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Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Advanced and Functional Ceramics and Glasses".

Deadline for manuscript submissions: closed (20 June 2022) | Viewed by 26363

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Special Issue Editor

Prof. Dr. Wojciech Pisarski

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Guest Editor

Institute of Chemistry, University of Silesia, 40-007 Katowice, Poland
Interests: rare earth doped materials; optical spectroscopy; luminescence

Special Issue Information

Dear Colleagues,

In the field of photonics and materials engineering there has recently been a great interest in glasses and ceramics doped with rare earth ions emitting visible light or infrared radiation. They are very promising photonic materials in relation to several multifunctional and industrial applications. In particular, rare earth doped glasses/ceramics play significant roles in solid-state lasers, broadband optical amplifiers, and up-conversion luminescence temperature sensors. Special attention has been paid to inorganic glasses applied to optical fiber technology. Studies of radiative and non-radiative relaxation processes and their mechanisms between the rare earth ions are necessary to obtain knowledge about luminescent glasses and ceramics. These phenomena are interesting and important from the scientific and technological points of view.

The aim of this Special Issue is to present novel results for luminescent glasses and ceramics which give important contributions to the development of scientific research in the field of glass/ceramic science and technology, applied spectroscopy, lasers, sensors, and fiber photonics. This Special Issue invites a wide range of research on rare earth doped glasses and ceramic materials: from synthesis, structure and properties to their potential optical applications.

I would like to invite you with great pleasure to submit a manuscript for this Special Issue. Full articles, short communications, and review papers are all welcome.

Prof. Dr. Wojciech Pisarski
Guest Editor

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Keywords

rare earth doped glasses/ceramics
structure–property relationship
spectroscopy
luminescence
radiative and non-radiative relaxation
up-conversion luminescence processes and optical temperature sensors
optical glass fibers
ceramic phosphors
solid-state lasers

Published Papers (12 papers)

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Editorial

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4 pages, 205 KiB

Open AccessEditorial

Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties and Their Optical Applications

by Wojciech A. Pisarski

Materials 2022, 15(22), 8099; https://doi.org/10.3390/ma15228099 - 16 Nov 2022

Cited by 6 | Viewed by 1392

Abstract

Glasses, glass-ceramics and ceramics belong to three important classes of engineering materials, which are useful in numerous multifunctional and industrial applications [...] Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

Research

Jump to: Editorial

12 pages, 3163 KiB

Open AccessArticle

Synthesis and Characterization of Li₂MgGeO₄:Ho³⁺

by Nikola Bednarska-Adam, Marta Kuwik, Ewa Pietrasik, Wojciech A. Pisarski, Tomasz Goryczka, Bogusław Macalik and Joanna Pisarska

Materials 2022, 15(15), 5263; https://doi.org/10.3390/ma15155263 - 29 Jul 2022

Cited by 6 | Viewed by 1373

Abstract

In this work, the synthesis and characterization of Li₂MgGeO₄:Ho³⁺ ceramics were reported. The X-ray diffraction measurements revealed that the studied ceramics belong to the monoclinic Li₂MgGeO₄. Luminescence properties were analyzed in the visible spectral range. Green and red emission bands correspondent to the ⁵F₄,⁵S₂→⁵I₈ and ⁵F₅→⁵I₈ transitions of Ho³⁺ were observed, and their intensities were significantly dependent on activator concentration. Luminescence spectra were also measured under direct excitation of holmium ions or ceramic matrix. Holmium ions were inserted in crystal lattice Li₂MgGeO₄, giving broad blue emission and characteristic 4f-4f luminescent transitions of rare earths under the selective excitation of the ceramic matrix. The presence of the energy transfer process between the host lattice and Ho³⁺ ions was suggested. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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13 pages, 3619 KiB

Open AccessArticle

Size-Dependent Persistent Luminescence of YAGG:Cr³⁺ Nanophosphors

by Vitalii Boiko, Zhengfa Dai, Mykhailo Chaika, Karina Grzeszkiewicz, Jiang Li, Wieslaw Strek and Dariusz Hreniak

