Upconversion luminescence in transparent oxyfluoride glass ceramics containing hexagonal NaErF4

The authors wish to express gratitude to K. Smits for TEM measurements. This research is funded by the Latvian Council of Science, project “Novel transparent nanocomposite oxyfluoride materials for optical applications”, project No. LZP-2018/1-0335. GK wishes to expresses gratitude to Arnis Riekstins "MikroTik" donation. Donations are administered by the University of Latvia Foundation. © 2019. This work is licensed under a CC BY-NC-ND 4.0 license.Transparent oxyfluoride glass ceramics containing hexagonal NaErF4 nanocrystals were synthesized by a heat treatment of a precursor glass obtained by the melt quenching technique. Combined X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis revealed the formation of single phase nanocrystals in the glass ceramics. The enhancement of intensity and spectral change of upconversion luminescence (UCL) confirmed the presence of Er3+ ions in the crystalline phase of the glass ceramics. Dominant energy transfer processes were identified using the rate equation formalism. Time-resolved site-selective spectroscopy studies at low temperatures were employed to elucidate the local structure of Er3+ ions in the glass ceramics and microcrystalline NaErF4. The origin of multi-site formation in hexagonal NaErF4 lattice is discussed.----/ / /---- This is the preprint of the following article: Guna Krieke; Andris Antuzevics, Maris Springis, Uldis Rogulis, Upconversion luminescence in transparent oxyfluoride glass ceramics containing hexagonal NaErF4, Journal of Alloys and Compounds Volume 798 (2019), which has been published at https://www.sciencedirect.com/science/article/abs/pii/S0925346717304731. This article may be used for non-commercial purposes in accordance with Elsevier Terms and Conditions for Sharing and Self-Archiving. © 2019. This work is licensed under a CC BY-NC-ND 4.0 license.Latvian Council of Science LZP-2018/1-0335; University of Latvia Foundation; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART²

Non-Linear Optical Properties of Er3+–Yb3+-Doped NaGdF4 Nanostructured Glass–Ceramics

Transparent oxyfluoride glass–ceramics containing NaGdF4 nanocrystals were prepared by melt-quenching and doped with Er3+ (0.5 mol%) and different amounts of Yb3+ (0–2 mol%). The selected dopant concentration the crystallization thermal treatments were chosen to obtain the most efficient visible up-conversion emissions, together with near infrared emissions. The crystal size increased with dopant content and treatment time. NaGdF4 NCs with a size ranging 9–30 nm were obtained after heat treatments at Tg + 20–80 °C as confirmed by X-ray diffraction and high-resolution transmission electron microscopy. Energy dispersive X-ray analysis shows the incorporation of rare earth ions into the NaGdF4 nanocrystals. Near-infrared emission spectra, together with the up-conversion emissions were measured. The optical characterization of the glass–ceramics clearly shows that Er3+ and Yb3+ ions are incorporated in the crystalline phase. Moreover, visible up-conversion emissions could be tuned by controlling the nanocrystals size through appropriated heat treatment, making possible a correlation between structural and optical properties.This research was funded by Spanish National projects MAT2017-87035-C2-1-P/2-P (AEI/FEDER, UE), Basque Country University PPG17/07 and GIU17/014 and Basque Government PIBA2018-24. This study is part of the dissemination activities of project FunGlass. This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 739566. This study was also created in the frame of the project Centre for Functional and Surface Functionalized Glass (CEGLASS), ITMS code is 313011R453, operational program Research and innovation, co-funded from European Regional Development Fund

Spectroscopic properties of erbium-doped oxyfluoride phospho-tellurite glass and transparent glass-ceramic containing BaF2 nanocrystals

