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The Influence of La Doping and Heterogeneity on the Thermoelectric Properties of Sr3Ti2O7 Ceramics

Lu, Zhilun; Sinclair, Derek C.; Reaney, Ian M.


Zhilun Lu

Derek C. Sinclair

Ian M. Reaney


La-doping mechanisms and thermoelectric properties of Sr3Ti2O7 Ruddlesden–Popper (RP) ceramics sintered under air and flowing 5% H2 at 1773 K for 6 h have been investigated. Changes in lattice parameters and conductivity revealed a limited interstitial anion mechanism (~1 at.%) based on La3+ + ½O2−→Sr2+, which resulted in insulating samples when processed in air. In contrast, electronic donor-doping (La3+ + e− → Sr2+) and oxygen loss [O2− → ½ O2 (g) + 2 e−] are the dominant mechanism(s) in 5% H2-sintered ceramics with a solution limit of ~5 at.%. The increased solubility limit is attributed to the formation of Ti3+ during reduction, which compensates for the extra positive charge associated with La on the A-site and also to the occurrence of oxygen loss due to the reducing conditions. For 5% H2-sintered samples, an insulating surface layer was formed associated with SrO volatilization and oxygen uptake (during cooling) from the sintering. Unless removed, the insulating layer masked the conductive nature of the ceramics. In the bulk, significantly higher power factors were obtained for ceramics that were phase mixtures containing highly conductive perovskite-based (Sr,La)TiO3−δ (ST). This highlights the superior power factor properties of reduced perovskite-type ST phases compared to reduced RP-type Sr3Ti2O7 and serves as a precaution for the need to identify low levels of highly conducting perovskite phases when exploring rare-earth doping mechanisms in RP-type phases.

Journal Article Type Article
Acceptance Date Sep 25, 2015
Online Publication Date Oct 24, 2015
Publication Date 2016-02
Deposit Date Oct 23, 2021
Journal Journal of the American Ceramic Society
Print ISSN 0002-7820
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 99
Issue 2
Pages 515-522
Public URL