Chemical versus physical pressure effects on the structure transition of bilayer nickelates

TL;DR

This study compares chemical and physical pressure effects on the structural transition of bilayer nickelates, revealing that chemical substitution can increase the critical pressure needed for transition, contrary to expectations.

Contribution

It clarifies the distinct impacts of chemical versus physical pressure on bilayer nickelates and establishes a quantitative relationship between critical pressure and A-site cation size.

Findings

Chemical substitution increases the critical pressure for structural transition.

A linear relationship exists between critical pressure and average A-site cation size.

Replacing La with larger cations may reduce the required external pressure.

Abstract

The observation of high-$T_c$ superconductivity (HTSC) in concomitant with pressure-induced orthorhombic-tetragonal structural transition in the bilayer La$_{3}$Ni$_2$O$_7$ has sparked hopes of achieving HTSC by stabilizing the tetragonal phase at ambient pressure. To mimic the effect of external physical pressures, the application of chemical pressure via replacing La$^3$$^+$ with smaller rare-earth R$^3$$^+$ has been considered as a potential route. Here we clarify the distinct effects of chemical and physical pressures on the structural transition of bilayer nickelates through a combined experimental and theoretical investigation. Contrary to general expectations, we find that substitutions of smaller R$^3$$^+$ for La$^3$$^+$ in La$_{3-x}$R$_x$Ni$_2$O$_{7-\delta}$, despite of an overall lattice contraction, produce stronger orthorhombic structural distortions and thus require higher pressures to induce the structural transition. We established a quantitative relationship between the critical pressure $P_c$ for structural transition and the average size of $A$-site cations. A linear extrapolation of $P_c$ versus <$r_A$> yields a putative critical value of <$r_A$>$_c$ ~ 1.23 angstrom for $P_c$ ~ 1 bar. The negative correlation between $P_c$ and <$r_A$> indicates that it is unlikely to reduce $P_c$ to ambient by replacing La$^3$$^+$ with smaller R$^3$$^+$ ions. Instead, partial substitution of La$^3$$^+$ with larger cations such as alkaline-earth Sr$^2$$^+$ or Ba$^2$$^+$ might be a feasible approach. Our results provide valuable guidelines in the quest of ambient-pressure HTSC in bilayer nickelates.