Semiconductor quantum-well structures and superlattices are key building blocks in modern optoelectronics, but it is difficult to simultaneously realize defect-free epitaxial growth while fine tuning the chemical composition, layer thickness and band structure of each layer to achieve the desired performance. Here we demonstrate the modulation of the electronic structure—and consequently the optical properties—of organic semiconducting building blocks that are incorporated between the layers of perovskites through a facile solution processing step. Self-aggregation of the conjugated organic molecules is suppressed by functionalization with sterically demanding groups and single crystalline organic–perovskite hybrid quantum wells (down to one-unit-cell thick) are obtained. The energy and charge transfers between adjacent organic and inorganic layers are shown to be fast and efficient, owing to the atomically flat interface and ultrasmall interlayer distance of the perovskite materials. The resulting two-dimensional hybrid perovskites are very stable due to protection given by the bulky hydrophobic organic groups.
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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 1846391 [(4Tm)2PbI4], 1846392 [(BTm)2PbI4] and 1861843 [(2T)2PbI4]. Copies of the data can be obtained free of charge through https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the Article and its Supplementary Information or from the corresponding author on reasonable request.
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This work is supported by the US Office of Naval Research (award no. N00014-19-1-2296 to L.D.; programme managers: P. Armistead and J. Parker), the Davidson School of Chemical Engineering, College of Engineering and the Birck Nanotechnology Center of Purdue University. L.H., J.S and S.D acknowledge the support from US Department of Energy, Office of Basic Energy Sciences through award no. DE-SC0016356. B.W.B. acknowledges the support from US Air Force Office of Scientific Research (award no. FA9550-15-1-0449). The work on the single-crystal X-ray diffractions was supported by the National Science Foundation (award no. CHE 1625543). Work by V.B. and R.S. was financially supported by the National Science Foundation under award no. DMR-1729297. An award of computer time was provided by the Innovative and Novel Computational Impact on Theory and Experiment Program. This research used resources of the Argonne Leadership Computing Facility, which is a Department of Energy Office of Science User Facility supported under contract no. DE-AC02-06CH11357. S.J. thanks the Deutsche Forschungsgemeinschaft (German Research Foundation) for a postdoctoral fellowship (award no. 393196393). Transmission electron microscopy work is supported by the Center for High-resolution Electron Microscopy at ShanghaiTech University. The authors thank G. Wiederrecht and R. Schaller for assistance in the streak camera measurements; D. Zemlyanov for the ultraviolet photoelectron spectroscopy measurements; D. Kumar for grazing-incidence wide-angle X-ray scattering data processing; J. Mei for cyclic voltammetry measurements; and S. Beaudoin for atomic force microscopy measurements.
The authors declare no competing interests.
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Supplementary Figs., tables, methods and 1H, 13C NMR and FT-IR spectra.
CIF for compound (2T)2PbI4; CCDC reference: 1861843.
CIF for compound (4Tm)2PbI4; CCDC reference: 1846391.
CIF for compound (BTm)2PbI4; CCDC reference: 1846392.
Water immersion test.
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Gao, Y., Shi, E., Deng, S. et al. Molecular engineering of organic–inorganic hybrid perovskites quantum wells. Nat. Chem. 11, 1151–1157 (2019) doi:10.1038/s41557-019-0354-2