Starting from previous investigations in LiNbO3 bulk crystals, we studied the optical properties of Er3+ ions in Ti:LiNbO3 channel waveguides and investigated the waveguide-specific lattice environment of the Er3+ ions (“sites”) caused by the doping method used and the presence of a large number of Ti4+ ions. For that purpose the method of combined excitation–emission spectroscopy was applied for the first time to waveguides at low temperatures. Comparing the spectroscopic results obtained for the green, red, and near-IR luminescence (λ≈550, ≈650 and ≈980 nm) under direct (450 nm), 2-step (980 nm), and 3-step (1.5 μm) laser excitation, we found several distinguishable Er3+ sites which in terms of energy levels and relative numbers are similar to those in bulk material, but exhibit significantly different up-conversion efficiencies and strongly inhomogeneously broadened transitions. Moreover, we were able to distinguish isolated and cluster Er3+ sites by their characteristic excitation and emission transition energies and studied the respective excitation/relaxation channels. The cluster sites are most efficient in the up-conversion process, especially under 3-step excitation. Using accepted microscopic models for Er3+ and Ti4+ incorporation into the LiNbO3 crystal lattice, the site distribution and up-conversion mechanisms are elucidated and their consequences for laser applications in different spectral regions are discussed.
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