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Title: Colossal Volume Contraction in Strong Polar Perovskites of Pb(Ti,V)O3

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b08625· OSTI ID:1461291
 [1]; ORCiD logo [2];  [3];  [2];  [4];  [4];  [4];  [4];  [5];  [6];  [6];  [6];  [6];  [5]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]
  1. Univ. of Science and Technology Beijing (China). Dept. of Physical Chemistry; Wuhan Univ. of Science and Technology, Wuhan (China). State Key Lab. of Refractories and Metallurgy; Tokyo Inst. of Technology (Japan). Materials and Structures Lab.
  2. Univ. of Science and Technology Beijing (China). Dept. of Physical Chemistry
  3. Chinese Academy of Sciences (CAS), Beijing (China). Technical Inst. of Physics and Chemistry, Center for Crystal R&D and Key Lab. of Functional Crystals and Laser Technology
  4. Tokyo Inst. of Technology (Japan). Materials and Structures Lab.
  5. Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Division
  6. Wuhan Univ. of Science and Technology, Wuhan (China). State Key Lab. of Refractories and Metallurgy
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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 X 10-5/ºC (25-550 ºC). 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. This 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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Natural Science Foundation of China (NSFC); Thousand Talents Plan (China); Ministry of Education (MOE) (China); Japan Synchrotron Radiation Research Inst. (JASRI), Hyogo (Japan); Kanagawa Inst. of Industrial Science and Technology (KISTEC), Kanagawa (Japan)
Grant/Contract Number:
AC02-06CH11357; 91422301; 21231001; 21590793; 2015B1127; 2016A1060; 2016B1850
OSTI ID:
1461291
Journal Information:
Journal of the American Chemical Society, Vol. 139, Issue 42; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 47 works
Citation information provided by
Web of Science

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Cited By (11)

Negative thermal expansion and the role of hybridization in perovskite-type PbTiO 3 -Bi(Cu 0.5 Ti 0.5 )O 3 journal January 2020
Large spontaneous polarization in polar perovskites of PbTiO 3 –Bi(Zn 1/2 Ti 1/2 )O 3 journal January 2018
Temperature controlled formation of polar copper phosphonates showing large dielectric anisotropy and a dehydration-induced switch from ferromagnetic to antiferromagnetic interactions journal January 2018
Colossal Negative Thermal Expansion in Electron‐Doped PbVO 3 Perovskites journal July 2018
Polar layered coordination polymers incorporating triazacyclononane-triphosphonate metalloligands journal January 2020
A case of multifunctional intermetallic compounds: negative thermal expansion coupling with magnetocaloric effect in (Gd,Ho)(Co,Fe) 2 journal January 2019
Huge impact of compressive strain on phase transition temperatures in epitaxial ferroelectric K x Na 1−x NbO 3 thin films journal June 2019
Colossal Negative Thermal Expansion in Electron-Doped PbVO 3 Perovskites journal June 2018
Giant isotropic negative thermal expansion in Y-doped samarium monosulfides by intra-atomic charge transfer journal January 2019
Enhanced tetragonality and large negative thermal expansion in a new Pb/Bi-based perovskite ferroelectric of (1 − x )PbTiO 3 – x Bi(Zn 1/2 V 1/2 )O 3 journal January 2019
Progress of Research in Negative Thermal Expansion Materials: Paradigm Shift in the Control of Thermal Expansion journal July 2018

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