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Deterministic fabrication of arbitrary vertical heterostructures of two-dimensional Ruddlesden–Popper halide perovskites

Nature Nanotechnology volume 16, pages 159–165 (2021)Cite this article

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Abstract

Ruddlesden–Popper lead halide perovskites have emerged as a new class of two-dimensional semiconductors with tunable optoelectronic properties, potentially offering unlimited heterostructure configurations for exploration. However, the practical realization of such heterostructures is challenging because of the difficulty in achieving controllable direct synthesis or van der Waals integration of halide perovskites due to their mobile and fragile crystal lattices. Here we report direct growth of large-area nanosheets of diverse phase-pure Ruddlesden–Popper perovskites with thicknesses down to one monolayer at the solution–air interface and a reliable approach for gently transferring and stacking these nanosheets. These advances enable the deterministic fabrication of arbitrary vertical heterostructures and multi-heterostructures of Ruddlesden–Popper perovskites with greater structural degrees of freedom that define the electronic structures of the heterojunctions. Such rationally designed heterostructures exhibit interesting interlayer properties, such as interlayer carrier transfer and reduction of the photoluminescence linewidth, and could enable the exploration of exciton physics and optoelectronic applications.

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Fig. 1: Floating growth of large-area nanosheets of various phases of 2D RP perovskites.
Fig. 2: Pick-up of the floating RP perovskite thin sheets and characterization after transfer onto Si/SiO2 substrates.
Fig. 3: Fabrication and characterization of several types of vertical heterostructure of 2D RP perovskites.
Fig. 4: Fabrication and characterization of a (BA)2PbI4/(BA)2(MA)2Pb3I10/(BA)2(MA)Pb2I7 multi-heterostructure.

Data availability

The data presented in the Supplementary Information that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work is supported by the Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Award Number DE-FG02-09ER46664.

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Authors and Affiliations

  1. Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA

    Dongxu Pan, Yongping Fu, Natalia Spitha, Yuzhou Zhao, Chris R. Roy, Darien J. Morrow, Daniel D. Kohler, John C. Wright & Song Jin

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  1. Dongxu Pan
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Contributions

S.J., Y.F. and D.P. conceived the research. D.P. and Y.F. designed and conducted the experiments and analysed the experimental results. N.S. and D.D.K. conducted PLE and TRPL measurements and analysed the results. Y.Z. designed and built the transfer stage. D.J.M. and J.C.W. performed PL line profile analysis and assisted with the analysis of various spectroscopic results. C.R.R. helped with PL mapping. S.J. and J.C.W. supervised the project. D.P., Y.F. and S.J. co-wrote the manuscript with input from all authors.

Corresponding authors

Correspondence to Yongping Fu, John C. Wright or Song Jin.

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Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Nanotechnology thanks Dehui Li, Biwu Ma and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–22 and Table 1.

Supplementary Video 1

Supplementary Video 1 shows the growth of the nanosheets of (HA)2PbI4 in real time as they are floating on the precursor solution droplet. Layer-by-layer growth propagation across the whole sheets could be observed.

Supplementary Video 2

Supplementary Video 2 shows the growth of (HA)2(FA)Pb2I7. The video was recorded in real time in dark field with a 232 μm × 174 μm field of view. As the growth proceeded further, the thick spiral plate formed through dislocation-driven growth thickened, but the thin sheets next to it shrunk in size, in an Ostwald ripening process.

Source data

Source Data Fig. 1

Experimental data points of the PL spectra shown in Fig. 1c.

Source Data Fig. 2

Experimental data points of the extracted AFM height profiles shown in Fig. 2g–k.

Source Data Fig. 3

Experimental data points of the PL spectra shown in Fig. 3a(iv), b(iv) and c(iv).

Source Data Fig. 4

Experimental data points of the PL spectra shown in Fig. 4g.

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Pan, D., Fu, Y., Spitha, N. et al. Deterministic fabrication of arbitrary vertical heterostructures of two-dimensional Ruddlesden–Popper halide perovskites. Nat. Nanotechnol. 16, 159–165 (2021). https://doi.org/10.1038/s41565-020-00802-2

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