Rare-earth Doped Oxyfluoride Glass Research Articles

Optical Properties of Transparent Rare-Earth Doped Sol-Gel Derived Nano-Glass Ceramics.

Rare-earth doped oxyfluoride glass ceramics represent a new generation of tailorable optical materials with high potential for optical-related applications such as optical amplifiers, optical waveguides, and white LEDs. Their key features are related to the high transparency and remarkable luminescence properties, while keeping the thermal and chemical advantages of oxide glasses. Sol-gel chemistry offers a flexible synthesis approach with several advantages, such as lower processing temperature, the ability to control the purity and homogeneity of the final materials on a molecular level, and the large compositional flexibility. The review will be focused on optical properties of sol-gel derived nano-glass ceramics related to the RE-doped luminescent nanocrystals (fluorides, chlorides, oxychlorides, etc.) such as photoluminescence, up-conversion luminescence, thermoluminescence and how these properties are influenced by their specific processing, mostly focusing on the findings from our group and similar ones in the literature, along with a discussion of perspectives, potential challenges, and future development directions.

Optical properties and upconversion in rare earth doped oxyfluoride glasses

Ho3+ and Er3+-singly doped and Ho3+/Yb3+ and Er3+/Yb3+-codoped SiO2–Al2O3–MgO–MgF2 glasses were developed. Ho3+ and Er3+-singly doped glasses were analyzed by the Judd–Ofelt theory, and the intensity parameters obtained by Judd–Ofelt theory and by the linear relationship reported by Su were contrasted. Upconversion luminescence was observed in Ho3+/Yb3+ and Er3+/Yb3+-codoped glasses under 980 nm excitation.

Structural and Optical Investigation of Rare Earth Doped Oxyfluoride Glasses

UV-Vis and FTIR analyses have been performed on an aluminosilcate base glass doped with two different rare earths (Dy3+ and Eu3+) with varying concentrations. The glasses were prepared by conventional melt quenching technique. While the absorption intensity of the observed bands was found to increase with increase of RE concentration, the RE doping did not cause any new structural unit and the FTIR spectra practically remained unchanged.

Structure and distortion of lead fluoride nanocrystals in rare earth doped oxyfluoride glass ceramics

A series of rare earth (RE) doped oxyfluoride glasses with the composition of (45-x) SiO2-5Al2O3-40PbF2-10CdF2-xRe2O3 (x = 1, 5, 10, 15) (mol%) were prepared by a traditional melt-quenching method. Glass ceramics (GCs) were obtained after thermal treatment and characterized by X-ray diffraction (XRD) to investigate the nanocrystal structure and distortion. Both the dopant type and the doping level play an important role in the distortion of the PbF2-RE lattice. It is found that a cubic Pb3REF9 phase forms in low doping GCs, a tetragonal PbREF5 phase forms in middle doping GCs and cubic PbRE3F11 forms in high doping GCs. Accordingly, the site symmetry of RE(3+) dopants in β-PbF2 nanocrystal undergoes a transition of Oh···D4h···Oh with the increase of doping level. The change in the ligands coordinating the RE(3+) ions was further illustrated by the optical changes in Yb-doped GCs. This paper provides insights on the nanocrystal structure of RE at the atomic level and tries to make a complete description of the nanocrystal structure and distortion in these glass-ceramic materials, which will benefit the optimization of optical properties.

Rare earth doped silicate-oxyfluoride glass ceramics incorporating LaF3 nano-crystals for UV-LED color conversion

Rare earth doped oxyfluoride glass ceramics with LaF3 nano-crystals formed inside were fabricated for color converter of UV-LED. Among various rare earth ions, Dy3+ and Eu3+ showed practically utilizable visible emissions under UV-LED excitation of 365nm. The visible emission has been improved by the formation of LaF3 brought by heat treatment. X-ray diffraction and transmission electron microscopy along with its energy dispersive spectra confirmed the formation of LaF3 nano-crystals. Compositional dependence and the effects of heat treatment conditions on the visible emissions have been investigated. The CIE chromaticity coordinates of the glasses were also examined for Dy3+ singly doped and co-doped samples. The effect of LaF3 nano-crystals and co-dopants on the visible emission properties of Dy3+ was discussed.

Distribution of Nd3+ ions in oxyfluoride glass ceramics

It has been an open question whether Nd3+ ions are incorporated into the crystalline phase in oxyfluoride glass ceramics or not. Moreover, relative research has indicated that spectra characters display minor differences between before and after heat treatment in oxyfluoride glass compared to similar Er3+-, Yb3+-, Tm3+-, Eu3+-, etc.-doped materials. Here, we have studied the distribution of Nd3+ ions in oxyfluoride glass ceramics by X-ray diffraction quantitative analysis and found that almost none of the Nd3+ ions can be incorporated into the crystalline phase. In order to confirm the rationality of the process, the conventional mathematical calculation and energy-dispersive spectrometry line scanning are employed, which show good consistency. The distribution of Nd3+ ions in oxyfluoride glass ceramics reported here is significant for further optical investigations and applications of rare-earth doped oxyfluoride glass ceramics.

The tetragonal structure of nanocrystals in rare-earth doped oxyfluoride glass ceramics

Rare-earth doped oxyfluoride glasses and nanocrystalline glass ceramics have been prepared and studied by energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) aiming at investigating the structure and the symmetry of the nanocrystal as well as the site of the rare-earth ion. To solve the problem encountered by previous researchers due to glass host interference, we etched off glass matrix and released the fluoride nanocrystal, which is more convenient for EDS measurement. A tetragonal phase model with the chemical formula as PbREF(5) proved by quantitative EDS and XRD analyses has been proposed in this paper for the first time. Two specific crystalline phases with the same space group have been observed at 460 °C-500 °C and 520 °C-560 °C, respectively. Moreover, a super "pseudo-cubic" cell based on our tetragonal model may give a good explanation to the probable previous cubic-symmetry misunderstanding by researchers. Additionally, the thermodynamic mechanism of phase transition and the thermal stability related to the structure of nanocrystals in glass ceramics have been studied and supported by ab initio calculations and experimental methods. The structure and thermal stability of the nanocrystal and clear environment of the rare-earth ion reported here have far-reaching significance with respect to the optical investigations and further applications of rare-earth doped oxyfluoride glass ceramics.