Crystalline defects such as oxygen vacancies have been studied little by electron paramagnetic resonance (EPR) spectroscopy for silicate-based luminescent materials. In this study, lutetium oxyorthosilicate powders were prepared by the sol–gel method, using TEOS (silicon source) and rare earth salts as precursors. The cross-linking agent, Glymo, contributed silicon atoms to the precursor solution in all systems. The addition of Glymo to Lu₂SiO₅, Lu₂SiO₅:Eu and Lu₂SiO₅:Eu/Yb influenced the morphology and chemical structure of the powders, leading to Lu₂Si₂O₇ formation. The crystalline defects in the lutetium silicate systems were investigated by EPR spectroscopy, and several defects related to oxygen were identified, as well as impurities from the precursors. Photoluminescence emission spectra revealed Eu³⁺ transitions between ⁵D₀ → ⁷F₀, ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ under 258 nm excitation, in addition to oxygen vacancy emissions between 500 and 550 nm. Oxygen vacancies were identified and confirmed by correlating EPR and photoluminescence studies.

Eu³⁺-(5% mol)-doped Lu₂SiO₅ optical quality films were prepared using the sol–gel method and dip-coating technique from lutetium and europium salts as the lanthanide precursors and tetraethyl orthosilicate (TEOS) as the silicon source. To increase the thickness of the films, 3-Glycidyloxypropyl trimethoxysilane (Glymo) was added as the rheological agent during sol formation. Structural, morphological, and luminescent properties were investigated for Lu₂SiO₅, Eu³⁺:Lu₂SiO₅, and Eu³⁺:Lu₂SiO₅/Glymo in order to obtain high quality in luminescent films. X-ray diffraction (XRD) results show that the incorporation of the Eu³⁺ ions do not affect the A-Type and B-Type monoclinic crystalline phase typical of Lu₂SiO₅, even after five dipping cycles on quartz substrates and a final annealing process at 1100 °C. The morphology and topography of the films were studied by SEM and AFM. These techniques revealed films without surfactant that were uniform with low rugosity while the film with surfactant presented porous hills and valleys with uneven high values of roughness. The photoluminescence spectrum of Eu³⁺:Lu₂SiO₅ films showed 2 broad emission peaks centered at 589 nm and 612 nm. The presence of Glymo in the system promoted the formation of residual Lu₂Si₂O₇ compounds with the highest lifetime values compared with films without surfactant. The results of the films are promising for luminescent applications.