Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

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



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.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

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.


  1. Kirz, J., Jacobsen, C. & Howells, M. Soft X-ray microscopes and their biological applications. Q. Rev. Biophys. 28, 33–130 (1995).

    Article  Google Scholar 

  2. Ade, H. & Stoll, H. Near-edge X-ray absorption fine-structure microscopy of organic and magnetic materials. Nature Mater. 8, 281–290 (2009).

    Article  ADS  Google Scholar 

  3. Chao, W., Kim, J., Rekawa, S., Fischer, P. & Anderson, E. H. Demonstration of 12 nm resolution Fresnel zone plate lens based soft X-ray microscopy. Opt. Express 17, 17669–17677 (2009).

    Article  ADS  Google Scholar 

  4. Rehbein, S., Heim, S., Guttmann, P., Werner, S. & Schneider, G. Ultrahigh-resolution soft-X-ray microscopy with zone plates in high orders of diffraction. Phys. Rev. Lett. 103, 110801 (2009).

    Article  ADS  Google Scholar 

  5. Vila-Comamala, J. et al. Zone-doubled Fresnel zone plates for high-resolution hard X-ray full-field transmission microscopy. J. Synchrotron Radiat. 19, 705–709 (2012).

    Article  Google Scholar 

  6. Rodenburg, J. M. et al. Hard-X-ray lensless imaging of extended objects. Phys. Rev. Lett. 98 034801 (2007).

    Article  ADS  Google Scholar 

  7. Thibault, P. et al. High-resolution scanning X-ray diffraction microscopy. Science 321, 379–382 (2008).

    Article  ADS  Google Scholar 

  8. Dierolf, M. et al. Ptychographic X-ray computed tomography at the nanoscale. Nature 467, 436–439 (2010).

    Article  ADS  Google Scholar 

  9. Holler, M. et al. An instrument for 3D X-ray nano-imaging. Rev. Sci. Instrum. 83, 073703 (2012).

    Article  ADS  Google Scholar 

  10. Schropp, A. et al. Hard X-ray scanning microscopy with coherent radiation: beyond the resolution of conventional X-ray microscopes. Appl. Phys. Lett. 100, 253112 (2012).

    Article  ADS  Google Scholar 

  11. Kang, B. & Ceder, G. Battery materials for ultrafast charging and discharging. Nature 458, 190–193 (2009).

    Article  ADS  Google Scholar 

  12. Tarascon, J.-M. Key challenges in future Li-battery research. Phil. Trans. R. Soc. Math. Phys. Eng. Sci. 368, 3227–3241 (2010).

    Article  ADS  Google Scholar 

  13. Thibault, P., Dierolf, M., Bunk, O., Menzel, A. & Pfeiffer, F. Probe retrieval in ptychographic coherent diffractive imaging. Ultramicroscopy 109, 338–343 (2009).

    Article  Google Scholar 

  14. Howells, M. R. et al. An assessment of the resolution limitation due to radiation-damage in X-ray diffraction microscopy. J. Electron Spectrosc. Relat. Phenom. 170, 4–12 (2009).

    Article  Google Scholar 

  15. Kilcoyne, D. et al. A new scanning transmission X-ray microscope at the ALS for operation up to 2500 eV. AIP Conference Proceedings Vol 1234, 465–468 (2010).

  16. Bluhm, H. et al. Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source. J. Electron Spectrosc. Relat. Phenom. 150, 86–104 (2006).

    Article  Google Scholar 

  17. Kilcoyne, A. L. D. et al. Interferometer-controlled scanning transmission X-ray microscopes at the Advanced Light Source. J. Synchrotron Radiat. 10, 125–136 (2003).

    Article  Google Scholar 

  18. Marchesini, S., Schirotzek, A., Yang, C., Wu, H. & Maia, F. Augmented projections for ptychographic imaging. Inverse Problems 29, 115009 (2013).

    Article  ADS  MathSciNet  Google Scholar 

  19. Yashchuk, V. V. et al. Characterization of electron microscopes with binary pseudo-random multilayer test samples. Nucl. Instrum. Methods Phys. Res. A 649, 150–152 (2011).

    Article  ADS  Google Scholar 

  20. Jacobsen, C. et al. Diffraction-limited imaging in a scanning transmission X-ray microscope. Opt. Commun. 86, 351–364 (1991).

    Article  ADS  Google Scholar 

  21. Yuan, L.-X. et al. Development and challenges of LiFePO4 cathode material for lithium-ion batteries. Energy Environ. Sci. 4, 269–284 (2011).

    Article  Google Scholar 

  22. Malik, R., Aziz, A. & Ceder, G. A critical review of the Li insertion mechanisms in LiFePO4 electrodes. J. Electrochem. Soc. 160, A3179–A3197 (2013).

    Article  Google Scholar 

  23. Boesenberg, U. et al. Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation. Chem. Mater. 25, 1664–1672 (2013).

    Article  Google Scholar 

  24. Moreau, P., Mauchamp, V., Pailloux, F. & Boucher, F. Fast determination of phases in LixFePO4 using low losses in electron energy-loss spectroscopy. Appl. Phys. Lett. 94, 123111 (2009).

    Article  ADS  Google Scholar 

  25. Lerotic, M., Jacobsen, C., Schafer, T. & Vogt, S. Cluster analysis of soft X-ray spectromicroscopy data. Ultramicroscopy 100, 35–37 (2004).

    Article  Google Scholar 

  26. Chen, G., Song, X. & Richardson, T. J. Electron microscopy study of the LiFePO4 to FePO4 phase transition. Electrochem. Solid-State Lett. 9, A295–A298 (2006).

    Article  Google Scholar 

  27. Denes, P., Doering, D., Padmore, H. A., Walder, J.-P. & Weizeorick, J. A fast, direct X-ray detection charge-coupled device. Rev. Sci. Instrum. 80, 083302 (2009).

    Article  ADS  Google Scholar 

  28. Luke, D. R. Relaxed averaged alternating reflections for diffraction imaging. Inverse Problems 21, 37–50 (2005).

    Article  ADS  MathSciNet  Google Scholar 

  29. Dokko, K., Koizumi, S., Nakano, H. & Kanamura, K. Particle morphology, crystal orientation, and electrochemical reactivity of LiFePO4 synthesized by the hydrothermal method at 443 K. J. Mater. Chem. 17, 4803–4810 (2007).

    Article  Google Scholar 

Download references


All measurements were carried out at either beamline 11.0.2 or beamline 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.

Author information

Authors and Affiliations



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.

Corresponding author

Correspondence to David A. Shapiro.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2430 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing