Dependence of superconducting properties of (Ca,RE)(Fe,TM)As2 [(Ca,RE)112, TM: Co, Ni)] on RE elements (RE = La-Gd) was systematically investigated. Improvement of superconducting properties by Co or Ni co-doping was observed for all (Ca,RE)112, whic
h is similar to Co-co-doped (Ca,La)112 or (Ca,Pr)112. Tc of Co-co-doped samples decreased from 38 K for RE = La to 29 K for RE = Gd with decreasing ionic radii of RE3+. However, Co-co-doped (Ca,Eu)112 showed exceptionally low Tc = 21 K probably due to the co-existence of Eu3+ and Eu2+ suggested by longer interlayer distance dFe-Fe of (Ca,Eu)112 than other (Ca,RE)112.
Superconducting properties of Co-co-doped (Ca,RE)FeAs2 ((Ca,RE)112: RE = La, Pr) were investigated. Co-co-doping increased Tc of (Ca,Pr)112 while Mn-co-doping suppressed superconductivity of (Ca,RE)112. Co-co-doped (Ca,La)112 showed large diamagnetic
screening and sharper superconducting transition than Co-free (Ca,La)112. Tczero observed in resistivity measurements increased from 14 K to 30 K by Co-co-doping, while Tconset was not increased. The critical current density (Jc) of Co-co-doped (Ca,La)112 were approximately 2.1 x 104 Acm-2 and 3.2 x 103 Acm-2 at 2 K and 25 K, respectively, near zero field. These relatively high Jcs and large diamagnetic screening observed in susceptibility measurement as for polycrystalline bulks suggest bulk superconductivity of Co-co-doped (Ca,RE)112 compounds.
In order to clarify the origin of anomalous superconductivity in (Ca,RE)Fe2As2 system, Pr doped and Pr,Co co-doped CaFe2As2 single crystals were grown by the FeAs flux method. These samples showed two-step superconducting transition with Tc1 = 25~42
K, and Tc2 < 16 K, suggesting that (Ca,RE)Fe2As2 system has two superconducting components. Post-annealing performed for these crystals in evacuated quartz ampoules at various temperatures revealed that post-annealing at ~400{deg}C increased the c-axis length for all samples. This indicates that as-grown crystals have a certain level of strain, which is released by post-annealing at ~400{deg}C. Superconducting properties also changed dramatically by post-annealing. After annealing at 400{deg}C, some of the co-doped samples showed large superconducting volume fraction corresponding to the perfect diamagnetism below Tc2 and high Jc values of 104~105 Acm-2 at 2 K in low field, indicating the bulk superconductivity of (Ca,RE)Fe2As2 phase occurred below Tc2. On the contrary, the superconducting volume fraction above Tc2 was always very small, suggesting that 40 K-class superconductivity observed in this system is originating in the local superconductivity in the crystal.
Synthesis of a series of layered iron arsenides Ca1-xRExFeAs2 (112) was attempted by heating at 1000 C under a high-pressure of 2 GPa. The 112 phase successfully forms with RE = La, Ce, Nd, Sm, Eu and Gd, while Tb, Dy and Ho substituted and RE free s
amples does not contain the 112 phase. The Ce, Nd, Sm, Eu and Gd doped Ca1-xRExFeAs2 are new compounds. All of them exhibit superconducting transition except for the Ce doped sample. The behaviour of the critical temperature, with the RE ionic radii have been investigated.
A new iron-based superconductor (Ca,Pr)FeAs2 was discovered. Plate-like crystals of the new phase were obtained and crystal structure was investigated by single-crystal X-ray diffraction analysis. The structure was identified as the monoclinic system
with space group P21/m, and is composed of two Ca(Pr) planes, anti-fluorite Fe2As2 layers, and As2 zigzag chain layers. Plate-like crystals composed of the new phase showed superconductivity with Tc ~20 K in both magnetization and resistivity measurements.
