Scanning transmission electron microscopy (STEM) is capable of imaging at sub-Ångström resolution, simultaneously acquiring multiple signals resulting from the elastic and inelastic scattering of the electron probe. In this thesis theoretical advances are made, in tandem with experiment, to develop novel imaging techniques in STEM: the characterisation of surface reconstructions using secondary electrons, a method for elemental mapping, a method for studying electric and magnetic fields in a specimen and an investigation of specimen mis-tilt in annular bright-field imaging.