Wang Zj

Mechanism of Crystal Structure Transformation and Abnormal Reduction in Ca5–y(BO3)3–x(PO4)xF (CBPxF):yBi3+

Tricoordinated planar triangle (PO4)3- may be formed due to the structural differences between planar triangular (BO3)3- and tetrahedral (PO4)3- when (BO3)3- is gradually substituted by (PO4)3-. This transformation of structure may affect the luminescence properties of phosphor. Therefore, a series of Ca5- y(BO3)3- x(PO4) xF (CBP xF): yBi3+ ( y = 0.05, 0.15; x = 0-3), Ca5- y(PO4)3- X(BO3) XF (CPB XF): yBi3+ ( y = 0.05, 0.15; X = 0-1), Ca4.9(PO4)3F (CPF):0.1Eu3+, Ca4.95(PO4)3F (CPF):0.05Bi3+, and nCaF2/CaCl2 ( n = 0-0.1) are synthesized to explore transformation of the crystal structure on luminescence properties. In CBP xF:0.15Bi3+ ( x = 0-3), (PO4)3- is doped to substitute for (BO3)3-, the position of emission spectra remains unchanged and the emission intensity decreases rapidly with increasing x. The underlying main reason for that is formation of the triangular plane (PO4)3-, which has been verified by performing a series of verification experiments of CPB XF: yBi3+ ( y = 0.5, 0.15; X = 0-1). In CPB XF: yBi3+ ( y = 0.5, 0.15; X = 0-1), (BO3)3- is doped to substitute for (PO4)3-, P-O2 bond breaks and the coordination of (PO4)3- varies from four to three when 0.5 < X < 1; meanwhile, the crystal structure transforms from Ca5(PO4)3F (ICSD-9444) to Ca5(PO4)3F (ISCD-30261), which impedes abnormal reduction from Bi3+ to Bi2+. Furthermore, Bi3+ should non-luminance in the plane triangular (PO4)3-, but luminescence in (BO3)3-. Therefore, the emission intensity starts to increase and the emission position suddenly changes from 553 to 474 nm in CPB XF: yBi3+ ( y = 0.05, 0.15; 0.5 < X < 1). From this, the crystal structures of CBP xF: yBi3+ ( y = 0.05, 0.15; x = 0-3) has been inferred to transform from Ca5(BO3)3F (ISCD-65763) to Ca5(PO4)3F (ISCD-30261), and then to Ca5(PO4)3F (ISCD-9444) with x increasing. Emission position remains unchanged and the emission intensity decreases rapidly in CBP xF: yBi3+ ( y = 0.05, 0.15; x = 0-3) do to formation of the triangular plane (PO4)3-. In addition, the rate of abnormal reduction from Bi3+ to Bi2+ can be improved by reducing the electronegativity of the environment around the activator or increasing the ionization energy of the activator, which has been confirmed by verification experiments of CPF:0.05Bi3+, nCaF2/CaCl2 ( n = 0-0.1), and CPF:0.1Eu3+.