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Chemical composition mapping with nanometre resolution by soft X-ray microscopy

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Abstract

X-ray microscopy is powerful in that it can probe large volumes of material at high spatial resolution with exquisite chemical, electronic and bond orientation contrast1,2,3,4,5. The development of diffraction-based methods such as ptychography has, in principle, removed the resolution limit imposed by the characteristics of the X-ray optics6,7,8,9,10. Here, using soft X-ray ptychography, we demonstrate the highest-resolution X-ray microscopy ever achieved by imaging 5 nm structures. We quantify the performance of our microscope and apply the method to the study of delithiation in a nanoplate of LiFePO4, a material of broad interest in electrochemical energy storage11,12. We calculate chemical component distributions using the full complex refractive index and demonstrate enhanced contrast, which elucidates a strong correlation between structural defects and chemical phase propagation. The ability to visualize the coupling of the kinetics of a phase transformation with the mechanical consequences is critical to designing materials with ultimate durability.

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Figure 1: Layout of the soft X-ray ptychographic microscope.
Figure 2: Ptychographic reconstruction of a resolution test object.
Figure 3: X-ray microscopy of partially delithiated LiFePO4.
Figure 4: Results of chemical mapping.

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Acknowledgements

All measurements were carried out at either beamline 11.0.2 or beamline 5.3.2.1 at the Advanced Light Source (ALS). The ALS is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy (contract no. DE-AC02-05CH11231). The authors acknowledge the support of ALS technical and safety staff and discussions with J. Kirz and J. Spence. This work is partially supported by the Center for Applied Mathematics for Energy Research Applications (CAMERA), which is a partnership between Basic Energy Sciences (BES) and Advanced Scientific Computing Research (ASRC) at the US Department of Energy. The chemical imaging work on LiFePO4 carried out by Y.S.Y., J.C. and Y.S.M. was supported as part of the Northeastern Center for Chemical Energy Storage, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (award no. DE-SC0001294). The authors thank G. Chen (LBNL) for supplying the delithiated LiFePO4 sample. J.C. thanks T. Richardson and R. Kostecki (LBNL) for technical discussions.

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D.A.S., S.M., T.T., K.K., H.P., T.W. and J.C. conceived and planned the experiment. D.A.S., S.M., T.T., R.C., A.S., D.K., T.W., W.C. and L.Y. developed experimental techniques, software and equipment. W.C. and Y.S.Y. prepared the samples. D.A.S., T.T., K.K., D.K. and Y.S.Y. carried out the measurements. D.A.S., S.M. and F.M. developed data processing and ptychography reconstruction codes. D.A.S. and Y.S.Y. performed post-experiment data analysis and Y.S.Y., Y.S.M. and J.C. established the interpretation of the chemical maps. D.A.S., Y.S.Y. and J.C. prepared the manuscript, which incorporates input from all authors.

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Correspondence to David A. Shapiro.

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The authors declare no competing financial interests.

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Shapiro, D., Yu, YS., Tyliszczak, T. et al. Chemical composition mapping with nanometre resolution by soft X-ray microscopy. Nature Photon 8, 765–769 (2014). https://doi.org/10.1038/nphoton.2014.207

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