The ErF3-doped oxyfluoride phospho-tellurite glasses in the (40-x) TeO2-10P2O5-45 (BaF2-ZnF2) -5Na2O-xErF3 system (where x = 0.25, 0.50, 0.75, 1.00, and 1.25 mol%) have been prepared by the conventional melt-quenching method. The effect of erbium trifluoride addition on thermal, structure, and spectroscopic properties of oxyfluoride phospho-tellurite precursor glass was studied by differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR), and Raman spectroscopy as well as emission measurements, respectively. The DSC curves were used to investigate characteristic temperatures and thermal stability of the precursor glass doped with varying content of ErF3. FTIR and Raman spectra were introduced to characterize the evolution of structure and phonon energy of the glasses. It was found that the addition of ErF3 up to 1.25 mol% into the chemical composition of phospho-tellurite precursor glass enhanced 2.7 µm emission and upconversion. By controlled heat-treatment process of the host glass doped with the highest content of erbium trifluoride (1.25 mol%), transparent erbium-doped phospho-tellurite glass-ceramic (GC) was obtained. X-ray diffraction analysis confirmed the presence of BaF2 nanocrystals with the average 16 nm diameter in a glass matrix. Moreover, MIR, NIR, and UC emissions of the glass-ceramic were discussed in detail and compared to the spectroscopic properties of the glass doped with 1.25 mol% of ErF3 (the base glass)

Effect of processing on the structure and properties of glasses and glass-ceramics for photonic applications

Tesis Doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Física de Materiales. Fecha de lectura: 29-04-2019Esta tesis doctoral ha sido realizada en el Departamento de Vidrios del Instituto de Cerámica y Vidrio (ICV-CSIC) y desarrollada en el marco de los proyectos MAT2013- 48246-C2-1-P/2-P y MAT2017-87035-C2-1-P/-2-P(AEI/FEDER,UE). La estancia en el “Laboratory of Optical Fibre Technology” de la Universidad de Bialystok (Polonia) ha sido financiada por el COST Action: MP140

Enhanced Blue Emission from Transparent Oxyfluoride Glass Ceramics Containing Pr3+:BaF2 Nano-crystals

Transparent glass ceramics containing Pr3+:BaF2 nano-crystals in chemical composition of SiO2–BaF2–K2CO3–La2O3-Sb2O3 oxyfluoride glass systems have been prepared from melt quenching and with subsequent heat-treatment method. Luminescence and structural properties of these materials have been evaluated and the results are reported. Rietveld analysis of X-ray diffraction (XRD) patterns and investigation of transmission electron microscopy (TEM) confirmed the presence of BaF2 nano-crystals dispersed in the heat treated glass matrices. Measured UV-Vis-NIR absorption spectra have exhibited nine bands of the transitions 3H4 3P2, (1I6, 3P1), 3P0, 1D2, 1G4, 3F3,3F2, 3H6 and 3H5 from all the samples with non-degenerated 1I6 and 3P1 levels in the glass ceramics. The photoluminescence spectra show an enhancement in the intensities upon ceramization indicating the incorporation of Pr3+ ions in BaF2 nano-crystals which possess low phonon energy (346 cm-1). This has further been corroborated from the observation of a significant 3-fold increase in the relative intensity ratio of blue (3P0 3H4) to red (1D2 3H4, 3P0 3H6)emissions from glass-ceramics compared with the glass. It is due to a significant decrease of multiphonon non-radiative relaxation from 3P0 to 1D2 level of Pr3+ in glass ceramics. Time resolved spectra exhibit 3P0 level decays faster than 1D2 level

Reddish-Orange Luminescence from BaF2:Eu3+ Fluoride Nanocrystals Dispersed in Sol-Gel Materials

