Spinel and Elpasolite type X-Chromo-luminescent materials : Structureproperties relationship

Les matériaux luminescents sensibles à la température ou l’exposition auxrayons ultra-violets sont de plus en plus recherchés. Dans ces travaux, deux famillesde composés ont été synthétisés et caractérisés.La première famille est celle des composés ZnAl2O4 dopés aux ionsmanganèse de structure spinelle. Ces composés présentent des propriétés dethermo-chromo-luminescence irréversible avec une variation d’émission du rouge auvert en fonction de l’histoire thermique subie par le matériau. Ici les variations delongueurs d’onde d’émission sont dues au changement de l’environnement des ionsluminescents manganèse en fonction de la température. Il a été démontré que lagamme de température de commutation peut être modulée par une variation de lacomposition de la matrice hôte. La seconde famille est celle des elpasolites decomposition Rb2KInF6 dopé au cérium. Ces composés présentent des propriétés dephoto-chromo-luminescence réversible par oxydo-réduction entre les ions cérium etindium. Sous irradiation UV, il est possible de créer des espèces (In+) quiluminescent dans le rouge. Nous avons montré que le retour aux propriétés initialespeut avoir lieu sous irradiation UV à plus hautes longueurs d’onde ou par chauffage.La spécificité du phénomène associé à cette structure et cette compositionparticulière peut s’expliquer par des considérations structurales, la situation spatialedes ions cérium et indium permettant des échanges électroniques par recouvrementorbitalaire de ces deux ions.Research for luminescent materials sensitive to temperature or UV exposurevariation are increasing. Here we manage to synthesized and characterized materialswhich show such properties.First, spinel structure materials as ZnAl2O4 doped with manganesecompounds exhibit irreversible thermo-chromo-luminescence properties. Thismaterial shows a variation of emission wavelength from red to green with a variationof the thermal history of the sample. These variations are due to a modification of themanganese environment in the structure with the temperature. It was demonstratedthat the temperature range of the luminescence switch can be tuned by themodification of the matrix composition. Secondly, cerium-doped Rb2KInF6compounds with elpasolite structure exhibit reversible photo-chromo-luminescenceproperties. Under UV irradiation, new luminescent species (In+), created by redoxreaction between Ce3+ and In3+ species, and which emits in the red range, can beproduced. We demonstrate the reversibility of the phenomenon by UV irradiation orafter a thermal treatment. The specificity of these properties with this structure andthis composition can be explained by structural consideration: Ce3+ and In3+positioning in the cell allowing electronic exchanges between these ions thanks toorbital overlap

Matériaux X-Chromo-luminescents de type spinelle et elpasolite : relation structure-propriétés

Research for luminescent materials sensitive to temperature or UV exposurevariation are increasing. Here we manage to synthesized and characterized materialswhich show such properties.First, spinel structure materials as ZnAl2O4 doped with manganesecompounds exhibit irreversible thermo-chromo-luminescence properties. Thismaterial shows a variation of emission wavelength from red to green with a variationof the thermal history of the sample. These variations are due to a modification of themanganese environment in the structure with the temperature. It was demonstratedthat the temperature range of the luminescence switch can be tuned by themodification of the matrix composition. Secondly, cerium-doped Rb2KInF6compounds with elpasolite structure exhibit reversible photo-chromo-luminescenceproperties. Under UV irradiation, new luminescent species (In+), created by redoxreaction between Ce3+ and In3+ species, and which emits in the red range, can beproduced. We demonstrate the reversibility of the phenomenon by UV irradiation orafter a thermal treatment. The specificity of these properties with this structure andthis composition can be explained by structural consideration: Ce3+ and In3+positioning in the cell allowing electronic exchanges between these ions thanks toorbital overlap.Les matériaux luminescents sensibles à la température ou l’exposition auxrayons ultra-violets sont de plus en plus recherchés. Dans ces travaux, deux famillesde composés ont été synthétisés et caractérisés.La première famille est celle des composés ZnAl2O4 dopés aux ionsmanganèse de structure spinelle. Ces composés présentent des propriétés dethermo-chromo-luminescence irréversible avec une variation d’émission du rouge auvert en fonction de l’histoire thermique subie par le matériau. Ici les variations delongueurs d’onde d’émission sont dues au changement de l’environnement des ionsluminescents manganèse en fonction de la température. Il a été démontré que lagamme de température de commutation peut être modulée par une variation de lacomposition de la matrice hôte. La seconde famille est celle des elpasolites decomposition Rb2KInF6 dopé au cérium. Ces composés présentent des propriétés dephoto-chromo-luminescence réversible par oxydo-réduction entre les ions cérium etindium. Sous irradiation UV, il est possible de créer des espèces (In+) quiluminescent dans le rouge. Nous avons montré que le retour aux propriétés initialespeut avoir lieu sous irradiation UV à plus hautes longueurs d’onde ou par chauffage.La spécificité du phénomène associé à cette structure et cette compositionparticulière peut s’expliquer par des considérations structurales, la situation spatialedes ions cérium et indium permettant des échanges électroniques par recouvrementorbitalaire de ces deux ions

