Structural collapse and superconductivity in rare-earth-doped CaFe2As2

Aliovalent rare-earth substitution into the alkaline-earth site of CaFe2As2 single crystals is used to fine tune structural, magnetic, and electronic properties of this iron-based superconducting system. Neutron and single-crystal x-ray scattering experiments indicate that an isostructural collapse of the tetragonal unit cell can be controllably induced at ambient pressures by the choice of substituent ion size. This instability is driven by the interlayer As-As anion separation, resulting in an unprecedented thermal expansion coefficient of 180 x 10(-6) K-1. Electrical transport and magnetic susceptibility measurements reveal abrupt changes in the physical properties through the collapse as a function of temperature, including a reconstruction of the electronic structure. Superconductivity with onset transition temperatures as high as 47 K is stabilized by the suppression of antiferromagnetic order via chemical pressure, electron doping, or a combination of both. Extensive investigations are performed to understand the observations of partial volume-fraction diamagnetic screening, ruling out extrinsic sources such as strain mechanisms, surface states, or foreign phases as the cause of this superconducting phase that appears to be stable in both collapsed and uncollapsed structures.