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Multiple magnetic interactions and large inverse magnetocaloric effect in TbSi and TbSi 0.6 Ge 0.4

We present a comprehensive investigation of the electronic structure, magnetization, specific heat, and crystallography of TbSi (FeB structure type) and TbSi 0.6 ⁢Ge 0.4 (CrB structure type) compounds. Both TbSi and TbSi 0.6 ⁢Ge 0.4 exhibit two antiferromagnetic (AFM) transitions at T N⁢1 ≈ 58 and 57 K, and T N⁢2 ≈ 36 and 44 K, respectively, along with an onset of weak metamagneticlike transition around 6 T between T N⁢1 and T N⁢2 . High-resolution specific heat (C P ) measurements show the second- and first-order nature of the magnetic transition at T N⁢1 and T N⁢2 , respectively, for both samples. However, in the case of TbSi, the low-temperature (LT) AFM to high-temperature (HT) AFM transition takes place via an additional AFM phase at the intermediate temperature (IT), where both LT to IT AFM and IT to HT AFM phase transitions exhibit a first-order nature. Both TbSi and TbSi 0.6 ⁢Ge 0.4 manifest significant magnetic entropy changes (Δ⁢S M ) of 9.6 and 11.6 J/kg-K, respectively, for Δ⁢μ 0 ⁢H=7 T, at T N⁢2 . The HT AFM phase of TbSi 0.6 ⁢Ge 0.4 is found to be more susceptible to the external magnetic field, causing a significant broadening in the peaks of Δ⁢S M curves at higher magnetic fields. Temperature- and field-dependent specific-heat data have been utilized to construct the complex HT phase diagram of these compounds. As a result, temperature-dependent x-ray diffraction measurements demonstrate substantial magnetostriction and anisotropic thermal expansion of the unit cell in both samples.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Materials Data on TbSi by Materials Project

TbSi crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Tb4+ is bonded in a 7-coordinate geometry to seven equivalent Si4- atoms. There are a spread of Tb–Si bond distances ranging from 2.96–3.17 Å. Si4- is bonded in a 9-coordinate geometry to seven equivalent Tb4+ and two equivalent Si4- atoms. Both Si–Si bond lengths are 2.50 Å.

36 MATERIALS SCIENCE↗

Materials Data on TbSI by Materials Project

TbSI crystallizes in the hexagonal P-6 space group. The structure is three-dimensional. there are two inequivalent Tb3+ sites. In the first Tb3+ site, Tb3+ is bonded in a distorted trigonal planar geometry to three S2- and six I1- atoms. All Tb–S bond lengths are 2.63 Å. There are a spread of Tb–I bond distances ranging from 3.64–3.68 Å. In the second Tb3+ site, Tb3+ is bonded in a trigonal planar geometry to three equivalent S2- and six equivalent I1- atoms. All Tb–S bond lengths are 2.63 Å. All Tb–I bond lengths are 3.69 Å. There are two inequivalent S2- sites. In the first S2- site, S2- is bonded in a trigonal planar geometry to three Tb3+ and six I1- atoms. There are four shorter (3.67 Å) and two longer (3.68 Å) S–I bond lengths. In the second S2- site, S2- is bonded in a trigonal planar geometry to three equivalent Tb3+ and six equivalent I1- atoms. All S–I bond lengths are 3.65 Å. There are two inequivalent I1- sites. In the first I1- site, I1- is bonded to six Tb3+ and six S2- atoms to form a mixture of distorted face and edge-sharing ITb6S6 cuboctahedra. In the second I1- site, I1- is bonded to six equivalent Tb3+ and six equivalent S2- atoms to form a mixture of distorted face and edge-sharing ITb6S6 cuboctahedra.

36 MATERIALS SCIENCE↗