The development of high-power white light-emitting diodes demands highly efficient and stable all-inorganic color converters. In this respect, phosphor-glass/ceramic composites show great promise as they could combine the merits of high quantum efficiency of phosphors and high chemical and thermal stabilities of glass/ceramic matrices. However, strong interfacial reaction between phosphors and matrices at high temperature results in quantum efficiency loss of the embedded phosphors, and traditional solutions rely on high-pressure consolidation techniques. Here we report the intrinsic inhibition of interfacial reaction by using silica glass rather than multicomponent glasses as the matrix. The embedment of phosphors is achieved via a pressureless sintering method, rendering these color-tunable phosphor-glass composites not only accessible to three-dimensional printing technique, but also highly efficient (internal quantum efficiency >90.0%), thermally stable at 1200 °C and hydrothermally stable at 200 °C. Our results provide a facile and general strategy for developing all-inorganic functional composites.

We investigated moderate-temperature oxygen diffusion mechanisms in Sr 2 ScGaO 5 with Brownmillerite structure type. From oxygen isotope 18 O− 16 O exchange experiments we determined that oxygen mobility sets in above 550 °C. Temperature-dependent neutron and X-ray (synchrotron) diffraction experiments allowed us to correlate the oxygen mobility with a subtle phase transition of the orthorhombic room-temperature structure with I2mb space group toward Imma, going along with a disorder of the (GaO 4 ) ∞ -tetrahedral chains. From lattice dynamical simulations we could clearly evidence that dynamic switching of the (GaO 4 ) ∞ -tetrahedral chains from its R to L configuration sets in at 600 °C, thus correlating oxygen diffusion with the dynamic disorder. Oxygen ion diffusion pathways are thus constrained along the onedimensional oxygen vacancy channels, which is a different diffusion mechanism compared to that of the isostructural CaFeO 2.5 , where diffusion of the apical oxygen atoms into the vacant lattice sites are equally involved in the diffusion pathway. The proposed ordered room-temperature structure in I2mb is strongly supported by 17 O, 45 Sc, and 71 Ga NMR measurements, which indicate the presence of crystallographically unique sites and the absence of local disordering effects below the phase transition. The electric field gradient tensor components measured at the nuclear sites are found to be in excellent agreement with calculated values using the WIEN2k program. The oxygen site assignment has been independently confirmed by 17 O{ 45 Sc} transfer of adiabatic populations double-resonance experiments.

Metal–organic framework (MOF) glasses are a newly discovered family of melt-quenched glasses. Despite considerable progress in understanding the nature of MOF glasses, their photonic functionalities have not been found so far. Here, we report on the first breakthrough regarding the photonic functionalities of MOF glasses, that is, finding of the luminescence in melt-quenched MOF glasses. The finding was achieved on a zeolitic imidazolate framework (ZIF) series, that is, the ZIF-62 series: Zn 1– x Co x (Im) 1.7 (bIm) 0.3 , x = 0, 0.1, and 0.5, where Co substitutes Zn in ZIF-62 forming single-phased solid solutions. Remarkably, we observed broadband mid-infrared (Mid-IR) luminescence (in the wavelength range of 1.5–4.8 μm) in both the crystalline and amorphous solid solutions. The intensity of the luminescence in ZIF glass is gradually enhanced by increasing the level of Co concentration. The observed Mid-IR emission originates from d–d transition of Co ions. The discovery of the luminescence in ZIF-62 glass may pave the way toward new photonic applications of bulk MOF glasses.

An R2O–B2O3–SiO2 (R = Li, Na, K) polarizing glass containing Ag nanorods is prepared by thermal elongation–reduction technology. The transverse and longitudinal plasmon absorption peaks of the embedded Ag nanorods are near 460 and 720 nm, respectively. When the polarization of the laser is parallel to the long axis of the Ag nanorods, the nonlinear absorption coefficient β = 0.82 cm GW–1 and the nonlinear refractive index n2 = –1.5 × 10–4 cm2 GW–1. When the polarization of light is perpendicular to the long axis of the Ag nanorods β = 0.12 cm GW–1 and n2 = –7.2 × 10–5 cm2 GW–1 and the appropriate one‐ and two‐photon figures of merit (FOM), W = 1.6 and T = 0.16, respectively, are obtained, which satisfies the demand, W > 1 and T < 1, for applications in all optical switching, where W is a one‐photon FOM, and T is a two‐photon FOM.

