Tuning the range, magnitude, and sign of the thermal expansion in intermetallic Mn3(Zn, M)x N(M = Ag, Ge)

Neutron diffraction is used to reveal the origin and control of the thermal expansion properties of the cubic intermetallic compounds Mn₃Zn_xN and Mn₃[Zn-(Ag,Ge)]_xN. We show that the introduction of Zn vacancies induces and stabilizes an antiferromagnetic phase with huge spin-lattice coupling that can be tuned to achieve zero thermal expansion (ZTE) over a wide temperature range. We further show that the antiferromagnetic ordering temperature (T_N) that controls this ZTE can be tuned by chemical substitution, again on the Zn site, to adjust the span of ZTE temperatures from well above room temperature to well below. This establishes a quantitative relationship and mechanism to precisely control the ZTE of a single material, enabling it to be tailored for specific device applications.