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Studies of Multiferroic Palladium Perovskites.

Dhiren K Pradhan1,2, Ajay K Mishra1, Shalini Kumari2,3

  • 1Geophysical Laboratory, Carnegie Institution for Science, Washington, DC, 20015, USA.

Scientific Reports
|February 10, 2019
PubMed
Summary

We investigated palladium-substituted lead titanate and zirconate-titanate, revealing unique domain structures and multiple phase transitions under pressure. Palladium primarily substitutes titanium sites.

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Area of Science:

  • Materials Science
  • Condensed Matter Physics
  • Crystallography

Background:

  • Lead titanate and lead zirconate-titanate are perovskite ferroelectrics with applications in electronic devices.
  • Understanding the effects of aliovalent substitution, such as with palladium, is crucial for tuning their properties.
  • High-pressure studies reveal fundamental phase transition mechanisms in these materials.

Purpose of the Study:

  • To characterize palladium-substituted lead titanate and lead zirconate-titanate using various advanced techniques.
  • To determine the valence state and substitutional site of palladium (Pd) ions.
  • To investigate the structural and phase transition behavior under high pressure.

Main Methods:

  • Atomic Force Microscopy (AFM) for domain structure analysis.
  • X-ray Bragg reflections and X-ray Absorption Spectra (XAS) for structural and electronic state determination.
  • Raman Spectroscopy and X-ray Diffraction (XRD) for phase transition studies under pressure.

Main Results:

  • Palladium substitution is found to be almost entirely on the Ti-sites, with both Pd+4 and Pd+2 valence states.
  • AFM revealed unusual threefold vertical and fourfold in-plane domain vertices, explained by Voronoi pattern rules.
  • High-pressure studies showed Raman soft modes and a nearly second-order displacive phase transition, involving multiple transitions between 1 and 17 GPa.

Conclusions:

  • Palladium substitution in lead titanate and zirconate-titanate leads to novel domain configurations.
  • The material undergoes complex structural phase transitions under pressure, with distinct anomalies observed at different pressure ranges.
  • The findings provide insights into the interplay of substitution, domain structure, and pressure-induced phase transitions in ferroelectric perovskites.