Surface Pyroelectricity in Cubic SrTiO₃

Abstract Symmetry‐imposed restrictions on the number of available pyroelectric and piezoelectric materials remain a major limitation as 22 out of 32 crystallographic material classes exhibit neither pyroelectricity nor piezoelectricity. Yet, by breaking the lattice symmetry it is possible to circumvent this limitation. Here, using a unique technique for measuring transient currents upon rapid heating, direct experimental evidence is provided that despite the fact that bulk SrTiO₃ is not pyroelectric, the (100) surface of TiO₂‐terminated SrTiO₃ is intrinsically pyroelectric at room temperature. The pyroelectric layer is found to be ≈1 nm thick and, surprisingly, its polarization is comparable with that of strongly polar materials such as BaTiO₃. The pyroelectric effect can be tuned ON/OFF by the formation or removal of a nanometric SiO₂ layer. Using density functional theory, the pyroelectricity is found to be a result of polar surface relaxation, which can be suppressed by varying the lattice symmetry breaking using a SiO₂ capping layer. The observation of pyroelectricity emerging at the SrTiO₃ surface also implies that it is intrinsically piezoelectric. These findings may pave the way for observing and tailoring piezo‐ and pyroelectricity in any material through appropriate breaking of symmetry at surfaces and artificial nanostructures such as heterointerfaces and superlattices.