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Three-dimensional atomic structure and local chemical order of medium- and high-entropy nanoalloys - Nature.com

Abstract

Medium- and high-entropy alloys (M/HEAs) mix several principal elements with near-equiatomic composition and represent a model-shift strategy for designing previously unknown materials in metallurgy1,2,3,4,5,6,7,8, catalysis9,10,11,12,13,14 and other fields15,16,17,18. One of the core hypotheses of M/HEAs is lattice distortion5,19,20, which has been investigated by different numerical and experimental techniques21,22,23,24,25,26. However, determining the three-dimensional (3D) lattice distortion in M/HEAs remains a challenge. Moreover, the presumed random elemental mixing in M/HEAs has been questioned by X-ray and neutron studies27, atomistic simulations28,29,30, energy dispersive spectroscopy31,32 and electron diffraction33,34, which suggest the existence of local chemical order in M/HEAs. However, direct experimental observation of the 3D local chemical order has been difficult because energy dispersive spectroscopy integrates the composition of atomic columns along the zone axes7,32,34 and diffuse electron reflections may originate from planar defects instead of local chemical order35. Here we determine the 3D atomic positions of M/HEA nanoparticles using atomic electron tomography36 and quantitatively characterize the local lattice distortion, strain tensor, twin boundaries, dislocation cores and chemical short-range order (CSRO). We find that the high-entropy alloys have larger local lattice distortion and more heterogeneous strain than the medium-entropy alloys and that strain is correlated to CSRO. We also observe CSRO-mediated twinning in the medium-entropy alloys, that is, twinning occurs in energetically unfavoured CSRO regions but not in energetically favoured CSRO ones, which represents, to our knowledge, the first experimental observation of correlating local chemical order with structural defects in any material. We expect that this work will not only expand our fundamental understanding of this important class of materials but also provide the foundation for tailoring M/HEA properties through engineering lattice distortion and local chemical order.

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Fig. 1: The 3D atomic structure and lattice distortion of M/HEA nanoparticles.
Fig. 2: 3D strain tensor measurements of the M/HEA nanoparticles.
Fig. 3: Experimental observation of the correlation between CSRO and twinning in MEAs.
Fig. 4: The twin-formation energy (ETF) calculated from the experimental 3D atomic coordinates and species of the MEAs.

Data availability

All the raw and processed experimental data are available on GitHub (https://github.com/AET-MEA-HEA/Supplementary-Data-Codes).

Code availability

All the MATLAB source codes for the 3D reconstruction, atom tracing and data analysis of this paper are available on GitHub (https://github.com/AET-MEA-HEA/Supplementary-Data-Codes).

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Acknowledgements

This work was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Division of Materials Sciences and Engineering under award no. DE-SC0010378. The ADF-STEM imaging with TEAM 0.5 was performed at the Molecular Foundry, which is supported by the Office of Science, Office of Basic Energy Sciences of the US DOE under contract no. DE-AC02-05CH11231. J.D. was supported by the Natural Science Foundation of China (grant no. 12004294) and the HPC platform of Xi’an Jiaotong University.

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Author notes

  1. These authors contributed equally: Saman Moniri, Yao Yang, Jun Ding

Authors and Affiliations

  1. Department of Physics and Astronomy and California NanoSystems Institute, University of California, Los Angeles, Los Angeles, CA, USA

    Saman Moniri, Yao Yang, Yakun Yuan, Jihan Zhou, Long Yang, Fan Zhu, Yuxuan Liao & Jianwei Miao

  2. Center for Alloy Innovation and Design, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an, China

    Jun Ding

  3. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Yonggang Yao & Liangbing Hu

  4. National Center for Electron Microscopy, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Peter Ercius

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Contributions

J.M. initiated and directed the project; Y. Yao and L.H. synthesized the samples; J.Z., P.E. and J.M. discussed and/or carried out the AET experiments; Y. Yang, Y. Yuan, S.M. and J.M. performed image reconstruction, atom tracing and classification for the AET experiments. S.M., Y. Yang, Y. Yuan, L.Y., F.Z., Y.L., J.D. and J.M. analysed the data and interpreted the results; J.D. performed the DFT calculations and molecular dynamics simulations with input from S.M., Y. Yang, Y. Yuan and J.M.; J.M., S.M. and Y. Yang wrote the paper. All authors commented on the paper.

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Correspondence to Jianwei Miao.

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Extended data figures and tables

Extended Data Fig. 1 EDS maps of the HEA nanoparticles.

a, Low-resolution ADF-STEM image of the nanoparticles. Scale bars, 20 nm. b-i, EDS maps showing the distribution of Co (b), Ni (c), Ru (d), Rh (e), Pd (f), Ag (g), Ir (h) and Pt (i) in the nanoparticles.

Extended Data Fig. 2 3D precision estimation.

a, b, Comparison between a representative experimental (after denoising) (a) and a multi-slice calculated image (b) of MEA-3. The multi-slice images were convolved with a Gaussian function to match the incoherence effects in the experimental images. Scale bar, 2 nm. c, Histogram of the deviation of the 3D atomic positions between the experimental atomic model and that obtained from 55 multi-slice images. The root-mean-square deviation of the histogram is 19.5 pm.

Extended Data Fig. 3 Experimental 3D atomic models of the other six M/HEA nanoparticles.

a-f, Experimental atomic models of four MEAs and two HEAs, named MEA-3 (a), MEA-4 (b), MEA-5 (c), MEA-6 (d), HEA-3 (e) and HEA-4 (f), in which the yellow circles represent the atoms along the twin boundaries in (a-c) and grey circles indicate the atoms on the grain boundary in (c). Scale bar, 1 nm.

