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This paper is aimed at explaining the effects of Tb3+ concentration on structure and luminescence properties and clarifying the concentration quenching mechanism of Tb3+. The lattice of BaF2 decreases with the increase of Tb3+ ions concentration. The emission spectrum of BaF2:Tb3+ consists of blue emission band and green emission band and corresponds to the transition of 5D3→7FJ (J = 0, 1, 2, 4,...