Synthesis and spectroscopy of system envolving tungstates and rare earth ions

Author(s)

Cláudia Akemi Kodaira

• Document type: Doctoral Thesis
• Press: São Paulo.
• Institution: Universidade de São Paulo (USP). Conjunto das Químicas (IQ e FCF) (CQ/DBDCQ)
• Defense date: 2003-03-14

Examining board members

Hermi Felinto de Brito; Vera Regina Leopoldo Constantino; Sidney José Lima Ribeiro; Osvaldo Antônio Serra; Gilmar Patrocínio Thim

• Advisor: Hermi Felinto de Brito

Abstract

The studies about the photoluminescent properties of the rare earth tungstates Eu2(WO4)3 and Gd2(WO4)3:RE3+ (RE3+ = Eu, Sm and Tb) obtained via three different methods of preparation were reported: i) ceramic method, which is the older one and uses high temperatures (>1000 ºC) and long periods of heating, with the physical mixture of the reagents in the powder form, grinding and calcination, ii) Pechini method, which consists on the complexation of cations in citric acid and ethylene glycol medium, forming a polymeric network that promotes the formation of RE tungstates at lower temperatures (~750 ºC) and iii) combustion method, which is based on a exothermic reaction between metal nitrates and an organic fuel, reaching rapidly high temperatures (>1000 ºC). The characterization of the RE tungstates was made using the following techniques: a) X-Ray diffraction - the XRD patterns showed characteristic peaks of the tungstates described in the literature, which are isostructural in the lanthanidic series, forming the scheelite structure; b) IV spectroscopy - absorption bands assigned to the unit [WO4] were observed in the spectra, confirming the Td point group; c) thermal analysis - the TG/DTG curves evidenced that the obtaining temperature of the RE tungstates lies around 750 ºC; d) scanning and transmission electronic microscopes - the micrographs illustrated the morphology and the particle size of the obtained systems and e) diffuse reflectance spectroscopy - the reflectance spectrum confirmed the position of the O→W charge transfer band around 265 nm. The photoluminescent properties of the compounds were studied based on the intraconfigurational transitions f5 (Sm3+), f6 (Eu3+) and f8 (Tb3+). The excitation spectra showed broad bands in the UV region, assigned to the LMCT O→W and O→TR3+ LMCT. In the case of the Eu2(WO4)3 compound, when the excitation is monitored in the 7F0→5L6 intraconfigurational transition of the Eu3+ ion (394 nm), the emission spectra show narrow bands coming from the 5D0 emitting level and also from the 5DJ states (J = 1, 2 and 3) at both temperatures 298 and 77 K. On the other hand, when the emission spectra are monitored in the O→W (260 nm) and O→Eu3+ (310 nm) LMCT bands, they do not show bands coming from the 5D3, 5D2 and 5D1 (5DJ→7FJ´) emitting levels. This phenomenon evidences the resonance crossover between the LMCT states and the 5DJ levels (J = 1, 2 and 3). The high value of the Ω2 intensity parameters of the Eu3+ compounds reflects the hypersensitive behavior of the 5D0→7F2 transition, indicating that the TR3+ ion lies in a highly polarizable chemistry environment. The quantum efficiencies values for the Gd2(WO4)3:Eu3+ compounds are higher than for the Eu2(WO4)3 compound due to the major radiative contribution in the doped systems. We must consider that the Eu2(WO4)3 compound contains higher concentration of Eu3+ ions, generating proximity and resulting in the non-radiative energy transfer among these ions. We observed that the highest quantum efficiency value was for the Gd2(WO4)3:Eu3+ (1%) system, which was obtained by the Pechini method. The micrographs and the XRD patterns showed that the morphology and the crystallites size of the compounds depend on the used method. The CIE (Commission Internationale d\'Eclairage) coordinates were determined. (AU)