Spinel and Elpasolite type X-Chromo-luminescent materials : Structureproperties relationship

Les matériaux luminescents sensibles à la température ou l’exposition auxrayons ultra-violets sont de plus en plus recherchés. Dans ces travaux, deux famillesde composés ont été synthétisés et caractérisés.La première famille est celle des composés ZnAl2O4 dopés aux ionsmanganèse de structure spinelle. Ces composés présentent des propriétés dethermo-chromo-luminescence irréversible avec une variation d’émission du rouge auvert en fonction de l’histoire thermique subie par le matériau. Ici les variations delongueurs d’onde d’émission sont dues au changement de l’environnement des ionsluminescents manganèse en fonction de la température. Il a été démontré que lagamme de température de commutation peut être modulée par une variation de lacomposition de la matrice hôte. La seconde famille est celle des elpasolites decomposition Rb2KInF6 dopé au cérium. Ces composés présentent des propriétés dephoto-chromo-luminescence réversible par oxydo-réduction entre les ions cérium etindium. Sous irradiation UV, il est possible de créer des espèces (In+) quiluminescent dans le rouge. Nous avons montré que le retour aux propriétés initialespeut avoir lieu sous irradiation UV à plus hautes longueurs d’onde ou par chauffage.La spécificité du phénomène associé à cette structure et cette compositionparticulière peut s’expliquer par des considérations structurales, la situation spatialedes ions cérium et indium permettant des échanges électroniques par recouvrementorbitalaire de ces deux ions.Research for luminescent materials sensitive to temperature or UV exposurevariation are increasing. Here we manage to synthesized and characterized materialswhich show such properties.First, spinel structure materials as ZnAl2O4 doped with manganesecompounds exhibit irreversible thermo-chromo-luminescence properties. Thismaterial shows a variation of emission wavelength from red to green with a variationof the thermal history of the sample. These variations are due to a modification of themanganese environment in the structure with the temperature. It was demonstratedthat the temperature range of the luminescence switch can be tuned by themodification of the matrix composition. Secondly, cerium-doped Rb2KInF6compounds with elpasolite structure exhibit reversible photo-chromo-luminescenceproperties. Under UV irradiation, new luminescent species (In+), created by redoxreaction between Ce3+ and In3+ species, and which emits in the red range, can beproduced. We demonstrate the reversibility of the phenomenon by UV irradiation orafter a thermal treatment. The specificity of these properties with this structure andthis composition can be explained by structural consideration: Ce3+ and In3+positioning in the cell allowing electronic exchanges between these ions thanks toorbital overlap

Spinel and Elpasolite type X-Chromo-luminescent materials : Structureproperties relationship

