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Coherent approach to two-dimensional heterolayered oxychalcogenides using molten hydroxides

Nature Synthesis volume 1, pages 729–737 (2022)Cite this article

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Abstract

Heterolayered structures consist of two or more different types of layer and can exhibit exceptional physical properties. Rational routes to synthesize new members of such compounds are required because most of these compounds have been discovered unintentionally. So far there is no generic method to vertically stack chemically different layers to form two-dimensional compounds owing to a lack of understanding of the synthesis of these materials. Here we report the use of molten hydroxides as unconventional solutions for the rapid stacking of oxide and chalcogenide layers with precise composition control. In addition, the crystal growth of heterolayered phases can be achieved by the reaction of different components at their diffusion front in molten hydroxides. This approach creates conditions in which the building blocks for each heterolayer can coexist, enabling heterolayered structures and bypassing the challenges of traditional solid-state chemistry methods where short reactant diffusion lengths predominate. This crystal growth methodology for heterolayers is also applicable to systems that do not form congruent melts at high temperatures.

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Fig. 1: Crystal structures and formation paths for [Sr2Mn1-xO2][Cu2-yLiyQ2] heterolayers.
Fig. 2: Panoramic synthesis to explore reaction pathways to [Sr2Mn1−xO2][(Cu1−yLiy)2Q2] in molten LiOH–LiCl.
Fig. 3: Crystal growth by diffusion.
Fig. 4: Crystal growth processes.

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Data availability

The data that support the plots within this paper and other findings of this study are available in the Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, with deposition numbers 2109506–2109520, corresponding to the compounds shown in the Supplementary Tables: 1 (Sr2Mn0.6Cu1.6Li0.4S2, CCDC 2109509), 2 (Sr2Mn0.5O2Cu1.31Li0.69Se2, CCDC 2109506), 3 (Sr2CoO2Cu1.81S2, CCDC 2109519), 4 (Sr2CoO2Cu2Se2, CCDC 2109507), 5 (Sr2NiO2Cu2Se2, CCDC 2109510), 6 (Ba2Co0.54Cu2O2Se2, CCDC 2109508), 7 (Sr2Mn0.56O2Ag1.84Li0.16Se2, CCDC 2109514), 8 (Ba3Ag2Fe1.82O3.73Se2, CCDC 2109513), 9 (Ba2Co0.68O2Ag2Se2, CCDC 2109515), 10 (Ba2Cu0.79O1.33Ag1.24Li0.76Se2, CCDC 2109511), 11 (Ba2Zn0.66O1.42Ag2Se2, CCDC 2109512), 12 (CoCu2Li5.51O2Se3, CCDC 2109517), 13 (SrMn0.5OCu3.63S2.5, CCDC 2109518), 14 (Sr2Ni0.7O2Cu2Se2, CCDC 2109516) and 15 (Sr2Cu0.68O2Cu2Se2, CCDC 2109520). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

This work was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Use of the Center for Nanoscale Materials, including SEM and the ACAT, an Office of Science user facility, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. Work at the beamlines 17-BM-B, 15-ID and 20-BM-B at the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-06CH11357. NSF’s ChemMatCARS Sector 15 is supported by the Divisions of Chemistry (CHE) and Materials Research (DMR), National Science Foundation, under grant number NSF/CHE-1834750.

Author information

Authors and Affiliations

  1. Materials Science Division, Argonne National Laboratory, Lemont, IL, USA

    Xiuquan Zhou, Hsien-Hau Wang, Duck Young Chung & Mercouri G. Kanatzidis

  2. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Christos D. Malliakas & Mercouri G. Kanatzidis

  3. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL, USA

    Andrey A. Yakovenko & Mahalingam Balasubramanian

  4. United States Naval Academy, Annapolis, MD, USA

    Brandon Wilfong

  5. NSF’s ChemMatCARS, The University of Chicago, Lemont, IL, USA

    Suyin G. Wang & Yu-Sheng Chen

  6. Center for Nanoscale Materials, Argonne National Laboratory, Lemont, IL, USA

    Lei Yu & Jianguo Wen

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  1. Xiuquan Zhou
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Contributions