Extended Data Fig. 4 Twin boundaries and dislocations in the M/HEAs.

a-e, The twin boundaries of three representative MEAs (a, twin-free; b, single twin; c, double twins) and two HEAs (d, single twin; e, double twins), showing more diffuse twin boundaries in the HEAs with each boundary spreading to the neighbouring atomic layers. The twin order parameter of 1 and −1 represents a hcp (i.e., twinning) and fcc structure, respectively. f, Two Shockley partial dislocations in MEA-5 with opposite Burgers vectors \(\frac{a}{6}\left[121\right]\) and \(\frac{a}{6}[\bar{1}\,\bar{2}\bar{1}]\), as the gliding process was frozen near the boundary during the rapid cooling process of the nanoparticle. g, A screw dislocation in MEA-2 with the Burgers vector \(\frac{a}{2}[110]\), where the zigzag lines in light blue show the characteristic feature of the screw dislocation. h, A Shockley partial dislocation in HEA-4 with the Burgers vector \(\frac{a}{6}\left[121\right]\), which exists near the boundary of the nanoparticle. i, A screw dislocation in HEA-3 with the Burgers vector \(\frac{a}{2}[110]\). Scale bars, 1 nm (a); and 5 Å (f).

Extended Data Fig. 5 3D distribution of the other four CSRO parameters of twin-free MEA-1 and double-twinned MEA-2.

a-d, 3D distribution of \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), and \({\alpha }_}\) in MEA-1, showing the formation of local chemical-order pockets. e-h, Histogram of the average \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), and \({\alpha }_}\) values for each atomic layer along the [111] direction in MEA-1. i-l, 3D distribution of \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), and \({\alpha }_}\) in MEA-2 (the twins labelled as yellow planes), exhibiting more heterogeneous CSRO than twin-free MEA-1 (a-d). m-p, Histogram of the average \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), and \({\alpha }_}\) values for each atomic layer along the [111] direction in MEA-2. Scale bar, 1 nm.

Extended Data Fig. 6 3D distribution of the six CSRO parameters in double-twinned MEA-3.

a-f, 3D distribution of \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), and \({\alpha }_}\), where the twins are labelled as yellow planes. g-l, Histogram of the average \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), \({\alpha }_}\), and \({\alpha }_}\) values for each atomic layer along the [111] direction, where the yellow bars indicate the twin positions. Scale bar, 1 nm.

Extended Data Fig. 7 Twin formation energy (ETF) calculated from experimental 3D atomic coordinates of double-twinned MEA-3.

a-c, Calculation of ETF of the double-twinned MEA by fixing one twin (top yellow circles) and moving the other twin along the [111] direction, in which the three representative atomic configurations show a twin separation by 0 (i.e., a single twin) (a), 9 (b), and 13 atomic layers (c). d, Histogram of ETF as a function of the twin separation. The experimentally determined twin separation is 9 atomic layers (yellow bar), which is next to the minimum ETF with a twin separation of 10 layers. Scale bar, 1 nm.

Extended Data Fig. 8 3D distribution of the six CSRO parameters in twin-free HEA-1.

a-f, 3D distribution of \({\alpha }_{11}\), \({\alpha }_{22}\), \({\alpha }_{33}\), \({\alpha }_{12}\), \({\alpha }_{13}\), and \({\alpha }_{23}\), which are more heterogeneous than those of the twin-free MEAs (Fig. 3a,b, Extended Data Fig. 5a–d). g-l, Histograms of the average \({\alpha }_{11}\), \({\alpha }_{22}\), \({\alpha }_{33}\), \({\alpha }_{12}\), \({\alpha }_{13}\), and \({\alpha }_{23}\) values for the atomic layer along the [111] direction. Scale bar, 1 nm.

Extended Data Fig. 9 3D distribution of the six CSRO parameters in double-twinned HEA-2.

a-f, 3D distribution of \({\alpha }_{11}\), \({\alpha }_{22}\), \({\alpha }_{33}\), \({\alpha }_{12}\), \({\alpha }_{13}\), and \({\alpha }_{23}\), exhibiting greater local chemical fluctuations than the double-twinned MEA (Fig. 3e,f, Extended Data Figs. 5i–l and 6a–f). g-l, Histograms of the average \({\alpha }_{11}\), \({\alpha }_{22}\), \({\alpha }_{33}\), \({\alpha }_{12}\), \({\alpha }_{13}\), and \({\alpha }_{23}\) values of the atomic layer along the [111] direction. m, Histogram of the average values for the six CSRO parameters of a DFT-calculated bulk HEA, twin-free HEA-1, and double-twinned HEA-2. Scale bar, 1 nm.

Extended Data Table 1 Metal precursors used for the synthesis of M/HEA nanoparticles
Full size table
Extended Data Table 2 AET data collection, processing, reconstruction, refinement and statistics of the ten M/HEA nanoparticles
Full size table
Extended Data Table 3 Unpaired t-test on the 3D atomic displacements of MEA-1, MEA-2, HEA-1 and HEA-2
Full size table

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Moniri, S., Yang, Y., Ding, J. et al. Three-dimensional atomic structure and local chemical order of medium- and high-entropy nanoalloys. Nature 624, 564–569 (2023). https://ift.tt/C4zAiJB

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  • DOI: https://ift.tt/C4zAiJB

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