Free-Spin Dominated Magnetocaloric Effect in Dense Gd(3+) Double Perovskites

[Image: see text] Frustrated lanthanide oxides with dense magnetic lattices are of fundamental interest for their potential in cryogenic refrigeration due to a large ground state entropy and suppressed ordering temperatures but can often be limited by short-range correlations. Here, we present examples of frustrated fcc oxides, Ba(2)GdSbO(6) and Sr(2)GdSbO(6), and the new site-disordered analogue Ca(2)GdSbO(6) ([CaGd](A)[CaSb](B)O(6)), in which the magnetocaloric effect is influenced by minimal superexchange (J(1) ∼ 10 mK). We report on the crystal structures using powder X-ray diffraction and the bulk magnetic properties through low-field susceptibility and isothermal magnetization measurements. The Gd compounds exhibit a magnetic entropy change of up to −15.8 J/K/mol(Gd) in a field of 7 T at 2 K, a 20% excess compared to the value of −13.0 J/K/mol(Gd) for a standard in magnetic refrigeration, Gd(3)Ga(5)O(12). Heat capacity measurements indicate a lack of magnetic ordering down to 0.4 K for Ba(2)GdSbO(6) and Sr(2)GdSbO(6), suggesting cooling down through the liquid 4-He regime. A mean-field model is used to elucidate the role of primarily free-spin behavior in the magnetocaloric performance of these compounds in comparison to other top-performing Gd-based oxides. The chemical flexibility of the double perovskites raises the possibility of further enhancement of the magnetocaloric effect in the Gd(3+)fcc lattices.