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The ternary phase, Yb14CdSb11, has been synthesized by flux and polycrystalline methods. The crystal structure is determined via single-crystal X-ray diffraction, revealing that it crystallizes in the Ca14AlSb11 structure type (I41/acd space group with unit cell parameters of a = 16.5962(2) & Aring; and c = 22.1346(5) & Aring;, 90 K, Z = 8, R1 = 2.65%, and wR2 = 4.58%). The polycrystalline form of the compound is synthesized from a stoichiometric reaction of Yb4Sb3, CdSb, Yb, and Sb. The elemental composition is confirmed using scanning electron microscopy and energy-dispersive spectroscopy, and phase purity is verified by powder X-ray diffraction. Thermoelectric measurements, including resistivity, Seebeck coefficient, thermal conductivity, Hall carrier concentration, and Hall mobility, are conducted from 300 to 1273 K. Yb14CdSb11 exhibits a peak zT = 0.90 at 1200 K. Carrier concentration and Hall mobility range from 6.99 x 1020-1.01 x 1021 cm-3 and 4.45-9.35 x 10-1 cm2 V-1 s-1, respectively. This carrier concentration is lower than that reported for the Zn or Mn analogs leading to a lower thermoelectric figure of merit at high temperatures. However, with appropriate doping, this phase should also be a promising p-type candidate for high-temperature energy conversion applications.
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The High-Temperature Polymorph of LiBF 4
The single-crystal-to-single-crystal phase transition is determined using X-ray crystallography on LiBF4, resolving a longstanding ambiguity in the existence of a high-temperature polymorph of LiBF4. LiBF4 possesses an endothermic phase change at 28.2 °C with ΔH = 1180 J mol-1 and ΔS = 3.92 J mol-1K-1 based on DSC. Single-crystal X-ray diffraction shows that the low temperature phase collected at 200K is a twinned trigonal P system with a twin law indicating reflection through the 110 plane. The same crystal collected above the phase transition temperature at 313 K is a C-centered orthorhombic system describable as the superposition of the two low-temperature twin geometries undergoing interconversion. The geome-tries of the high- and low-temperature phases are consistent with the calorimetry experiments, and with previous NMR find-ings indicating BF4 geometric reorientations above 300 K.
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- Award ID(s):
- 2138432
- PAR ID:
- 10488774
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry Letters
- Volume:
- 15
- Issue:
- 3
- ISSN:
- 1948-7185
- Page Range / eLocation ID:
- 782 to 784
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.jpclett.3c02961
