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An advanced three-dimensional mapping approach utilizing reflection high-energy electron diffraction (RHEED) is introduced. The application of the method is demonstrated in detail by resolving the crystal structure and epitaxial relations of individual components within epitaxially grown magnetically ordered Co/MnF2/CaF2/Si(001) heterostructures. The electron diffraction results are cross-checked using synchrotron X-ray diffraction measurements. A number of advantages of the three-dimensional mapping technique as compared to conventional electron diffraction are demonstrated. Not least amongst these is the possibility to build arbitrary planar cross sections and projections through reciprocal space, including the plan-view projection onto the plane parallel to the sample surface, which is otherwise impossible to obtain.

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