Carried out research has shown that the shape and cathodoluminescence intensity of nanostructured SnO₂ films is the reflection of structural state of analyzed object, and therefore the measurement of CL is effective method for characterization of thin metal oxide films, which have low photoluminescence intensity at room temperatures. It was found that cathodoluminescence of undoped and (Cu-, Fe-, or Co)-doped SnO₂ films, deposited by spray pyrolysis, is characterized by the presence of several broad emission bands in the range of the wavelength 370-650 nm, which intensity depends on deposition conditions and the following thermal treatment. The most intensive band on CL spectra of as-deposited films is the one at 500 nm. At that the growth of pyrolysis temperature is accompanied by a considerable increase of the CL intensity. It was established that SnO₂ doping by Cu, Fe, or Co leads to the decrease of CL and PL intensity. On the contrary, the annealing promotes the increase of the CL intensity, which is connected with improvement of SnO₂ films’ crystallinity. After annealing at Т~850 ^оС, an intensive band peaked at 370 nm appears in spectra for films with big size of crystallites. At that the doping does not change general character of CL spectra change, observed during annealing process. It was suggested the mechanism, explaining changes taking place in CL and PL spectra. It was made an assumption that observed transformation of CL spectra is connected with the change of both grain size and concentration of structural defects in SnO₂ surface layer. It was concluded that the radiative recombination takes place through shallow donor levels, associated with oxygen-vacancies, and trapped centers, forming deep levels, located at 0.8-0.9, 1.35-1.45 and ~ 1.6 eV from the top of valence band.

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