Sharp luminescence system in titanium dioxide with zero-phonon transition at 1.573 eV

In this paper, we discuss near-IR steady-state and time-resolved low-temperature (5 K) luminescence of crystalline titanium dioxide (TiO2) powders with different particle sizes. Upon optical excitation with quantum energy close to 3.1 eV, the near-IR luminescence of all the powders reveals a very similar characteristic spectrum, which includes a narrow 1.573 eV line, a set of wider peaks in 1.565–1.545 eV range, and a broad band at ∼1.42 eV. The spectrum remains unchanged when using different excitation quanta, thus indicating that all components are governed by the same luminescence system. It is also confirmed by identic two-exponential luminescence decays with characteristic decay times 70 μs and 400 μs observed for all parts of the spectrum. The properties of the luminescent system are not sensitive to the crystallite size reduction to 10 nm, and its intensity sharply increases after annealing converting the anatase phase into rutile. A comparison of the spectrum with TiO2 phonon density of states indicates that 1.573 eV peak is a zero-phonon transition, and 1.545–1.565 eV structure is due to interaction with bulk phonons of rutile phase. The band at 1.42 eV seems to be due to non-adiabatic electron-phonon coupling. The data obtained clearly indicates that the luminescent system is governed by inner shells of transition elements located in rutile lattice. This transition element can be vanadium as it follows from ICP-MS data and theoretical modeling. The detected luminescent system provides a convenient optical marker of TiO2, including nanoform, and thus can be useful for some applications related to medicine, biology, as well as the food industry.