Nanocrystalline transparent BaF2:Eu3+ glass-ceramic materials emitting reddish-orange light were fabricated using a low-temperature sol-gel method. Several experimental techniques were used to verify structural transformation from precursor xerogels to sol-gel glass-ceramic materials containing fluoride nanocrystals. Thermal degradation of xerogels was analyzed by thermogravimetric analysis (TG) and di erential scanning calorimetry method (DSC). The presence of BaF2 nanocrystals dispersed in sol-gel materials was confirmed by the X-ray di raction (XRD) analysis and transmission electron microscopy (TEM). In order to detect structural changes in silica network during annealing process, the infrared spectroscopy (IR-ATR) was carried out. In particular, luminescence spectra of Eu3+ and their decays were examined in detail. Some spectroscopic parameters of Eu3+ ions in glass-ceramics containing BaF2 nanocrystals were determined and compared to the values obtained for precursor xerogels. It was observed, that the intensities of two main red and orange emission bands corresponding to the 5D0!7F2 electric-dipole transition (ED) and the 5D0!7F1 magnetic-dipole (MD) transition are changed significantly during transformation from xerogels to nanocrystalline BaF2:Eu3+ glass-ceramic materials. The luminescence decay analysis clearly indicates that the measured lifetime 5D0 (Eu3+) considerably enhanced in nanocrystalline BaF2:Eu3+ glass-ceramic materials compared to precursor xerogels. The evident changes in luminescence spectra and their decays suggest the successful migration of Eu3+ ions from amorphous silica network to low-phonon BaF2 nanocrystals

Development of visible-to-ultraviolet upconversion phosphors for light-activated antimicrobial surfaces

A new form of antimicrobial surface was developed, which relies on an optical mechanism rather than chemical inactivation of microorganisms. Through the photoluminescence process of upconversion, low energy photons can be amplified into higher energy photons, and in this case, phosphors capable of converting visible light into germicidal UVC radiation were synthesized. Host crystals were doped with a praseodymium activator ion and shown to emit UVC photons upon excitation by blue or violet light. Surface coatings were prepared and proof-of-concept experiments demonstrated that, under exposure to a household fluorescent lamp, sufficient UVC radiation was emitted from the surfaces to achieve observable inactivation of surface bacterial spores and inhibition of biofilm growth. Material engineering was conducted to achieve higher optical conversion efficiency, wherein lithium codoping and development of alternative oxyfluoride host crystals were found to significantly improve upconversion emission. Implications of polychromatic excitation were investigated by conducting photoluminescence spectroscopy under combined laser beam excitation, while the effects of other application parameters are also discussed. These findings show that upconversion-based antimicrobial materials have strong potential for offering sustainable and effective technology for the prevention of diseases.PhDCommittee Chair: Jaehong Kim; Committee Member: Angus Wilkinson; Committee Member: Ching-hua Huang; Committee Member: John Crittenden; Committee Member: Seung Soon Jan

Effect of Partial Crystallization on the Structural and Luminescence Properties of Er3+-Doped Phosphate Glasses

Er-doped phosphate glass ceramics were fabricated by melt-quenching technique followed by a heat treatment. The effect of the crystallization on the structural and luminescence properties of phosphate glasses containing Al2O3, TiO2, and ZnO was investigated. Themorphological and structural properties of the glass ceramics were characterized by Field Emission-Scanning Electron Microscopy (FE-SEM), X-ray Diffraction (XRD), and micro-Raman spectroscopy. Additionally, the luminescence spectra and the lifetime values were measured in order to study the influence of the crystallization on the spectroscopic properties of the glasses. The volume ratio between the crystal and the glassy phases increased along with the duration of the heat treatment. The crystallization of the glass ceramics was confirmed by the presence of sharp peaks in the XRD patterns and different crystal phases were identified depending on the glass composition. Sr(PO3)2 crystals were found to precipitate in all the investigated glasses. As evidenced by the spectroscopic properties, the site of the Er3+ ions was not strongly affected by the heat treatment except for the fully crystallized glass ceramic which does not contain Al2O3, TiO2, and ZnO. An increase of the lifetime was also observed after the heat treatment of this glass. Therefore, we suspect that the Er3+ ions are incorporated in the precipitated crystals only in this glass ceramic