Entropy driven reverse-metal-to-insulator transition and delta-temperatural transports in metastable perovskites of correlated rare-earth nickelate

TL;DR

This paper reveals an entropy-driven reverse-metal-to-insulator transition in metastable rare-earth nickelate perovskites, highlighting the role of orbital entropy in phase stability and introducing temperature-dependent transport properties for device applications.

Contribution

It uncovers a reversible, entropy-dominated phase transition in ReNiO3, expanding understanding of MIT mechanisms beyond Coulomb energy effects and demonstrating temperature-controlled transport phenomena.

Findings

Discovered a reverse-metal to insulator transition (R-MIT) below the conventional TMIT.

Identified delta-temperatural transport with exponential resistivity decrease at higher temperatures.

Showed that compositional and strain modifications influence the transition sharpness and temperature range.

Abstract

The metal to insulator transition (MIT) in Mott-Hubbard systems is one of the most important discoveries in condensed matter physics, and results in abrupt orbital transitions from the insulating to metallic phases by elevating temperature across a critical point (TMIT). Although the MIT was previously expected to be mainly driven by the orbital Coulomb repulsion energy, the entropy contribution to the orbital free energy that also determines the relative stability of the metallic and insulating phases was largely overlooked. Herein, we demonstrate an orbital-entropy dominated reversible electronic phase transition in the metastable perovskite family of correlated rare-earth nicklates (ReNiO3), in addition to their previously known MIT driven by orbital Coulomb energies. In reverse to MIT, the resistivity of ReNiO3 abruptly increases by 2-3 orders by elevating T across another critical point (TR-MIT) below TMIT, and such transition is named as reverse-metal to insulator transition (R-MIT). Combining the afterwards exponentially decreasing resistivity in the insulating phase of ReNiO3 at further temperature elevation, a distinguished delta-temperatural transport character is established, which is potentially applicable for locking the working temperatures range for electric devices. The TR-MIT is shown to be enhanced via reducing the compositional complexity and size of Re or imparting bi-axial compressive strains, and meanwhile the transition sharpness of delta-temperatural transport is reduced. Our discovery indicates that temperature range for a thermodynamically stable insulating phase of ReNiO3 is in between of TR-MIT and TMIT, while a new conductive phase with high orbital entropy is formed by further descending temperature below TR-MIT.