Department of Chemistry, Columbia University, New York, NY, 10027, USA.
Department of Energy Conversion and Storage, Technical University of Denmark, Roskilde, 4000, Denmark.
Adv Mater. 2019 Nov;31(44):e1904733. doi: 10.1002/adma.201904733. Epub 2019 Sep 18.
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 SrTiO is not pyroelectric, the (100) surface of TiO -terminated SrTiO 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 BaTiO . The pyroelectric effect can be tuned ON/OFF by the formation or removal of a nanometric SiO 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 SiO capping layer. The observation of pyroelectricity emerging at the SrTiO 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.
对称施加的限制可用的热释电和压电材料仍然是一个主要的限制,因为 22 出 32 个晶体学材料类既没有热释电性也没有压电性。然而,通过打破晶格对称性,可以规避这一限制。在这里,使用一种独特的测量方法来测量快速加热时的瞬态电流,直接提供了实验证据表明,尽管大块 SrTiO 不是热释电的,但 TiO 终止的 SrTiO 的(100)表面在室温下本质上是热释电的。发现热释电层约为 1nm 厚,令人惊讶的是,其极化强度与 BaTiO 等强极性材料相当。通过形成或去除纳米级 SiO 层,可以调节热释电效应的开/关。使用密度泛函理论,发现热释电性是由于表面的极化弛豫引起的,可以通过使用 SiO 覆盖层来改变晶格对称性的破坏来抑制。在 SrTiO 表面观察到热释电性的出现也意味着它本质上是压电的。这些发现可能为在任何材料中观察和调整压电和热释电性铺平道路,通过在表面和人工纳米结构(如异质结和超晶格)上适当打破对称性来实现。