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High-pressure synthesis of Ruddlesden–Popper nitrides

Nature Chemistry volume 16, pages 1723–1731 (2024)Cite this article

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Abstract

Layered perovskites with Ruddlesden–Popper-type structures are fundamentally important for low-dimensional properties, for example, photovoltaic hybrid iodides and superconducting copper oxides. Many such halides and oxides are known, but analogous nitrides are difficult to stabilize due to the high cation oxidation states required to balance the anion charges. Here we report the high-pressure synthesis of three single-layer Ruddlesden–Popper (K2NiF4 type) nitrides—Pr2ReN4, Nd2ReN4 and Ce2TaN4—along with their structural characterization and properties. The R2ReN4 materials (R = Pr and Nd) are metallic, and Nd2ReN4 has a ferromagnetic Nd3+ spin order below 15 K. Thermal decomposition gives R2ReN3 with a Peierls-type distortion and chains of Re–Re multiply bonded dimers. Ce2TaN4 has a structural transition driven by octahedral tilting, with local distortions and canted magnetic Ce3+ order evidencing two-dimensional Ce3+/Ce4+ charge ordering correlations. Our work demonstrates that Ruddlesden–Popper nitrides with varied structural, electronic and magnetic properties can be prepared from high-pressure synthesis, opening the door to related layered nitride materials.

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Fig. 1: Powder X-ray diffraction and neutron diffraction analysis of the K2NiF4-type nitrides Pr2ReN4, Nd2ReN4 and Ce2TaN4.
Fig. 2: Electronic and magnetic properties of Pr2ReN4.
Fig. 3: Magnetic properties of Nd2ReN4.
Fig. 4: Thermal decomposition of R2ReN4 to R2ReN3 (R = Pr, Nd).
Fig. 5: Temperature-dependent powder X-ray diffraction of Ce2TaN4.
Fig. 6: Magnetic properties of Ce2TaN4.

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Data availability

Crystallographic information on the R2MN4-type materials at all measured temperatures is made available through the Cambridge Crystallographic Data Centre (CCDC) by quoting reference numbers 2312701 (300 K), 2312702 (1.6 K) and 2312703 (150 K) for Ce2TaN4; 2312720 (1.5 K), 2312721 (25 K), 2312722 (10 K), 2312723 (300 K), 2312724 (150 K) and 2312725 (15 K) for Nd2ReN4; and 2312726 (1.5 K), 2312727 (300 K) and 2312728 (20 K) for Pr2ReN4. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All raw data files of powder diffraction, powder neutron diffraction and magnetization measurements are made available through the Open Data LMU repository under https://doi.org/10.5282/ubm/data.448.

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Acknowledgements

We gratefully acknowledge funding from the Deutsche Forschungsgemeinschaft through Emmy-Noether programme KL 3368/3-1 (S.D.K.) and the LMU Excellence Programme (S.D.K.). We gratefully acknowledge the allocation of beamtime at the ISIS WISH diffractometer (proposal 2220381) and the Institut Laue-Langevin D20 beamline (proposal 88413, https://doi.org/10.5291/ILL-DATA.5-31-2949).

Author information

Authors and Affiliations

  1. Department of Chemistry, Ludwig-Maximilians-Universität München, Munich, Germany

    M. Weidemann, D. Werhahn, C. Mayer, S. Kläger & Simon D. Kloß

  2. Institut Laue-Langevin, Grenoble, France

    C. Ritter

  3. ISIS Neutron and Muon Source, STFC Rutherford Appleton Laboratory, Didcot, UK

    P. Manuel

  4. Centre for Science at Extreme Conditions, University of Edinburgh, Edinburgh, UK

    J. P. Attfield

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Contributions

M.W. and D.W. performed physical measurements on the Ruddlesden–Popper materials, C.M. prepared samples of Ce2TaN4 and S.K. performed and analysed X-ray photoelectron spectroscopy measurements. C.R. and P.M. are beamline scientists who performed neutron diffraction measurements and aided in the analysis of data. J.P.A. aided in the analysis of data and writing of the paper. S.D.K. supervised the project, performed synthesis experiments, analysed data and wrote the paper.

Corresponding author

Correspondence to Simon D. Kloß.

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Nature Chemistry thanks Shintaro Ishiwata and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Scanning electron microscopy.

Scanning electron microscopy images of a Pr2ReN4, b Nd2ReN4 and c Ce2TaN4.

