  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
choice of substituent ion size. This instability is driven by the interlayer
As-As anion separation, resulting in an unprecedented thermal expansion
coefficient of $180\times 10^{-6}$ 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.
