TY - JOUR
T1 - Localized Symmetry Breaking for Tuning Thermal Expansion in ScF3 Nanoscale Frameworks
AU - Hu, Lei
AU - Qin, Feiyu
AU - Sanson, Andrea
AU - Huang, Liang Feng
AU - Pan, Zhao
AU - Li, Qiang
AU - Sun, Qiang
AU - Wang, Lu
AU - Guo, Fangmin
AU - Aydemir, Umut
AU - Ren, Yang
AU - Sun, Chengjun
AU - Deng, Jinxia
AU - Aquilanti, Giuliana
AU - Rondinelli, James M.
AU - Chen, Jun
AU - Xing, Xianran
N1 - Funding Information:
This work was supported by the National Natural Science Foundation of China (grant nos. 91422301, 21231001, and 21590793), the Changjiang Young Scholars Award, the National Program for Support of Top-notch Young Professionals, the Fundamental Research Funds for the Central Universities, China, and the Special Foundation of the Director of Technical Institute of Physics and Chemistry. L.F.H. and J.M.R. were supported by the Office of Naval Research under Grant No. N00014-16-1-2280 and the National Science Foundation under Grant No. DMR-1454688. The use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-AC02-06CH11357).
PY - 2018/4/4
Y1 - 2018/4/4
N2 - The local symmetry, beyond the averaged crystallographic structure, tends to bring unusual performances. Negative thermal expansion is a peculiar physical property of solids. Here, we report the delicate design of the localized symmetry breaking to achieve controllable thermal expansion in ScF3 nanoscale frameworks. Intriguingly, an isotropic zero thermal expansion is concurrently engineered by localized symmetry breaking, with a remarkably low coefficient of thermal expansion of about +4.0 × 10-8/K up to 675 K. This mechanism is investigated by the joint analysis of atomic pair distribution function of synchrotron X-ray total scattering and extended X-ray absorption fine structure spectra. A localized rhombohedral distortion presumably plays a critical role in stiffening ScF3 nanoscale frameworks and concomitantly suppressing transverse thermal vibrations of fluorine atoms. This physical scenario is also theoretically corroborated by the extinction of phonon modes with negative Grüneisen parameters in rhombohedral ScF3. The present work opens an untraditional chemical modification route to achieve controllable thermal expansion by breaking local symmetries in materials.
AB - The local symmetry, beyond the averaged crystallographic structure, tends to bring unusual performances. Negative thermal expansion is a peculiar physical property of solids. Here, we report the delicate design of the localized symmetry breaking to achieve controllable thermal expansion in ScF3 nanoscale frameworks. Intriguingly, an isotropic zero thermal expansion is concurrently engineered by localized symmetry breaking, with a remarkably low coefficient of thermal expansion of about +4.0 × 10-8/K up to 675 K. This mechanism is investigated by the joint analysis of atomic pair distribution function of synchrotron X-ray total scattering and extended X-ray absorption fine structure spectra. A localized rhombohedral distortion presumably plays a critical role in stiffening ScF3 nanoscale frameworks and concomitantly suppressing transverse thermal vibrations of fluorine atoms. This physical scenario is also theoretically corroborated by the extinction of phonon modes with negative Grüneisen parameters in rhombohedral ScF3. The present work opens an untraditional chemical modification route to achieve controllable thermal expansion by breaking local symmetries in materials.
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U2 - 10.1021/jacs.8b00885
DO - 10.1021/jacs.8b00885
M3 - Article
C2 - 29558621
AN - SCOPUS:85044944526
VL - 140
SP - 4477
EP - 4480
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 13
ER -