Dependence of and transport properties on the Cu valence (n=2,3) superconductors

We have determined the oxygen content and the Cu valence by iodometric titiration of single-phase (Formula presented)(Formula presented)(Formula presented)(Formula presented) (n=2,3), Hg-1212 and Hg-1223, superconductors postannealed under various conditions in either a reducing or an oxidizing atmosphere. Their lattice parameters, (Formula presented), resistivity, and the thermoelectric power have been systematically investigated as a function of Cu valence. Hg-1212 exhibits a parabolic or "bell-shaped" relationship between (Formula presented) and the Cu valence similar to that reported for (Formula presented)(Formula presented) (Hg-1201), while only a half of the parabola is observed for Hg-1223. The systematic variations in the resistivity and the thermoelectric power as well as the relationship between (Formula presented) and the Cu valence confirm that the Hg-1223 sample with the highest (Formula presented) of 135 K is almost optimally doped. Both Hg-1212 and Hg-1223 as well as Hg-1201 exhibit their maximum (Formula presented) values at the same nominal Cu valence of approximately 2.20 which is also comparable to those for other high-(Formula presented) cuprate superconductors. This coincidence of the Cu valence for optimally doped states suggests that the simple ionic model where each excess oxygen in the Hg-(Formula presented) charge reservoir supplies two holes is appropriate in the present Hg-12(n-1)n samples.