Shape-preserving transformation of carbonate minerals into lead halide perovskite semiconductors based on ion exchange/insertion reactions

Abstract

Biological and bio-inspired mineralization processes yield a variety of three-dimensional structures with relevance for fields such as photonics, electronics and photovoltaics. However, these processes are only compatible with specific material compositions, often carbonate salts, thereby hampering widespread applications. Here we present a strategy to convert a wide range of metal carbonate structures into lead halide perovskite semiconductors with tunable bandgaps, while preserving the 3D shape. First, we introduce lead ions by cation exchange. Second, we use carbonate as a leaving group, facilitating anion exchange with halide, which is followed rapidly by methylammonium insertion to form the perovskite. As proof of principle, pre-programmed carbonate salt shapes such as vases, coral-like forms and helices are transformed into perovskites while preserving the morphology and crystallinity of the initial micro-architectures. This approach also readily converts calcium carbonate biominerals into semiconductors, furnishing biological and programmable synthetic shapes with the performance of artificial compositions such as perovskite-based semiconductors.

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Fig. 1: Reaction scheme for the synthesis of CH3NH3PbX3 perovskites from carbonate salts (MCO3).
Fig. 2: Conversion of metal carbonate microstructures into CH3NH3PbX3 perovskites.
Fig. 3: Photoluminescence of perovskite microstructures.
Fig. 4: Complex arbitrarily shaped perovskites from synthetic and biological mineral architectures.

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Acknowledgements

The authors thank T. Coenen for assistance with the cathodoluminescence measurements, S. Brittman for technical help and discussions, L.M.C. Janssen for help with the manuscript and J.C. Weaver for identification of the biominerals. W.L.N. thanks the Netherlands Organization for Scientific Research (NWO) for financial support from a VENI grant. E.C.G. was partially supported by the European Research Council under the European Union’s Seventh Framework Programme (FP/2007–2013)/ERC grant agreement no. 337328, ‘NanoEnabledPV’ and by an STW VIDI grant. S.M. acknowledges funding from the European Research Council (grant agreement no. 695343). Scanning electron microscopy was performed at the fabrication and characterization facilities of the Amsterdam nanoCenter, supported by NWO.

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T.H., L.H. and H.C.H. contributed equally to this work. E.C.G. and W.L.N. conceived the initial idea. T.H., L.H. and H.C.H. designed, performed and analysed the experiments. I.B. designed and performed the methylamine detection. S.M. performed the cathodoluminescence analysis, and G.W.P.A. performed the photoluminescence lifetime measurements. W.L.N. wrote the manuscript, with input of all the other authors.

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Correspondence to Willem L. Noorduin.

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Supplementary information

41557_2018_64_MOESM2_ESM.mp4

Real-time movie of the conversion of a 3.5 cm sized sand dollar into CH3NH3PbBr3 by dripping a CH3NH3Br solution on the PbCO3 converted sand dollar surface under 365-nm UV illumination

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Supplementary synthesis and characterization details

Supplementary Movie 1

Real-time movie of the conversion of a 3.5 cm sized sand dollar into CH3NH3PbBr3 by dripping a CH3NH3Br solution on the PbCO3 converted sand dollar surface under 365-nm UV illumination

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Holtus, T., Helmbrecht, L., Hendrikse, H.C. et al. Shape-preserving transformation of carbonate minerals into lead halide perovskite semiconductors based on ion exchange/insertion reactions. Nature Chem 10, 740–745 (2018). https://doi.org/10.1038/s41557-018-0064-1

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