Simon Cassidy

Abstract:

Sr2CrO2Cr2As2 and Ba2CrO2Cr2As2 with Cr2+ ions in CrO2 sheets and in CrAs layers crystallize with the Sr2Mn3Sb2O2 structure (space group I4/mmm, Z = 2) and lattice parameters a = 4.00800(2) Å, c = 18.8214(1) Å (Sr2CrO2Cr2As2) and a = 4.05506(2) Å, c = 20.5637(1) Å (Ba2CrO2Cr2As2) at room temperature. Powder neutron diffraction reveals checkerboard-type antiferromagnetic ordering of the Cr2+ ions in the arsenide layers below TN1_Sr, of 600(10) K (Sr2CrO2Cr2As2) and TN1_Ba 465(5) K (Ba2CrO2Cr2As2) with the moments initially directed perpendicular to the layers in both compounds. Checkerboard-type antiferromagnetic ordering of the Cr2+ ions in the oxide layer below 230(5) K for Ba2CrO2Cr2As2 occurs with these moments also perpendicular to the layers, consistent with the orientation preferences of d4 moments in the two layers. In contrast, below 330(5) K in Sr2CrO2Cr2As2, the oxide layer Cr2+ moments are initially oriented in the CrO2 plane; but on further cooling, these moments rotate to become perpendicular to the CrO2 planes, while the moments in the arsenide layers rotate by 90° with the moments on the two sublattices remaining orthogonal throughout [behavior recently reported independently by Liu et al. [Liu et al. Phys. Rev. B 2018, 98, 134416]]. In Sr2CrO2Cr2As2, electron diffraction and high resolution powder X-ray diffraction data show no evidence for a structural distortion that would allow the two Cr2+ sublattices to couple, but high resolution neutron powder diffraction data suggest a small incommensurability between the magnetic structure and the crystal structure, which may account for the coupling of the two sublattices and the observed spin reorientation. The saturation values of the Cr2+ moments in the CrO2 layers (3.34(1) μB (for Sr2CrO2Cr2As2) and 3.30(1) μB (for Ba2CrO2Cr2As2)) are larger than those in the CrAs layers (2.68(1) μB for Sr2CrO2Cr2As2 and 2.298(8) μB for Ba2CrO2Cr2As2) reflecting greater covalency in the arsenide layers.

Abstract:

Solid solutions between the known compounds Ca2FeO3CuCh and Sr2FeO3CuCh (Ch = S, Se) in which there are two fairly similar sites (8 and 9 coordinate) for the alkaline earth cations are not attainable under standard high temperature solid state syntheses under thermodynamic control. Instead compounds with greater condensation of FeO5 square pyramids form as these afford one 8-coordinate site and one 12-coordinate site for the alkaline earths which is better suited to the sizemismatched cations in the compounds Sr3-xCaxFe2O5Cu2Ch2 (Ch = S, Se; x = 1, 2). Sr2CaFe2O5Cu2S2, SrCa2Fe2O5Cu2S2, Sr2CaFe2O5Cu2Se2 and SrCa2Fe2O5Cu2Se2 all crystallise in the tetragonal space group I4/mmm with two formula units in the unit cell with the crystal structure first described for Sr3Fe2O5Cu2S2. Oxide slabs composed of vertex-sharing FeO5 square pyramids are separated by Cu2Ch2 anti-fluorite-type layers. The larger Sr2+ ions have a strong preference for the 12-coordinate site in the oxide slabs, while Ca2+ cations dominate the 8-coordinate sites separating the oxide and chalcogenide slabs. Powder neutron diffraction reveals that all the compounds display antiferromagnetic long range ordering of the Fe3+ moments with ordering temperatures well above room temperature and exceeding 526 K in the case of Ca2SrFe2O5Cu2Se2.

Abstract:

Polycrystalline samples of the monoclinic perovskites CaLa2Ni2-xCuxWO9 (x ​= ​0.25 and 0.5) have been prepared and characterised by neutron diffraction and magnetometry. The Ni2+, Cu2+ and W6+ cations are partially ordered over two crystallographically-distinct six-coordinate sites such that one is ~63% occupied by W6+ and both are occupied by Ni2+ and Cu2+ in a ratio of (2-x):x. The composition x ​= ​0.25 behaves as a spin glass below 35 ​K whereas x ​= ​0.5 is ferrimagnetic below 120 ​K with an ordered moment of 0.774(5) μB per magnetic cation. The atomic moments order in a G-type pattern and the imbalance in the number of magnetic cations on the two sites results in a net magnetisation.

Abstract:

Polycrystalline samples of the monoclinic perovskites CaLa2Ni2-xCuxWO9 (x = 0.25 and 0.5) have been prepared and characterised by neutron diffraction and magnetometry. The Ni2+, Cu2+ and W6+ cations are partially ordered over two crystallographically-distinct six-coordinate sites such that one is ∼63% occupied by W6+ and both are occupied by Ni2+ and Cu2+ in a ratio of (2-x):x. The composition x = 0.25 behaves as a spin glass below 35 K whereas x = 0.5 is ferrimagnetic below 120 K with an ordered moment of 0.774(5) μB per magnetic cation. The atomic moments order in a G-type pattern and the imbalance in the number of magnetic cations on the two sites results in a net magnetisation.

Abstract:

CaKFe4As4 (1144) is a unique stoichiometric iron-based superconductor which harbours high upper critical fields and large critical current densities. In this work, we describe a study to optimize the synthesis conditions of stoichiometric polycrystalline samples of CaKFe4As4 and asses their structural, magnetic and transport properties. The samples were prepared over a wide temperature range (900-1100°C) and the pure phase formation is centered around 955°C. Outside this temperature region, impurity phases of KFe2As2 and CaFe2As2 can also form. Magnetic susceptibility and resistivity measurements establish that the critical temperature reaches ~34 K for the optimum synthesis conditions and the critical current reaches 2 × 104 A-cm−2. The post-annealing process demonstrates the stability of the 1144 phase up to 500°C, however, under higher temperature annealing, phase degradation occurs. Our study indicates that the formation of phase-pure 1144 occurs over a much narrower window and its highly prone to multi-phase formation as compared with the 122 family. As a result, the superconducting properties are enhanced for the pure 1144 phase but they are likely to be affected by the inter and intra-granular behaviour originating from the microstructural nature of polycrystalline CaKFe4As4, similar to other iron-based superconductors. Based on our study, we construct the phase diagram for polycrystalline 1144 and compared it with that reported for 1144 single crystal.