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

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