Date of Award

1-1-2015

Language

English

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

College/School/Department

Department of Chemistry

Content Description

1 online resource (xiv, 114 pages) : color illustrations.

Dissertation/Thesis Chair

Paul J Toscano

Committee Members

Alok M Srivastava, Mehmet Yigit

Keywords

Centroid, Exciton, Lanthanides, Luminescence, octahedral, Rare earth metals, Coordination compounds, Electronic excitation

Subject Categories

Chemistry

Abstract

In this dissertation, we have studied the luminescence of the lanthanide ions (Ce3+, Eu2+, Eu3+, Tb3+, and Pr3+), specifically in the highly symmetric octahedral coordination. This high symmetry coordination readily permits the optical properties of the luminescent ions to be determined spectroscopically. Relevant optical parameters such as the Stokes Shift (∆S), red shift (D(2+, 3+, A), crystal field splitting (Ɛcfs), and centroid sift (Ɛc), along with the excitation and emission spectra, are presented. Three different crystal structures were studied, namely, M2+Al2B2O7 (M2+ = Ca, Sr, Ba) doped with Eu2+ and Ce3+, KBaLn3+(BO3)2 (M3+ = all lanthanides, Y, Sc) doped with Ce3+, Eu3+, and Pr3+, and the Ca9Ln3+(PO4)7 (M3+ = Al, Sc, Y, Lu, Gd, La) doped with Ce3+ and Pr3+. These crystal structures were chosen, because they all contain an octahedrally coordinated cation of either M2+ or M3+. Finally, we determined a method to predict the centroid shift of Ce3+ or Eu2+ based on the energy of the host lattice exciton emission. This was done by analyzing data presented in the historical literature.

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