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By trial and error, it was found that surface attachment of the Ag X/Au1-X alloy required a clean gold adhesion layer. Otherwise, the alloy would delaminate from the substrate during HNO3 etching. Freshly sputtered gold surfaces adhered AgX/Au1-X the best i.e, it was best to use freshly made samples as opposed to making a bunch of gold samples and then periodically cleaning one when necessary with either H2SO4:H2O2 or H 2O2:NH4OH:H2O, although in preliminary trials thermally deposited gold when used immediately usually adhered alloy upon etching
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2O), although in preliminary trials thermally deposited gold when used immediately usually adhered alloy upon etching.
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28
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33847694590
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These QCM thicknesses will be used for convenience for the sample designation throughout the text. Cross-sectional SEM images were taken for a variety of the different thicknesses to determine a direct physical thickness. Typically, the SEM thickness values were ∼0.9 of the QCM values.
-
These QCM thicknesses will be used for convenience for the sample designation throughout the text. Cross-sectional SEM images were taken for a variety of the different thicknesses to determine a direct physical thickness. Typically, the SEM thickness values were ∼0.9 of the QCM values.
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29
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33847696000
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This particular configuration was recommended by the manufacturer to ensure an even coating
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This particular configuration was recommended by the manufacturer to ensure an even coating.
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Values were obtained directly from calibration data for our XPS instrument
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Values were obtained directly from calibration data for our XPS instrument.
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33847758516
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Also, EDS typically probes ∼1 mm into a sample and thin (<100 nm) films needed to be tested, so XPS was substituted for EDS since it probes the top ∼5-10 nm of a surface.
-
Also, EDS typically probes ∼1 mm into a sample and thin (<100 nm) films needed to be tested, so XPS was substituted for EDS since it probes the top ∼5-10 nm of a surface.
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33847699201
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For a visual simulation of the dealloying process, see
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For a visual simulation of the dealloying process, see http://www.deas.harvard.edu/matsci/downdata/dealloying-movie.avi.
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33847762115
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Values of surface areas for desired etch times of given starting alloy film thicknesses can be interpolated from the complete set of data and associated plots in the Supporting Information. In general, the film thickness surface correlations are nonlinear
-
Values of surface areas for desired etch times of given starting alloy film thicknesses can be interpolated from the complete set of data and associated plots in the Supporting Information. In general, the film thickness surface correlations are nonlinear.
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51
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33847756976
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This type of behavior was typical of a spinodal decomposition process. For example see: Chan, J. W, Hilliard, J. E. J. Chem. Phys. 1959, 31, 688-699 or ref 2
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This type of behavior was typical of a spinodal decomposition process. For example see: Chan, J. W.; Hilliard, J. E. J. Chem. Phys. 1959, 31, 688-699 or ref 2.
-
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52
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33847767375
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More extensive comparisons are given in the Supporting Information
-
More extensive comparisons are given in the Supporting Information.
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56
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33847700738
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The goodness of each fit was defined by the global nonlinear least squares fit error between the experimental and simulated Δ, Ψ spectra
-
The goodness of each fit was defined by the global nonlinear least squares fit error between the experimental and simulated Δ, Ψ spectra.
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17144462249
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Discrepancies between the simulations and the experimental data could be due to using bulk Au dielectric constants. When using EMT models with Au nanoparticles, an additional term may be required to account for either classical scattering of the conduction electrons from the particle surface as it becomes comparable to or smaller than the electron mean free path (the so-called limited electron mean free path effect) or quantum mechanically because of dipole transitions between sp electron eigenstates which become discrete as a result of the small dimensions of the particle. Briefly, a dielectric function for Au nanoparticles can be written as a combination of an interband term approximated by Lorentz oscillators accounting for the response of the d electrons and a Drude term considering the free conduction electrons, For a more detailed description see ref 53 or 54, The features in the case of np-Au could possibly be approximated by aggregated nanoparticles, so using modified optical
-
Discrepancies between the simulations and the experimental data could be due to using bulk Au dielectric constants. When using EMT models with Au nanoparticles, an additional term may be required to account for either classical scattering of the conduction electrons from the particle surface as it becomes comparable to or smaller than the electron mean free path (the so-called limited electron mean free path effect) or quantum mechanically because of dipole transitions between sp electron eigenstates which become discrete as a result of the small dimensions of the particle. Briefly, a dielectric function for Au nanoparticles can be written as a combination of an interband term approximated by Lorentz oscillators accounting for the response of the d electrons and a Drude term considering the free conduction electrons. (For a more detailed description see ref 53 or 54.) The features in the case of np-Au could possibly be approximated by aggregated nanoparticles, so using modified optical constants could result in more accurate simulations. Also, discrepancies arising from image dipole effects because of the presence of an interface or optical screening may drastically change the optical response, but better fits to experimental results have come from evaluating the optical response not with Bruggeman EMT but as a result of the presence of optical dipoles at an interface [Wormeester, H.; Kooij, E. S.; Mewe, A.; Rekveld, S.; Poelsema B. Thin Solid Films 2004, 455-456, 323-334].
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