Journal
JOURNAL OF MATERIALS CHEMISTRY C
Volume 4, Issue 24, Pages 5779-5786Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6tc01719c
Keywords
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Funding
- EPSRC [EP/L017563/1]
- Engineering and Physical Sciences Research Council [EP/L017563/1, EP/L027348/1] Funding Source: researchfish
- EPSRC [EP/L027348/1] Funding Source: UKRI
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Precise control of electronic and/or ionic conductivity in electroceramics is crucial to achieve the desired functional properties as well as to improve manufacturing practices. We recently reported the conventional piezoelectric material Na1/2Bi1/2TiO3 (NBT) can be tuned into a novel oxide-ion conductor with an oxide-ion transport number (t(ion)) > 0.9 by creating bismuth and oxygen vacancies. A small Bi-excess in the nominal starting composition (Na0.50Bi0.50+xTiO3+3x/2, x = 0.01) or Nb-donor doping (Na(0.50)Bi(0.50)Ti(1-y)NbyO(3+y/2), 0.005 <= y <= 0.030) can reduce significantly the electrical conductivity to create dielectric behaviour by filling oxygen vacancies and suppressing oxide ion conduction (t(ion) <= 0.10). Here we show a further increase in the starting Bi-excess content (0.02 <= x <= 0.10) reintroduces significant levels of oxide-ion conductivity and increases t(ion) similar to 0.4-0.6 to create mixed ionic/electronic behaviour. The switch from insulating to mixed conducting behaviour for x 4 0.01 is linked to the presence of Bi-rich secondary phases and we discuss possible explanations for this effect. Mixed conducting behaviour with tion similar to 0.5-0.6 can also be achieved with lower levels of Nb-doping (y similar to 0.003) due to incomplete filling of oxygen vacancies without the presence of secondary phases. NBT can now be compositionally tailored to exhibit three types of electrical behaviour; Type I (oxide-ion conductor); Type II (mixed ionic-electronic conductor); Type III (insulator) and these results reveal an approach to fine-tune tion in NBT from near unity to zero. In addition to developing new oxide-ion and now mixed ionic/electronic NBT-based conductors, this flexibility in control of oxygen vacancies allows fine-tuning of both the dielectric/piezoelectric properties and design manufacturing practices for NBT-based multilayer piezoelectric devices.
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