**Abstract**

The realization of three-dimensional (3D)-architected nanostructures, that is, the transformation from novel two-dimensional (2D) film-based devices to 3D complex nanodevices, is of crucial importance with the progress of scaling down devices to nanometer order. However, little attention has been devoted to controlling the atomic ordering and structures of side-surfaces on 3D structures, while techniques for controlling and investigating 2D surfaces, namely, surface science, have been established only for planar 2D surfaces. We have established an original methodology that enables atomic orderings and arrangements of surfaces with arbitrary directions to be observed on 3D figured structures by developing diffraction and microscopy techniques. An original technique, namely, directly and quantitatively viewing the side- and facet-surfaces at the atomic scale by reflection highenergy electron diffraction (RHEED) and low-energy electron diffraction (LEED), can be used to determine process parameters in etching. This chapter introduces methods of evaluation by RHEED and LEED based on a reciprocal space map and methods of creating various atomically flat 111 f g and {100} side-surfaces of 3D Si nano-architectures and tilted 111 f g facet-surfaces fabricated by lithography dry and wet etching processes, followed by annealing treatment in vacuum.

**Keywords:** side-surface, facet-surface, atomically flat, Si, lithography, dry etching, wet etching, electron diffraction, reciprocal space map
