High-quality and sizable single crystals are crucial for studying the intrinsic properties of unconventional superconductors, which are lacking in the 1111 phase of the Fe-based superconductors.Here we report the successful growth of CaFeAsF single crystals with the sizes of 1-2 mm using the self-flux method. Owning to the availability of the high-quality single crystals, the structure and transport properties were investigated with a high reliability. The structure was refined by using the single-crystal x-ray diffraction data, which confirms the reports earlier on the basis of powder data. A clear anomaly associated with the structural transition was observed at 121 K from the resistivity, magnetoresistance, and magnetic susceptibility measurements. Another kink-feature at 110 K, most likely an indication of the antiferromagnetic transition, was also detected in the resistivity data. Our results supply a basis to propel the physical investigations on the 1111 phase of the Fe-based superconductors.

Millimeter sized single crystals of CaFe 1−x Co x AsF were grown using a self-flux method. It is found that high-quality single crystals can be grown from three approaches with different initial raw materials. The chemical compositions and crystal structure were characterized carefully. The c-axis lattice constant is suppressed by the Co substitution. Superconductivity with the critical transition T c as high as 21 K was confirmed by both the resistivity and magnetic susceptibility measurements in the sample with x = 0.12. Moreover, it is found that T c can be enhanced for about 1 K under the very small hydrostatic pressure of 0.22 GPa, which is more quickly than that reported in the polycrystalline samples. Our results is a promotion for the physical investigations of 1111 phase iron-pnictide superconductors.