This invention provides compositions of matter that contain an electron emitting substance and an expansion material. The expansion material may, for example, be an intercalation compound. When a film is formed from the composition, expansion of the expansion material typically causes rupturing or fracturing of the film. No further treatment of the surface of the film is typically required after expansion of the expansion material to obtain good emission properties. A surface formed from such a fractured film acts as an efficient electron field emitter and thus is useful in vacuum microelectronic devices.