One Structure, Two Elements-LuGe2 Superconductor vs Ordinary Metallic Conductor LuSn2. A Case Study on How Site-Selective Germanium for Tin Atom Substitution Leads to Modulating of the Charge Distribution.

The substitution of chemically similar elements in a given crystal structure is an effective way to enhance physical properties, but the understanding on such improvements is usually impeded because the substitutions are random, and the roles of the different atoms cannot be distinguished by crystallographic symmetry. Herein, we provide a detailed crystallographic analysis and property measurements for the continuous solid solutions LuGexSn2-x (0 < x < 2). The results show that there is no apparent change of the global symmetry, with the end-members LuGe2 and LuSn2, as well as the intermediate LuGexSn2-x compositions adopting the ZrSi2 type structure (space group Cmcm, Pearson index oC12). Yet, the refinements of the crystal structures from single-crystal X-ray diffraction data show that Ge-Sn atom substitutions are not random, but occur preferentially at the zigzag chain. The patterned distribution of two group 14 elements leads to a significant variation in chemical bonding and charge ordering within the other structural fragment, the 2D square nets, thereby resulting in tuned electron transport. The enhancement is greater than that for the typical Bloch-Gruneisen model and more akin to that for the parallel-resistor model. Magnetization measurements on single crystals show bulk superconductivity in all LuGexSn2-x samples with shielding fractions as high as 90%. Specific heat data confirm the effect to originate from residual metallic tin in the material, indicating that Sn atom substitutions in the 2D square nets cause disruptions of the hypervalent bonding and local anisotropy, which ultimately leads to vanishing of the superconducting state in the end-member LuGe2. This work sheds light on how the complexity in chemical interactions by two different carbon congeners leads to changes in the physical properties and how they can be correlated with the induced charge distribution. These studies also provide a general approach to modulation of charge density and. thus, of emerging physical properties in other classes of intermetallic systems based on the main-group elements of groups 13 to 15.