Among insulating materials containing point defects, Lithium Fluoride, LiF, is a radiation sensitive material well known in dosimetry and as active medium in optically pumped optolectronic devices. Primary and aggregate electronic defects, known as colour centres (CCs), can be efficiently produced in LiF by low-penetrating radiation. A novel imaging detector for soft X-ray microscopy, based on photoluminescence from laser active CCs, is currently under development. The continuous shrinking dimensions of photonic devices has prompted us to use thin LiF films, directly grown by thermal evaporation on different substrates, as recording media in Extreme Ultra-Violet contact-lithography experiments for the fabrication of permanent, regular, light-emitting microstructures, produced with high spatial resolution on large areas in short exposure times. The experiments were performed by using geometrical masks in an excimer-pumped laser-plasma source and the samples analyzed by confocal laser scanning microscopy. Strong visible photoluminescence at room temperature was measured from very thin surface layers. A preliminary comparison between the optical response of CCs in thin LiF films grown on glass and silicon substrates with respect to LiF crystals was performed. The polycrystalline LiF films show a higher sensitivity, which is discussed taking into account light confinement effect in the investigated planar structures.