Layered α-form ZrNX (X: Cl and Br) compounds with high quality were prepared by chemical vapor transport. The intercalation of alkali metal A (A: Li, Na, K, Rb) was carried out to realize electron doping into the orthogonal [Zr2N2] layers. The Rietveld refinement analysis reveals that the [Zr2N2] crystalline layers in the intercalation compounds shift mutually in the ab plane when compared with the hosts. Magnetic measurements show that the intercalation compounds A x ZrNX are changed into superconductors with transition temperature T c of up to 12 K. Upon the cointercalation of solvent molecules such as THF, T c decreases to as low as 6.1 K with increasing the interlayer spacing d up to 14 Å, which is similar to the d dependence of T c recently found in electron-doped α-form TiNX series. We also succeeded in synthesizing another new polymorph of α-Zr2N2S by the topochemical reaction between α-form ZrNX and Na2S. α-Zr2N2S (space group: Immm, a = 4.1375(1) Å, b = 3.5422(1) Å, and c = 11.5204(3) Å) has the same α-[Zr2N2] layers, whereas the interlayer spacing between two adjacent [Zr2N2] layers is effectively decreased by 1/3 when compared with the parent compounds of ZrNX.
Journal of Superconductivity and Novel Magnetism – Springer Journals
Published: Apr 9, 2017
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