Local structural and chemical ordering of nanosized Pt3±δCo probed by multiple-scattering x-ray absorption spectroscopy

Giorgia Greco, Agnieszka Witkowska, Emiliano Principi, Marco Minicucci, and Andrea Di Cicco
Phys. Rev. B 83, 134103 – Published 5 April 2011

Abstract

This work reports a detailed investigation of the local structure and chemical disorder of a Pt3±δCo thin film and Pt3±δCo nanoparticles. We have used a combination of techniques including x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and high-resolution transmission electron microscopy (TEM). High-quality XAS spectra at the Co K edge and Pt L3 edge have been analyzed using double-edge multiple-scattering data analysis. Structural extended x-ray absorption fine structure (EXAFS) refinements have been performed accounting for the reduction of the coordination numbers and degeneracy of three-atom configurations, resulting from the measured size distribution and stoichiometry. The important effect of chemical ordering on pair and three-atom configurations has been studied using computer simulations based on a simple model accounting for substitutional disorder, defined by an order parameter s. It has been found that individual EXAFS signals related to the minority species (Co) are extremely sensitive to substitutional disorder so their intensities, especially those of the collinear three-atom configurations, can be used as a measure of the ordering level. The thin film has been found to be chemically disordered (s0.4), in agreement with previous estimates. The Pt3±δCo nanoalloy has been found to be partially ordered (s=0.6±0.1) while the local structure around Co atoms is characterized by a higher level of structural disorder as compared to the bulk-like thin film. The robust approach for nanomaterial characterization used in this work combining different techniques can, in principle, be applied for structural refinements of any binary nanocrystalline functional system.

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  • Received 30 November 2010

DOI:https://doi.org/10.1103/PhysRevB.83.134103

©2011 American Physical Society

Authors & Affiliations

Giorgia Greco1,*, Agnieszka Witkowska2,†, Emiliano Principi1, Marco Minicucci1, and Andrea Di Cicco1,3

  • 1CNISM, School of Science and Technology, Physics Division, University of Camerino, I-62032 Camerino (MC), Italy
  • 2Department of Solid State Physics, Gdansk University of Technology, PL-80-233 Gdansk, Poland
  • 3IMPMC-CNRS, Université P.et M. Curie, 140 rue de Lourmel, F-75015 Paris, France

  • *giorgiagreco80@gmail.it
  • agnieszka@mif.pg.gda.pl

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Issue

Vol. 83, Iss. 13 — 1 April 2011

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