TY - JOUR
T1 - Colossal Volume Contraction in Strong Polar Perovskites of Pb(Ti,V)O3
AU - Pan, Zhao
AU - Chen, Jun
AU - Jiang, Xingxing
AU - Hu, Lei
AU - Yu, Runze
AU - Yamamoto, Hajime
AU - Ogata, Takahiro
AU - Hattori, Yuichiro
AU - Guo, Fangmin
AU - Fan, Xi'An
AU - Li, Yawei
AU - Li, Guangqiang
AU - Gu, Huazhi
AU - Ren, Yang
AU - Lin, Zheshuai
AU - Azuma, Masaki
AU - Xing, Xianran
N1 - Funding Information:
This work was supported by the National Natural Science Foundation of China (Grant Nos. 91422301, 21231001, and 21590793), National Program for Support of Top-notch Young Professionals, the Program for Chang Jiang Young Scholars, and the Fundamental Research Funds for the Central Universities, China. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The high-temperature synchrotron radiation experiments were performed at the BL44B2 and BL19B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2015B1127, 2016A1060, and 2016B1850). We acknowledge the help from Kanagawa Institute of Industrial Science and Technology.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/10/25
Y1 - 2017/10/25
N2 - The unique physical property of negative thermal expansion (NTE) is not only interesting for scientific research but also important for practical applications. Chemical modification generally tends to weaken NTE. It remains a challenge to obtain enhanced NTE from currently available materials. Herein, we successfully achieve enhanced NTE in Pb(Ti1-xVx)O3 by improving its ferroelectricity. With the chemical substitution of vanadium, lattice tetragonality (c/a) is highly promoted, which is attributed to strong spontaneous polarization, evidenced by the enhanced covalent interaction in the V/Ti-O and Pb-O2 bonds from first-principles calculations. As a consequence, Pb(Ti0.9V0.1)O3 exhibits a nonlinear and much stronger NTE over a wide temperature range with a volumetric coefficient of thermal expansion αV = -3.76 × 10-5/°C (25-550 °C). Interestingly, an intrinsic giant volume contraction (∼3.7%) was obtained at the composition of Pb(Ti0.7V0.3)O3 during the ferroelectric-to-paraelectric phase transition, which represents the highest value ever reported. Such volume contraction is well correlated to the effect of spontaneous volume ferroelectrostriction. The present study extends the scope of the NTE family and provides an effective approach to explore new materials with large NTE, such as through adjusting the NTE-related ferroelectric property in the family of ferroelectrics.
AB - The unique physical property of negative thermal expansion (NTE) is not only interesting for scientific research but also important for practical applications. Chemical modification generally tends to weaken NTE. It remains a challenge to obtain enhanced NTE from currently available materials. Herein, we successfully achieve enhanced NTE in Pb(Ti1-xVx)O3 by improving its ferroelectricity. With the chemical substitution of vanadium, lattice tetragonality (c/a) is highly promoted, which is attributed to strong spontaneous polarization, evidenced by the enhanced covalent interaction in the V/Ti-O and Pb-O2 bonds from first-principles calculations. As a consequence, Pb(Ti0.9V0.1)O3 exhibits a nonlinear and much stronger NTE over a wide temperature range with a volumetric coefficient of thermal expansion αV = -3.76 × 10-5/°C (25-550 °C). Interestingly, an intrinsic giant volume contraction (∼3.7%) was obtained at the composition of Pb(Ti0.7V0.3)O3 during the ferroelectric-to-paraelectric phase transition, which represents the highest value ever reported. Such volume contraction is well correlated to the effect of spontaneous volume ferroelectrostriction. The present study extends the scope of the NTE family and provides an effective approach to explore new materials with large NTE, such as through adjusting the NTE-related ferroelectric property in the family of ferroelectrics.
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U2 - 10.1021/jacs.7b08625
DO - 10.1021/jacs.7b08625
M3 - Article
C2 - 28994586
AN - SCOPUS:85032261542
SN - 0002-7863
VL - 139
SP - 14865
EP - 14868
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 42
ER -