How to Quantify Electrons in Plasmonic Colloidal Metal Oxide Nanocrystals

Shubert-Zuleta, Sofia A.; Tandon, Bharat; Roman, Benjamin J.; Gan, Xing Yee; Milliron, Delia J.

doi:10.26434/chemrxiv-2022-h010f

Cited by 6 publications

(11 citation statements)

References 47 publications

(102 reference statements)

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“…Furthermore, the addition of TEMPO after photodoping reverts the effect on LSPR, bringing the LSPR peak back to its initial position and intensity. These conclusions are supported by similar dynamics of LSPR peak position and intensity, as reported in the literature (Brozek et al, 2016;Ghini et al, 2021b;Shubert-Zuleta et al, 2023). Indeed, in these studies, the authors were investigating the effect of different electron scavengers on photodoped NCs.…”

Section: Temposupporting

confidence: 85%

Light-driven reversible charge transfers from ITO nanocrystals

Rebecchi,

Rubino,

Camellini

et al. 2023

Front. Chem.

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The combination of semiconductors and redox active molecules for light-driven energy storage systems has emerged as a powerful solution for the exploitation of solar batteries. On account of this, transparent conductive oxide (TCO) nanocrystals (NCs) demonstrated to be interesting materials, thanks to the photo-induced charge accumulation enabling light harvesting and storage. The charge transfer process after light absorption, at the base of the proper use of these semiconductors, is a key step, often resulting in non-reversible transformations of the chemicals involved. However, if considering the photocharging through TCO NCs not only as a charge provider for the system but potentially as part of the storage role, the reversible transformation of the redox compound represents a crucial aspect. In this paper, we explore the possible interaction of indium tin oxide (ITO) NCs and typical redox mediators commonly employed in catalytic applications with a twofold scope of enhancing or supporting the light-induced charge accumulation on the metal oxide NC side and controlling the reversibility of the whole process. The work presented focuses on the effect of the redox properties on the doped metal oxide response, both from the stability point of view and the photodoping performance, by monitoring the changes in the optical behavior of ITO/redox hybrid systems upon ultraviolet illumination.

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Section: Temposupporting

confidence: 85%

Light-driven reversible charge transfers from ITO nanocrystals

Rebecchi,

Rubino,

Camellini

et al. 2023

Front. Chem.

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“…The lower plasmon absorption intensity in smaller sizes was attributed in other plasmonic NCs to faster relaxation in the NC surface 54 or changes in the vacancy concentration. 55 Moving on to the next reaction step of the cation exchange, Figure 4b shows the absorption of the resulting w-InP NCs after the exchange of Cu + to In 3+ . The stronger quantum confinement in the smaller NCs causes a slight although smeared blue shift in the band gap.…”

Section: Methodssupporting

confidence: 61%

Size and Emission Control of Wurtzite InP Nanocrystals Synthesized from Cu_3–xP by Cation Exchange

Stone,

Li,

Naor

et al. 2023

Chem. Mater.

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Phosphide-based nanocrystals (NCs), including InP and Cu 3−x P, are relevant for applications in light-emitting devices and catalysis, yet their synthetic design is limited in terms of size range and homogeneity. We report the synthesis of uniform and size-controlled emissive wurtzite-phase InP NCs formed via cation exchange from Cu 3−x P. First, size-controlled Cu 3−x P NCs are synthesized by the formation of metallic Cu 0 NCs and their phosphidation to Cu 3−x P. By changing the ligands and precursor concentrations, the NC size is varied between 5 and 13 nm. Using cation exchange, InP NCs are then generated. As the surface of InP NCs is prone to oxidation and defects that decrease their emission, we performed a reaction with NOBF 4 . This yields InP NCs with resolved absorption features and efficient band-gap emission as a result of impurity removal and surface passivation. The effect of water, acid, and halides on the balance of NC etching and surface passivation is studied. With this approach, high-quality wurtzite InP NCs are obtained while the emission is tuned between 810 and 600 nm. The obtained NCs are potential building blocks for catalytic and optoelectronic applications.

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“…The observed agreement in carrier density suggests that NOBF 4 is an appropriate titrant for WO 3−x , which has been observed to not be the case for Sn:In 2 O 3 . 29 Such an observation may reflect the enhanced stability due to TOPO passivation, removing interfacial compensation centers, as previously suggested by the Milliron 29 and Strouse 19,30 groups as reasons for the lack of agreement between modeling and chemical titrations.…”

Section: ■ Results and Discussionmentioning

confidence: 89%

Plasmon-Induced Hot-Carrier Excited-State Dynamics in Plasmonic Semiconductor Nanocrystals

Kuszynski,

Fabiano,

Nguyen

et al. 2023

J. Phys. Chem. C

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The variance of carrier relaxation pathways for WO3–x plasmonic semiconductor nanocrystals (PSNCs) is monitored by transient absorption spectroscopy following excitation of the localized surface plasmon resonance (LSPR) versus the optical band gap (E g,opt). Excitation of the LSPR leads to efficient hot carrier population above the Fermi level in WO3–x via Landau damping, in analogy to noble metal LSPR relaxation mechanisms. Hot carrier depopulation occurs on the femtosecond timescale, observed as the concomitant recovery of an LSPR bleach with the appearance of discrete interband and intraband photoinduced absorption features. By comparison, the direct excitation of E g,opt results in trion recombination at donor–acceptor sites within the WO3–x NC, consistent with exciton decay dynamics observed for typical wide-band-gap semiconductor NCs. From the analysis of pump power dependency data, a hot-carrier electron–phonon coupling constant of 1.47 × 1011 J K–1 s–1 cm–3 is extracted. The direct comparison of the decay dynamics following E g,opt versus LSPR excitation confirms that the observed plasmon in trioctylphosphine oxide passivated, spherical WO3–x is a resonance state in which hot carriers are generated only from excitation on resonance with the LSPR frequency. This study on WO3–x PSNCs provides a toolset that can be used to evaluate the role of hot carriers following LSPR excitation of n-type, plasmonic transparent conducting oxide NCs, where enhancement of photocatalysis, photovoltaic performance, and optical enhancement has been reported.

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How to Quantify Electrons in Plasmonic Colloidal Metal Oxide Nanocrystals

Cited by 6 publications

References 47 publications

Light-driven reversible charge transfers from ITO nanocrystals

Light-driven reversible charge transfers from ITO nanocrystals

Size and Emission Control of Wurtzite InP Nanocrystals Synthesized from Cu_3–xP by Cation Exchange

Plasmon-Induced Hot-Carrier Excited-State Dynamics in Plasmonic Semiconductor Nanocrystals

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How to Quantify Electrons in Plasmonic Colloidal Metal Oxide Nanocrystals

Cited by 6 publications

References 47 publications

Light-driven reversible charge transfers from ITO nanocrystals

Light-driven reversible charge transfers from ITO nanocrystals

Size and Emission Control of Wurtzite InP Nanocrystals Synthesized from Cu3–xP by Cation Exchange

Plasmon-Induced Hot-Carrier Excited-State Dynamics in Plasmonic Semiconductor Nanocrystals

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Size and Emission Control of Wurtzite InP Nanocrystals Synthesized from Cu_3–xP by Cation Exchange