Gradual transition from insulator to semimetal of Ca$_{1-x}$Eu$_{x}$B$_{6}$ with increasing Eu concentration

TL;DR

This study uses ESR to track how Eu substitution in CaB6 transitions from insulating to semimetallic behavior, revealing changes in local environment and electronic properties with increasing Eu concentration.

Contribution

It provides detailed ESR analysis showing the gradual insulator-to-semimetal transition in Ca$_{1-x}$Eu$_{x}$B$_{6}$, highlighting the evolution of local environments and electronic states.

Findings

ESR spectra show a transition from insulating to metallic environments with increasing Eu.

Fine and hyperfine structures are observable up to x≈0.15, then disappear at higher Eu concentrations.

Line broadening and shape changes indicate the emergence of semimetallic character and magnetic polarons.

Abstract

The local environment of Eu$^{2+}$ ($4f^{7}$, $S=7/2$) in Ca$_{1-x}$Eu$_{x}$B$_{6}$ ($0.003\leqslant x\leqslant 1.00$) is investigated by means of electron spin resonance (ESR). For $x\lesssim 0.003$ the spectra show resolved \textit{fine} and \textit{hyperfine} structures due to the cubic crystal \textit{electric} field and nuclear \textit{hyperfine} field, respectively. The resonances have Lorentzian line shape, indicating an \textit{insulating} environment for the Eu$^{2+}$ ions. For $0.003\lesssim x\lesssim 0.07$, as $x$ increases, the ESR lines broaden due to local distortions caused by the Eu/Ca ions substitution. For $0.07\lesssim x\lesssim 0.30$, the lines broaden further and the spectra gradually change from Lorentzian to Dysonian resonances, suggesting a coexistence of both \textit{insulating} and \textit{metallic} environments for the Eu$^{2+}$ ions. In contrast to Ca$_{1-x}$Gd$_{x}$B$_{6}$, the \textit{fine} structure is still observable up to $x\approx 0.15$. For $x\gtrsim 0.30 $ the \textit{fine} and \textit{hyperfine} structures are no longer observed, the line width increases, and the line shape is purely Dysonian anticipating the \textit{semimetallic} character of EuB$_{6}$. This broadening is attributed to a spin-flip scattering relaxation process due to the exchange interaction between conduction and Eu$^{2+}$ $4f$ electrons. High field ESR measurements for $x\gtrsim 0.15$ reveal smaller and anisotropic line widths, which are attributed to magnetic polarons and Fermi surface effects, respectively.