Extended Data Fig. 2 PND data of Pr2ReN4.

Rietveld fits for Pr2ReN4 to WISH PND data collected at a 1.5 K, b 20, and c 300 K. Q is in Å−1.

Extended Data Fig. 3 PND data of Nd2ReN4.

Rietveld fits for Nd2ReN4 to WISH PND data collected at a 1.5, b 10, c 15 K, d 25 K, e 150 K, and f 300 K. Q is in Å−1.

Extended Data Fig. 4 Micrograph of sintered Pr2ReN4 sample.

Sintered piece of Pr2ReN4 as obtained from the high-pressure experiment used for resistivity measurements. Contacts are made with gold-wire and Ag-varnish.

Extended Data Fig. 5 Resistivity measurement of Nd2ReN4.

Resistivity measurement made on a cold-pressed pellet of Nd2ReN4 with the van der Pauw method. The rise in resistivity by a factor of ca. 3 between 300 and 2 K is likely due to grain boundary effects. The activation energy, extracted from the linear part of the plot from a fit of log(ρ) vs. 1/T is ca. 2 meV, suggesting grain boundary resistances between particles with metallic conductivity.

Extended Data Fig. 6 Susceptibility measurements of R2ReN4.

Susceptibility measurements of R2ReN4 in fields of 3 T for a Pr2ReN4 and 0.1 T for b Nd2ReN4. Curie-Weiss fits yielded for Pr: µeff = 3.68(1) µB/Pr3+ and Θ = −25.9(3) K, for Nd: µeff = 3.65(1) µB / Nd3+ and Θ = 4.0(9) K.

Extended Data Fig. 7 Magnetic powder neutron diffraction of Nd2ReN4.

Magnetic structure Rietveld refinement of 10−15 K difference PND data of Nd2ReN4. Magnetic reflections (k-vector (0 0 0)) are indexed based on the nuclear structure. The intensity mismatches at higher Q-space reflect small thermal changes in the crystal structure. Q is in Å−1.

Extended Data Fig. 8 Temperature dependent measurements on R2ReN4 and R2ReN3.

Temperature-evolution of lattice parameters, volume, phase fraction (p.f.), as well as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) for Pr2ReN4 (left, black) and Nd2ReN4 (right, black). Lattice parameters of the R2ReN3 phases are displayed as orange diamonds.

Extended Data Fig. 9 Rietveld fits for Ce2TaN4.

ILL D20 data collected at several temperatures. Q is in Å−1.

Supplementary information

Supplementary Information

Supplementary Figs. 1–4, Discussion and Tables 1–28.

Supplementary Data 1

Crystallographic data for Ce2TaN4 at 1.6 K; CCDC reference no. 2312702.

Supplementary Data 2

Crystallographic data for Ce2TaN4 at 150 K; CCDC reference no. 2312703.

Supplementary Data 3

Crystallographic data for Ce2TaN4 at 300 K; CCDC reference no. 2312701.

Supplementary Data 4

Crystallographic data for Nd2ReN4 at 1.5 K; CCDC reference no. 2312720.

Supplementary Data 5

Crystallographic data for Nd2ReN4 at 10 K; CCDC reference no. 2312722.

Supplementary Data 6

Crystallographic data for Nd2ReN4 at 15 K; CCDC reference no. 2312725.

Supplementary Data 7

Crystallographic data for Nd2ReN4 at 25 K; CCDC reference no. 2312721.

Supplementary Data 8

Crystallographic data for Nd2ReN4 at 150 K; CCDC reference no. 2312724.

Supplementary Data 9

Crystallographic data for Nd2ReN4 at 300 K; CCDC reference no. 2312723.

Supplementary Data 10

Crystallographic data for Pr2ReN4 at 1.5 K; CCDC reference no. 2312726.

Supplementary Data 11

Crystallographic data for Pr2ReN4 at 20 K; CCDC reference no. 2312728.

Supplementary Data 12

Crystallographic data for Pr2ReN4 at 300 K; CCDC reference no. 2312727.

Supplementary Data 13

The single-crystal X-ray diffraction crystallographic data for Pr2ReN4 at 300 K; CCDC reference no. 2312727.

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Weidemann, M., Werhahn, D., Mayer, C. et al. High-pressure synthesis of Ruddlesden–Popper nitrides. Nat. Chem. 16, 1723–1731 (2024). https://doi.org/10.1038/s41557-024-01558-1

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