Evolution of precipitate morphology during heat treatment and its implications for the superconductivity in KxFe1.6+ySe2 single crystals

We study the relationship between precipitate morphology and superconductivity in KxFe1.6+ySe2 single crystals grown by self-flux method. Scanning electron microscopy (SEM) measurements revealed that the superconducting phase forms a network in the samples quenched above iron vacancy order-disorder transition temperature Ts, whereas it aggregates into micrometer-sized rectangular bars and aligns as disconnected chains in the furnace-cooled samples. Accompanying this change in morphology the superconducting shielding fraction is strongly reduced. By post-annealing above Ts followed by quenching in room temperature water, the network recovers with a superconducting shielding fraction approaching 80% for the furnace-cooled samples. A reversible change from network to bar chains was realized by a secondary heat treatment in annealed samples showing a large shielding fraction, that is, heating above Ts followed by slow cooling across Ts. The large shielding fraction observed in KxFe1.6+ySe2 single crystals actually results from an uniform and contiguous distribution of superconducting phase. Through the measurements of temperature dependent x-ray diffraction, it is found that the superconducting phase precipitates while the iron vacancy ordered phase forms together by cooling across Ts in KxFe1.6+ySe2 single crystals. It is a solid solution above Ts, where iron atoms randomly occupy both Fe1 and Fe2 sites in the iron vacancy disordering status; and phase separation is driven by the iron vacancy order-disorder transition upon cooling. However, neither additional iron in the starting mixtures nor as-quenching at high temperatures can extend the miscibility gap to the KFe2Se2 side. Disciplines Condensed Matter Physics | Materials Science and Engineering Comments This article is from Physical Review B 86 (2012): 144507, doi:10.1103/PhysRevB.86.144507. This article is available at Iowa State University Digital Repository: http://lib.dr.iastate.edu/ameslab_pubs/38 PHYSICAL REVIEW B 86, 144507 (2012) Evolution of precipitate morphology during heat treatment and its implications for the superconductivity in KxFe1.6+ ySe2 single crystals Y. Liu,* Q. Xing, K. W. Dennis, R. W. McCallum, and T. A. Lograsso Division of Materials Sciences and Engineering, Ames Laboratory, USDOE, Ames, Iowa 50011, USA (Received 19 August 2012; revised manuscript received 23 September 2012; published 8 October 2012) We study the relationship between precipitate morphology and superconductivity in KxFe1.6+ySe2 single crystals grown by self-flux method. Scanning electron microscopy (SEM) measurements revealed that the superconducting phase forms a network in the samples quenched above iron vacancy order-disorder transition temperature Ts , whereas it aggregates into micrometer-sized rectangular bars and aligns as disconnected chains in the furnace-cooled samples. Accompanying this change in morphology the superconducting shielding fraction is strongly reduced. By post-annealing above Ts followed by quenching in room temperature water, the network recovers with a superconducting shielding fraction approaching 80% for the furnace-cooled samples. A reversible change from network to bar chains was realized by a secondary heat treatment in annealed samples showing a large shielding fraction, that is, heating above Ts followed by slow cooling across Ts . The large shielding fraction observed in KxFe1.6+ySe2 single crystals actually results from an uniform and contiguous distribution of superconducting phase. Through the measurements of temperature dependent x-ray diffraction, it is found that the superconducting phase precipitates while the iron vacancy ordered phase forms together by cooling across Ts in KxFe1.6+ySe2 single crystals. It is a solid solution above Ts , where iron atoms randomly occupy both Fe1 and Fe2 sites in the iron vacancy disordering status; and phase separation is driven by the iron vacancy order-disorder transition upon cooling. However, neither additional iron in the starting mixtures nor as-quenching at high temperatures can extend the miscibility gap to the KFe2Se2 side. DOI: 10.1103/PhysRevB.86.144507 PACS number(s): 74.70.Xa, 74.81.Bd, 74.25.F−