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An intrinsic growth instability in isotropic materials leads to quasi-two-dimensional nanoplatelets

Nature Materials volume 16, pages 743–748 (2017)Cite this article

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Abstract

Colloidal nanoplatelets are atomically flat, quasi-two-dimensional sheets of semiconductor that can exhibit efficient, spectrally pure fluorescence. Despite intense interest in their properties, the mechanism behind their highly anisotropic shape and precise atomic-scale thickness remains unclear, and even counter-intuitive for commonly studied nanoplatelets that arise from isotropic crystal structures (such as zincblende CdSe and lead halide perovskites). Here we show that an intrinsic instability in growth kinetics can lead to such highly anisotropic shapes. By combining experimental results on the synthesis of CdSe nanoplatelets with theory predicting enhanced growth on narrow surface facets, we develop a model that explains nanoplatelet formation as well as observed dependencies on time and temperature. Based on standard concepts of volume, surface and edge energies, the resulting growth instability criterion can be directly applied to other crystalline materials. Thus, knowledge of this previously unknown mechanism for controlling shape at the nanoscale can lead to broader libraries of quasi-two-dimensional materials.

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Figure 1: The formation of CdSe NPLs in isotropic melts of Cd(carboxylate)2 and elemental Se.
Figure 2: Thickness transitions in CdSe NPLs.
Figure 3: Theory of the intrinsic growth instability leading to NPLs.
Figure 4: Shape distribution of nanocrystals grown via kinetic Monte Carlo simulations.

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Acknowledgements

This work was supported by ETH Research Grant ETH-38 14-1, by the Swiss National Science Foundation under Grant Nos 200021-140617 and 200020-159228, and by the US Office of Naval Research (ONR) through the Naval Research Laboratory’s Basic Research Program (SCE). F.D.O. benefited from an ONR Global travel grant. S.J.P.K. acknowledges funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement No. 339905 (QuaDoPS Advanced Grant). Computations were performed at the ETH High-Performance Computing Cluster Euler and the DoD Major Shared Resource Center at AFRL. We thank A. Sánchez-Ferrer for assistance with the X-ray scattering measurements and R. Mezzenga for equipment access. We acknowledge L. Frenette, O. Hirsch, P. Kumar, D. Koziej, V. Lin, M. Mazzotti, K. McNeill, S. Meyer, M. Niederberger, F. Rabouw, A. Rossinelli, H. Schönberg, O. Waser, C. Willa, F. Rechberger and M. Bärtsch for technical assistance and discussions. We utilized the ScopeM facility at ETH Zurich for electron microscopy.

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  1. Andreas Riedinger and Florian D. Ott: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Mechanical and Process Engineering, Optical Materials Engineering Laboratory, ETH Zurich, 8092 Zurich, Switzerland

    Andreas Riedinger, Florian D. Ott, Aniket Mule, Sergio Mazzotti, Philippe N. Knüsel, Stephan J. P. Kress, Ferry Prins & David J. Norris

  2. Center for Computational Materials Science, Naval Research Laboratory, Washington DC 20375, USA

    Steven C. Erwin

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Contributions

A.R., F.D.O., S.C.E. and D.J.N. conceived the experiments and model. Syntheses and optical spectroscopy were performed by A.R., A.M. and P.N.K. X-ray diffraction, differential scanning calorimetry, nuclear magnetic resonance spectroscopy, electron microscopy and energy-dispersive X-ray spectroscopy were carried out by A.R. and P.N.K. Polarized optical and fluorescence microscopy was performed by A.R. with help from S.J.P.K. and F.P. Calculations and simulations were performed by F.D.O. and S.M. The NPL growth model was developed by F.D.O. and S.C.E. with input from A.R. and D.J.N. Both S.C.E. and D.J.N. supervised the work. A.R., F.D.O., S.C.E. and D.J.N. wrote the manuscript. All authors contributed to the discussion of the results and to the revision of the manuscript.

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Correspondence to Steven C. Erwin or David J. Norris.

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Riedinger, A., Ott, F., Mule, A. et al. An intrinsic growth instability in isotropic materials leads to quasi-two-dimensional nanoplatelets. Nature Mater 16, 743–748 (2017). https://doi.org/10.1038/nmat4889

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