I deal with photoelectron microscopy (PEEM) and spectroscopy (XPS
 when excited by X-rays and UPS with ultraviolet radiation) 
at a NanoESCA instrument on various 
materials. These must be at least slightly conductive and have a 
smooth surface, like metals, semiconductors, thin organic layers
 and even ultra-thin non-conductive layers on 
conductive substrates. Various combinations of 
microscopy with spectroscopy are also possible, 
including angle-resolved photoemission spectroscopy (ARPES).