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Compositional diversity and intriguing structural features have made Zintl phases excellent candidates as thermoelectric materials. Zintl phase with 21-4-18 composition has shown high thermoelectric performance in the mid- to high-temperature ranges. The complex crystal structure and favorable transport properties of these compounds indicate the potential for high thermoelectric efficiency. Arsenic-based Eu21Zn4As18, belonging to the Ca21Mn4Sb18 structure type, exhibits a semiconductor-like p-type transport behavior and has a calculated band gap of 0.49 eV. The compound is paramagnetic at high temperatures, with an antiferromagnetic transition occurring at T-N = similar to 10 K. The moment obtained from the Curie-Weiss data fit aligns with Eu2+ ions. At the same time, the field-dependent measurement at 2 K indicates complex magnetic ordering with a saturation moment consistent with Eu2+ ions. Pristine Eu21Zn4As18 exhibits an ultralow lattice thermal conductivity of 0.40 W m(-1) K-1 at 873 K. Electronic transport properties measurement shows evidence of bipolar conduction across much of the measured temperature range (450-780 K). However, the Seebeck coefficient remains extremely high (>440 mu V K-1) across this range, indicating the potential for high zT if an appropriate dopant is found. This work represents the first report on the temperature-dependent thermal conductivity, Seebeck coefficient, and thermoelectric efficiency of the arsenic-containing Zintl phase with 21-4-18 composition, showcasing its promise for further optimization of the thermoelectric performance.
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This content will become publicly available on February 12, 2027
Synthesis, Structure, and Properties of the Complex Zintl Phase Eu9Zn4.5As9: A Candidate Topological Insulator and Thermoelectric Material
Reported are the synthesis and detailed analysis of the crystal and electronic structure of the novel Zintl phase Eu9Zn4.5As9. This material was identified in the densely populated Eu–Zn–As compositional space. For structure determination and for property measurements, suitable single crystals of this compound were grown from either Sn- or Pb-flux. Single-crystal X-ray diffraction methods indicate that Eu9Zn4.5As9 crystallizes in the orthorhombic crystal system with the space group Pnma (a = 12.1953(7) Å, b = 4.3730(2) Å, c = 42.674(2) Å) and is formally isostructural to Ca9Mn4+xSb9, the less common “9–4–9” type. The structure is heavily disordered, with multiple partially occupied sites, yet, according to the Zintl-Klemm formalism, a charge-balanced composition (Eu2+)9(Zn2+)4.5(As3−)9 is attained. Electronic structure calculations for a model, disorder-free structure indicate no energy gap between the valence and the conduction bands and suggest (semi)metallic behavior. Preliminary susceptibility measurements confirm the expected divalent nature of Eu2+ ([Xe] 4f7 ground state).
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- Award ID(s):
- 2440354
- PAR ID:
- 10671628
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Crystals
- Volume:
- 16
- Issue:
- 2
- ISSN:
- 2073-4352
- Page Range / eLocation ID:
- 137
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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