Abstract:Here we report on discovery of (Ca 4 Al 2 O 6-y )(Fe 2 Pn 2 ) (Pn = As and P) (Al-42622(Pn)) superconductor using high-pressure synthesis technique. Al-42622(Pn) exhibit superconductivity for both Pn = As and P with the transition temperatures of 28.3 K and 17.1 K, respectively. The a-lattice parameters of Al-42622(Pn) (a = 3.713 Å and 3.692 Å for Pn = As and P, respectively) are smallest among the iron-pnictide superconductors. Correspondingly, Al-42622(As) has the smallest As-Fe-As bond angle (102.1 °) and the largest As distance from the Fe planes (1.500 Å). PACS number(s):74.70. Dd, 74.62.Bf,74.10 (Ln = Dy). In this study, we have applied the HP technique in synthesizing materials containing perovskite-type blocking layers which are extremely small and therefore cannot be synthesized under ambient conditions. Along this line, we have discovered a series of (Ca 4 Al 2 O 6-y )(Fe 2 Pn 2 ) (Pn = As and P) (abbreviated as Al-42622(Pn)) superconductors with T c = 28.3 K and 17.1 K, respectively. As a consequence of HP synthesis, the synthesized compounds possess the unique structural characteristics never realized in the existing Fe-based superconductors, namely, shortest a-axis lattice parameters, smallest As-Fe-As bond angle, and longest As-Fe plane distance. Here we demonstrate the synthesis method and the characterization of Al-42622(Pn).Polycrystalline samples of Al-42622(Pn) were synthesized by the solid-state reaction method using a cubic-anvil-type HP apparatus. It should be noted that one cannot synthesize Al-42622(Pn) by conventional ambient pressure synthesis [11].Starting materials were powders of CaO, Al, As, P, Fe and Fe 2 O 3 . The powders were mixed with a nominal composition of (Ca 4 Al 2 O 6-y )(Fe 2 Pn 2 ). Here the oxygen content 6-y was controlled by adjusting the ratio of Fe and Fe 2 O 3 . We have found that the purity of the obtained samples strongly depends on the oxygen content in the starting composition. The suitable oxygen content turned out to be 6 -y = 5.6 ~ 5.8. The starting materials were ground using an agate mortar and pressed into a pellet in a glove box filled with N 2 gas. The pellet was loaded in a high-pressure cell and heated at 1150 and 1300 °C for Pn = As and P, respectively, under a pressure of 4.5 GPa for 1 h.Powder X-ray diffraction (XRD) patterns were measured using CuK α radiation.
Applied Physics Letters 97(2010)172506page 4 4 Neutron scattering measurement was carried out using the high-resolution powder diffractometer HERMES of the Institute for Materials Research, Tohoku University, installed at the JRR-3 reactor of JAEA in Japan. Incident neutron wavelength was fixed at 1.8484 Å using a Ge monochromator. The data were analyzed by the Rietveld method using the Rietan program. The dc magnetic susceptibility was measured using a SQUID magnetometer (Quantum Design MPMS) under a magnetic field of 5 Oe. The resistivity was measured by a four-probe method. between Fe layers is shorter for Al-42622(P) compared to Al-42622(As).In Fig. 3 T-dependent resistivity...