The work is devoted to the controlled crystal growth procedure providing of optimal doping of dielectric halide materials (LiF crystals in particular). Two series of LiF crystals were studied. One series is represented by ultra- and nominal pure crystals, as well as crystals doped with polyvalent oxides (Nb 2 O 5 , WO 3 and TiO 2 ), which were grown by classical Kyropoulos method in vacuum, second series involves crystals grown using the skull method. It is shown that the skull technique is a quite efficient method of variously doped LiF crystal growth as compare with the classic Kyropoulos method.