Response of Various Yb3+-Doped Oxide Glasses to Different Radiation Treatments.

The radiation effects of electrons and protons on the spectroscopic and optical properties of oxide glasses doped with Yb3+ in various glass systems were investigated to understand the impact of the glass composition on the glass photo-response. Changes in the optical and emission properties were seen after the radiation treatment, and the magnitude of the changes depended on the irradiation source and dose. For all the investigated materials, the absorption coefficients in the 200-550 nm range increase post-irradiation, revealing the formation of defects in the glasses during the irradiation. While the spectroscopic properties of the tellurite glass remain unchanged, a small reduction in the Yb3+ emission intensity was seen after irradiating the phosphate, borosilicate, and germanate glasses, indicating that a reduction of Yb3+ to Yb2+ might occur in these glasses during the radiation treatment. The changes in the optical and spectroscopic properties after proton irradiation are small as they are localized at the surface of the glasses due to the shallow penetration depth of the proton in the glass. Even though the doses are small, the electron irradiation produces larger changes in the optical and spectroscopic properties since the electrons penetrate the entire volume of the glasses. All the changes in the optical and spectroscopic properties of the glasses were successfully reversed after a short heat treatment revealing the reversible nature of the photo-response of the investigated glasses.

Radiation-Induced Defects and Effects in Germanate and Tellurite Glasses.

This review focuses on the radiation-induced changes in germanate and tellurite glasses. These glasses have been of great interest due to their remarkable potential for photonics, in terms of extended transmission window in the mid-infrared, ability of rare-earth loading suitable with a laser, and amplification in the near- and mid-infrared or high nonlinear optical properties. Here, we summarize information about possible radiation-induced defects, mechanisms of their formation, and the influence of the glass composition on this process. Special attention is paid to laser-induced structural modification of these glasses, including possible mechanisms of the laser-glass interaction, laser-induced crystallization, and waveguide writing. It is shown that these methods can be used for photostructuring of the glass and have great potential for practical applications.

Photochromic Behavior of ZnO/MoO3 Interfaces.

ZnO/MoO3 powder mixture exhibits a huge photochromic effect in comparison with the corresponding single oxides. The coloring efficiency of such combined material after UV-light irradiation was studied in terms of intensity, kinetics, and ZnO/MoO3 powder ratio. Additionally, the incidence of the pretreatment step of the ZnO and MoO3 powders under different atmospheres (air, Ar or Ar/H2 flow) was analyzed. The huge photochromic effect discovered herein was interpreted as the creation of "self-closed Schottky barrier" at the solid/solid interfaces between the two oxides, associated with the full redox reaction which can be pictured by the equation ZnO1-ε + MoO3 → ZnO + MoO3-ε. Remarkable optical contrast between virgin and color states as well as self-bleaching in dark allowing the reversibility of the photochromism is emphasized. From this first discovery, deeper characterization of the self-bleaching process shows that the photochromic mechanism is complex with a bleaching efficiency (possibility to come back to the virgin material optical properties without any deterioration) and a bleaching kinetics, which are both dependent on the coloring irradiation time. This demonstrates that the oxygen exchange through the Schottky interface proceeds in at least two convoluted steps: an anionic surface exchange allowing a reversibility of the redox reaction followed by bulk diffusion of the exchanged anions which are then definitively trapped. An emergent "negative photochromism effect" (i.e., photochromism associated with a self-bleaching instead of a darkening under irradiation) is observed after a long irradiation time.

Tailoring the Composition of Eu3+-Doped Y3NbO7 Niobate: Structural Features and Luminescent Properties Induced by Spark Plasma Sintering.

The defective fluorite-related Y3NbO7 host lattice was doped with Eu3+ ions to understand the influence of spark plasma sintering (SPS) process on this host lattice. The intrinsic disorder due to the occurrence of oxygen vacancies results in amorphous-type responses of the luminescent cations, and the spectral distribution varies as a function of the niobium content. Two spectral fingerprints of europium emissions were clearly enhanced. The correlation between luminescence, X-ray diffraction, and electron diffraction characterizations shows the existence of local inhomogeneity. Indeed, the particular nonequilibrium sintering conditions allowed pointing out a lack of miscibility within the Y3NbO7 solid solution domain. Thus, the SPS pellet is a composite of two extreme compositions. This phase demixing is mainly induced by the pressure coupled with a current effect that makes possible ionic migration in this Y3NbO7 ionic conductive matrix.

Optical contrast and cycling of bistable luminescence properties in Rb2KIn(1-x)CexF6 compounds.

Irradiation cycling was performed to evaluate the ageing of the redox process observed on cerium-doped Rb2KInF6 compounds. An on-off switch of monovalent indium luminescence is observed for the lowest cerium doped material, whereas a nice colourimetric contrast between a bluish-green and orange emission is generated for the material with the highest cerium content. Photoluminescent properties combined with X-ray diffraction, chemical analysis and magnetism measurements allowed an accurate characterization of the system. A complete explanation of the optical behaviour is therefore proposed. Finally, printing tests were performed to illustrate the good functionality of the prepared materials for UV sensitivity.