Materials 2022, 15(13), 4407; https://doi.org/10.3390/ma15134407 - 22 Jun 2022

Cited by 3 | Viewed by 1444

Abstract

In the current work, YAGG:Cr³⁺ nanophosphors were synthesized by the Pechini method and then annealed at different temperatures in the range 800–1300 °C. The structure and morphology of the samples were characterized by X-ray Powder Diffraction (XRPD). The lattice parameters and average crystalline sizes as site occupation by Al³⁺ and Ga³⁺ ions were calculated from the Rietveld refinement data. To investigate the effect of crystalline size of the materials on their optical properties: excitation and emission spectra were recorded and analyzed. Finally, the effect of crystalline size on the probability of carrier recombination leading to PersL was determined experimentally with thermoluminescence analyses. The T_max-T_stop method was applied to determine the trap type and particle size (calcination temperature) effect on their redistribution. A correlation between structural changes and trap redistribution was found. In particular, the extinction of high-temperature TL maximum with increasing annealing temperatures is observed, while low-temperature TL maximum increases and reaches a maximum when the lattice parameter reaches saturation. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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13 pages, 2574 KiB

Open AccessArticle

Crystallization Mechanism and Optical Properties of Antimony-Germanate-Silicate Glass-Ceramic Doped with Europium Ions

by Piotr Golonko, Karolina Sadowska, Tomasz Ragiń, Marcin Kochanowicz, Piotr Miluski, Jan Dorosz, Marta Kuwik, Wojciech Pisarski, Joanna Pisarska, Magdalena Leśniak, Dominik Dorosz and Jacek Żmojda

Materials 2022, 15(11), 3797; https://doi.org/10.3390/ma15113797 - 26 May 2022

Cited by 2 | Viewed by 1377

Abstract

Glass-ceramic is semi-novel material with many applications, but it is still problematic in obtaining fibers. This paper aims to develop a new glass-ceramic material that is a compromise between crystallization, thermal stability, and optical properties required for optical fiber technology. This compromise is made possible by an alternative method with a controlled crystallization process and a suitable choice of the chemical composition of the core material. In this way, the annealing process is eliminated, and the core material adopts a glass-ceramic character with high transparency directly in the drawing process. In the experiment, low phonon antimony-germanate-silicate glass (SGS) doped with Eu³⁺ ions and different concentrations of P₂O₅ were fabricated. The glass material crystallized during the cooling process under conditions similar to the drawing processes’. Thermal stability (DSC), X-ray photo analysis (XRD), and spectroscopic were measured. Eu³⁺ ions were used as spectral probes to determine the effect of P₂O₅ on the asymmetry ratio for the selected transitions (⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂). From the measurements, it was observed that the material produced exhibited amorphous or glass-ceramic properties, strongly dependent on the nucleator concentration. In addition, the conducted study confirmed that europium ions co-form the EuPO₄ structure during the cooling process from 730 °C to room temperature. Moreover, the asymmetry ratio was changed from over 4 to under 1. The result obtained confirms that the developed material has properties typical of transparent glass-ceramic while maintaining high thermal stability, which will enable the fabrication of fibers with the glass-ceramic core. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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13 pages, 3786 KiB

Open AccessArticle

Near-IR Luminescence of Rare-Earth Ions (Er³⁺, Pr³⁺, Ho³⁺, Tm³⁺) in Titanate–Germanate Glasses under Excitation of Yb³⁺

by Karolina Kowalska, Marta Kuwik, Joanna Pisarska and Wojciech A. Pisarski

Materials 2022, 15(10), 3660; https://doi.org/10.3390/ma15103660 - 20 May 2022

Cited by 10 | Viewed by 2143

Abstract

Inorganic glasses co-doped with rare-earth ions have a key potential application value in the field of optical communications. In this paper, we have fabricated and then characterized multicomponent TiO₂-modified germanate glasses co-doped with Yb³⁺/Ln³⁺ (Ln = Pr, Er, Tm, Ho) with excellent spectroscopic properties. Glass systems were directly excited at 980 nm (the ²F_7/2 → ²F_5/2 transition of Yb³⁺). We demonstrated that the introduction of TiO₂ is a promising option to significantly enhance the main near-infrared luminescence bands located at the optical telecommunication window at 1.3 μm (Pr³⁺: ¹G₄ → ³H₅), 1.5 μm (Er³⁺: ⁴I_13/2 → ⁴I_15/2), 1.8 μm (Tm³⁺: ³F₄ → ³H₆) and 2.0 μm (Ho³⁺: ⁵I₇ → ⁷I₈). Based on the lifetime values, the energy transfer efficiencies (η_ET) were estimated. The values of η_ET are changed from 31% for Yb³⁺/Ho³⁺ glass to nearly 53% for Yb³⁺/Pr³⁺ glass. The investigations show that obtained titanate–germanate glass is an interesting type of special glasses integrating luminescence properties and spectroscopic parameters, which may be a promising candidate for application in laser sources emitting radiation and broadband tunable amplifiers operating in the near-infrared range. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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14 pages, 3266 KiB

