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Canadian Centre for Electron Microscopy, Department of Chemistry, Brockhouse Institute for Materials Research,
and Department of Materials Science and Engineering, McMaster University, Hamilton, Canada, L8S 4M1
INTRODUCTION
In complex transition metal oxides, the coordination and
oxidation state of the transition metals is of fundamental
importance. Both are known to be related to the structural,
electronic, magnetic, catalytic, and ionic transport properties of
(complex) oxides.13 The coordination and valency of transition
metals in complex oxides can be determined by bulk methods
like Mo ssbauer spectroscopy and in some conditions by
diraction techniques. However, local changes in coordination
can be the key factors in materials applications.4,5 For example,
coordination changes at surfaces are of vital importance for
many catalytic processes while changes at defects like twin
boundaries, grain boundaries, and interfaces can greatly aect
the electronic, optical, and transport properties of bulk
materials and thin lms. The spatial resolution needed for the
determination of coordination for these important problems is
however not oered by classical bulk techniques like Mossbauer
or diraction methods.
Atomic resolution elemental mapping has become feasible
over the past years by means of spatially resolved electron
energy-loss spectroscopy (EELS) and, more recently, energy
dispersive X-ray spectroscopy in a scanning transmission electron
microscope (STEM-EELS and STEM-EDX)611 and has been
used for local structure renement.12 Even though STEM-EDX
appears to allow more straightforward data acquisition and
interpretation as compared to EELS, ne structure information
like bonding or coordination cannot be obtained from X-ray
2012 American Chemical Society
Chemistry of Materials
Article
EXPERIMENTAL SECTION
Chemistry of Materials
Article
Figure 3. Atomic resolution elemental maps for Ca, O, Fe, and Co along the [100] zone axis. (a) Raw Data. (b) Smoothed data. (c) Double
channelling, inelastic Bloch wave image simulations for Ca, O, Fe and Co. The maps clearly show that Co and Fe are intermixed in each Co/Fe
column, and demonstrate the repetition of the octahedral and tetrahedral coordination layers. (d) Averaged EELS spectra over the entire region
showing the Fe/Co ne structure in the octahedral and tetrahedral layers at an energy resolution of 1 eV.
was simulated using a relativistically corrected Dipole approximation
with a hard Bethe ridge cuto.
Chemistry of Materials
Article
Figure 4. EELS data acquired at high energy resolution and atomic spatial resolution. (a) Fe-L2,3 edge summed over the rst octahedral (red) and
tetrahedral (blue) layer. (b) Survey image indicating the area used for octahedral (red) and tetrahedral (blue) data summation (3 pixel width).
(c) Co-L2,3 edge summed over the rst octahedral (red) and tetrahedral layer (blue).
Figure 5. Octahedral and tetrahedral EELS maps generated by tting the average components to the atomic resolution data. The octahedral
component (b) and tetrahedral component (c) peak at the corresponding Fe/Co intermixed layers, as clearly evidenced by the intensity proles over
the full image width.
Chemistry of Materials
Article
CONCLUSION
We have demonstrated the possibility of coordination mapping
by atomically resolved high resolution EELS in an aberrationcorrected electron microscope, through the example of single
valency/mixed coordination cation compound Ca2FeCoO5.
Detailed analysis of the ne structure of the Co-L2,3 and the
Fe-L2,3 edges showed small variations in the ne structure that
could be attributed to Co/Fe in tetrahedral or Co/Fe in
octahedral coordination and that were in excellent agreement
with literature spectra for octahedral and tetrahedral coordinated Fe 3+/Co 3+. Using the spectra from octahedral/
tetrahedral Fe/Co layers as an internal reference (and in the
future possibly theoretical spectra to identify unknown
materials), the coordination of the Fe and Co atoms in the
compound could be mapped at atomic resolution. These
experiments open the gate for coordination determination at
surfaces, defects, and grains boundaries in a plethora of complex
oxide materials that have been out of reach in the past because
of the lack of suitable analysis techniques for the study of
valence and coordination as input for solving their structure.
AUTHOR INFORMATION
Corresponding Author
*E-mail: stuart.turner@ua.ac.be.
Notes
ACKNOWLEDGMENTS
A.M. Abakumov is thanked for fruitful discussions. S.T. gratefully
acknowledges the Fund for Scientic Research Flanders (FWO).
J.E.G. and G.A.B. acknowledge the support of the NSERC of
Canada through Discovery Grants. The Canadian Centre for
Electron Microscopy is a National Facility supported by NSERC
and McMaster University and was funded by the Canada
Foundation for Innovation and the Ontario Government. Part of
this work was supported by funding from the European Research
Council under the FP7, ERC Grant N 246791 COUNTATOMS
and ERC Starting Grant N 278510 VORTEX. The EMAT
microscope is partially funded by the Hercules fund of the Flemish
Government.
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