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Molecular engineering of organic–inorganic hybrid perovskites quantum wells

Nature Chemistry volume 11, pages 1151–1157 (2019)Cite this article

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Abstract

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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Fig. 1: The structures of the conjugated organic ligands and 2D hybrid perovskites.
Fig. 2: Optical properties of the hybrid halide perovskites quantum wells.
Fig. 3: Time- and spectral-resolved PL spectroscopy.
Fig. 4: Stability of hybrid halide perovskite quantum wells.

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Data availability

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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Acknowledgements

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.

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  1. Alexander Liebman-Peláez

    Present address: Department of Physics, University of California, Berkeley, CA, USA

Authors and Affiliations

  1. Charles D. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, USA

    Yao Gao, Enzheng Shi, Stephen B. Shiring, Bryan W. Boudouris, Brett M. Savoie & Letian Dou

  2. Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Shibin Deng, Jordan M. Snaider, Matthias Zeller, Bryan W. Boudouris & Libai Huang

  3. School of Physical Science and Technology, ShanghaiTech University, Shanghai, China

    Chao Liang, Biao Yuan & Yi Yu

  4. Department of Chemistry, Duke University, Durham, NC, USA

    Ruyi Song & Volker Blum

  5. Department of Mechanical Engineering and Materials Science, Duke University, Durham, NC, USA

    Svenja M. Janke & Volker Blum

  6. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Alexander Liebman-Peláez & Chenhui Zhu

  7. School of Materials Engineering, Purdue University, West Lafayette, IN, USA

    Pilsun Yoo & Peilin Liao

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Contributions

L.D. conceived the idea and supervised the project. Y.G. carried out the materials synthesis, structural characterizations and data analysis. E.S. synthesized the nanocrystals. J.S., S.D. and L.H. carried out the ultrafast spectroscopy measurements and data analysis. S.B.S. and B.S. performed molecular dynamics simulations. C.L., B.Y. and Y.Y. carried out high-resolution transmission electron microscopy measurements and data analysis. A.L.-P. and C.Z. carried out grazing-incidence wide-angle X-ray scattering measurements. P.Y., P.L., R.S., S.J. and V.B. performed density functional theory simulations. M.Z. collected single-crystal X-ray data and solved and refined the crystal structures. B.W.B. provided characterization facilities and participated data analysis and manuscript preparation. Y.G. and L.D. wrote the manuscript. All authors discussed the results and revised the manuscript.

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Correspondence to Letian Dou.

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Supplementary information

Supplementary Information

Supplementary Figs., tables, methods and 1H, 13C NMR and FT-IR spectra.

Crystallographic data

CIF for compound (2T)2PbI4; CCDC reference: 1861843.

Crystallographic data

CIF for compound (4Tm)2PbI4; CCDC reference: 1846391.

Crystallographic data

CIF for compound (BTm)2PbI4; CCDC reference: 1846392.

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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). https://doi.org/10.1038/s41557-019-0354-2

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