Synthesis of a 12R-type hexagonal perovskite solid solution Sr3NdNb(3-x)Ti(x)O(12-δ) and the influence of acceptor doping on electrical properties

• Published in: Dalton transactions : an international journal of inorganic chemistry 2015-04, Vol.44 (16), p.7643-7653
• Main Authors: Chinelatto, Adilson L, Boulahya, Khalid, Pérez-Coll, Domingo, Amador, Ulises, Tabacaru, Corina, Nicholls, Simon, Hoelzel, Markus, Sinclair, Derek C, Mather, Glenn C
• Format: Article
• Language: English
• Subjects: Calcium Compounds - chemistry; Crystallography, X-Ray; Dielectric Spectroscopy; Electric Conductivity; Microscopy, Electron, Transmission; Molecular Conformation; Neodymium - chemistry; Niobium - chemistry; Oxides - chemistry; Strontium - chemistry; Temperature; Titanium - chemistry
• ISSN: 1477-9234
• DOI: 10.1039/c5dt00170f

A solid solution forms for Sr3NdNb(3-x)Ti(x)O(12-δ) with approximate limits 0 ≤ x ≤ 0.06. The system crystallizes with a 12R-type hexagonal perovskite structure in the space group R3, as determined by neutron diffraction and selected area electron diffraction. The electrical properties of the end members have been investigated by impedance spectroscopy in the temperature range 550-800 °C under various gas atmospheres and as a function of oxygen and water-vapour partial pressure. Proton transport dominates under wet oxidising conditions in the temperature range 550-700 °C, as confirmed by the H(+)/D(+) isotope effect. Acceptor doping considerably enhances proton conductivity with a value of 3.3 × 10(-6) S cm(-1) for the bulk response of x = 0.06 at 700 °C in moistened air. The presence of a -¼ slope for both doped and undoped samples in the range 10(-19) ≤ pO2 ≤ 10(-8) atm at 900 °C indicates n-type transport under reducing conditions following the extrinsic model attributable to acceptor centres. The conductivity is essentially independent of pO2 at 600 °C under dry oxidising conditions, consistent with oxide-ion transport; a positive power-law dependence at higher temperature indicates extrinsic behaviour and a significant electron-hole contribution. The dielectric constant at RT of nominally stoichiometric Sr3NdNb3O12 is εr ∼ 37, with a moderately high quality factor of Q × f ∼ 16,400 GHz at fr ∼ 6.4 GHz. The temperature coefficient of resonant frequency of x = 0 is τf ∼ 12 ppm °C(-1), which lowers to -3 ppm °C(-1) for the Ti-doped phase x = 0.06.