Discussion on the structure stability and the luminescence switch under irradiation of a Ce-doped elpasolite compound.

Ce-doped Rb2 KInF6 elpasolite has the potential for tunable luminescence due to an unusual reversible redox process between the cerium and indium cations. Coupled with a deep understanding of the luminescence properties, XRD analysis and DFT calculations are used to locate the doping elements in the host lattice. The origin explanation of the charge-transfer mechanism that causes a decrease or increase in the blue-green cerium emission in opposition to the red indium emission is discussed regarding the crystallographic structure, the connection of the metallic cations and their equilibrium valence. Still detectable after nineteen years, the optical contrast created under irradiation makes this material a good candidate as photosensor for data storage.

Three-dimensional porous metal-radical frameworks based on triphenylmethyl radicals.

Lanthanide coordination polymers {[Ln(PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1), Gd (2), and Eu (3)] and {[Ln(αH-PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1'), Gd (2'), and Eu (3')] have been prepared by reacting Ln(III) ions with tricarboxylate-perchlorotriphenylmethyl/methane ligands that have a radical (PTMTC(3-)) or closed-shell (αH-PTMTC(3-)) character, respectively. X-ray diffraction analyses reveal 3D architectures that combine helical 1D channels and a fairly rare (6,3) connectivity described with the (4(2).8)·(4(4).6(2).8(5).10(4)) Schäfli symbol. Such 3D architectures make these polymers porous solids upon departure of the non-coordinated guest-solvent molecules as confirmed by the XRD structure of the guest-free [Tb(PTMTC)(EtOH)(2)H(2)O] and [Tb(αH-PTMTC)(EtOH)(2)H(2)O] materials. Accessible voids represent 40% of the cell volume. Metal-centered luminescence was observed in Tb(III) and Eu(III) coordination polymers 1' and 3', although the Ln(III)-ion luminescence was quenched when radical ligands were involved. The magnetic properties of all these compounds were investigated, and the nature of the {Ln-radical} (in 1 and 2) and the {radical-radical} exchange interactions (in 3) were assessed by comparing the behaviors for the radical-based coordination polymers 1-3 with those of the compounds with the diamagnetic ligand set. Whilst antiferromagnetic {radical-radical} interactions were found in 3, ferromagnetic {Ln-radical} interactions propagated in the 3D architectures of 1 and 2.

Emission-photoactivity cross-processing of mesoporous interfacial charge transfer in Eu3+ doped titania.

Periodic mesoporous Eu(3+) doped titania materials were obtained through the EISA (Evaporation Induced Self Assembly) process. Eu(3+) ions, entrapped within the semi-crystalline walls of the highly porous framework, appear to be advantageous during the probing of surface photochemical reactions. Its emission intensity is very sensitive to the presence of physisorbed molecules, in gas or liquid phase, that reside within the pores. In particular, strong fluctuations in intensity of the (5)D(0)→(7)F(2) transition were observed under UV light exposure on the time scale of tens of seconds. The emission modulation dynamics show a strong correlation with the crystallinity of the titania matrix. Correlation of the emission with the photocatalytic activity of the semiconductor for photodegradation of an organic molecule is observed. A model is proposed to describe the involved mechanisms.

Correlation between luminescence and EPR spectroscopy as evidence of ytterbium pair formation in Li6Ln(BO3)3:Yb3+ (Ln=Gd, Y) borate single crystals.

Synthesized powders and grown single crystals of nominal compositions Li(6)Ln(BO(3))(3):Yb(3+) (Ln=Y, Gd) were investigated by means of powder and single-crystal X-ray diffraction (XRD), as well as optical near-IR spectroscopy in conjunction with electron paramagnetic resonance (EPR) spectroscopy. The appearance of two distinct zero-phonon lines suggests the existence of two kinds of Yb(3+) ions in the single crystals. The XRD results exclude the possibility of a phase transition occurring between room and low temperatures. EPR spectra of single crystals show the presence of both isolated ions and pairs of ytterbium ions substituted for Y(3+). A strong temperature dependence of the intensity of Yb-Yb pairs resonance lines coincides with temperature dependence of emission peak at 978 nm, confirming a common origin of the defect giving rise to these spectra. Calculated from EPR spectra, the distance between pairs of Yb(3+) is in good agreement with crystallographic ones: R=3.856 Å, R(cryst) =3.849 Å.

Three-dimensional open-frameworks based on Ln(III) ions and open-/closed-shell PTM ligands: synthesis, structure, luminescence, and magnetic properties.

