Effect of symmetry reduction on the electronic transitions in polytypic GdAl3(BO3)4:Eu:Tb crystals

• Eu3+ and Tb3+ absorption bands were identified in diverse GAB crystals.
• Crystal field splitting and shifting of the electronic transitions were shown.
• The 7F0,1,2 and 5D0,1,2 levels of the Eu3+ ions were successfully determined.

The existence of a recently described monoclinic phase (C2/c, Z = 8) (Beregi et al., 2012) in addition to the well-known Huntite type rhombohedral (R32) polytypic modification of the GdAl3(BO3)4 (GAB) crystal at room temperature provides a unique possibility to investigate the incorporation of rare earth dopants into slightly modified crystal lattice by spectroscopic methods. In these characteristic GAB structures the dopant ions, e.g. Tb3+ or Eu3+, possess slightly different neighbor geometries and local symmetries. The Tb3+: 7F6 → 5D4 and Eu3+: 7F0,1,2 → 5D0,1,2 electronic transitions were successfully identified in the absorption spectra using polarization, concentration and temperature dependent measurements in both polytypic modifications. The positions of the investigated Tb lines are shifted by up to 10 cm−1 due to symmetry changes. In addition, some of the Eu lines show splittings of about 4–30 cm−1 as a consequence of the change of the local environment. From the room temperature absorption measurements some of the low energy crystal field levels of 7F and 5D states of the Eu3+ ions were successfully determined for both modifications.