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Title: Localized Symmetry Breaking for Tuning Thermal Expansion in ScF3 Nanoscale Frameworks

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b00885· OSTI ID:1435043
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [2];  [2];  [5];  [2];  [6];  [7];  [6];  [6];  [2];  [8]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [2]
  1. Univ. of Science and Technology, Beijing (China). Dept. of Physical Chemistry; Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  2. Univ. of Science and Technology, Beijing (China). Dept. of Physical Chemistry
  3. Univ. of Padova, Padova (Italy). Dept. of Phyics and Astronomy
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  5. Zhengzhou Univ., Zhengzhou (China). International Lab. for Quantum Functional Materials of Henan, School of Physics and Engineering
  6. Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Division
  7. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering; Koc University, Sariyer, Istanbul (Turkey). Dept. of Chemistry
  8. Elettra Sincrotrone Trieste, Basovizza, Trieste (Italy)
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The local symmetry, beyond the averaged crystallographic structure, tends to bring unu-sual performances. Negative thermal expansion is a peculiar physical property of solids. Here in this paper, we report the delicate design of the localized symmetry breaking to achieve the controllable thermal expansion in ScF3 nano-scale 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 675K. This mechanism is investigated by the joint analysis of atomic pair dis-tribution 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 nano-scale 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 the rhombohedral ScF3. The present work opens an untraditional chemical modification to achieve controllable thermal expansion by breaking local symmetries of materials.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NSFC); USDOE Office of Science - Office of Basic Energy Sciences - Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1435043
Journal Information:
Journal of the American Chemical Society, Vol. 140, Issue 13; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science

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Cited By (5)

Cone-spiral magnetic ordering dominated lattice distortion and giant negative thermal expansion in Fe-doped MnNiGe compounds journal January 2020
Perovskite-related ReO3-type structures journal January 2020
On the switching between negative and positive thermal expansion in framework materials journal May 2019
On the switching between negative and positive thermal expansion in framework materials text January 2019
On the switching between negative and positive thermal expansion in framework materials text January 2019

Figures / Tables (4)

Figure 1(p. 2)figure Figure 1
Figure 2(p. 3)figure Figure 2
Figure 3(p. 4)figure Figure 3
Figure 4(p. 4)figure Figure 4

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72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS