Single-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy

Huzan, Myron S.; Fix, Manuel; Aramini, Matteo; Bencok, Peter; Mosselmans, J. Frederick W.; Hayama, Shusaku; Breitner, Franziska A.; Gee, Leland B.; Titus, Charles J.; Arrio, Marie-Anne; Jesche, Anton; Baker, Michael L.

doi:10.1039/d0sc03787g

Title: Single-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy

Journal Article · Wed Oct 07 00:00:00 EDT 2020 · Chemical Science

DOI:https://doi.org/10.1039/d0sc03787g· OSTI ID:1768832

^[1]; Fix, Manuel ^[2]; Aramini, Matteo ^[3]; Bencok, Peter ^[3];

^[3]; Hayama, Shusaku ^[3]; Breitner, Franziska A. ^[2];

^[4];

^[4]; Arrio, Marie-Anne ^[5]; Jesche, Anton ^[2];

^[1]

Univ. of Manchester (United Kingdom)
Univ. of Augsburg (Germany)
Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
Stanford Univ., CA (United States)
Sorbonne Univ., Paris (France)

Large single-ion magnetic anisotropy is observed in lithium nitride doped with iron. The iron sites are two-coordinate, putting iron doped lithium nitride amongst a growing number of two coordinate transition metal single-ion magnets (SIMs). Uniquely, the relaxation times to magnetisation reversal are over two orders of magnitude longer in iron doped lithium nitride than other 3d-metal SIMs, and comparable with high-performance lanthanide-based SIMs. To understand the origin of these enhanced magnetic properties a detailed characterisation of electronic structure is presented. Access to dopant electronic structure calls for atomic specific techniques, hence a combination of detailed single-crystal X-ray absorption and emission spectroscopies are applied. Together K-edge, L_2,3-edge and Kβ X-ray spectroscopies probe local geometry and electronic structure, identifying iron doped lithium nitride to be a prototype, solid-state SIM, clean of stoichiometric vacancies where Fe lattice sites are geometrically equivalent. Extended X-ray absorption fine structure and angular dependent single-crystal X-ray absorption near edge spectroscopy measurements determine Fe^I dopant ions to be linearly coordinated, occupying a D_6h symmetry pocket. The dopant engages in strong 3dπ-bonding, resulting in an exceptionally short Fe–N bond length (1.873(7) Å) and rigorous linearity. It is proposed that this structure protects dopant sites from Renner–Teller vibronic coupling and pseudo Jahn–Teller distortions, enhancing magnetic properties with respect to molecular-based linear complexes. The Fe ligand field is quantified by L_2,3-edge XAS from which the energy reduction of 3d_z² due to strong 4s mixing is deduced. Quantification of magnetic anisotropy barriers in low concentration dopant sites is inhibited by many established methods, including far-infrared and neutron scattering. We deduce variable temperature L₃-edge XAS can be applied to quantify the J = 7/2 magnetic anisotropy barrier, 34.80 meV (~280 cm^–1), that corresponds with Orbach relaxation via the first excited, M_J = ±5/2 doublet. The results demonstrate that dopant sites within solid-state host lattices could offer a viable alternative to rare-earth bulk magnets and high-performance SIMs, where the host matrix can be tailored to impose high symmetry and control lattice induced relaxation effects.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Royal Society of Chemistry; German Research Foundation (DFG)

Grant/Contract Number:: AC02-76SF00515; RM1802-4019; JE748/1

OSTI ID:: 1768832

Journal Information:: Chemical Science, Vol. 11, Issue 43; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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