TY - JOUR
T1 - Fe3-xInSnxO6(x = 0, 0.25, or 0.5)
T2 - A Family of Corundum Derivatives with Sn-Induced Polarization and Above Room Temperature Antiferromagnetic Ordering
AU - Frank, Corey E.
AU - McCabe, Emma E.
AU - Orlandi, Fabio
AU - Manuel, Pascal
AU - Tan, Xiaoyan
AU - Deng, Zheng
AU - Jin, Changqing
AU - Croft, Mark
AU - Emge, Thomas
AU - Yu, Shukai
AU - Wang, Huaiyu
AU - Gopalan, Venkatraman
AU - Lapidus, Saul
AU - Wu, Mei Xia
AU - Li, Man Rong
AU - Gross, Juliane
AU - Burger, Paul
AU - Mielewczyk-Gryń, Aleksandra
AU - Klimczuk, Tomasz
AU - Xie, Weiwei
AU - Walker, David
AU - Greenblatt, Martha
N1 - Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/6/14
Y1 - 2022/6/14
N2 - Three new double corundum derivative compounds, Fe3-xInSnxO6 (x = 0. 0.25, or 0.5), were synthesized at high pressure and temperature (6 GPa and 1400-1450 °C). All of the compounds order antiferromagnetically well above room temperature (TN = 608, 532, and 432 K for x = 0, 0.25, and 0.5, respectively). The x = 0 phase crystallizes as centrosymmetric R3¯ c, but the inclusion of closed-shell d10 Sn4+ induces x = 0.25 and 0.5 to crystallize as noncentrosymmetric R3c. Microprobe measurements indicate that for x = 0.25 and 0.5, the substitution of Sn4+ is not offset by vacancies, which implies the presence of Fe2+, as corroborated by X-ray absorption near-edge spectroscopy and single-crystal X-ray structure refinements. Neutron powder diffraction experiments on x = 0.5 indicate that these compounds are canted A-type antiferromagnets that, like Fe2O3 and InFeO3, consist of ferromagnetic layers that stack antiferromagnetically with a single magnetic transition. Weak ferromagnetic interactions persist to very high temperatures. Temperature-dependent second harmonic generation (SHG) measurements on x = 0.25 and 0.5 show a SHG response with ferroelectric-like hysteretic maxima that correspond with the respective magnetic transitions, which suggest coupling of the magnetic and polarization order. These new compounds provide more information about fine-tuning the electronic, magnetic, and structural properties of corundum-derived mutlferroics in the search for tunable high-temperature magnetoelectric materials.
AB - Three new double corundum derivative compounds, Fe3-xInSnxO6 (x = 0. 0.25, or 0.5), were synthesized at high pressure and temperature (6 GPa and 1400-1450 °C). All of the compounds order antiferromagnetically well above room temperature (TN = 608, 532, and 432 K for x = 0, 0.25, and 0.5, respectively). The x = 0 phase crystallizes as centrosymmetric R3¯ c, but the inclusion of closed-shell d10 Sn4+ induces x = 0.25 and 0.5 to crystallize as noncentrosymmetric R3c. Microprobe measurements indicate that for x = 0.25 and 0.5, the substitution of Sn4+ is not offset by vacancies, which implies the presence of Fe2+, as corroborated by X-ray absorption near-edge spectroscopy and single-crystal X-ray structure refinements. Neutron powder diffraction experiments on x = 0.5 indicate that these compounds are canted A-type antiferromagnets that, like Fe2O3 and InFeO3, consist of ferromagnetic layers that stack antiferromagnetically with a single magnetic transition. Weak ferromagnetic interactions persist to very high temperatures. Temperature-dependent second harmonic generation (SHG) measurements on x = 0.25 and 0.5 show a SHG response with ferroelectric-like hysteretic maxima that correspond with the respective magnetic transitions, which suggest coupling of the magnetic and polarization order. These new compounds provide more information about fine-tuning the electronic, magnetic, and structural properties of corundum-derived mutlferroics in the search for tunable high-temperature magnetoelectric materials.
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U2 - 10.1021/acs.chemmater.2c00312
DO - 10.1021/acs.chemmater.2c00312
M3 - Article
AN - SCOPUS:85131966735
SN - 0897-4756
VL - 34
SP - 5020
EP - 5029
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 11
ER -