The preparation and phase diagrams of (${^{7}}$Li${_{1-x}}$Fe${_{x}}$OD)FeSe and (Li${_{1-x}}$Fe${_{x}}$OH)FeSe superconductors

TL;DR

This study maps the phase diagrams of two FeSe-based superconductors, revealing how lattice parameters correlate with critical temperature and clarifying the absence of antiferromagnetism in certain samples, with implications for understanding doping effects.

Contribution

It provides detailed phase diagrams and clarifies the role of lattice structure and impurities in the superconductivity of (${^{7}}$Li${_{1-x}}$Fe${_{x}}$OD)FeSe and (Li${_{1-x}}$Fe${_{x}}$OH)FeSe.

Findings

Correlation between tetragonality and $T_{c}$.

No antiferromagnetic order below 120 K in non-superconducting samples.

Impurities like Fe${_{3}}$O${_{4}}$ and LixFeO2 cause observed magnetic transitions.

Abstract

We report the phase diagram for the superconducting system (${^{7}}$Li${_{1-x}}$Fe${_{x}}$OD)FeSe and contrast it with that of (Li${_{1-x}}$Fe${_{x}}$OH)FeSe both in single crystal and powder forms. Samples were prepared via hydrothermal methods and characterized with laboratory and synchrotron X-ray diffraction, high-resolution neutron powder diffraction (NPD), and high intensity NPD. We find a correlation between the tetragonality of the unit cell parameters and the critical temperature, $T_{c}$, which is indicative of the effects of charge doping on the lattice and formation of iron vacancies in the FeSe layer. We observe no appreciable isotope effect on the maximum $T_{c}$ in substituting H by by D. The NPD measurements definitively rule out an antiferromagnetic ordering in the non-superconducting (Li${_{1-x}}$Fe${_{x}}$OD)FeSe samples below 120 K, which has been reported in non-superconducting (Li${_{1-x}}$Fe${_{x}}$OH)FeSe.$^{1}$ A likely explanation for the observed antiferromagnetic transition in (Li${_{1-x}}$Fe${_{x}}$OH)FeSe samples is the formation of impurities during their preparation such as Fe${_{3}}$O${_{4}}$ and LixFeO2, which express a charge ordering transition known as the Verwey transition near 120 K. The concentration of these oxide impurities is found to be dependent on the concentration of the lithium hydroxide reagent and the use of H${_{2}}$O vs. D${_{2}}$O as the solvent during synthesis. We also describe the reaction conditions that lead to some of our superconducting samples to exhibit ferromagnetism below $T_{c}$.