title: Electronic properties of Ag nanoparticle arrays. A Kelvin probe and high resolution XPS study.
abstract: The electronic properties of citrate stabilised Ag nanoparticles with sizes ranging from 4 to 35 nm were investigated by the Kelvin probe method and high resolution XPS. Two and three dimensional assemblies of the particles were prepared by electrostatic adsorption from aqueous solution onto poly-l-lysine modified surfaces. The work function of the Ag particles increased from 5.29 +/- 0.05 to 5.53 +/- 0.05 eV as the particle size decreased. These values are approximately 0.8 eV higher than for clean polycrystalline Ag surfaces. The origin of these remarkable high work functions cannot be explained in terms of either citrate induced changes in the surface dipole or image forces in the confined metallic domains. High resolution XPS spectra of the Ag 3d(5/2) core level were characterised by broad bands and a 0.4 eV shift towards lower binding energies for the smallest particles. Comparisons with reported studies on extended Ag surfaces indicate that as-grown particles exhibit partially oxidised surfaces. The behaviour of the work function further suggests that the strength of the Ag-O bonding increases with decreasing particle sizes. These findings are highly relevant to the interpretation of the catalytic properties of Ag nanoparticles.
authors.affiliation: Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012, Bern, Switzerland.
authors.forename: Mathias
authors.initials: M
authors.lastname: Schnippering
authors.forename: Michel
authors.initials: M
authors.lastname: Carrara
authors.forename: Annette
authors.initials: A
authors.lastname: Foelske
authors.forename: Rüdiger
authors.initials: R
authors.lastname: Kötz
authors.forename: David J
authors.initials: DJ
authors.lastname: Fermín
mesh_terms: D000327:Adsorption; D004566:Electrodes; D004583:Electrons; D053758:Nanoparticles / Q000737:chemistry*; D036103:Nanotechnology / Q000379:methods*; D010316:Particle Size; D012680:Sensitivity and Specificity; D012834:Silver / Q000737:chemistry*; D013053:Spectrophotometry / Q000379:methods; D055672:Static Electricity; D013499:Surface Properties; D014867:Water / Q000737:chemistry; D014965:X-Rays
chemical_list: D014867:Water; D012834:Silver