A series of isostructural open-framework coordination polymers formulated as [Ln(dmf)(3)(ptmtc)] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5); PTMTC = polychlorotriphenylmethyl tricarboxylate) and [Ln(dmf)(2)H(2)O(αH-ptmtc)] (Ln = Sm (1'), Eu (2'), Gd (3'), Tb (4'), Dy (5')) have been obtained by treating Ln(III) ions with PTMTC ligands with a radical (PTMTC(3-)) or a closed-shell character (αH-PTMTC(3-)). X-ray diffraction analyses reveal that these coordination polymers possess 3D architectures that combine large channels and fairly rare lattice complex T connectivity. In addition, these compounds show selective framework dynamic sorption properties. For both classes of ligands, the ability to act as an antenna in Ln sensitization processes has been investigated. No luminescence was observed for compounds 1-5, and 3' because of the PTMTC(3-) ligand and/or Gd(III) ion characteristics. Conversely, photoluminescence measurements show that 1', 2', 4', and 5' emit dark orange, red, green, and dark cyan metal-centered luminescence. The magnetic properties of all of these compounds have been investigated. The nature of the {Ln-radical} exchange interaction in these compounds has been assessed by comparing the behavior of the radical-based coordination polymers 1-5 with those of the compounds with the diamagnetic ligand set. While antiferromagnetic {Sm-radical} interactions are found in 1, ferromagnetic {Ln-radical} interactions propagate in the 3D architectures of 3, 4, and 5 (Ln = Gd, Tb, and Dy, respectively). This procedure also provided access to information on the {Ln-Ln} exchange existing in these magnetic systems.

Modulation of the luminescence quantum efficiency for blue luminophor {Al(salophen)}(+) by ester-substituents.

A series of Al(III) complexes of a salophen (N,N'-bis(salicylidene)-o-phenylenediamine) derivative with an ester substituent at the C5 position of the salicylidene rings have been prepared and their luminescence properties investigated. All exhibit a bright blue emission (lambda(em) = 478 nm) that is observed neither for other metal ions nor with the non-functionalized ligand. Moreover, the ester-R group (Me, (t)Bu, Ph) was found to significantly affect the quantum yields (varphi = 12 to 20%) of the luminophor. DFT calculations have been undertaken to reveal the influence of the ester and its R-group on the frontier molecular orbitals. Preparation and photoluminescence properties in solution and solid state are reported. The crystal structure of a pyridine oxide adduct [L(tBu)Al(PyO)(2)].NO(3), where L(tBu) stands for the tButyl-ester functionalized Schiff base, has been solved.

Europium-doped mesoporous titania thin films: rare-earth locations and emission fluctuations under illumination.

Herein, Eu(III)-doped 3D mesoscopically ordered arrays of mesoporous and nanocrystalline titania are prepared and studied. The rare-earth-doped titania thin films-synthesized via evaporation-induced self-assembly (EISA)-are characterized by using environmental ellipsoporosimetry, electronic microscopy (i.e. high-resolution scanning electron microscopy, HR-SEM, and transmission electron microscopy, HR-TEM), X-ray diffraction, and luminescence spectroscopy. Structural characterizations show that high europium-ion loadings can be incorporated into the titanium-dioxide walls without destroying the mesoporous arrangement. The luminescence properties of Eu(III) are investigated by using steady-state and time-resolved spectroscopy via excitation of the Eu(III) ions through the titania host. Using Eu(III) luminescence as a probe, the europium-ion sites can be addressed with at least two different environments within the mesoporous framework, namely, a nanocrystalline environment and a glasslike one. Emission fluctuations ((5)D(0)-->(7)F(2)) are observed upon continuous UV excitation in the host matrix. These fluctuations are attributed to charge trapping and appear to be strongly dependent on the amount of europium and the level of crystallinity.

Optical properties of zinc oxide nanoparticles and nanorods synthesized using an organometallic method.

The emission properties of nanocrystalline ZnO particles prepared following an organometallic synthetic method are investigated. Spherical particles and nanorods are studied. The shape of the particles and the ligands used are shown to influence the luminescence properties in the visible domain. Two different emissions are observed at 440 nm (approximately 2.82 eV) and at 580 nm (approximately 2.14 eV) that are associated with the presence of surface defects on the particles. The first emission corresponds to the well-known yellow emission located at 580 nm (approximately 2.14 eV) with a lifetime of 1850 ns for 4.0 nm size ZnO nanoparticles. The second emission at 440 nm (approximately 2.82 eV) is observed when amine functions are present. This strong blue emission is associated with an excitation energy less than that associated with the yellow emission displaying a lifetime of nine nanoseconds. A possible hole trapping effect by the amine groups on the surface of the ZnO particles is discussed as the origin of this emission. The modification of the intensities between the two visible emissions for different particle shapes is proposed to be related to a specific location of the amine ligands on the surface of the particles.