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Two-dimensional halide perovskite lateral epitaxial heterostructures

Abstract

Epitaxial heterostructures based on oxide perovskites and III–V, II–VI and transition metal dichalcogenide semiconductors form the foundation of modern electronics and optoelectronics1,2,3,4,5,6,7. Halide perovskites—an emerging family of tunable semiconductors with desirable properties—are attractive for applications such as solution-processed solar cells, light-emitting diodes, detectors and lasers8,9,10,11,12,13,14,15. Their inherently soft crystal lattice allows greater tolerance to lattice mismatch, making them promising for heterostructure formation and semiconductor integration16,17. Atomically sharp epitaxial interfaces are necessary to improve performance and for device miniaturization. However, epitaxial growth of atomically sharp heterostructures of halide perovskites has not yet been achieved, owing to their high intrinsic ion mobility, which leads to interdiffusion and large junction widths18,19,20,21, and owing to their poor chemical stability, which leads to decomposition of prior layers during the fabrication of subsequent layers. Therefore, understanding the origins of this instability and identifying effective approaches to suppress ion diffusion are of great importance22,23,24,25,26. Here we report an effective strategy to substantially inhibit in-plane ion diffusion in two-dimensional halide perovskites by incorporating rigid π-conjugated organic ligands. We demonstrate highly stable and tunable lateral epitaxial heterostructures, multiheterostructures and superlattices. Near-atomically sharp interfaces and epitaxial growth are revealed by low-dose aberration-corrected high-resolution transmission electron microscopy. Molecular dynamics simulations confirm the reduced heterostructure disorder and larger vacancy formation energies of the two-dimensional perovskites in the presence of conjugated ligands. These findings provide insights into the immobilization and stabilization of halide perovskite semiconductors and demonstrate a materials platform for complex and molecularly thin superlattices, devices and integrated circuits.

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Fig. 1: 2D halide perovskite lateral heterostructures stabilized by conjugated ligands.
Fig. 2: TEM characterization of the (2T)2PbI4–(2T)2PbBr4 heterostructure.
Fig. 3: Periodic ripples in (2T)2PbI4–(2T)2PbBr4 lateral heterostructures.
Fig. 4: The library of 2D halide perovskite lateral heterostructures, multiheterostructures and superlattices.
Fig. 5: Proposed band alignments and electrical characteristics of the heterostructures.

Data availability

All data related to this study are available from the corresponding author on reasonable request.

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Acknowledgements

This work is supported by the Office of Naval Research (grant no. N00014-19-1-2296, programme managers P. Armistead and J. Parker), the National Science Foundation (grant no. 1939986-ECCS, programme manager P. Lane), and at Purdue University, the Davidson School of Chemical Engineering, College of Engineering, and the Birck Nanotechnology Center. TEM work is supported by funding from the National Science Foundation of China (grant no. 21805184), the National Science Foundation Shanghai (grant no. 18ZR1425200) and the Center for High-resolution Electron Microscopy (CħEM) at ShanghaiTech University (grant no. EM02161943). P.Y. acknowledges support from the US Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-05CH11231. J.K acknowledges support from the Air Force Office of Scientific Research (FATE MURI, grant no. FA9550-15-1-0514). B.M.S. acknowledges support from the Air Force Office of Scientific Research (grant no. FA9550-18-S-0003, programme manager K. Caster). We thank L. Huang, B. Boudouris and S. Li for discussions.

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E.S. synthesized and characterized the 2D perovskite materials; B.Y. and Y.Y. performed TEM characterization and data analysis; S.B.S. and B.M.S. performed molecular dynamics simulations and data analysis; Y. Gao performed organic ligand synthesis; A., Y. Guo, C.S., M.L., P.Y. and J.K. participated in materials characterization and data analysis; E.S. and L.D. wrote the manuscript; all authors read and revised the manuscript.

Corresponding authors

Correspondence to Brett M. Savoie or Yi Yu or Letian Dou.

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Shi, E., Yuan, B., Shiring, S.B. et al. Two-dimensional halide perovskite lateral epitaxial heterostructures. Nature 580, 614–620 (2020). https://doi.org/10.1038/s41586-020-2219-7

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