Open AccessCommunication

Spectroscopic Properties of Inorganic Glasses Doped with Pr³⁺: A Comparative Study

by Joanna Pisarska, Marta Kuwik and Wojciech A. Pisarski

Materials 2022, 15(3), 767; https://doi.org/10.3390/ma15030767 - 20 Jan 2022

Cited by 4 | Viewed by 1648

Abstract

The results presented in this communication concern visible and near-IR emission of Pr³⁺ ions in selected inorganic glasses, i.e., borate-based glass with Ga₂O₃ and BaO, lead-phosphate glass with Ga₂O₃, gallo-germanate glass modified by BaO/BaF₂, and multicomponent fluoride glass based on InF₃. Glasses present several emission bands at blue, reddish orange, and near-infrared spectral ranges, which correspond to 4f–4f electronic transitions of Pr³⁺. The profiles of emission bands and their relative intensity ratios depend strongly on glass-host. Visible emission of Pr³⁺ ions is tuned from red/orange for borate-based glass to nearly white light for multicomponent fluoride glass based on InF₃. The positions and spectral linewidths for near-infrared luminescence bands at the optical telecommunication window corresponding to the ¹G₄ → ³H₅, ¹D₂ → ¹G₄, and ³H₄ → ³F₃,³F₄ transitions of Pr³⁺ are dependent on glass-host matrices and excitation wavelengths. Low-phonon fluoride glasses based on InF₃ and gallo-germanate glasses with BaO/BaF₂ are excellent candidates for broadband near-infrared optical amplifiers. Spectroscopic properties of Pr³⁺-doped glasses are compared and discussed in relation to potential optical applications. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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23 pages, 5671 KiB

Open AccessArticle

Investigation of the TeO₂/GeO₂ Ratio on the Spectroscopic Properties of Eu³⁺-Doped Oxide Glasses for Optical Fiber Application

by Magdalena Lesniak, Jakub Zeid, Bartłomiej Starzyk, Marcin Kochanowicz, Marta Kuwik, Jacek Zmojda, Piotr Miluski, Agata Baranowska, Jan Dorosz, Wojciech Pisarski, Joanna Pisarska and Dominik Dorosz

Materials 2022, 15(1), 117; https://doi.org/10.3390/ma15010117 - 24 Dec 2021

Cited by 9 | Viewed by 2836

Abstract

This study presented an analysis of the TeO₂/GeO₂ molar ratio in an oxide glass system. A family of melt-quenched glasses with the range of 0–35 mol% of GeO₂ has been characterized by using DSC, Raman, MIR, refractive index, PLE, PL spectra, and time-resolved spectral measurements. The increase in the content of germanium oxide caused an increase in the transition temperature but a decrease in the refractive index. The photoluminescence spectra of europium ions were examined under the excitation of 465 nm, corresponding to ⁷F₀ → ⁵D₂ transition. The PSB (phonon sidebands) analysis was carried out to determine the phonon energy of the glass hosts. It was reported that the red (⁵D₀ → ⁷F₂) to orange (⁵D₀ → ⁷F₁) fluorescence intensity ratio for Eu³⁺ ions decreased from 4.49 (Te0Ge) to 3.33 (Te15Ge) and showed a constant increase from 4.58 (Te20Ge) to 4.88 (Te35Ge). These optical features were explained in structural studies, especially changes in the coordination of ^[4]Ge to ^[6]Ge. The most extended lifetime was reported for the Eu³⁺ doped glass with the highest content of GeO₂. This glass was successfully used for the drawing of optical fiber. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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15 pages, 2477 KiB

Open AccessArticle

Transition Metals (Cr³⁺) and Lanthanides (Eu³⁺) in Inorganic Glasses with Extremely Different Glass-Formers B₂O₃ and GeO₂

by Karolina Kowalska, Marta Kuwik, Justyna Polak, Joanna Pisarska and Wojciech A. Pisarski