Les matériaux luminescents sensibles à la température ou l’exposition auxrayons ultra-violets sont de plus en plus recherchés. Dans ces travaux, deux famillesde composés ont été synthétisés et caractérisés.La première famille est celle des composés ZnAl2O4 dopés aux ionsmanganèse de structure spinelle. Ces composés présentent des propriétés dethermo-chromo-luminescence irréversible avec une variation d’émission du rouge auvert en fonction de l’histoire thermique subie par le matériau. Ici les variations delongueurs d’onde d’émission sont dues au changement de l’environnement des ionsluminescents manganèse en fonction de la température. Il a été démontré que lagamme de température de commutation peut être modulée par une variation de lacomposition de la matrice hôte. La seconde famille est celle des elpasolites decomposition Rb2KInF6 dopé au cérium. Ces composés présentent des propriétés dephoto-chromo-luminescence réversible par oxydo-réduction entre les ions cérium etindium. Sous irradiation UV, il est possible de créer des espèces (In+) quiluminescent dans le rouge. Nous avons montré que le retour aux propriétés initialespeut avoir lieu sous irradiation UV à plus hautes longueurs d’onde ou par chauffage.La spécificité du phénomène associé à cette structure et cette compositionparticulière peut s’expliquer par des considérations structurales, la situation spatialedes ions cérium et indium permettant des échanges électroniques par recouvrementorbitalaire de ces deux ions.Research for luminescent materials sensitive to temperature or UV exposurevariation are increasing. Here we manage to synthesized and characterized materialswhich show such properties.First, spinel structure materials as ZnAl2O4 doped with manganesecompounds exhibit irreversible thermo-chromo-luminescence properties. Thismaterial shows a variation of emission wavelength from red to green with a variationof the thermal history of the sample. These variations are due to a modification of themanganese environment in the structure with the temperature. It was demonstratedthat the temperature range of the luminescence switch can be tuned by themodification of the matrix composition. Secondly, cerium-doped Rb2KInF6compounds with elpasolite structure exhibit reversible photo-chromo-luminescenceproperties. Under UV irradiation, new luminescent species (In+), created by redoxreaction between Ce3+ and In3+ species, and which emits in the red range, can beproduced. We demonstrate the reversibility of the phenomenon by UV irradiation orafter a thermal treatment. The specificity of these properties with this structure andthis composition can be explained by structural consideration: Ce3+ and In3+positioning in the cell allowing electronic exchanges between these ions thanks toorbital overlap

ZnAl2O4 as potential sensor : variation of luminescence with thermal history

ZnAl2O4 spinel powders were prepared using the Pechini or co-precipitation synthetic route and were then treated at different temperatures (600-1350 °C). These powders were characterised by X-ray diffraction, scanning electron microscopy (SEM), diffuse reflectance and luminescence measurements. SEM investigations and the X-ray patterns showed that the spinel crystallite size was dependent on the synthetic route and the treatment temperature. In addition, the structural evolution was investigated by Rietveld refinements. The inversion rate decrease was correlated with the temperature, leading to a direct spinel phase for the sample treated at high temperature. Furthermore, luminescence measurements showed various emissions linked to the presence of defects in the matrix structure. The two main emissions observed were attributed to oxygen vacancy and Zn in the interstitial positions (as revealed by differential Fourier maps). The luminescence spectra exhibited strong differences between 1200 °C and 1350 °C. At the higher temperature, the characteristic emission spectra can be attributed to the direct spinel phase. The indirect-direct spinel transformation can be monitored through the change in the optical properties and correlated to the thermal history of the sample

ZnAl2O4 as potential sensor : variation of luminescence with thermal history

ZnAl2O4 spinel powders were prepared using the Pechini or co-precipitation synthetic route and were then treated at different temperatures (600-1350 °C). These powders were characterised by X-ray diffraction, scanning electron microscopy (SEM), diffuse reflectance and luminescence measurements. SEM investigations and the X-ray patterns showed that the spinel crystallite size was dependent on the synthetic route and the treatment temperature. In addition, the structural evolution was investigated by Rietveld refinements. The inversion rate decrease was correlated with the temperature, leading to a direct spinel phase for the sample treated at high temperature. Furthermore, luminescence measurements showed various emissions linked to the presence of defects in the matrix structure. The two main emissions observed were attributed to oxygen vacancy and Zn in the interstitial positions (as revealed by differential Fourier maps). The luminescence spectra exhibited strong differences between 1200 °C and 1350 °C. At the higher temperature, the characteristic emission spectra can be attributed to the direct spinel phase. The indirect-direct spinel transformation can be monitored through the change in the optical properties and correlated to the thermal history of the sample

