Structure, properties and chemistry of layered oxypnictides

Description

This thesis reports the synthesis and characterisation of the layered oxypnictides Sr₂MO₃FeAs (M = Sc, V and Cr) and CeOMnAs. In these materials the choice of transition metal cation at the tetrahedral site in the arsenide layer chiefly dictates the physical properties that are observed. The bulk of this work has focussed on the development of a new family of iron arsenide superconductor with the general formula Sr₂MO₃FeAs (M = Sc, V, Cr). This structure is comprised of anti-PbO-type [FeAs]^- layers which alternate with insulating [Sr₂MO₃]⁺ oxide fragments that resemble a portion of the K₂NiF₄ structure. In contrast to other FeAs parent materials, no member of the Sr₂MO₃FeAs family exhibits any strong evidence for long range Fe order or a tetragonal to orthorhombic distortion upon cooling. Attempts to electron and hole dope Sr₂ScO₃FeAs into the superconducting regime have as yet been unsuccessful. Although Sr₂ScO₃FeAs shows no evidence for Fe ordering, a checkerboard arrangement of Cr³⁺ spins in the ab-plane is observed below 40 K (k = (½, ½, 0)) analogous to that seen in Pr₂CuO₄. The partial substitution of Fe²⁺ (d⁶) by Co²⁺ (d⁷) in Sr₂CrO₃Fe_1-xCo_xAs has been shown to be a fruitful strategy for electron-doping this material into the superconducting regime with T_c maximised at 18 K in Sr₂CrO₃Fe_0.92Co_0.08As. It is also established that this substitution influences the ordering on the Cr sub-lattice with a doubling in the size of the magnetic cell along the c axis (k = (½, ½, ½)). Sr₂VO₃FeAs, a rare example of an “undoped” superconductor (T_c = 25 K), is shown to be electron-doped by mixed valence vanadium +3.13(5). Magnetometry measurements also reveal a series of magnetic transitions in Sr₂VO₃FeAs, however μSR and powder neutron diffraction studies suggest that this system is some way from commensurate long range order. In contrast to Sr₂CrO₃FeAs, electron-doping strategies in Sr₂VO₃FeAs have the effect of decreasing T_c and ultimately suppressing superconductivity entirely as Sr₂V_1-xTi_xO₃FeAs and Sr₂VO₃Fe_1-xCo_xAs materials are over electron-doped. Sr₂V_1-xMg_xO₃FeAs samples were also prepared, but rather than this strategy hole-doping the FeAs layer it preferentially oxidises vanadium towards V⁴⁺. This substitution also has a considerable effect on the superconducting critical temperature (T_c) which is raised as high as 31 K in Sr₂V_0.775Mg_0.225O₃FeAs. The isovalent substitution of Sr²⁺ by Ca²⁺ in Sr_2-xCa_xVO₃FeAs has been shown to strongly influence the superconducting properties of this material and a clear correlation between the evolution of T_c and the shape of the FeAs₄ tetrahedron has been established. These results demonstrate that superconductivity in iron-based superconductors is extremely sensitive to both electron count and the crystal structure. Finally, investigations into the manganese oxide arsenide CeOMnAs reveal room temperature ordering of Mn²⁺ spins and a spin reorientation transition of Mn moments at 36 K. This transition is concomitant with Ce ordering and an apparent weak structural distortion, demonstrating that f electrons are able to dictate the orientation of Mn moments.

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1. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.572877

Tags

537.6233

Additional Fields

Identifer	oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:572877
Date	January 2012
Creators	Corkett, Alex J.
Contributors	Clarke, Simon J.
Publisher	University of Oxford
Source Sets	Ethos UK
Detected Language	English
Type	Electronic Thesis or Dissertation
Source	http://ora.ox.ac.uk/objects/uuid:d6740be0-42a1-408c-b063-cf5b267365aa