The crystal growth conditions of compounds of the series Srn+1IrnO3n+1 (n=1, 2 and ∞) are investigated. It was found that the ratio of IrO2:SrCO3 in the starting mixture is the most important variable in determining the phase formed. Good quality samples of Sr3Ir2O7 were found to have a sharp change in gradient at the Néel temperature of 287.5 K and no secondary T* transition between 230 K and 260 K. All crystals of Sr3Ir2O7 grown were found to be heavily oxygen deficient by EPMA regardless of the crystal growth conditions used with an average stoichiometry of Sr2:87Ir2O6:27. Adding more electrons via replacing strontium with lanthanum causes (Sr(1-x)Lax)3Ir2O7 to become metallic by x=0.072, which also fully quenches the long-range antiferromagnetic order. Heat capacity and resistivity measurements show that metallic (Sr(1-x)Lax)3Ir2O7 is a weakly correlated Fermi-liquid metal. Given that there are only subtle changes to the structure upon lanthanum doping, the metal-insulator transition is a result of electron doping rather than structural distortions. No structural phase transitions were found up to a temperature of 800°C and no additional evidence was found to support the Bbcb space group model of the structure of Sr3Ir2O7. Using crystals five times better in quality than those reported in the literature, SrIrO3 was found to be a Fermi-liquid metal, rather than a non-Fermi liquid metal as previously reported, and no superconductivity was found down to temperatures of 20 mK. A known Pt(III) compound, CaPt2O4, was found to be a weakly correlated metal down to 2 K and a novel Pt(III) based compound, K2CaPt3-δ O6 (δ ≈ 0.4), was discovered. K2CaPt3δ-O6 has a structure consisting of monolayers of edge-sharing PtO6 octahedra separated by layers of ordered K+ and Ca2+ ions in a 2:1 ratio. The structure of K2CaPt3-δO6 was found to be flexible to doping with copper, causing the magnetic properties to change from temperature independent to paramagnetic.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:716580 |
| Date | January 2016 |
| Creators | Hunter, Emily Claire |
| Contributors | Stock, Christopher ; Attfield, John ; Loveday, John ; De Vries, Mark |
| Publisher | University of Edinburgh |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/1842/22008 |
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