Cleavable quaternary oxychlorides with high magnetic ordering temperatures

May, Andrew F.; Yumnam, George; Hermann, Raphael P.; Calder, Stuart; Lefler, Benjamin M.; May, Steven J.; Brubaker, Zachary E.; Brahlek, Matthew; Xu, Xiaodong; Ovchinnikov, Dmitry; McGuire, Michael A.

doi:10.1103/PhysRevMaterials.9.034002

Title: Cleavable quaternary oxychlorides with high magnetic ordering temperatures

Journal Article · Mon Mar 24 00:00:00 UTC 2025 · Physical Review Materials

DOI: https://doi.org/10.1103/PhysRevMaterials.9.034002 · OSTI ID:2573363

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^[1]; Xu, Xiaodong ^[3]; Ovchinnikov, Dmitry ^[4];

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Drexel Univ., Philadelphia, PA (United States)
Univ. of Washington, Seattle, WA (United States)
Univ. of Washington, Seattle, WA (United States); Univ. of Kansas, Lawrence, KS (United States)

Quaternary oxychlorides derived from Ruddlesden–Popper 3d transition metal oxides offer a route to cleavable crystals with bulk antiferromagnetic ordering temperatures reaching at least 550 K. Here, we study the magnetic, optical, and mechanical behavior of Sr₂FeO₃Cl, Ca₂FeO₃Cl, Ca₃Fe₂O₅Cl₂, and Sr₃Fe₂O₅Cl₂. Through optical absorption measurements, we show that these antiferromagnetic semiconductors have optical band gaps of ≈2.1(1) eV. The magnetic ordering symmetries and temperatures were probed by neutron powder diffraction and Mössbauer spectroscopy on polycrystalline samples, demonstrating Néel temperatures (T_N) near room temperature in the single layer Sr₂FeO₃Cl (T_N ≈ 311 K) and Ca₂FeO₃Cl (T_N ≈ 360 K), and the double-layer compound Sr₃Fe₂O₅Cl₂ has T_N ≈ 545 K. The high-spin moments of Fe³⁺ lie within the basal plane and the magnetic structures are compensated within each magnetic layer and characterized by magnetic propagation vectors k = ($$\frac{1}{2}$$ $$\frac{1}{2}$$ 0). Magnetization results demonstrate the quasi-2D nature of the magnetism, with a broad maximum in the susceptibility near 2T_N for Sr₂FeO₃Cl. Scotch tape tests and mechanical exfoliation onto SiO₂ confirm the micaceous nature of these crystals with cleavage down to a single unit cell (two magnetic layers) achieved for Sr₃Fe₂O₅Cl₂. In conclusion, this paper highlights strong antiferromagnetic interactions, semiconducting band gaps, and cleavability of quaternary Fe-based oxychlorides and motivates future work on crystals and exfoliated flakes of these and related oxyhalide systems.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725; SC0025319

OSTI ID:: 2573363

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 3 Vol. 9; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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