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Synthesis pathways to thin films of stable layered nitrides

Nature Synthesis volume 3, pages 1471–1480 (2024) Cite this article

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Abstract

Controlled synthesis of metastable materials away from equilibrium is of interest in materials chemistry. Thin-film deposition methods with rapid condensation of vapour precursors can readily synthesize metastable phases but often struggle to yield the thermodynamic ground state. Growing thermodynamically stable structures using kinetically limited synthesis methods is important for practical applications in electronics and energy conversion. Here we reveal a synthesis pathway to thermodynamically stable, ordered layered ternary nitride materials, and discuss why disordered metastable intermediate phases tend to form. We show that starting from elemental vapour precursors leads to a 3D long-range-disordered MgMoN2 thin-film metastable intermediate structure, with a layered short-range order that has a low-energy transformation barrier to the layered 2D-like stable structure. This synthesis approach is extended to ScTaN2, MgWN2 and MgTa2N3, and may lead to the synthesis of other layered nitride thin films with unique semiconducting and quantum properties.

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Fig. 1: Examples of layered, 2D-like crystal structures among multivalent ternary nitrides.
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Fig. 2: Chemical composition and crystal structure of MgMoN2.
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Fig. 3: Local short-range atomic order in metastable RS-MgMoN2.
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Fig. 4: In situ measurements of the MgMoN2 RS–RL phase transformation.
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Fig. 5: 3D-to-2D synthesis pathway for MgMoN2 and extension to other materials chemistries.
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Data availability

The data used in the graphs are published in Supplementary Information alongside the paper. Datasets for XRD, AES, PDF and nanocalorimetry figures are also available via figshare at https://doi.org/10.6084/m9.figshare.26344993 (ref. 51). Crystal structure figure files are available via figshare at https://doi.org/10.6084/m9.figshare.26345092 (ref. 52).

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Acknowledgements

This work was authored in part at the National Renewable Energy Laboratory (NREL), operated by the Alliance for Sustainable Energy, LLC, for the US Department of Energy (DOE) under contract number DE-AC36-08GO28308. Funding was provided by the Office of Science (SC), Basic Energy Sciences (BES), Materials Chemistry programme, as a part of the Early Career Award ‘Kinetic Synthesis of Metastable Nitrides’ (experimental results), with contribution from NSF career award number DMR-1945010 (computational results). Nanocalorimeter fabrication was performed in part at the NIST Center for Nanoscale Science & Technology (CNST). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory is supported by the DOE’s SC, BES under contract number DE-AC02-76SF00515. This research used resources of the Advanced Photon Source, a US DOE Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under contract number DE-AC02-06CH11357. R.W.S. acknowledges support from the Director’s Fellowship within NREL’s Laboratory Directed Research and Development programme. We thank C. Perkins for help with AES analysis; N. Strange for assistance with SSRL data collection; U. Ruett and M. Miller for assistance with APS data collection; and B. Julien and K. Yazawa for useful discussions. This work used high-performance computing resources located at NREL and sponsored by the Office of Energy Efficiency and Renewable Energy. Certain commercial equipment, instruments or materials are identified in this document. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology (NIST), nor does it imply that the products identified are necessarily the best available for the purpose. The views expressed in the article do not necessarily represent the views of the DOE or the US Government.

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Authors and Affiliations

  1. National Renewable Energy Laboratory, Golden, CO, USA

    Andriy Zakutayev, Christopher L. Rom, Sage R. Bauers & Rebecca W. Smaha

  2. Colorado School of Mines, Golden, CO, USA

    Matthew Jankousky, Laszlo Wolf & Vladan Stevanovic

  3. National Institute of Standards and Technology, Gaithersburg, MD, USA

    Yi Feng & David A. LaVan

  4. Argonne National Laboratory, Lemont, IL, USA

    Olaf Borkiewicz

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Contributions

A.Z., Y.F., C.L.R., S.R.B., O.B., D.A.L. and R.W.S. conducted experimental measurements. M.J., L.W. and V.S. performed theoretical calculations. A.Z. conceived the study, synthesized the materials, supervised the work and wrote the paper with edits from R.W.S., M.J., L.W., V.S. and all other coauthors.

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Correspondence to Andriy Zakutayev.

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Nature Synthesis thanks Xiaojun Kuang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information (download PDF )

Supplementary Figs. 1–12, Table 1 and PDF calculation methods.

Source data

Source Data Fig. 2 (download XLSX )

Source data for measured chemical composition and crystal structure of RS- and RL-MgMoN2.

Source Data Fig. 3 (download XLSX )

Source data for pair distribution function measurements and calculations in metastable RS-MgMoN2.

Source Data Fig. 4 (download XLSX )

Source data for in situ measurements and calculations of the MgMoN2 RS–RL transformation pathway.

Source Data Fig. 5 (download XLSX )

Source data for polymorph sampling and X-ray diffraction for MgMoN2 and other materials chemistries.

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Zakutayev, A., Jankousky, M., Wolf, L. et al. Synthesis pathways to thin films of stable layered nitrides. Nat. Synth 3, 1471–1480 (2024). https://doi.org/10.1038/s44160-024-00643-0

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