Enhancement of the Luminescent Properties of a New Red-Emitting Phosphor, Mn₂(HPO₃)F₂, by Zn Substitution

The Mn(2)(HPO(3))F(2) phase has been synthesized as single crystals by using mild hydrothermal conditions. The compound crystallizes in the orthorhombic Pnma space group, with unit cell parameters of a = 7.5607(8), b = 10.2342(7), and c = 5.5156(4) Å, with Z = 4. The crystal structure consists of a three-dimensional framework formed by alternating (010) layers of [MnO(3)F(3)] octahedra linked up by three connected [HPO(3)] tetrahedra. Luminescence measurements were performed at different temperatures between 10 and 150 K. The 10 K emission spectrum of the octahedrally coordinated Mn(II) cation exhibits a broad band centered at around 615 nm corresponding to the (4)T(1) → (6)A(1) transition. In order to explore the effect of the Mn(II) concentration and the possibility of enhancing the luminescence properties of the Mn(II) cation in Mn(2)(HPO(3))F(2), different intermediate composition members of the finite solid solution with the general formula (Mn(x)Zn(1-x))(2)(HPO(3))F(2) were prepared and their luminescent properties studied. The magnetic and specific heat behavior of M(2)(HPO(3))F(2) (M = Mn, Fe) have also been investigated. The compounds exhibit a global antiferromagnetic ordering with a spin canting phenomenon detected at approximately 30 K. The specific heat measurements show sharp λ-type peaks at 29.7 and 33.5 K for manganese and iron compounds, respectively. The total magnetic entropy is consistent with spin S = 5/2 and S = 2 of Mn(II) and Fe(II) cations.