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Single-nanoparticle phase transitions visualized by four-dimensional electron microscopy

Nature Chemistry volume 5, pages 395–402 (2013)Cite this article

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Abstract

The advancement of techniques that can probe the behaviour of individual nanoscopic objects is of paramount importance in various disciplines, including photonics and electronics. As it provides images with a spatiotemporal resolution, four-dimensional electron microscopy, in principle, should enable the visualization of single-nanoparticle structural dynamics in real and reciprocal space. Here, we demonstrate the selectivity and sensitivity of the technique by visualizing the spin crossover dynamics of single, isolated metal–organic framework nanocrystals. By introducing a small aperture in the microscope, it was possible to follow the phase transition and the associated structural dynamics within a single particle. Its behaviour was observed to be distinct from that imaged by averaging over ensembles of heterogeneous nanoparticles. The approach reported here has potential applications in other nanosystems and those that undergo (bio)chemical transformations.

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Figure 1: Single-nanoparticle 4D-EM.
Figure 2: Structure, spin crossover and dynamics of Fe(pyrazine)Pt(CN)4 nanoparticles.
Figure 3: Equilibrium phase-transition behaviour.
Figure 4: Single-nanoparticle morphology dynamics.
Figure 5: Real- and reciprocal–space time profiles.
Figure 6: Particle-dependent dynamics.

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Acknowledgements

This work was supported by the National Science Foundation and the Air Force Office of Scientific Research in the Gordon and Betty Moore Center for Physical Biology at the California Institute of Technology. R.M.V. acknowledges funding from the Swiss National Science Foundation. We thank S. Tae Park for helpful collaboration in the phase-transition simulations, which will be published later in a full report.

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Authors and Affiliations

  1. Physical Biology Center for Ultrafast Science and Technology, Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, 91125, California, USA

    Renske M. van der Veen, Oh-Hoon Kwon & Ahmed H. Zewail

  2. Département de Chimie Physique, Université de Genève, Genève, CH-1211, Switzerland

    Antoine Tissot & Andreas Hauser

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  1. Renske M. van der Veen
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  2. Oh-Hoon Kwon
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  3. Antoine Tissot
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Contributions

R.M.V., O.H.K. and A.H.Z. conceived and designed the experiments. R.M.V. and O.H.K. performed the experiments. A.H. and A.M.T. contributed materials and performed sample characterization. R.M.V., O.H.K., A.M.T., A.H. and A.H.Z. discussed the results and commented on the manuscript.

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Correspondence to Ahmed H. Zewail.

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The authors declare no competing financial interests.

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van der Veen, R., Kwon, OH., Tissot, A. et al. Single-nanoparticle phase transitions visualized by four-dimensional electron microscopy. Nature Chem 5, 395–402 (2013). https://doi.org/10.1038/nchem.1622

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