Spectral properties of Yb3+∕Ni2+ codoped transparent silicate glass ceramics containing LiGa5O8 nanocrystals were investigated. The near-infrared emission intensity of Ni2+ was largely increased with Yb3+ codoping due to Yb3+→Ni2+ energy transfer. The qualitative calculation of the energy transfer constant Cs-a and rate Ps-a showed that the Yb3+→Ni2+ energy transfer was much greater than in the opposite direction. Yb3+∕Ni2+ codoped glass ceramics with 0.75mol% Yb2O3 exhibited a near-infrared emission with full width at half maximum of 290nm and fluorescent lifetime of 920μs. The glass ceramics are promising for broadband optical amplification.

Recently, metal−organic frameworks (MOFs) have been confirmed to be stable in a vitreous state, thus stimulating growing interest in the discovery of the physicochemical properties of these newly explored types of glasses. Herein, we examine the nonlinearoptical (NLO) response of Zn-and Zn−Co-based zeolitic imidazolate framework-62 (ZIF-62) glasses using an open-aperture Z-scan technique. We reveal that the Zn-ZIF-62 glass does not characterize a saturable absorption feature (1030 nm femtosecond laser) owing to its low optical absorption in the near-infrared (NIR) spectral region. In contrast, a NIR absorption band (1100 nm) has been observed in Zn−Co-ZIF-62 glass, which exhibits a strong NLO response with a high modulation depth of 63.85%. We attribute the observed NLO response to transient saturation of the 4 T 1 ( 4 F) level of Co ions upon femtosecond laser excitation. The intriguing NLO properties of this MOF glass may enable potential applications in the photonics fields for sensing and optical modulation.

The synthesis of bifunctional mesoporous silica nanoparticles is described. Two chemically orthogonal functionalities are incorporated into mesoporous silica by co-condensation of tetraethoxysilane with two orthogonally functionalized triethoxyalkylsilanes. Post-functionalization is achieved by orthogonal surface chemistry. A thiol-ene reaction, Cu-catalyzed 1,3-dipolar alkyne/azide cycloaddition, and a radical nitroxide exchange reaction are used as orthogonal processes to install two functionalities at the surface that differ in reactivity. Preparation of mesoporous silica nanoparticles bearing acidic and basic sites by this approach is discussed. Particles are analyzed by solid state NMR spectroscopy, elemental analysis, infrared-spectroscopy, and scanning electron microscopy. As a first application, these particles are successfully used as cooperative catalysts in the Henry reaction.

The vitrification of hybrid materials (e.g., metal–organic frameworks and coordination polymers) is considered as the fourth generation of glass. To extend the hybrid glass family with photonic functionalities, we report a crystalline metal inorganic–organic complex (MIOC) (i.e., ZnCl2(HbIm)2, HbIm = benzimidazole) with a one-dimensional hydrogen bonded chain that can be melted to a stable liquid at elevated temperatures and subsequently quenched to form a large-sized bulk glass under ambient atmosphere with excellent thermal and chemical stability. Benefiting from the moderate glass-forming ability of the MIOC, we succeeded in the fabrication of the first MIOC glass fibers with diameters of 7–200 μm. The doping of the MIOC fibers by organic dyes results in anisotropic photoluminescence. Furthermore, the as-prepared MIOC bulk glass can be employed as the stable and inert host for inorganic phosphors, which leads to the development of a novel phosphor-in-MIOC glass composite and enables the fabrication of high-power white light-emitting diodes. Our findings make the ZnCl2(HbIm)2-based MIOC glass a promising material for photonic applications.