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

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 $x=x_{\text{c}}$.

5 pages, 4 figures