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Abstract Iron nitrides are possible constituents of the cores of Earth and other terrestrial planets. Pressure‐induced magnetic changes in iron nitrides and effects on compressibility remain poorly understood. Here we report synchrotron X‐ray emission spectroscopy (XES) and X‐ray diffraction (XRD) results for ε‐Fe7N3and γ′‐Fe4N up to 60 GPa at 300 K. The XES spectra reveal completion of high‐ to low‐spin transition in ε‐Fe7N3and γ′‐Fe4N at 43 and 34 GPa, respectively. The completion of the spin transition induces stiffening in bulk modulus of ε‐Fe7N3by 22% at ~40 GPa, but has no resolvable effect on the compression behavior of γ′‐Fe4N. Fitting pressure‐volume data to the Birch‐Murnaghan equation of state yieldsV0 = 83.29 ± 0.03 (Å3),K0 = 232 ± 9 GPa,K0′ = 4.1 ± 0.5 for nonmagnetic ε‐Fe7N3above the spin transition completion pressure, andV0 = 54.82 ± 0.02 (Å3),K0 = 152 ± 2 GPa,K0′ = 4.0 ± 0.1 for γ′‐Fe4N over the studied pressure range. By reexamining evidence for spin transition and effects on compressibility of other candidate components of terrestrial planet cores, Fe3S, Fe3P, Fe7C3, and Fe3C based on previous XES and XRD measurements, we located the completion of high‐ to low‐spin transition at ~67, 38, 50, and 30 GPa at 300 K, respectively. The completion of spin transitions of Fe3S, Fe3P, and Fe3C induces elastic stiffening, whereas that of Fe7C3induces elastic softening. Changes in compressibility at completion of spin transitions in iron‐light element alloys may influence the properties of Earth's and planetary cores.
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High‐Resolution In‐Situ Synchrotron X‐Ray Studies of Inorganic Perovskite CsPbBr 3 : New Symmetry Assignments and Structural Phase Transitions
Abstract Perovskite photovoltaic ABX3systems are being studied due to their high energy‐conversion efficiencies with current emphasis placed on pure inorganic systems. In this work, synchrotron single‐crystal diffraction measurements combined with second harmonic generation measurements reveal the absence of inversion symmetry below room temperature in CsPbBr3. Local structural analysis by pair distribution function and X‐ray absorption fine structure methods are performed to ascertain the local ordering, atomic pair correlations, and phase evolution in a broad range of temperatures. The currently accepted space group assignments for CsPbBr3are found to be incorrect in a manner that profoundly impacts physical properties. New assignments are obtained for the bulk structure: (above ≈410 K),P21/m(between ≈300 K and ≈410 K), and the polar groupPm(below ≈300 K), respectively. The newly observed structural distortions exist in the bulk structure consistent with the expectation of previous photoluminescence and Raman measurements. High‐pressure measurements reveal multiple low‐pressure phases, one of which exists as a metastable phase at ambient pressure. This work should help guide research in the perovskite photovoltaic community to better control the structure under operational conditions and further improve transport and optical properties.
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- PAR ID:
- 10366783
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Science
- Volume:
- 8
- Issue:
- 18
- ISSN:
- 2198-3844
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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