Luminescence switch of Mn-Doped ZnAl2O4 powder with temperature

Manganese-doped ZnAl2O4 phosphors were prepared by the Pechini synthesis route and treated at various temperatures from 600 to 1350 °C. The samples were characterized by TEM-EDX, XRD, EPR, and their diffuse reflectance and luminescence properties were investigated. The structural analysis showed the high solubility limit of manganese in this spinel matrix and allowed the determination of the global inversion rate, which characterizes the cation distribution in the A and B sites of the spinel structure. As the annealing temperature increased, this factor decreased leading to a more direct matrix. EPR analysis showed that, besides Mn3+ to Mn2+ reduction, the local environment of Mn2+ cations changed with the annealing temperature, which was also reflected in the evolution of the optical properties. As the annealing temperature increased, the red luminescence related to the presence of divalent manganese in octahedral sites faded and was replaced by a new green emission due to Mn(II) ions located in tetrahedral sites within the spinel structure. For 0.5% Mn-doped ZnAl2O4, this red to green luminescence switch occurred for samples treated between 1200 and 1350 °C. Moreover, the Al-overstoichiometric samples (Mn:ZnAl2.2O4+δ) showed that it is possible to modify the temperature range and the kinetics of this variation in emission wavelength. These tuneable properties suggest that Mn-doped spinels are potential candidates for developing stable and highly sensitive thermal sensors.Matériaux avancés pour capteurs optiques

CoMoO4/CuMo0.9W0.1O4 mixture as an efficient piezochromic sensor to detect temperature/pressure shock parameters.

A mixture of two piezochromic compounds can be used as a universal shock detector, i.e., to determine the shock pressure without knowing a priori the temperature at which the shock occurred. For this purpose, both piezochromic compounds must exhibit different temperature influences in their transition-pressure values. This demonstration uses two piezochromic compounds (CoMoO4 and CuMoO4-type oxides) that exhibit a first-order phase transition between their two allotropic forms associated with a drastic color change. The colorimetric coordinates of the mixture indicate the pressure and temperature of a shock

CoMoO4/CuMo0.9W0.1O4 mixture as an efficient piezochromic sensor to detect temperature/pressure shock parameters.

A mixture of two piezochromic compounds can be used as a universal shock detector, i.e., to determine the shock pressure without knowing a priori the temperature at which the shock occurred. For this purpose, both piezochromic compounds must exhibit different temperature influences in their transition-pressure values. This demonstration uses two piezochromic compounds (CoMoO4 and CuMoO4-type oxides) that exhibit a first-order phase transition between their two allotropic forms associated with a drastic color change. The colorimetric coordinates of the mixture indicate the pressure and temperature of a shock

Luminescence properties and pigment properties of A-doped (Zn,Mg)MoO4 triclinic oxides (with A = Co, Ni, Cu or Mn)

First, we describe the phase diagram in between two oxides, ZnMoO4 and MgMoO4, with P-1 triclinic and C2/m monoclinic space groups, respectively. Based on the discovery of a large solid solution phase with a P-1 triclinic space group ranging from ZnMoO4 to Mg0.9Zn0.1MoO4, in this study, we investigate the potential influence of the magnesium/zinc ratio on the pigment/luminescent properties of compounds in the triclinic solid solution domain with formulae t-Mg1−x−yZnxAyMoO4, with 0.1 ≤ x ≤ 1 and with A2+ being a phosphor (Mn2+ (y = 0.01)) or chromophore cation (Co2+, Ni2+, or Cu2+ (y =0.1)). Various bright colours were obtained depending on the doping ion. Optical properties were fully interpreted by spectroscopic investigation and indexing of the absorption/excitation bands. Near white luminescence is obtained for both un-doped and Mn-doped t-Mg1−xZnxMoO4 compounds, revealing a potential use as a white source. Bright yellow, blue or pale cyan colours can be achieved using nickel, cobalt or copper as chromophores, respectively, and the colours of the t-Mg1−x−yZnxAyMoO4 are moderately impacted by the Mg/Zn ratio.Revêtements Piézochromes Réversibles pour la Détection d'Impacts sur Supports Composite