Di Nuzzo Daniele, Cui Linsong, Greenfield Jake L, Zhao Baodan, Friend Richard H, Meskers Stefan C J
Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, United Kingdom.
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
ACS Nano. 2020 Jun 23;14(6):7610-7616. doi: 10.1021/acsnano.0c03628. Epub 2020 Jun 3.
Hybrid organic-inorganic perovskites allow the synthesis of high-quality, nanostructured semiconducting films via easily accessible solution-based techniques. This has allowed tremendous development in optoelectronic applications, primarily solar cells and light-emitting diodes. Allowed by the ease of access to nanostructure, chirality has recently been introduced in semiconducting perovskites as a promising way to obtain advanced control of charge and spin and for developing circularly polarized light sources. Circular polarization of photoluminescence (CPL) is a powerful tool to probe the electronic structure of materials. However, CPL in chiral perovskites has been scarcely investigated, and a study in bulk thin films and at room temperature is still missing. In this work, we fabricate bromine-based chiral perovskites by using a bulky chiral organic cation mixed with CsBr, resulting in Ruddlesden-Popper perovskite thin films. We measure CPL on these films at room temperature and, by using unpolarized photoexcitation, we record a degree of circular polarization of photoluminescence in the order of 10 and provide a full spectral characterization of CPL. Our results show that chirality is imparted on the electronic structure of the semiconductor; we hypothesize that the excess in polarization of emitted light originates from the charge in the photogenerated Wannier exciton describing an orbit in a symmetry-broken environment. Furthermore, our experiments allow the direct measurement of the magnetic dipole moment of the optical transition, which we estimate to be ≥0.1 . Finally, we discuss the implications of our findings on the development of chiral semiconducting perovskites as sources of circularly polarized light.
有机-无机杂化钙钛矿能够通过易于实现的基于溶液的技术合成高质量的纳米结构半导体薄膜。这使得光电子应用领域取得了巨大发展,主要是太阳能电池和发光二极管。由于易于制备纳米结构,手性最近被引入到半导体钙钛矿中,这是一种有望实现对电荷和自旋进行先进控制以及开发圆偏振光源的方法。光致发光的圆偏振(CPL)是探测材料电子结构的有力工具。然而,手性钙钛矿中的CPL很少被研究,并且在室温下对体相薄膜的研究仍然缺失。在这项工作中,我们通过使用与CsBr混合的大体积手性有机阳离子制备了溴基手性钙钛矿,得到了Ruddlesden-Popper钙钛矿薄膜。我们在室温下测量了这些薄膜的CPL,并且通过非偏振光激发,记录了光致发光圆偏振度约为10,并提供了CPL的全光谱表征。我们的结果表明手性被赋予了半导体的电子结构;我们推测发射光偏振的过量源于光生万尼尔激子中的电荷,该电荷在对称破缺环境中描绘一个轨道。此外,我们的实验允许直接测量光学跃迁的磁偶极矩,我们估计其≥0.1。最后,我们讨论了我们的发现对开发作为圆偏振光源的手性半导体钙钛矿的意义。