Quantum spin liquid and electric quadrupolar states of single crystal Tb$_{2+x}$Ti$_{2-x}$O$_{7+y}$

TL;DR

This study investigates the ground states of Tb$_{2+x}$Ti$_{2-x}$O$_{7+y}$, revealing a dome-shaped electric quadrupolar phase boundary and suggesting a quantum spin-liquid state in a specific stoichiometry range.

Contribution

It provides detailed phase diagrams of Tb$_{2+x}$Ti$_{2-x}$O$_{7+y}$, linking off-stoichiometry to quantum spin-liquid and quadrupolar states through specific heat measurements.

Findings

Quadrupolar phase has a dome-shaped boundary in the x-T diagram.

Quantum spin-liquid state exists for x < -0.0025.

Phase transition between states is first-order.

Abstract

The ground states of the frustrated pyrochlore oxide Tb$_{2+x}$Ti$_{2-x}$O$_{7+y}$, sensitively depending on the small off-stoichiometry parameter $x$, have been studied by specific heat measurements using well characterized samples. Single crystal Tb$_{2+x}$Ti$_{2-x}$O$_{7+y}$ boules grown by the standard floating zone technique are shown to exhibit concentration ($x$) gradient. This off-stoichiometry parameter is determined by precisely measuring the lattice constant of small samples cut from a crystal boule. Specific heat shows that the phase boundary of the electric quadrupolar state has a dome structure in the $x$-$T$ phase diagram with the highest $T_{\text{c}} \simeq 0.5$ K at about $x = 0.01$. This phase diagram suggests that the putative U(1) quantum spin-liquid state of Tb$_{2+x}$Ti$_{2-x}$O$_{7+y}$ exists in the range $x<x_{\text{c}} \simeq -0.0025 $, which is separated from the quadrupolar state via a first-order phase-transition line $x=x_{\text{c}}$.