Home > News & Events : News > 2023.04 > Discovering Hidden Order in Disordered Crystals -New Material Analysis Method Combining Resonant X-Ray Diffraction and Solid-State NMR-

Discovering Hidden Order in Disordered Crystals -New Material Analysis Method Combining Resonant X-Ray Diffraction and Solid-State NMR-

April 27, 2023

April 27, 2023

Tokyo Institute of Technology
Yamagata University
Japan Synchrotron Radiation Research Institute
High Energy Accelerator Research Organization (KEK)
J-PARC Center

 Discovering Hidden Order in Disordered Crystals

-New Material Analysis Method

Combining Resonant X-Ray Diffraction and Solid-State NMR-

Determining the precise structure of a crystalline solid is a challenging endeavor. Materials properties such as ion conduction and chemical stability, are heavily influenced by the chemical (occupational) order and disorder. However, the techniques that scientists typically use to elucidate unknown crystal structures suffer from serious limitations.

For instance, X-ray and neutron diffraction methods are powerful techniques to reveal the atomic positions and arrangement in the crystal lattice.  However, they may not be adequate for distinguishing different atomic species with similar X-ray scattering factors and similar neutron scattering lengths.

To tackle this issue, a research team led by Professor Masatomo Yashima of Tokyo Institute of Technology (Tokyo Tech) in Japan sought to develop a novel and more powerful approach to analyze the order and disorder in crystals. They combined four different techniques to analyze the crystal structure of an important ionic conductor, Ba7Nb4MoO20. “We chose Ba7Nb4MoO20 as Ba7Nb4MoO20-based oxides and related compounds are a class of emerging materials with interesting properties such as high ionic conduction and high chemical stability,” explains Prof. Yashima. “However, given that both the Mo6+ and Nb5+ cations have similar scattering powers, all structural analyses of Ba7Nb4MoO20 until now have been performed assuming complete Mo/Nb disorder.”

As described in their recent paper published in Nature Communications, the researchers used an approach that combined two experimental techniques, resonant X-ray diffraction (RXRD) and solid-state nuclear magnetic resonance (NMR) aided by computational calculations based on density functional theory (DFT). The NMR provided direct experimental evidence that the Mo atoms occupy only the crystallographic M2 site in Ba7Nb4MoO20, indicating the chemical order of Mo atoms.

Next, the researchers used RXRD to quantify the occupancy factors of Mo and Nb atoms. They found that the occupancy factor of Mo atoms was 0.5 at the M2 site but zero at all other sites. Interestingly, the M2 site is close to the oxide-ion conducting, oxygen-deficient layer of Ba7Nb4MoO20. This suggests that the Mo atoms at the M2 site have key role in the high ion conduction of Ba7Nb4MoO20. Furthermore, DFT calculations indicated that the Mo ordering stabilizes Mo excess composition exhibiting high ionic conductivity. Positions, occupancy, and atomic displacements of protons and oxide ions were also determined by neutron diffraction.

 “Our results demonstrate that the Mo order affects the material properties of Ba7Nb4MoO20,” highlights Prof. Yashima. “In this regard, our work represents a major advance in our understanding of the correlation between the crystal structure and the material properties of ionic conductors.” Further, in contrast to single-crystal X-ray and neutron diffraction, the proposed approach can even be extended to other polycrystalline and powdered samples.

Overall, the methodology presented in this study can open up new avenues for an in-depth analysis of chemical order/disorder in materials. In turn, this could lead to the development of physics, chemistry, and materials science and technology.

Only time will tell what other hidden orders and disorders we will stumble upon!



Yuta Yasui1 Masataka Tansho2, Kotaro Fujii1, Yuichi Sakuda1, Atsushi Goto2, Shinobu Ohki2, Yuuki Mogami2, Takahiro Iijima3, Shintaro Kobayashi4, Shogo Kawaguchi4, Keiichi Osaka5, Kazutaka Ikeda6,7,8, Toshiya Otomo6,7,8,9, Masatomo Yashima1*
Title: Hidden chemical order in disordered Ba7Nb4MoO20 revealed by resonant X-ray diffraction and solid-state NMR
Journal: Nature Communications
DOI: DOI:10.1038/s41467-023-37802-4

1Department of Chemistry, School of Science, Tokyo Institute of Technology

2NMR Station, National Institute for Materials Science (NIMS)

3Institute of Arts and Sciences, Yamagata University

4Diffraction and Scattering Division, Japan Synchrotron Radiation Research Institute (JASRI), SPring-8

5Industrial Application and Partnership Division, Japan Synchrotron Radiation Research Institute (JASRI), SPring-8

6Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK)

7J-PARC Center, High Energy Accelerator Research Organization (KEK)

8School of High Energy Accelerator Science, The Graduate University for Advanced Studies

9Graduate School of Science and Engineering, Ibaraki University

*Corresponding author’s email: yashima@cms.titech.ac.jp

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