TY - JOUR
T1 - Polar-Nonpolar Transition-Type Negative Thermal Expansion with 11.1% Volume Shrinkage by Design
AU - Nishikubo, Takumi
AU - Imai, Takashi
AU - Sakai, Yuki
AU - Mizumaki, Masaichiro
AU - Kawaguchi, Shogo
AU - Oshime, Norihiro
AU - Shimada, Ayumu
AU - Sugawara, Kento
AU - Ohwada, Kenji
AU - Machida, Akihiko
AU - Watanuki, Tetsu
AU - Kurushima, Kosuke
AU - Mori, Shigeo
AU - Mizokawa, Takashi
AU - Azuma, Masaki
N1 - Funding Information:
This work was partially supported by JSPS KAKENHI Grant Numbers JP18H05208, JP18H05518, JP19H02618, JP19H05625, JP19H05819, and JP22H01976, by JST-CREST (JPMJCR22O1), by QST President's Strategic Grant (QST Advanced Study Laboratory), and by Kanagawa Institute of Industrial Science and Technology. The synchrotron radiation experiments were conducted at SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (Proposal Numbers 2018A1636, 2018A1667, 2018B1860, 2019A1045, 2019A1251, 2019A1688, 2019A1805, 2020A1773, 2020A1646, 2020A3761, 2020A3762, 2022A1250, and 2022A1567).
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/2/14
Y1 - 2023/2/14
N2 - Chemical substitution for the tuning of the working temperature of phase-transition-type negative thermal expansion (NTE) materials generally reduces the volume shrinkage during the transition. We have investigated the effects of electron doping and reduction of 6s2 lone-pair activity in PbVO3 with a large polar distortion (c/a = 1.23) and found that the combination of Bi and Sr substitutions for Pb enables a temperature-induced polar to non-polar transition with 11% volume shrinkage, even larger than the pressure-induced volume collapse of PbVO3 (∼10.6%), and is the largest value among the NTE materials reported so far. The domain structure of the coexisting cubic and tetragonal phases with such a huge volume difference was successfully observed by high-angle annular dark-field scanning transmission electron microscopy and the spatial distribution of domains by Bragg coherent X-ray diffraction imaging. The temperature hysteresis is reduced by repeated heating/cooling cycles, suggesting that the changes in the domain structure dominate the NTE properties.
AB - Chemical substitution for the tuning of the working temperature of phase-transition-type negative thermal expansion (NTE) materials generally reduces the volume shrinkage during the transition. We have investigated the effects of electron doping and reduction of 6s2 lone-pair activity in PbVO3 with a large polar distortion (c/a = 1.23) and found that the combination of Bi and Sr substitutions for Pb enables a temperature-induced polar to non-polar transition with 11% volume shrinkage, even larger than the pressure-induced volume collapse of PbVO3 (∼10.6%), and is the largest value among the NTE materials reported so far. The domain structure of the coexisting cubic and tetragonal phases with such a huge volume difference was successfully observed by high-angle annular dark-field scanning transmission electron microscopy and the spatial distribution of domains by Bragg coherent X-ray diffraction imaging. The temperature hysteresis is reduced by repeated heating/cooling cycles, suggesting that the changes in the domain structure dominate the NTE properties.
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U2 - 10.1021/acs.chemmater.2c02304
DO - 10.1021/acs.chemmater.2c02304
M3 - Article
AN - SCOPUS:85146566545
SN - 0897-4756
VL - 35
SP - 870
EP - 878
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 3
ER -