Sercel Peter C, Vardeny Zeev Valy, Efros Alexander L
Department of Applied Physics and Materials Science, California Institute of Technology, Pasadena, California 91125, USA.
Department of Physics and Astronomy, University of Utah, Salt Lake City, UT 84112, USA.
Nanoscale. 2020 Sep 17;12(35):18067-18078. doi: 10.1039/d0nr05232a.
We demonstrate theoretically that non-chiral perovskite layers can exhibit circular dichroism (CD) in the absence of a magnetic field and without chiral activation by chiral molecules. The effect is shown to be due to splitting of helical excitonic states which can form in structures of orthorhombic or lower symmetry that exhibit Rashba spin effects. The selective coupling of these helical exciton states to helical light is shown to give rise to circular dichroism. Polarization dependent absorption is shown to occur due to the combined effect of Rashba splitting, in-plane symmetry breaking, and the effect of the exciton momentum on its fine structure, which takes the form of Zeeman splitting in an effective magnetic field. This phenomenon, which can be considered as a manifestation of extrinsic chirality, results in significant CD with an anisotropy factor of up to 30% in orthorhombic perovskite layers under off-normal, top illumination conditions, raising the possibility of its observation in non-chiral perovskite structures.
我们从理论上证明,非手性钙钛矿层在没有磁场且没有手性分子进行手性激活的情况下,也能表现出圆二色性(CD)。结果表明,这种效应是由于在具有Rashba自旋效应的正交晶系或更低对称性结构中形成的螺旋激子态分裂所致。这些螺旋激子态与螺旋光的选择性耦合会产生圆二色性。由于Rashba分裂、面内对称性破缺以及激子动量对其精细结构的影响(在有效磁场中表现为塞曼分裂)的综合作用,会出现偏振依赖吸收。这种现象可被视为外在手性的一种表现,在非正入射的顶部照明条件下,正交晶系钙钛矿层中会产生高达30%的各向异性因子的显著圆二色性,这增加了在非手性钙钛矿结构中观察到该现象的可能性。