Transparent bulk glass-ceramics containing ZnF2, K2SiF6, and KZnF3 nanocrystals are successfully obtained from xKF-xZnF2-(100 - 2x)SiO2 oxyfluoride glasses for the first time to the best of our knowledge. The glass transition temperatures of heat-treated samples increase with time and approach values that resemble the temperatures chosen for thermal treatment. During nucleation and crystal growth, the residual glass around the crystals is depleted in fluoride which as glass component usually leads to a decrease in viscosity. The crystallization behavior notably depends on the glass composition and changes within a small range from x = 20 to 22.5 mol %. The occurrence of liquid/liquid phase separation in dependence of the composition is responsible for the physicochemical changes. Two different microstructures of droplet and interpenetrating phase separation and their compositional evolution are observed by replica transmission electron microscopy technique in the multicomponent glassy system. This study suggests that the size and crystal phase of precipitated crystallites can be controlled by the initial phase separation.

Transparent glass ceramics have been prepared in the Ga(2)S(3)-GeS(2)-CsCl pseudoternary system using appropriate heat treatment time and temperature. In situ X-ray diffraction at the heat treatment temperature and (133)Cs and (71)Ga solid-state nuclear magnetic resonance have been performed in function of annealing time to understand the crystallization process. Both techniques have evidenced the nucleating agent role played by gallium with the formation of Ga(2)S(3) nanocrystals. On the other hand, cesium is incorporated very much later into the crystallites during the ceramization. Moreover, the addition of CsCl, which is readily integrated into the glassy network, permits us to shift the optical band gap toward shorter wavelength. Thus, new glass ceramics transmitting in the whole visible range up to 11.5 mum have been successfully synthesized from the (Ga(2)S(3))(35)-(GeS(2))(25)-CsCl(40) base glass composition.

CdSe quantum dots (QDs) doped glasses have been widely investigated for optical filters, LED color converter and other optical emitters. Unlike CdSe QDs in solution, it is difficult to passivate the surface defects of CdSe QDs in glass matrix, which strongly suppress its intrinsic emission. In this study, surface passivation of CdSe quantum dots (QDs) by Cd1−xZnxSe shell in silicate glass was reported. An increase in the Se/Cd ratio can lead to the partial passivation of the surface states and appearance of the intrinsic emission of CdSe QDs. Optimizing the heat-treatment condition promotes the incorporation of Zn into CdSe QDs and results in the quenching of the defect emission. Formation of CdSe/Cd1−xZnxSe core/graded shell QDs is evidenced by the experimental results of TEM and Raman spectroscopy. Realization of the surface passivation and intrinsic emission of II-VI QDs may facilitate the wide applications of QDs doped all inorganic amorphous materials.

International audienceGlass-ceramics were fabricated from the 80GeS2⋅20Ga2S3 chalcogenide glass using an appropriate heat-treatment at a fairly low temperature (T g+30°C) for different durations. Compared with the base glass, they present much-improved thermal shock resistance and fracture toughness, and meanwhile remain an excellent mid-IR transmission in 2-10-μm spectral region. XRD results indicate that the enhanced mechanical properties are mainly due to the appearance of Ga2S3 crystals, and only a very small amount of GeS2 was precipitated on the surface. Bulk and powder samples heat-treated at 458°C for different durations were used to study the evolution of the two crystallization peaks using DSC measurement. It is found that the precipitation of Ga2S3 phase is responsible for the exotherm of first crystallization peak and that of GeS2 phase for the second one. The crystallization mechanism was also examined using the nonisothermal method, and the considerably low activation energy (E c) and high crystallization rate constant (K) for the first crystallization peak illustrate a much easier precipitation of Ga2S3 phase than that of GeS2 phase, which is in good accordance with the ceramization process

Nickel ion doped transparent bulk glass-ceramics containing K 2 SiF 6 , ZnF 2 , and KZnF 3 nanocrystals were elaborated to show the prospect that this novel group of oxyfluoride glass-ceramics is promising for transition metal ion based photonics. These new oxyfluoride glass-ceramics exhibit a new broadband luminescence of Ni 2+ ions in the intriguing near-IR spectral region ranging from 1200 to 2400 nm. Ni 2+ ions are incorporated into the precipitated K 2 SiF 6 , ZnF 2 , and KZnF 3 crystals, which provide octahedral sites for Ni 2+ and make it optically active. Taking into account the microstructure of phase separation observed by replica TEM, a detailed mechanism of phaseseparation-assisted nanocrystallization was described for these oxyfluoride glasses. These results allow one to establish a full physical model of the nanocrystallization mechanism. For the precipitation of fluoride crystallites, not only can the nanometric size be explained but also the formation of different crystal phases can be controlled by the initial amorphous phase separation of droplet or interpenetrating structure with a sufficiently elaborated glass design.

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Surface plasmon resonance (SPR) of noble metal nanoparticles (NPs) fostered a new area of nanophotonics, especially in the selective photon absorption and scattering. The precipitation of Ag NPs in glass would enhance the emission efficiency. Here, we studied the effects of annealing temperature (resulted in the increased Ag NPs’ concentration) or AgCl concentration on the luminescence properties of Er3+/Yb3+ codoped bismuth-germanate glasses which were synthesized by a single-step melting–quenching technique. The SPR peak of Ag NPs appears around 600 nm, and the size of precipitated Ag NPs (spherical, hexagonal) ranges from 5 to 15 nm. With the precipitation of the Ag NPs, more intense green (527 nm, 548 nm) and red (661 nm) upconversion (UC) emission bands are observed up to 7.7, 10.1, and 6.5 folds in the glass containing 1 wt % AgCl annealed at 480 °C for 24 h, respectively. The Ag NPs embedded glasses showed significantly local field change that allowed for more bright UC emission by SPR.

Transparent KF-ZnF(2)-SiO(2) glass-ceramics were prepared with the precipitation of KZnF(3)Ni(2+) nanocrystals. During excitation with a wavelength of 405 nm at room temperature, a broadband near-IR emission centered at 1695 nm with the FWHM of more than 350 nm was observed, which is originated from the T(2g)3(F3)→A(2g)3(F3) transition of octahedral Ni(2+) incorporated in the KZnF(3) crystalline phase. In comparison to oxide glass-ceramics, a redshift of the luminescence is observed, which is due to the low crystal field of these octahedral Ni(2+). The shift and extension of near-IR emission in the KZnF(3):Ni(2+) nanocrystals embedded in a glassy matrix do not only complete the broadband emission in the whole near-IR region for the Ni(2+) ions-based photonics, but also open an easy way to approach the broadband optical amplifier and tunable lasers operating in the wavelength region near 1800 nm, which was up to now achieved by codoping of several types of active ions.