Competition between Depletion Effects and Coupling in the Plasmon Modulation of Doped Metal Oxide Nanocrystals

Tandon, Bharat; Agrawal, Ankit; Heo, Sungyeon; Milliron, Delia J.

doi:10.1021/acs.nanolett.9b00079

Cited by 53 publications

(76 citation statements)

References 46 publications

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“…Broadening due to NC-NC LSPR coupling has been reported previously in gel and thin film assemblies of ITO NCs, though the extent of broadening is greater in this study. 7,69,82 In samples that remain free-flowing but where SAXS suggests cluster formation, e.g. Γ = 50, the LSPR is slightly broadened, as expected for LSPR coupling between nearby NCs (Figure 3e).…”

Section: Ligandsupporting

confidence: 59%

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

Domínguez

Howard²,

Maier³

et al. 2020

Preprint

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<div>The use of dynamically bonding molecules designed to reversibly link solvent-dispersed nanocrystals (NCs) is a promising strategy to form colloidal assemblies with controlled structure and macroscopic properties. In this work, tin-doped indium oxide NCs are functionalized with ligands that form reversible covalent bonds with linking molecules to drive assembly of NC gels. We monitor gelation using small angle X-ray scattering and characterize how changes in the gel structure affect infrared optical properties arising from the localized surface plasmon resonance of the NCs. The assembly is reversible because of the designed linking chemistry, and we disassemble the gels using two strategies: addition of excess NCs to change the ratio of linking molecules to NCs and addition of a capping molecule that displaces</div><div>the linking molecules. The assembly behavior is rationalized using a thermodynamic perturbation theory to compute the phase diagram of the NC–linking molecule mixture. Coarse-grained molecular dynamics simulations reveal the competition between loop and bridge linking motifs essential for understanding NC gelation. This combined experimental, computational, and theoretical work provides a platform for controlling and designing the properties of reversible colloidal assemblies that incorporate NC and solvent compositions beyond those compatible with other contemporary (e.g, DNA-based) linking strategies.</div>

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Section: Ligandsupporting

confidence: 59%

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

Domínguez

Howard²,

Maier³

et al. 2020

Preprint

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show abstract

Section: Ligandsupporting

confidence: 56%

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

et al. 2020

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The use of dynamically bonding molecules designed to reversibly link solvent-dispersed nanocrystals (NCs) is a promising strategy to form colloidal assemblies with controlled structure and macroscopic properties. In this work, tin-doped indium oxide NCs are functionalized with ligands that form reversible covalent bonds with linking molecules to drive assembly of NC gels. We monitor gelation using small angle X-ray scattering and characterize how changes in the gel structure affect infrared optical properties arising from the localized surface plasmon resonance of the NCs. The assembly is reversible because of the designed linking chemistry, and we disassemble the gels using two strategies: addition of excess NCs to change the ratio of linking molecules to NCs and addition of a capping molecule that displacesthe linking molecules. The assembly behavior is rationalized using a thermodynamic perturbation theory to compute the phase diagram of the NC-linking molecule mixture. Coarse-grained molecular dynamics simulations reveal the competition between loop and bridge linking motifs essential for understanding NC gelation. This combined experimental, computational, and theoretical work provides a platform for controlling and designing the properties of reversible colloidal assemblies that incorporate NC and solvent compositions beyond those compatible with other contemporary (e.g, DNA-based) linking strategies. File list (2) download file view on ChemRxiv Manuscript.pdf (3.07 MiB) download file view on ChemRxiv Supporting Information.pdf (2.48 MiB)

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“…Electrochromic films of nanorods do indeed show higher intrinsic CE than nanoplatelets (Figure 2d), although the difference is less dramatic than suggested by single nanocrystal simulations. LSPR coupling 20,25 and polydispersity 24 may account for this weaker-than-expected sensitivity of intrinsic CE to nanocrystal shape. Overall, the combination of both sources of anisotropy influence both intrinsic CE and total optical modulation, with practical consequences for near-infrared electrochromic devices.…”

Section: Toc Graphics Main Textmentioning

confidence: 97%

“…Nanocrystal size can also influence peak shifts and intensity changes under electrochemical charging owing to changes in the degree of LSPR coupling, so nanocrystal volume also needs to be similar to avoid these convoluting effects. 20 The previously reported synthetic methods were modified to fine-tune nanocrystal size and shape and preserve similar surface area and volume between two samples: nanorods and nanoplatelets. 24 Thus, the interplay between anisotropy in nanocrystal shape and the intrinsic crystalline structure can be directly studied.…”

Section: Toc Graphics Main Textmentioning

confidence: 99%

“…Single nanocrystal simulations of LSPR reveal the influence of shape and crystalline anisotropy on electrochromic modulation in nanoplatelets and nanorods. Although films of plasmonic nanocrystals have different optical responses than dilute dispersions, due to film reflections and inter-particle LSPR coupling, 20,25 models of LSPR scattering in single nanocrystal can provide insight on optical modulation. Furthermore, the consistent film thickness and porosity between films of nanorods and nanoplatelets ensure that differences in optical spectra are mostly due to intrinsic material properties.…”

Section: Toc Graphics Main Textmentioning

confidence: 99%

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Influence of Crystalline and Shape Anisotropy on Electrochromic Modulation in Doped Semiconductor Nanocrystals

Heo

Cho²,

Dahlman³

et al. 2020

Preprint

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<p></p><p><a>Localized surface plasmon resonance (LSPR) modulation appearing in the near-infrared range in doped semiconductor nanocrystals enriches electrochromic performance. Although crystalline and shape anisotropies influence LSPR spectra, study of their impact on electrochromic modulation are lacking. Here, we study how crystalline anisotropy in hexagonal cesium-doped tungsten oxide nanorods and nanoplatelets affects essential metrics of electrochromic modulation—coloration efficiency (CE) and volumetric capacity—using different sizes of electrolyte cations (tetrabutylammonium, sodium, and lithium) as structurally sensitive electrochemical probes. Nanorod films show higher CE than nanoplatelets in all of electrolytes owing to low effective mass along the crystalline c-axis. When using sodium cations, which diffuse through one-dimensional hexagonal tunnels, electrochemical capacity is significantly greater for platelets than for nanorods. This difference is explained by the hexagonal tunnel sites being more accessible in platelets than in nanorods. Our work sheds light on the role of shape and crystalline anisotropy on charge capacity and CE both of which contribute to overall modulation. </a></p><br><p></p>

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Competition between Depletion Effects and Coupling in the Plasmon Modulation of Doped Metal Oxide Nanocrystals

Cited by 53 publications

References 46 publications

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

Influence of Crystalline and Shape Anisotropy on Electrochromic Modulation in Doped Semiconductor Nanocrystals

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