Valence change and magnetic order in YbMn6Ge(6-x)Sn(x)

The YbMn(6)Ge(6-x)Sn(x) compounds (0 < x < 6) have been investigated using x-ray diffraction, magnetic measurements, neutron diffraction and (170)Yb Mössbauer spectroscopy. The YbMn(6)Ge(6-x)Sn(x) system comprises three solid solutions: (i) 0 < x ≤ 1.1, (ii) 3.2 ≤ x ≤ 4.6 and (iii) 5.3 ≤ x < 6, all of which crystallize in the hexagonal (P6/mmm) HfFe(6)Ge(6)-type structure. The substitution of Sn for Ge yields changes in the type of magnetic order (antiferromagnetic, helimagnetic, ferromagnetic, conical and ferrimagnetic), in the easy magnetization direction (from easy axis to easy plane) as well as in the valence state of Yb (from trivalent to divalent). The Mn moments order at or above room temperature, while magnetic ordering of the Yb sublattice is observed at temperatures up to 110 K. While Yb is trivalent for x ≤ 1.1 and divalent for x ≥ 5.3, both magnetic and (170)Yb Mössbauer spectroscopy data suggest that there is a gradual reduction in the average ytterbium valence through the intermediate solid solution (3.2 ≤ x ≤ 4.6), and that intermediate valence Yb orders magnetically, a very unusual phenomenon. Analysis of the (170)Yb Mössbauer spectroscopy data suggests that the departure from trivalency starts as early as x = 3.2 and the loss of ytterbium moment is estimated to occur at an average valence of ∼2.5+.