Structural and magnetic properties of the geometrically frustrated 3d and 5d s = ½ Double Perovskites Sr2CuWO6, Ba2YWO6 and LaSrMgWO6
Burrows, Oliver James
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Double perovskites with a single s = ½ magnetic ion and rocksalt order can show geometric frustration, due to arrangement of electron spins such that they cannot satisfy all nearest-neighbour antiferromagnetic interactions simultaneously. This can give rise to exotic magnetic states at low temperature. Compounds with unpaired 4d and 5d electrons have in this respect been studied far less than 3d compounds. Here, results of studies on the compounds Sr2CuWO6, Ba2YWO6 and LaSrMgWO6 are presented. The synthesis of the previously reported compound Ba2Y1WO6 (W5 +, 5d1) was attempted by many methods, but yttrium deficiencies were present in all samples. This led to the series Ba2YxWO6 with ⅔ ≤ x ≤ 0.8, dependent on the synthesis conditions. The x = ⅔ compound is known to exist as a metastable cubic phase and an 18H rhombohedral thermodynamic phase. The one-third vacant B sites on the x = ⅔ cubic material are doped with lithium, resulting in the Ba2Y2/3LixWO6 compound. This thesis focuses on the new x = 0.75 phase, and characterises its structural and magnetic properties. The Jahn-Teller distorted Sr2CuWO6, with the Cu2+ (3d9) magnetic ion, has an elongated c axis leading to separation of ab planes. This compound had been proposed as a pseudo-2D spin liquid model candidate, following a lack of evidence of transition to long-range order in SQUID magnetometry and heat capacity. However, recent μSR measurements did show a transition to long-range ordered state at 24K. This thesis details further bulk and local probe measurements which indicate that the low-temperature state is type-2 antiferromagnetic, and which point to a thermally activated spin-liquid-like state which occurs between 24K and ∼100K. La0.5Sr1.5MgWO6, has also been synthesised. The 1:1 compound LaSrMgWO6 had previously been reported as W5+ and described as “pseudo-cubic”: X-ray and neutron diffraction studies here characterise the low-temperature structure within the P2₁/n monoclinic space group, and suggest that no ordering of the atoms on the A site is observed.