High-temperature evolution of the incommensurate composite crystal Ca0.83CuO2

The crystal structure of the composite crystal Ca0.83CuO2 was investigated by synchrotron powder diffraction at high temperature. The incommensurate modulated structure was firstly analyzed at room temperature (RT) and successfully solved by adopting the (3D + 1)-dimensional symmetry P21/m(α0γ)0s. The composite crystal is featured by a non-uniform distribution of Ca ions occupying octahedral sites formed by the spatial arrangement by the infinite 1D CuO2 chains. By approaching 500 K, Ca0.83CuO2 undergoes a structural rearrangement ruled by the shrinking of the Ca interatomic distances. The high-temperature crystalline phase is characterized by a different incommensurate periodicity requiring the recombination of the Ca/CuO2 balance featuring the composite intergrowth of the two almost independent sub-structures. We ascertain that the new crystalline form is stable up to 950 K near to the limit of the thermal decomposition.