Two-dimensional organic semiconductor-incorporated perovskites are a promising family of hybrid materials for optoelectronic applications, owing in part to their inherent quantum well architecture. Tuning their structures and properties for specific properties, however, has remained challenging. Here we report a general method to tune the dimensionality of phase-pure organic semiconductor-incorporated perovskite single crystals during their synthesis, by judicious choice of solvent. The length of the conjugated semiconducting organic cations and the dimensionality (n value) of the inorganic layers can be manipulated at the same time. The energy band offsets and exciton dynamics at the organic–inorganic interfaces can therefore be precisely controlled. Furthermore, we show that longer and more planar π-conjugated organic cations induce a more rigid inorganic crystal lattice, which leads to suppressed exciton–phonon interactions and better optoelectronic properties as compared to conventional two-dimensional perovskites. As a demonstration, optically driven lasing behaviour with substantially lower lasing thresholds was realized.
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Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers CCDC 2151387 ((2T)2(MA)Pb2I7), CCDC 2151388 ((2T)2(MA)2Pb3I10), CCDC 2151389 ((3T)2PbI4), CCDC 2151390 ((3T)2(MA)Pb2I7), CCDC 2151391 ((4Tm)2(MA)Pb2I7) and CCDC 2191050 ((3T)2(MA)2Pb3I10). Crystallographic data can be obtained free of charge through https://www.ccdc.cam.ac.uk/structures/. All the input and output files relevant to the theoretical simulations in this work have been deposited to NOMAD; access the following for more information: https://doi.org/10.17172/NOMAD/2023.03.18-1. All other data are available in the manuscript or Supplementary Information. All materials are available upon request to L.D. Source data are provided with this paper.
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We thank D. Mitzi and M. K. Jana for help with single-crystal X-ray diffraction studies. We also thank K. Zhao and X. Wang at the School of Mechanical Engineering, Purdue University for the nanoindentation experiments. The work of J.Y.P. and L.D. is supported by the National Science Foundation under award no. 2110706-DMR (crystal synthesis). The work of L.J. and L.H. is supported by the US Department of Energy, Office of Basic Energy Sciences under award no. DE-SC0022082 (spectroscopy characterization). The work of R.S. and V.B. is supported by the National Science Foundation under award no. DMR-1729297 (DFT calculations). The work of J.L. and Y.S.Z. is supported by the New Cornerstone Science Foundation through the Xplorer Prize. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy Office of Science User Facility operated under contract no. DE-AC02-05CH11231. The single-crystal X-ray diffractometer was purchased with support from the National Science Foundation under award no. CHE 1625543. This research used resources of the Advanced Light Source, which is a US Department of Energy Office of Science User Facility, under contract no. DE-AC02-05CH11231.
V.B. is a member of the executive board of MS1P e.V., the non-profit organization that licences the FHI-aims electronic structure code used in this work. V.B. does not receive any financial gains from this position. L.D. and Y.G. are inventors of a patent application (US10618889B2, active) related to the molecular design of the organic cations and the synthesis of the hybrid crystals presented in this work. All other authors declare no competing interests.
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Supplementary Figs. 1–36, Tables 1–10, references and appendix.
Crystal structure for 2T n = 2.
Crystal structure for 2T n = 3.
Crystal structure for 3T n = 1.
Crystal structure for 3T n = 2.
Crystal structure for 3T n = 3.
Crystal structure for 4Tm n = 2.
Graph source data for Supplementary Fig. 11.
Graph source data for Supplementary Fig. 12.
Graph source data for Supplementary Fig. 29.
Graph source data for Supplementary Fig. 30.
Graph source data for Supplementary Fig. 31.
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Graph source data for Supplementary Fig. 33.
Graph source data for Supplementary Fig. 34.
Graph source data for Supplementary Fig. 35.
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Park, J.Y., Song, R., Liang, J. et al. Thickness control of organic semiconductor-incorporated perovskites. Nat. Chem. 15, 1745–1753 (2023). https://doi.org/10.1038/s41557-023-01311-0