Materials 2021, 14(23), 7156; https://doi.org/10.3390/ma14237156 - 24 Nov 2021

Cited by 6 | Viewed by 1982

Abstract

Glasses containing two different network-forming components and doped with optically active ions exhibit interesting properties. In this work, glass systems based on germanium dioxide and boron trioxide singly doped with lanthanides (Eu³⁺) and transition metals (Cr³⁺) ions are research subjects. Optical spectroscopy was the major research tool used to record excitation and emission spectra in a wide spectral range for studied systems. The emitted radiation of glasses doped with Cr³⁺ ions is dominated by broadband luminescence centered at 770 nm and 1050 nm (⁴T₂ → ⁴A₂). Interestingly, the increase of concentration of one of the oxides contributed to the detectable changes of the R-line (²E → ⁴A₂) of Cr³⁺ ions. Moreover, EPR spectroscopy confirmed the paramagnetic properties of the obtained glasses. The influence of molar ratio GeO₂:B₂O₃ on spectroscopic properties for Eu³⁺ ions is discussed. The intensity of luminescence bands due to transitions of trivalent europium ions as well as the ratio R/O decrease with the increase of B₂O₃. On the other hand, the increase in concentration B₂O₃ influences the increasing tendency of luminescence lifetimes for the ⁵D₀ state of Eu³⁺ ions. The results will contribute to a better understanding of the role of the glass host and thus the prospects for new optical materials. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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24 pages, 6876 KiB

Open AccessArticle

Structural and Photoluminescence Investigations of Tb³⁺/Eu³⁺ Co-Doped Silicate Sol-Gel Glass-Ceramics Containing CaF₂ Nanocrystals

by Natalia Pawlik, Barbara Szpikowska-Sroka, Tomasz Goryczka, Joanna Pisarska and Wojciech A. Pisarski

Materials 2021, 14(4), 754; https://doi.org/10.3390/ma14040754 - 05 Feb 2021

Cited by 10 | Viewed by 2801

Abstract

In this work, the series of Tb³⁺/Eu³⁺ co-doped xerogels and derivative glass-ceramics containing CaF₂ nanocrystals were prepared and characterized. The in situ formation of fluoride crystals was verified by an X-ray diffraction technique (XRD) and transmission electron microscopy (TEM). The studies of the Tb³⁺/Eu³⁺ energy transfer (ET) process were performed based on excitation and emission spectra along with luminescence decay analysis. According to emission spectra recorded under near-ultraviolet (NUV) excitation (351 nm, ⁷F₆ → ⁵L₉ transition of Tb³⁺), the mutual coexistence of the ⁵D₄ → ⁷F_J (J = 6–3) (Tb³⁺) and the ⁵D₀ → ⁷F_J (J = 0–4) (Eu³⁺) luminescence bands was clearly observed. The co-doping also resulted in gradual shortening of a lifetime from the ⁵D₄ state of Tb³⁺ ions, and the ET efficiencies were varied from η_ET = 11.9% (Tb³⁺:Eu³⁺ = 1:0.5) to η_ET = 22.9% (Tb³⁺:Eu³⁺ = 1:2) for xerogels, and from η_ET = 25.7% (Tb³⁺:Eu³⁺ = 1:0.5) up to η_ET = 67.4% (Tb³⁺:Eu³⁺ = 1:2) for glass-ceramics. Performed decay analysis from the ⁵D₀ (Eu³⁺) and the ⁵D₄ (Tb³⁺) state revealed a correlation with the change in Tb³⁺–Eu³⁺ and Eu³⁺–Eu³⁺ interionic distances resulting from both the variable Tb³⁺:Eu³⁺ molar ratio and their partial segregation in CaF₂ nanophase. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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10 pages, 1672 KiB

Open AccessArticle

Phonon Sideband Analysis and Near-Infrared Emission in Heavy Metal Oxide Glasses

by Joanna Pisarska, Wojciech A. Pisarski, Radosław Lisiecki and Witold Ryba-Romanowski

