Low temperature red luminescence of a fluorinated Mn-doped zinc selenite

Joseba Orive; Rolindes Balda; Joaquín Fernández; Luis Lezama; María I. Arriortua

doi:10.1039/C3DT51224J

Low temperature red luminescence of a fluorinated Mn-doped zinc selenite†

Joseba Orive,^a Rolindes Balda,^bc Joaquín Fernández,^bc Luis Lezama^d and María I. Arriortua*^a

* Corresponding authors

^a Departamento de Mineralogía y Petrología, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Apdo. 644, 48080 Bilbao, Spain
E-mail: joseba.orive@ehu.es, maribel.arriortua@ehu.es
Fax: +34 946 013 500
Tel: +34 946 015 984

^b Departamento de Física Aplicada I, Escuela Técnica Superior de Ingeniería, Alda. Urquijo s/n, 48013 Bilbao, Spain
E-mail: rolindes.balda@ehu.es, joaquin.fernandez@ehu.es
Fax: +34 946 014 178
Tel: +34 946 014 044

^c Centro de Física de Materiales CSIC-UPV/EHU and Donostia International Physics Center, Apdo. 1072, 20080 San Sebastián, Spain

^d Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Apdo. 644, 48080 Bilbao, Spain
E-mail: luis.lezama@ehu.es
Fax: +34 946 013 500
Tel: +34 946 012 703

Abstract

M₂(SeO₃)F₂ (M = Zn (1), Mn (2)) stoichiometric phases together with the Zn_2−xMn_x(SeO₃)F₂ compound doped at various concentrations (x = 0.002–0.2) were synthesized by employing mild hydrothermal conditions. These compounds have been characterized by scanning electron microscopy (SEM), Rietveld refinement of the X-ray powder diffraction patterns, ICP-Q-MS, thermogravimetric and thermodiffractometric analyses, and IR, UV/vis and electron paramagnetic resonance (EPR) spectroscopies. Compounds 1 and 2 crystallize in the orthorhombic Pnma space group with lattice parameters: a = 7.27903(4), b = 10.05232(6) and c = 5.26954(3) Å for the zinc species and a = 7.50848(9), b = 10.3501(12) and c = 5.47697(6) Å for the manganese phase, with Z = 4. The crystal structures of these compounds are isotypic and are built up from a 3D framework constructed by (010) sheets of [MO₃F₃] octahedra linked up by [SeO₃] building units. Luminescence measurements of Mn₂(SeO₃)F₂ were performed at different temperatures between 10 and 150 K. At 10 K, the emission spectrum consists of a broad band peaked at around 660 nm related to the ⁴T_1g → ⁶A_1g transition in octahedrically coordinated Mn²⁺. Moreover, the influence of temperatures up to 295 K and the Mn concentration on the luminescent properties of the Zn_2−xMn_x(SeO₃)F₂ system were systematically studied. Magnetic measurements of 2 show antiferromagnetic coupling as the major interactions exhibiting a spin canting at low temperature.

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Low temperature red luminescence of a fluorinated Mn-doped zinc selenite†

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Low temperature red luminescence of a fluorinated Mn-doped zinc selenite

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