Magnetocaloric materials undergoing reversible phase transitions are highly desirable for magnetic refrigeration applications. (Mn,Fe)₂(P,Si) alloys exhibit a giant magnetocaloric effect accompanied by a magnetoelastic transition, while the noticeable irreversibility causes drastic degradation of the magnetocaloric properties during consecutive cooling cycles. In the present work, we performed a comprehensive study on the magnetoelastic transition of the (Mn,Fe)₂(P,Si) alloys by high-resolution transmission electron microscopy, in situ field- and temperature-dependent neutron powder diffraction as well as density functional theory calculations (DFT). We found a generalized relationship between the thermal hysteresis and the transition-induced elastic strain energy for the (Mn,Fe)₂(P,Si) family. The thermal hysteresis was greatly reduced from 11 to 1 K by a mere 4 at.% substitution of Fe by Mo in the Mn_1.15Fe_0.80P_0.45Si_0.55 alloy. This reduction is found to be due to a strong reduction in the transition-induced elastic strain energy. The significantly enhanced reversibility of the magnetoelastic transition leads to a remarkable improvement of the reversible magnetocaloric properties, compared to the parent alloy. Based on the DFT calculations and the neutron diffraction experiments, we also elucidated the underlying mechanism of the tunable transition temperature for the (Mn,Fe)₂(P,Si) family, which can essentially be attributed to the strong competition between the covalent bonding and the ferromagnetic exchange coupling. The present work provides not only a new strategy to improve the reversibility of a first-order magnetic transition but also essential insight into the electron-spin-lattice coupling in giant magnetocaloric materials.

We performed neutron-diffraction experiments and density functional theory calculations to study the magnetostructural coupling in MnCoGeBx (x=0, 0.01, and 0.05) alloys. By varying the amount of boron addition, we are able to freely switch the magnetostructural coupling on and off in the MnCoGe alloys. It is found that the boron addition stabilizes the high-temperature hexagonal phase due to the reduced interatomic distances and the enhanced covalent bonding. The hexagonal-orthorhombic structural transition shifts to low temperatures with the boron addition and coincides with the paramagnetic-ferromagnetic (PM-FM) transition in the MnCoGeB0.01 alloy. With a further increase in the boron addition, the structural and magnetic transitions are decoupled again. The hexagonal-orthorhombic structural transition is significantly suppressed in the MnCoGeB0.05 alloy, although subtle distortions in the hexagonal structure are evidenced by a canted spin arrangement below 75 K. The MnCoGe and MnCoGeB0.01 alloys show a collinear FM structure, having a much larger Mn moment than the MnCoGeB0.05 alloy. The relatively small Mn moment in the MnCoGeB0.05 alloy can be attributed to the shortened Mn-Mn distance and the enhanced overlap of the 3d orbitals between the neighboring Mn atoms. The uncovered relationship between the structural evolution and the sizable magnetic moment in the present work offers more insight into the magnetostructural coupling in the MnCoGe-based alloys.

The influence of Nb substitution on the structure, magnetoelastic transition and magnetocaloric properties has been investigated for the Mn_1.1Fe_0.85-xNb_xP_0.43Si_0.57 alloys. The substitution for Fe by merely 4.7 at.% Nb (i.e. x = 0.04) significantly diminishes the thermal hysteresis from 10 to 1 K due to the reduced structural discontinuity crossing the magnetoelastic transition. This also improves the mechanical stability. The Curie temperature of the magnetoelastic transition is lowered by approximately 11.6 K per at.% of the Nb substitution, originating from the enhanced covalent bonding that favors the paramagnetic state. The giant magnetocaloric effect is still retained in the Nb-substituted alloys.