Size dependence investigations of hot electron cooling dynamics in metal/adsorbates nanoparticles

Bauer, Christophe; Abid, Jean‐Pierre; Girault, Hubert H.

doi:10.1016/j.chemphys.2005.06.040

Cited by 19 publications

(28 citation statements)

References 64 publications

(105 reference statements)

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“…Recently, Bauer and coworkers have described a phenomenological model in which the interface between the Au NP and an organic adlayer changes the rate at which plasmonic electrons equilibrate to form a thermal distribution by providing pathways for redistribution of the hot electrons' kinetic energy. The authors adopt the name "ultrafast chemical interface scattering (UCIS)" for this mechanism, as it is consistent with chemistryinduced localized surface plasmon (LSP) damping that has long been observed in small NPs in the colloid field (17)(18)(19)(20).…”

mentioning

confidence: 92%

Identification of parameters through which surface chemistry determines the lifetimes of hot electrons in small Au nanoparticles

Aruda

Tagliazucchi

Sweeney

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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This paper describes measurements of the dynamics of hot electron cooling in photoexcited gold nanoparticles (Au NPs) with diameters of ∼3.5 nm, and passivated with either a hexadecylamine or hexadecanethiolate adlayer, using ultrafast transient absorption spectroscopy. Fits of these dynamics with temperature-dependent Mie theory reveal that both the electronic heat capacity and the electron-phonon coupling constant are larger for the thiolated NPs than for the aminated NPs, by 40% and 30%, respectively. Density functional theory calculations on ligand-functionalized Au slabs show that the increase in these quantities is due to an increased electronic density of states near the Fermi level upon ligand exchange from amines to thiolates. The lifetime of hot electrons, which have thermalized from the initial plasmon excitation, increases with increasing electronic heat capacity, but decreases with increasing electronphonon coupling, so the effects of changing surface chemistry on these two quantities partially cancel to yield a hot electron lifetime of thiolated NPs that is only 20% longer than that of aminated NPs. This analysis also reveals that incorporation of a temperaturedependent electron-phonon coupling constant is necessary to adequately fit the dynamics of electron cooling. two-temperature model | dissipation T his paper describes an observed dependence of two physical properties-the electronic heat capacity and the electronphonon coupling magnitude-of small (diameter of ∼3.5 nm), completely absorptive plasmonic gold nanoparticles (Au NPs) on the surface chemistry of the NPs. The electronic heat capacity, quantified by the coefficient γ, is the amount of energy required to change the temperature of a population of electrons in the NP. The magnitude of the electron-phonon coupling, quantified by the coefficient g, is a measure of the rate of exchange of energy between the electrons and the lattice. Upon photoexcitation of the Au NPs at the absorption maximum of their plasmon resonance, the plasmonic electron oscillation in the NPs rapidly decoheres to form a thermally equilibrated population of hot electrons (1-8). Within the commonly used "two-temperature model (2TM)," the rate of subsequent cooling of these electrons is dictated by the initial electronic temperature of the particle and the efficiency of dissipation of electronic energy into available vibrational modes. These properties, in turn, depend on the electronic heat capacity of the system and the magnitude of electron-phonon coupling. Our observed dependence of the coefficients γ and g on the chemical structure of the organic adlayer therefore implies that electronic states that participate in the electron cooling process are not only those of the gold lattice, but also orbitals at the metal-organic interface-that is, the surface chemistry of the NPs influences the rate of hot electron cooling.Interest in using metal and semiconductor NPs as optical and/or electronic components within energy conversion systems (9, 10) has inspired studies of ene...

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mentioning

confidence: 92%

Identification of parameters through which surface chemistry determines the lifetimes of hot electrons in small Au nanoparticles

Aruda

Tagliazucchi

Sweeney

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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“…[26][27][28]30,54 For our experimental conditions, we can estimate from the absorption cross section and the heat capacity of gold that every AuNP absorbs approximately 500 photons (assuming an extinction coefficient of 1.3·10 7 M -1 cm -1 , which was linearly interpolated for the 5.7 nm AuNPs from the values given in Ref. 59 and corrected for the fact that we excited at 400 nm and not in the Plasmon resonance), resulting in an initial temperature jump of 1000200 K at the highest pump fluence we considered, 110 J/m 2 .…”

