Rashba Band Splitting and Bulk Photovoltaic Effect Induced by Halogen Bonds in Hybrid Layered Perovskites
Jie Xue
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorYuling Huang
SUSTech Energy Institute for Carbon Neutrality, Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen, 518055 P. R. China
Search for more papers by this authorDr. Yang Liu
Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 P. R. China
Search for more papers by this authorZhongwei Chen
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorDr. Herman H.-Y. Sung
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorProf. Dr. Ian D. Williams
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorProf. Dr. Zonglong Zhu
Department of Chemistry, City University of Hong Kong, Kowloon, 999077 Hong Kong Hong Kong
Search for more papers by this authorCorresponding Author
Prof. Dr. Lingling Mao
Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xihan Chen
SUSTech Energy Institute for Carbon Neutrality, Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen, 518055 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Haipeng Lu
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorJie Xue
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorYuling Huang
SUSTech Energy Institute for Carbon Neutrality, Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen, 518055 P. R. China
Search for more papers by this authorDr. Yang Liu
Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 P. R. China
Search for more papers by this authorZhongwei Chen
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorDr. Herman H.-Y. Sung
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorProf. Dr. Ian D. Williams
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorProf. Dr. Zonglong Zhu
Department of Chemistry, City University of Hong Kong, Kowloon, 999077 Hong Kong Hong Kong
Search for more papers by this authorCorresponding Author
Prof. Dr. Lingling Mao
Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xihan Chen
SUSTech Energy Institute for Carbon Neutrality, Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen, 518055 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Haipeng Lu
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077 Hong Kong (SAR), China
Search for more papers by this authorGraphical Abstract
We reported a new series of 2D perovskites featuring thickness-dependent hydrogen and halogen bonding interactions. The strength of non-covalent interaction has a direct impact on the structure symmetry and optoelectronic properties. Stronger halogen interaction leads to centrosymmetry, whereas weaker halogen bonds give rise to non-centrosymmetric structures, Rashba splitting, suppressed radiative recombination, and bulk photovoltaic effect.
Abstract
Non-covalent interactions play an essential role in directing the self-assembly of hybrid organic–inorganic crystals. In hybrid halide perovskites, hydrogen bonding has been the paramount non-covalent interaction. Here, we show another non-covalent interaction, namely, the halogen bond interaction, that directs a symmetry-breaking assembly in a new series of two-dimensional (2D) perovskites (ICH2CH2NH3)2(CH3NH3)n−1PbnI3n+1 (n is the layer thickness, n=1–4). Structural analysis shows that the halogen bond strength varies with the layer thickness. For the odd number (n=1, 3) layered perovskites, stronger halogen interaction leads to centrosymmetric structures, whereas for the n=2 layered perovskites, weaker halogen bonds result in non-centrosymmetric structures. Transient reflection spectroscopy shows a suppressed radiative recombination rate (k2≈0) and prolonged spin lifetime for n=2 structure, suggesting an enhanced Rashba band splitting effect. The structural asymmetry is further confirmed with a reversible bulk photovoltaic effect. Our work provides a new design strategy to enable hybrid perovskites with emerging properties and functionalities associated with structural asymmetry.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Supporting Information
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| anie202304486-sup-0001-checkCIF_n_4.pdf279.3 KB | Supporting Information |
| anie202304486-sup-0001-EIA_n_2(2).cif2.1 MB | Supporting Information |
| anie202304486-sup-0001-EIA_n_3(2).cif416.8 KB | Supporting Information |
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