Colossal negative thermal expansion in BiNiO3 induced by intermetallic charge transfer

Masaki Azuma, Wei-tin Chen, Hayato Seki, Michal Czapski, Smirnova Olga, Kengo Oka, Masaichiro Mizumaki, Tetsu Watanuki, Naoki Ishimatsu, Naomi Kawamura, Shintaro Ishiwata, Matthew G. Tucker, Yuichi Shimakawa, J. Paul Attfield

Research output: Contribution to journalArticlepeer-review


The unusual property of negative thermal expansion is of fundamental interest and may be used to fabricate composites with zero or other controlled thermal expansion values. Here we report that colossal negative thermal expansion (defined as linear expansion < -10(-4) K-1 over a temperature range similar to 100 K) is accessible in perovskite oxides showing charge-transfer transitions. BiNiO3 shows a 2.6% volume reduction under pressure due to a Bi/Ni charge transfer that is shifted to ambient pressure through lanthanum substitution for Bi. Changing proportions of coexisting low-and high-temperature phases leads to smooth volume shrinkage on heating. The crystallographic linear expansion coefficient for Bi0.95La0.05NiO3 is -137x10(-6) K-1 and a value of -82x10(-6) K-1 is observed between 320 and 380 K from a dilatometric measurement on a ceramic pellet. Colossal negative thermal expansion materials operating at ambient conditions may also be accessible through metal-insulator transitions driven by other phenomena such as ferroelectric orders.

Original languageEnglish
Article number347
Pages (from-to)-
Number of pages5
JournalNature Communications
Publication statusPublished - Jun 2011




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