We study the spontaneous scalarization of spherically symmetric, static and asymptotically Anti-de Sitter (aAdS) black holes in a scalar-tensor gravity model with non-mininal coupling of the form $phi^2left(alpha{cal R} + gamma {cal G}right)$, where $alpha$ and $gamma$ are constants, while ${cal R}$ and ${cal G}$ are the Ricci scalar and Gauss-Bonnet term, respectively. Since these terms act as an effective ``mass for the scalar field, non-trivial values of the scalar field in the black hole space-time are possible for {it a priori} vanishing scalar field mass. In particular, we demonstrate that the scalarization of an aAdS black hole requires the curvature invariant $-left(alpha{cal R} + gamma {cal G}right)$ to drop below the Breitenlohner-Freedman bound close to the black hole horizon, while it asymptotes to a value well above the bound. The dimension of the dual operator on the AdS boundary depends on the parameters $alpha$ and $gamma$ and we demonstrate that -- for fixed operator dimension -- the expectation value of this dual operator increases with decreasing temperature of the black hole, i.e. of the dual field theory. When taking backreaction of the space-time into account, we find that the scalarization of the black hole is the dual description of a phase transition in a strongly coupled quantum system, i.e. corresponds to a holographic phase transition. A possible application are liquid-gas quantum phase transitions, e.g. in $^4$He. Finally, we demonstrate that extremal black holes with $AdS_2times S^2$ near-horizon geometry {it cannot support regular scalar fields on the horizon} in the scalar-tensor model studied here.
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