Journal of Luminescence

Systematics of 4f electron energies relative to host bands by resonant photoemission of rare earth doped optical materials

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Relative energies of 4fn electronic states and crystal band states are important for a fundamental understanding of rare-earth-doped optical materials and a practical understanding of each material's potential performance in specific applications. With this motivation, the 4fn ground state binding energies of rare earth ions have been studied in the gallium garnets using resonant photoemission spectroscopy and compared with the aluminum and iron garnets. The 4d-4f photoemission resonance was used to separate and identify the 4fn and valence band components of the spectra, and theoretical 4f photoemission spectra were fit to experimental results to accurately determine electron binding energies. A two-parameter empirical model was used to successfully describe the relative energies of the 4fn ground states in these materials. The success of this empirical model indicates that measurements on as few as two different rare earth ions in a host are sufficient to predict the energies of all rare earth ions in that host. This analysis shows that systematic shifts in the relative energies of 4fn states and crystal band states between different garnets arise entirely from shifts of the band states, while each rare earth ion maintains the same absolute binding energy for all garnets studied. These results suggest that further studies of additional host compounds using both photoemission and optical spectroscopy will rapidly lead to a broader picture of the host crystal's effect on 4f electron binding energies. © 2001 Elsevier Science B.V. All rights reserved.