Manganese Luminescent Centers of Different Valence in Yttrium Aluminum Borate Crystals

https://doi.org/10.3390/ma16020537

We present an extensive study of the luminescence characteristics of Mn impurity ions in a YAl₃(BO₃)₄:Mn crystal, in combination with X-ray fluorescence analysis and determination of the valence state of Mn by XANES (X-ray absorption near-edge structure) spectroscopy. The valences of manganese Mn²⁺(d⁵) and Mn³⁺(d⁴) were determined by the XANES and high-resolution optical spectroscopy methods shown to be complementary. We observe the R₁ and R₂ luminescence and absorption lines characteristic of the ²E ↔ ⁴A₂ transitions in d³ ions (such as Mn⁴⁺ and Cr³⁺) and show that they arise due to uncontrolled admixture of Cr³⁺ ions. A broad luminescent band in the green part of the spectrum is attributed to transitions in Mn²⁺. Narrow zero-phonon infrared luminescence lines near 1060 nm (9400 cm⁻¹) and 760 nm (13,160 cm⁻¹) are associated with spin-forbidden transitions in Mn³⁺: ¹T₂ → ³T₁ (between excited triplets) and ¹T₂ → ⁵E (to the ground state). Spin-allowed ⁵T₂ → ⁵E Mn³⁺ transitions show up as a broad band in the orange region of the spectrum. Using the data of optical spectroscopy and Tanabe–Sugano diagrams we estimated the crystal-field parameter Dq and Racah parameter B for Mn³⁺ in YAB:Mn as Dq = 1785 cm⁻¹ and B = 800 cm⁻¹. Our work can serve as a basis for further study of YAB:Mn for the purposes of luminescent thermometry, as well as other applications.