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Thermally stable coexistence of liquid and solid phases in gallium nanoparticles

Abstract

Gallium (Ga), a group III metal, is of fundamental interest due to its polymorphism and unusual phase transition behaviours. New solid phases have been observed when Ga is confined at the nanoscale. Herein, we demonstrate the stable coexistence, from 180 K to 800 K, of the unexpected solid γ-phase core and a liquid shell in substrate-supported Ga nanoparticles. We show that the support plays a fundamental role in determining Ga nanoparticle phases, with the driving forces for the nucleation of the γ-phase being the Laplace pressure in the nanoparticles and the epitaxial relationship of this phase to the substrate. We exploit the change in the amplitude of the evolving surface plasmon resonance of Ga nanoparticle ensembles during synthesis to reveal in real time the solid core formation in the liquid Ga nanoparticle. Finally, we provide a general framework for understanding how nanoscale confinement, interfacial and surface energies, and crystalline relationships to the substrate enable and stabilize the coexistence of unexpected phases.

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Figure 1: HRTEM images of Ga nanoparticles deposited on the various substrates of sapphire, glass and Si(100).
Figure 2: Details by HRTEM images of the solid-core/liquid-shell Ga nanoparticles on sapphire, as well as of the Ga solid/sapphire interface and of the Ga solid/Ga liquid interface.
Figure 3: Energy and force balance for Ga nanoparticles on sapphire and on glass, respectively, and linear dependence of the size of the solid core on the nanoparticle size.
Figure 4: Real-time plasmon resonance ellipsometry monitoring of the nucleation and growth of the Ga nanoparticles.
Figure 5: LSPR spectra acquired as a function of temperature for approximately 100-nm-diameter Ga nanoparticles supported on sapphire.

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Acknowledgements

We thank all of the students and colleagues in our groups who are actively involved with nanoparticle research. M.L. acknowledges the support of the CNR STM 2014 programme. M.L. and K.H. acknowledge the support of the European Commission under the H2020 grant TWINFUSYON (GA692034).

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M.L. and A.S.B. conceived and designed the experiments. M.L. performed the experiments. S.R. conducted FIB work. A.S. conducted TEM characterization. K.H. performed thermodynamic modelling. A.S.B. supervised the work. All authors discussed the results, commented on the manuscript and co-wrote the paper.

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Correspondence to Maria Losurdo or April S. Brown.

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Losurdo, M., Suvorova, A., Rubanov, S. et al. Thermally stable coexistence of liquid and solid phases in gallium nanoparticles. Nature Mater 15, 995–1002 (2016). https://doi.org/10.1038/nmat4705

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