Low work function materials are disclosed together with methods for their manufacture and integration with electrodes used in thermionic conversion applications (specifically microminiature thermionic conversion applications). The materials include a mixed oxide system and metal in a compositionally modulated structure comprised of localized discontinuous structures of material that are deposited using techniques suited to IC manufacture, such as rf sputtering or CVD. The structures, which can include layers are then heated to coalescence yielding a thin film that is both durable and capable of electron emission under thermionic conversion conditions used for microminiature thermionic converters. Using the principles of the invention, thin film electrodes (emitters and collectors) required for microconverter technology are manufactured using a single process deposition so as to allow for full fabrication integration consistent with batch processing, and tailoring of emission/collection properties. In the preferred embodiment, the individual layers include mixed BaSrCaO, scandium oxide and tungsten.