The work was conceived by X.Z., D.Y.C. and M.G.K. with input from all authors. X.Z. carried out the synthesis, laboratory X-ray diffraction and elemental analysis. C.D.M. and X.Z. analysed the single-crystal diffraction data. X.Z., A.Y. and B.W. collected and analysed the in situ diffraction data. S.G.W. and Y.-S.C. collected the synchrotron single-crystal diffraction data. J.W. performed the TEM analysis and J.W. and L.Y. analysed the EELS spectra. M.B. carried out the XAS experiments. H.-H.W. collected the Raman spectra. D.-Y.C. and M.G.K. supervised the project.

Corresponding author

Correspondence to Mercouri G. Kanatzidis.

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Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Xiaolong Chen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Tables 1–15, Figs. 1–16 and experimental details.

Supplementary Data 1

Crystallographic data for compound Sr2Mn0.6Cu1.6Li0.4S2, CSD 2109509.

Supplementary Data 2

Crystallographic data for compound Sr2Mn0.5O2Cu1.31Li0.69Se2, CSD 2109506.

Supplementary Data 3

Crystallographic data for compound Sr2CoO2Cu1.81S2, CSD 2109519.

Supplementary Data 4

Crystallographic data for compound Sr2CoO2Cu2Se2, CSD 2109507.

Supplementary Data 5

Crystallographic data for compound Sr2NiO2Cu2Se2, CSD 2109510.

Supplementary Data 6

Crystallographic data for compound Ba2Co0.54Cu2O2Se2, CSD 2109508.

Supplementary Data 7

Crystallographic data for compound Sr2Mn0.56O2Ag1.84Li0.16Se2, CSD 2109514.

Supplementary Data 8

Crystallographic data for compound Ba3Ag2Fe1.82O3.73Se2, CSD 2109513.

Supplementary Data 9

Crystallographic data for compound Ba2Co0.68O2Ag2Se2, CSD 2109515.

Supplementary Data 10

Crystallographic data for compound Ba2Cu0.79O1.33Ag1.24Li0.76Se2, CSD 2109511.

Supplementary Data 11

Crystallographic data for compound Ba2Zn0.66O1.42Ag2Se2, CSD 2109512.

Supplementary Data 12

Crystallographic data for compound CoCu2Li5.51O2Se3, CSD 2109517.

Supplementary Data 13

Crystallographic data for compound SrMn0.5OCu3.63S2.5, CSD 2109518.

Supplementary Data 14

Crystallographic data for compound Sr2Ni0.7O2Cu2Se2, CSD 2109516.

Supplementary Data 15

Crystallographic data for compound Sr2Cu0.68O2Cu2Se2, CSD 2109520.

Source data

Source Data Fig. 1

Tab ‘Fig.1c’ shows Li occupancy versus lattice constant c. Tab ‘Fig.1d’ shows lattice constant c and temperature as a function of normalized [LiOH].

Source Data Fig. 2

Tabs ‘Fig2a_400C’, ‘Fig2a_500C’ and ‘Fig2a_600C’ are raw data for 1D diffraction patterns (two-theta versus intensity) for in situ reactions at 400, 500 and 600 °C, respectively. They form the 2D pattern shown in Fig. 2a and the reduced data shown in Fig. 2b. The tab ‘Fig. 2b’ shows temperature (T) versus normalized molar ratio at 400, 500 and 600 °C, respectively.

Source Data Fig. 3

Tab ‘Fig.3b’ contains the calculated concentration profile using 1D Fick’s law of diffusion with concentration as a function of x (in cm). Tab ‘Fig.3c’ contains the calculated concentration profile for x versus C at different reaction times (t) with t = 1, 5, 10 and 24 h.

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Zhou, X., Malliakas, C.D., Yakovenko, A.A. et al. Coherent approach to two-dimensional heterolayered oxychalcogenides using molten hydroxides. Nat. Synth 1, 729–737 (2022). https://doi.org/10.1038/s44160-022-00130-4

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