscale 2010, 2, 1494– 1499. (25) Kazuma, E.; Tatsuma, T.; In-Situ Nanoimaging of Photoinduced Charge Separation at the Plasmonic Au Nanoparticle-TiO2. Interface. Adv. Mater. Interfaces, 2014, 1, 1400066. (26) Matsubara, K.; Tatsuma, T. Morphological Changes and Multicolor Photochromism of Ag Nanoparticles Deposited on Single-Crystalline TiO2 Surfaces. Adv. Mater. 2007, 19, 2802–2806. (27) Matsubara, K.; Kelly, K. L.; Sakai, N.; Tatsuma, T. Effects of Adsorbed Water on Plasmon-Based Dissolution, Redeposition and Resulting Spectral Changes of Ag Nanoparticles on Single-Crystalline TiO2. Phys. Chem. Chem. Phys. 2008, 10, 2263– 2269. (28) Kazuma, E.; Sakai, N.; Tatsuma, T. Nanoimaging of Localized Plasmon-Induced Charge Separation. Chem. Commun. 2011, 47, 5777−5779. (29) Takahashi, Y.; Furukawa, Y.; Ishida, T.; Yamada, S. Site-selective NanoscalePolymerization of Pyrrole on Gold Nanoparticles via Plasmon Induced Charge Separation. Nanoscale 2016, 8, 8520–8524.


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(30) Minamimoto, H.; Toda, T.; Futashima, R.; Li, X. W.; Suzuki, K.; Yasuda, S.; Murakoshi, K. Visualization of Active Sites for Plasmon-Induced Electron Transfer Reactions Using Photoelectrochemical Polymerization of Pyrrole. J. Phys. Chem. C 2016, 120, 16051–16058. (31) Nishi, H.; Tatsuma, T. Oxidation Ability of Plasmon-Induced Charge Separation Evaluated on the Basis of Surface Hydroxylation of Gold Nanoparticles. Angew. Chem. Int. Ed. 2016, 55, 10771–10775. (32) Brongersma, M. L.; Halas, N. J.; Nordlander, P. Plasmon-induced Hot Carrier Science and Technology. Nat. Nanotechnol. 2015, 10, 25−34. (33) Uskov, A. V.; Protsenko, I. E.; Ikhsanov, R. S.; Babicheva, V. E.; Zhukovsky, S. V.; Lavrinenko, A. V.; O'Reilly, E. P.; Xu, H. X. Internal Photoemission from Plasmonic Nanoparticles: Comparison between Surface and Volume Photoelectric Effects. Nanoscale 2014, 6, 4716−4727. (34) Creutz, C.; Brunschwig, B. S.; Sutin, N. Interfacial Charge-Transfer Absorption: 3. Application to Semiconductor-Molecule Assemblies. J. Phys. Chem. B 2006, 110, 25181–25190. (35) Boerigter, C.; Aslam, U.; Linic, S. Mechanism of Charge Transfer from Plasmonic Nanostructures to Chemically Attached Materials. ACS Nano 2016, 10, 6108–6115. (36) Sherry, L. J.; Chang, S. H.; Schatz, G. C.; Van Duyne, R. P.; Wiley, B. J.; Xia, Y. N. Localized Surface Plasmon Resonance Spectroscopy of Single Silver Nanocubes. Nano Lett. 2005, 5, 2034–2038. (37) Ringe, E.; McMahon, J. M.; Sohn, K.; Cobley, C.; Xia, Y. N.; Huang, J. X.; Schatz, G. C.; Marks, L. D.; Van Duyne, R. P. Unraveling the Effects of Size, Composition, and


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Substrate on the Localized Surface Plasmon Resonance Frequencies of Gold and Silver Nanocubes: A Systematic Single-Particle Approach. J. Phys. Chem. C 2010, 114, 12511– 12516. (38) Saito, K.; Tatsuma, T. Asymmetric Three-Way Plasmonic Color Routers. Adv. Opt. Mater. 2015, 3, 883–887. (39) Im, S. H.; Lee, Y. T.; Wiley, B.; Xia, Y. N. Large-Scale Synthesis of Silver Nanocubes: The Role of HCl in Promoting Cube Perfection and Monodispersity. Angew. Chem. Int. Ed. 2005, 44, 2154–2157. (40) Jain, P. K.; Lee, K. S.; El-Sayed, I. H.; El-Sayed, M. A. Calculated Absorption and Scattering Properties of Gold Nanoparticles of Different Size, Shape, and Composition: Applications in Biological Imaging and Biomedicine. J. Phys. Chem. B 2006, 110, 7238– 7248. (41) Govorov, A. O.; Richardson, H. H. Generating Heat with Metal Nanoparticles. Nano Today 2007, 2, 30–38. (42) Dweydari, A. W.; Mee, C. H. B. Oxygen Adsorption on the (111) Face of Silver. Phys. Status Solidi A 1973, 17, 247–250. (43) Könenkamp, R. Carrier Transport in Nanoporous TiO2 Films. Phys. Rev. B 2000, 61, 11057–11064. (44) Frese, K. W. Jr.; Chen, C. Theoretical Models of Hot Carrier Effects at MetalSemiconductor Electrodes. J. Electrochem. Soc. 1992, 139, 3234–3243. (45) Lynch, D. W.; Hunter, W. R. In Handbook of Optical Constants of Solids; Palik, E. D., Ed.; Academic Press: New York, 1985.


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(46) Jellison, G. E.; Boatner, L. A.; Budai, J. D.; Jeong, B. S.; Norton, D. P. Spectroscopic Ellipsometry of Thin Film and Bulk Anatase (TiO2). J. Appl. Phys. 2003, 93, 9537–9541. (47) Konig, T. A. F.; Ledin, P. A.; Kerszulis, J.; Mahmoud, M. A.; El-Sayed, M. A.; Reynolds, J. R.; Tsukruk, V. V. Electrically Tunable Plasmonic Behavior of Nanocube– Polymer Nanomaterials Induced by a Redox-Active Electrochromic Polymer. ACS Nano 2014, 8, 6182–6192.


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Site-Selective Plasmonic Etching of Silver Nanocubes - American

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