Stabilization of an ambient pressure, collapsed tetragonal phase in   CaFe2As2 and tuning of the orthorhombic / antiferromagnetic transition   temperature by over 70 K by control of nano-precipitates
  We have found a remarkably large response of the transition temperature of CaFe2As2 single crystals grown out of excess FeAs to annealing / quenching temperature. Whereas crystals that are annealed at 400 C exhibit a first order phase transition from a high temperature tetragonal to a low temperature orthorhombic and antiferromagnetic state near 170 K, crystals that have been quenched from 960 C exhibit a transition from a high temperature tetragonal phase to a low temperature, non-magnetic, collapsed tetragonal phase below 100 K. By use of temperature dependent electrical resistivity, magnetic susceptibility, X-ray diffraction, Mossbauer spectroscopy and nuclear magnetic resonance measurements we have been able to demonstrate that the transition temperature can be reduced in a monotonic fashion by varying the annealing / quenching temperature from 400 to 850 C with the low temperature state remaining antiferromagnetic for transition temperatures larger than 100 K and becoming collapsed tetragonal / non-magnetic for transition temperatures below 90 K. This suppression of the orthorhombic / antiferromagnetic phase transition and its ultimate replacement with the collapsed tetragonal / non-magnetic phase is similar to what has been observed for CaFe2As2 under hydrostatic pressure. Transmission electron microscopy studies indicate that there is a temperature dependent, width of formation of CaFe2As2 with a decreasing amount of excess Fe and As being soluble in the single crystal at lower annealing temperatures. For samples quenched from 960 C there is a fine (of order 10 nm), semi-uniform distribution of precipitate that can be associated with an average strain field whereas for samples annealed at 400 C the excess Fe and As form mesoscopic grains that induce little strain throughout the CaFe2As2 lattice. 
S. Ran, S. L. Bud'ko, D. K. Pratt, A. Kreyssig, M. G. Kim, M. J.   Kramer, D. H. Ryan, W. N. Rowan-Weetaluktuk, Y. Furukawa,...
cond-mat.supr-con cond-mat.mtrl-sci