Surface Pyroelectricity in Cubic SrTiO3

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. Symmetry prohibits pyroelectricity from being present in the majority of crystallographic material classes, including centrosymmetric SrTiO3. Nonetheless, this study reports the emergence of pyroelectricity at the surface of SrTiO3 where the lattice symmetry is broken. The discovery paves the way for observing pyroelectricity and piezoelectricity in any material, independent of its bulk lattice symmetry.