Static Rashba Effect by Surface Reconstruction and Photon Recycling in the Dynamic Indirect Gap of APbBr3 (A = Cs, CH3NH3) Single Crystals
- Hongsun Ryu ,
- Dae Young ParkDae Young ParkDepartment of Energy Science, Sungkyunkwan University, Suwon 16419, South KoreaMore by Dae Young Park,
- Kyle M. McCallKyle M. McCallDepartment of Chemistry, Northwestern University, Evanston, Illinois 60208, United StatesLaboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Zurich 8093, SwitzerlandLaboratory for Thin Films and Photovoltaics, Empa-Swiss Federal Laboratories for Materials Science and Technology, Dübendorf CH-8600, SwitzerlandMore by Kyle M. McCall,
- Hye Ryung ByunHye Ryung ByunDepartment of Physics, Sogang University, Seoul 04107, South KoreaMore by Hye Ryung Byun,
- Yongjun LeeYongjun LeeDepartment of Energy Science, Sungkyunkwan University, Suwon 16419, South KoreaMore by Yongjun Lee,
- Tae Jung KimTae Jung KimDepartment of Physics, Kyung Hee University, Seoul 02447, South KoreaMore by Tae Jung Kim,
- Mun Seok JeongMun Seok JeongDepartment of Energy Science, Sungkyunkwan University, Suwon 16419, South KoreaMore by Mun Seok Jeong,
- Jeongyong KimJeongyong KimDepartment of Energy Science, Sungkyunkwan University, Suwon 16419, South KoreaMore by Jeongyong Kim,
- Mercouri G. KanatzidisMercouri G. KanatzidisDepartment of Chemistry, Northwestern University, Evanston, Illinois 60208, United StatesMore by Mercouri G. Kanatzidis, and
- Joon I. Jang*Joon I. Jang*Email: [email protected]Department of Physics, Sogang University, Seoul 04107, South KoreaMore by Joon I. Jang
Abstract
Recently, halide perovskites have gained significant attention from the perspective of efficient spintronics owing to the Rashba effect. This effect occurs as a consequence of strong spin–orbit coupling under a noncentrosymmetric environment, which can be dynamic and/or static. However, there exist intense debates on the origin of broken inversion symmetry since the halide perovskites typically crystallize into a centrosymmetric structure. In order to clarify the issue, we examine both dynamic and static effects in the all-inorganic CsPbBr3 and organic–inorganic CH3NH3PbBr3 (MAPbBr3) perovskite single crystals by employing temperature- and polarization-dependent photoluminescence excitation spectroscopy. The perovskite single crystals manifest the dynamic effect by photon recycling in the indirect Rashba gap, causing dual peaks in the photoluminescence. However, the effect vanishes in CsPbBr3 at low temperatures (<50 K) accompanied by a striking color change of the crystal, arising presumably from lower degrees of freedom for inversion symmetry breaking associated with the thermal motion of the spherical Cs cation compared with the polar MA cation in MAPbBr3. We also show that the static Rashba effect occurs only in MAPbBr3 below 90 K, presumably due to surface reconstruction via MA-cation ordering, which likely extends across a few layers from the crystal surface to the interior. We further demonstrate that this static Rashba effect can be completely suppressed upon surface treatment with polymethyl methacrylate (PMMA) coating. We believe that our results provide a rationale for the Rashba effects in halide perovskites.
Cited By
This article is cited by 9 publications.
- Donggyu Kim, Hongsun Ryu, Soo Yeon Lim, Kyle M. McCall, Jongwoo Park, Sungdo Kim, Tae Jung Kim, Jeongyong Kim, Yong Soo Kim, Mercouri G. Kanatzidis, Hyeonsik Cheong, Joon I. Jang. On the Origin of Room-Temperature Amplified Spontaneous Emission in CsPbBr3 Single Crystals. Chemistry of Materials 2021, 33 (18) , 7185-7193. https://doi.org/10.1021/acs.chemmater.1c00591
- Hongsun Ryu, Hye Ryung Byun, Kyle M. McCall, Dae Young Park, Tae Jung Kim, Mun Seok Jeong, Mercouri G. Kanatzidis, Joon I. Jang. Role of the A-Site Cation in Low-Temperature Optical Behaviors of APbBr3 (A = Cs, CH3NH3). Journal of the American Chemical Society 2021, 143 (5) , 2340-2347. https://doi.org/10.1021/jacs.0c11980
- Min Zhao, Hua Wang, Gaoyang Gou, Xiangdong Ding, Jun Sun. Emergence of bulk photovoltaic effect in anion-ordered perovskite sulfur diiodide MASbSI2 with spontaneous out-of-plane ferroelectricity. Materials Today Physics 2021, 21 , 100459. https://doi.org/10.1016/j.mtphys.2021.100459
- Ajay K. Poonia, Megha Shrivastava, Wasim J. Mir, J. Aneesh, Angshuman Nag, K. V. Adarsh. Intervalley polaronic biexcitons in metal halide perovskite quantum dots. Physical Review B 2021, 104 (16) https://doi.org/10.1103/PhysRevB.104.L161407
- Zhengjie Huang, Shai R. Vardeny, Tonghui Wang, Zeeshan Ahmad, Ashish Chanana, Eric Vetter, Shijia Yang, Xiaojie Liu, Giulia Galli, Aram Amassian, Z. Valy Vardeny, Dali Sun. Observation of spatially resolved Rashba states on the surface of CH 3 NH 3 PbBr 3 single crystals. Applied Physics Reviews 2021, 8 (3) , 031408. https://doi.org/10.1063/5.0053884
- Kai Leng, Runlai Li, Shu Ping Lau, Kian Ping Loh. Ferroelectricity and Rashba effect in 2D organic–inorganic hybrid perovskites. Trends in Chemistry 2021, 3 (9) , 716-732. https://doi.org/10.1016/j.trechm.2021.05.003
- Sizhan Liu, Alexander R. DeFilippo, Mahalingam Balasubramanian, Zhenxian Liu, SuYin Grass Wang, Yu‐Sheng Chen, Stella Chariton, Vitali Prakapenka, Xiangpeng Luo, Liuyan Zhao, Jovan San Martin, Yixiong Lin, Yong Yan, Sanjit K. Ghose, Trevor A. Tyson. High‐Resolution In‐Situ Synchrotron X‐Ray Studies of Inorganic Perovskite CsPbBr 3 : New Symmetry Assignments and Structural Phase Transitions. Advanced Science 2021, 8 (18) , 2003046. https://doi.org/10.1002/advs.202003046
- Eve M. Mozur, James R. Neilson. Cation Dynamics in Hybrid Halide Perovskites. Annual Review of Materials Research 2021, 51 (1) , 269-291. https://doi.org/10.1146/annurev-matsci-080819-012808
- Y. H. Shin, Halim Choi, C. Park, D. Park, M. S. Jeong, H. Nojiri, Z. Yang, Y. Kohama, Yongmin Kim. Combination of optical transitions of polarons with Rashba effect in methylammonium lead trihalide perovskites under high magnetic fields. Physical Review B 2021, 104 (3) https://doi.org/10.1103/PhysRevB.104.035205