Abstract
A series of hexagonal RMnO3 (R=Y, Ho–Lu) compounds are first annealed in various highly oxidizing conditions to show that for the largest R constituents, Y and Ho, it is possible to load the phases with large amounts of excess oxygen. Within the oxygen-annealed samples we identify new heavily-oxygenated phases, that is, YMnO3.35 and HoMnO3.34. The former is then thoroughly characterized by thermogravimetric analysis, X-ray diffraction and electron diffraction. These studies evidence a hexagonal sub-cell (aS≈3.578Å (aH/3), cS≈11.18Å, space group P63mc) and satellites, associated with two modulation vectors q→1⁎≈0.41a→S⁎+0.41b→S⁎+1/3c→S⁎andq→2⁎=(1/2). The results are interpreted by the formation of a modulated composite structure, resulting from the evolution of the hexagonal parent YMnO3+δ structure toward a reduced pyrochlore-type structure Y2Mn2O7−x, in long- and short-range ordering.
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