Tunable thermal expansion and magnetism in Zr-doped ScF3

The negative thermal expansion (NTE) behavior provides us an opportunity to design materials with controllable coefficient of thermal expansion (CTE). In this letter, we report a tunable isotropic thermal expansion in the cubic (Sc1−xZrx)F3+δ over a wide temperature and CTE range (αl = −4.0 to+ 16.8 × 10−6 K−1, 298–648 K). The thermal expansion can be well adjusted from strong negative to zero, and finally to large positive. Intriguingly, isotropic zero thermal expansion (αl = 2.6 × 10−7 K−1, 298–648 K) has been observed in the composition of (Sc0.8Zr0.2)F3+δ. The controllable thermal expansion in (Sc1−xZrx)F3+δ is correlated to the local structural distortion. Interestingly, the ordered magnetic behavior has been found in the zero thermal expansion compound of (Sc0.8Zr0.2)F3+δ at room temperature, which presumably correlates with the unpaired electron of the lower chemical valence of Zr cation. The present study provides a useful reference to control the thermal expansion and explore the multi-functionalization for NTE materials.