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Direct in situ determination of the polarization dependence of physisorption on ferroelectric surfaces

Nature Materials volume 7, pages 473–477 (2008)Cite this article

Abstract

The ability to manipulate dipole orientation in ferroelectric oxides holds promise as a method to tailor surface reactivity for specific applications. As ferroelectric domains can be patterned at the nanoscale1, domain-specific surface chemistries may provide a method for fabrication of nanoscale devices. Although studies over the past 50 yr have suggested that ferroelectric domain orientation may affect the energetics of adsorption, definitive evidence is still lacking2,3,4,5. Domain-dependent sticking coefficients are observed using temperature-programmed desorption and scanning surface potential microscopy, supported by first-principles calculations of the reaction coordinate. The first unambiguous observations of differences in the energetics of physisorption on ferroelectric domains are presented here for CH3OH and CO2 on BaTiO3 and Pb(Ti0.52Zr0.48)O3 surfaces.

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Figure 1: Surface and domain structure of BaTiO3 samples.
Figure 2: TPD spectra obtained following exposure of the BaTiO3 thin film to a subsaturation 20 L dose of CH3OH as a function of ferroelectric polarization.
Figure 3: Influence of CO2 adsorption on the surface potential of BaTiO3(001) and a PZT thin film.
Figure 4: Precursor-mediated molecular adsorption on defective ferroelectric oxide surfaces.

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Acknowledgements

We gratefully acknowledge support of this work by the NSF MRSEC program (grant no. DMR05-20020). A.M.K. and A.M.R. also acknowledge support from the US Air Force Office of Scientific Research (grant no. FA9550-07-1-0397) and the US Department of Energy, Division of Basic Energy Sciences (grant no. DE-FG02-07ER15920) and computational support from the HPCMO of the US DoD.

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  1. Dongbo Li and Mosha H. Zhao: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Materials Science and Engineering,

    Dongbo Li, J. Garra & D. A. Bonnell

  2. Department of Chemical and Biomolecular Engineering,

    Mosha H. Zhao & J. M. Vohs

  3. Department of Chemistry, The Makineni Theoretical Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA

    Mosha H. Zhao, A. M. Kolpak, A. M. Rappe & J. M. Vohs

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  1. Dongbo Li
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Correspondence to J. M. Vohs.

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Li, D., Zhao, M., Garra, J. et al. Direct in situ determination of the polarization dependence of physisorption on ferroelectric surfaces. Nature Mater 7, 473–477 (2008). https://doi.org/10.1038/nmat2198

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