Flux growth and liquid phase epitaxy of undoped and Mn⁶⁺-doped sulfates, tungstates, and molybdates

The Mn6+ ion is a promising activator ion for tunable and short-pulse laser materials because of its broadband luminescence in the spectral region 850-1600 nm and its simple 3d1 electronic configuration, which excludes an occurrence of undesirable exited-state absorption into higher 3d levels. However, hexavalent manganese can be stabilized only in the tetrahedral oxo-coordination and easily reduces to Mn5+ or Mn4+ at temperatures above 600°C. Recently, flux [1] and liquid-phase epitaxy (LPE) [2] growth of Mn6+-doped sulfates has been reported, while except for BaMoO4:Mn6+ [3] investigations on the mechanically more stable alkaline-earth-metal molybdates and tungstates as possible host materials for efficient Mn6+ incorporation have as yet not been reported. We investigated the growth conditions of undoped and Mn6+-doped MAO4, with M = Ca, Sr, Ba and A = S, Mo, W, from the ternary NaCl-KCl-CsCl solvent at temperatures 480-600°C. The growth rates increase in the series tungstates < molybdates < sulfates and depending on the cation, in the series Ca < Sr < Ba. The dopant ion Mn6+ can be easily incorporated into BaSO4, less well into BaMoO4 and BaWO4, whereas for Ca- and Sr-containing tungstates and molybdates no significant doping was found, independent on the concentration of Mn6+ in the liquid solution. Moreover, reduction of the Mn6+ ion cannot be avoided, even at the presence of oxidizing additives such as K2CO3 or NaOH. LPE was employed for growing Mn6+-doped layers of BaAO4 compounds. Growth velocities of 3-5 µm/h in the temperature interval from 490-540°C from chloridic solution, containing 0.3-1mol% of K2MnO4 with respect to the solute, delivered dark-pink BaSO4 and slightly green BaMoO4 and BaWO4 layers up to 200 µm in thickness. With respect to high Mn6+ doping levels, BaSO4 is the most suitable host material and its further investigation under different initial concentrations of manganese is currently underway. [1] T.C. Brunold, H.U. Güdel, Inorg. Chem. 36, 1946 (1997). [2] D. Ehrentraut, M. Pollnau, Appl. Phys. B 75, 59 (2002). [3] T.C. Brunold, H.U. Güdel, Chem. Phys. Lett. 249, 77 (1996).