Section: Heat Responsementioning

confidence: 99%

Response of Villin Headpiece-Capped Gold Nanoparticles to Ultrafast Laser Heating

et al. 2014

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The integrity of a small model protein, the 36-residue villin headpiece HP36 attached to gold nanoparticles (AuNP) is examined and its response to laser excitation of the AuNPs is investigated. To that end, it is first verified by stationary IR and CD spectroscopy together with denaturation experiments that the folded structure of the protein is fully preserved when attached to the AuNP surface. It is then shown by time-resolved IR spectroscopy that the protein does not unfold even upon the highest pump fluences that lead to local temperature jumps in the order of 1000 K of the phonon system of the AuNPs, since that temperature jump persists for too short a time of a few nanoseconds only to be destructive. Judged from a blue shift of the amide I band, indicating destabilized or a few broken hydrogen bonds, the protein either swells, becomes more unstructured from the termini, and/or changes its degree of solvation. In any case, it recovers immediately after the excess energy dissipates into the bulk solvent. The process is entirely reversible for millions of laser shots without any indication of aggregation of the protein and/or the AuNPs and with only a minor fraction of broken protein-AuNP thiol-bonds. The work provides important cornerstones in designing laser pulse parameters for maximal heating with protein-capped AuNPs without destroying the capping layer. Abstract:The integrity of a small model protein, the 36-residue villin headpiece HP36 attached to gold nanoparticles (AuNP) is examined and its response to laser excitation of the AuNPs is investigated. To that end, it is first verified by stationary IR and CD spectroscopy together with denaturation experiments that the folded structure of the protein is fully preserved when attached to the AuNP surface. It is then shown by time-resolved IR spectroscopy that the protein does not unfold even upon the highest pump fluences that lead to local temperature jumps in the order of 1000 K of the phonon system of the AuNPs, since that temperature jump persists for too short a time of a few nanoseconds only to be destructive. Judged from a blue shift of the amide I band, indicating destabilized or a few broken hydrogen bonds, the protein either swells, becomes more unstructured from the termini, and/or changes its degree of solvation. In any case, it recovers immediately after the excess energy dissipates into the bulk solvent. The process is entirely reversible for millions of laser shots without any indication of aggregation of the protein and/or the AuNPs and with only a minor fraction of broken protein-AuNP thiol-bonds. The work provides important cornerstones in designing laser pulse parameters for maximal heating with protein-capped AuNPs without destroying the capping layer.

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“…After the printing process, the EOGN wet films were subjected to photonic flash sintering. The EOGNs absorbed the emitted light stronger than the PI substrate and generated sufficient heat to dry and to adhere the EOGN film to PI . The conductivity of the patterns was examined by using a voltmeter and varied from ∼140 kΩ/mm for 2 IJPLs to ∼0.4 kΩ/mm for 20 IJPLs.…”

Section: Resultsmentioning

confidence: 84%

“…The EOGNs absorbed the emitted light stronger than the PI substrate and generated sufficient heat to dry and to adhere the EOGN film to PI. [58] The conductivity of the patterns was examined by using a voltmeter and varied from~140 kΩ/mm for 2 IJPLs to~0.4 kΩ/ mm for 20 IJPLs. This indicates an increase in film conductivity with IJPL, as expected.…”

Section: Ink Formulation and Inkjet Printingmentioning

confidence: 99%

Highly Loaded Mildly Edge‐Oxidized Graphene Nanosheet Dispersions for Large‐Scale Inkjet Printing of Electrochemical Sensors

et al. 2020

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Inkjet printing of electrochemical sensors using a highly loaded mildly edge-oxidized graphene nanosheet (EOGN) ink is presented. An ink with 30 mg/mL EOGNs is formulated in a mixture of N-methyl pyrrolidone and propylene glycol with only 30 min of sonication. The absence of additives, such as polymeric stabilizers or surfactants, circumvents reduced electrochemical activity of coated particles and avoids harsh postprinting conditions for additive removal. A single light pulse from a xenon flash lamp dries the printed EGON film within a fraction of a second and creates a compact electrode surface.An accurate coverage with only 30.4 μg of EOGNs per printed layer and cm 2 is achieved. The EOGN films adhere well to flexible polyimide substrates in aqueous solution. Electrochemical measurements were performed using cyclic voltammetry and differential pulse voltammetry. An all inkjet-printed threeelectrode living bacterial cell detector is prepared with EOGN working and counter electrodes and silver-based quasi-reference electrode. The presence of E. coli in liquid samples is recorded with four electroactive metabolic activity indicators.

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Size dependence investigations of hot electron cooling dynamics in metal/adsorbates nanoparticles

Cited by 19 publications

References 64 publications

Identification of parameters through which surface chemistry determines the lifetimes of hot electrons in small Au nanoparticles

Identification of parameters through which surface chemistry determines the lifetimes of hot electrons in small Au nanoparticles

Response of Villin Headpiece-Capped Gold Nanoparticles to Ultrafast Laser Heating

Highly Loaded Mildly Edge‐Oxidized Graphene Nanosheet Dispersions for Large‐Scale Inkjet Printing of Electrochemical Sensors

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