Materials 2021, 14(1), 121; https://doi.org/10.3390/ma14010121 - 30 Dec 2020

Cited by 12 | Viewed by 1802

Abstract

In this work, spectroscopic properties of europium and erbium ions in heavy metal oxide glasses have been studied. The phonon energy of the glass host was determined based on Eu³⁺ excitation spectra measurements. Near-IR emission spectra at 1550 nm related to ⁴I_13/2 → ⁴I_15/2 transition of erbium in heavy metal glasses were examined with special regards to luminescence bandwidth and measured lifetime. In particular, correlation between phonon energy and the measured lifetime ⁴I_13/2 (Er³⁺) was proposed. The luminescence lifetime for the ⁴I_13/2 upper laser state of erbium decreases with increasing phonon energy in glass matrices. Completely different results were obtained glass samples with europium ions, where the ⁵D₀ lifetime increases with increasing phonon energy. Our investigations suggest that the values of measured ⁵D₀ lifetime equal to radiative lifetimes for all heavy metal oxide glasses. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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15 pages, 5191 KiB

Open AccessArticle

Lead Borate Glasses and Glass-Ceramics Singly Doped with Dy³⁺ for White LEDs

by Agata Górny, Marta Kuwik, Wojciech A. Pisarski and Joanna Pisarska

Materials 2020, 13(21), 5022; https://doi.org/10.3390/ma13215022 - 07 Nov 2020

Cited by 16 | Viewed by 2475

Abstract

In this paper, some series of lead borate glasses and glass ceramics singly doped with Dy³⁺ ions were prepared and then studied using spectroscopic techniques. Our research includes mainly studies of the luminescence properties of received materials for white light. The luminescence bands associated with the characteristic ⁴F_9/2→⁶H_15/2 (blue), ⁴F_9/2→⁶H_13/2 (yellow) and ⁴F_9/2→⁶H_11/2 (red) transitions of trivalent dysprosium in lead borate systems are well observed. In particular, the Commission Internationale de I’Eclairage (CIE) chromaticity coordinates (x, y) were calculated in relation to potential applications for white light-emitting diodes (W-LEDs). Their values depend on the relative B₂O₃/PbO ratios and PbX₂ contents (where X = Cl, F, Br) in glass composition. For glass-ceramics, the chromaticity coordinates are changed significantly under different excitation wavelengths. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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20 pages, 10830 KiB

Open AccessArticle

Influence of Oxide Glass Modifiers on the Structural and Spectroscopic Properties of Phosphate Glasses for Visible and Near-Infrared Photonic Applications

by Marta Kuwik, Joanna Pisarska and Wojciech A. Pisarski

Materials 2020, 13(21), 4746; https://doi.org/10.3390/ma13214746 - 23 Oct 2020

Cited by 31 | Viewed by 2828

Abstract

The effect of oxide modifiers on multiple properties (structural and spectroscopic) of phosphate glasses with molar composition 60P₂O₅-(10−x)Ga₂O₃-30MO-xEu₂O₃ and 60P₂O₅-(10−y)Ga₂O₃-30MO-yEr₂O₃ (where M = Ca, Sr, Ba; x = 0, 0.5; y = 0, 1) were systematically examined and discussed. The local structure of systems was evidenced by the infrared (IR-ATR) and Raman spectroscopic techniques. The spectroscopic behaviors of the studied glass systems were determined based on analysis of recorded spectra (excitation and emission) as well as luminescence decay curves. Intense red and near-infrared emissions (1.5 μm) were observed for samples doped with Eu³⁺ and Er³⁺ ions, respectively. It was found that the value of fluorescence intensity ratio R/O related to ⁵D₀→⁷F₂ (red) and ⁵D₀→⁷F₁ (orange) transition of Eu³⁺ ions depends on the oxide modifiers MO in the glass host. However, no clear influence of glass modifiers on the luminescence linewidth (FWHM) was observed for phosphate systems doped with Er³⁺ ions. Moreover, the ⁵D₀ and ⁴I_13/2 luminescence lifetimes of Eu³⁺ and Er³⁺ ions increase with the increasing ionic radius of M²⁺ (M = Ca, Sr, Ba) in the host matrix. The obtained results suggest the applicability of the phosphate glasses with oxide modifiers as potential red and near-infrared photoluminescent materials in photonic devices. Full article

(This article belongs to the Special Issue Rare Earth Doped Glasses/Ceramics: Synthesis, Structure, Properties, and Optical Applications)

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