Bane to boon: intrinsic defect sensitized photoluminescence from Mn<sup>2+</sup> or rare-earth ion doped fluorosilicate photonic glasses

Hu, Qingliu; Gao, Zhigang; Lu, Xiaosong; Ren, Jing; He, Fei; Fang, Zaijin; Liu, Yinyao; Sun, Shiyu; Yang, Piaoping; Wang, Pengfei

doi:10.1039/c7tc04020b

Cited by 21 publications

(19 citation statements)

References 42 publications

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“…Hu et al 48 reported for instance emissions around 350, 510, and 670 nm in fluorosilicate glasses under excitation at 260 nm. Yet again, as argued by the authors, 48 arriving at an unequivocal model accounting for the nature of the luminescence defects continues to be an elusive task. In binary lead silicate glasses, 62 the intrinsic luminescence has been associated with transitions within the lead ions, or Pb-O and Pb-O-Pb linkages for higher lead concentrations.…”

Section: Pl Spectroscopy and Emission Dynamics Assessmentmentioning

confidence: 99%

Physico‐chemical properties of international simple glass (ISG) nuclear waste simulants: Luminescence baseline study

2022

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Borosilicate glass has been adopted internationally for the treatment of nuclear waste with the object of long‐term stabilization through vitrification. Aiming to facilitate experimental comparisons across laboratories, the six‐component international simple glass (ISG) was developed as benchmark. The original ISG produced by Mo‐SCI Corporation (Rolla, MO) was distributed and characterized for different physical properties thus serving as reference for further studies. Still, photoluminescence (PL) properties, which may be useful for scrutinizing radiation‐induced damage, have not been reported. Further, the original ISG contained significant iron impurities, which may present interference in various studies (e.g., optical). Consequently, two new ISG analogs lacking iron impurities (labeled ISG‐1 [closest composition to original ISG] and ISG‐2 [some MgO added at expense of CaO]) were synthesized by Corning Inc. (Corning, NY) (also doped with lanthanum for subsequent corrosion tests involving atom probe tomography), which remain to be fully characterized. Accordingly, this work was undertaken to perform a comprehensive study comparing the three ISG specimens. Various characterizations were then performed on the pristine glasses: X‐ray diffraction and vibrational spectroscopy (structural properties); static‐leach product consistency test (PCT, dissolution behavior); dilatometry and calorimetry measurements (thermal properties); and optical absorption with Tauc and Urbach plots analysis, followed by PL spectroscopy with decay kinetics assessment (optical properties). While the general structural features appeared similar among the glasses, the deconvolution of Raman spectra suggested a lower degree of connectivity in the silica network for ISG‐2. In addition, some differences were indicated from the PCT results and thermal properties assessed, which were discussed based on compositional variations. Further on, the optical properties were shown to be the most distinct. The optical absorption of the original ISG was characterized by Fe2+/Fe3+ impurities not detected for ISG‐1 and ISG‐2. The glasses all exhibited two main PL features (∼1.8 and 2.5 eV) with multiexponential decay behavior apparently of intrinsic origin. In addition, ISG‐1 and ISG‐2 showed a third high‐energy (∼3.4 eV) fast‐decaying contribution tentatively credited to tin impurities, which appeared most significantly for ISG‐1. The results are expected to serve as baseline for future studies simulating the effects of radioactive element decay.

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Section: Pl Spectroscopy and Emission Dynamics Assessmentmentioning

confidence: 99%

Physico‐chemical properties of international simple glass (ISG) nuclear waste simulants: Luminescence baseline study

2022

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“…The optimum UC PLQY value of FS glass (1.12%) is more than seven times larger than that of ZBLAN glass (0.15%). The thermodynamic stability of FS glass is much better than that of fluoride glass due to the introduction of strong SiO networks . The ultrahigh UC luminescence efficiency of this 70Si‐FS glass makes it a promising substitution for ZBLAN glass and an excellent gain matrix, even in high‐power fiber lasing applications.…”

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confidence: 91%

Phase‐Separation Engineering of Glass for Drastic Enhancement of Upconversion Luminescence

Fang

Chen

Peng

et al. 2019

Advanced Optical Materials

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earth (RE) ion-doped materials have been developed as significant gain matrices due to their high photoluminescence quantum yield (PLQY) and multiple-wavelength luminescence. [4,5] Recent decades have witnessed extensive investigations in doping methods and network structure design to obtain more efficient gain materials. [6,7] However, the requirements for high luminescence efficiency and excellent thermodynamic stability of optical materials are always contradictory, greatly restricting their applications in, e.g., high-temperature, high-humidity, and high-power laser pumping environments. Generally, the luminescence efficiency of an optical material is inversely proportional to the multiphonon nonradiative transition probability (W p ) of the intermediate state energy level for RE ions. [8] The luminescence process, especially for the upconversion (UC) process, is normally associated with a large number of intermediate state energy levels. Furthermore, its value (W p ) depends on the maximum phonon energy (ћω) of the elastic structure of condensed matter, and it increases dramatically with increasing ћω (as described in Equations (S1)-(S3) of the Supporting Information). [9] Traditionally, one class of soft material with extremely low ћω values, including fluorides, chalcogenides, and halogenides, has been widely Optical gain materials are of fundamental importance for various applications, such as lasers, lighting, optical communication, microscopy, and spectroscopy. However, the requirements for high luminescence efficiency and excellent thermodynamic stability of materials are always contradictory. As a result, wide applications of optical materials in high-temperature, high-humidity, and high-power laser-irradiated environments are restricted. Here, a facile approach based on phase-separation engineering is proposed to modulate the thermodynamic stability and enhance the luminescence efficiency of optical gain materials. It is shown that the thermodynamic stability and luminescence efficiency of the phase-separated fluorosilicate (FS) gain glass are both enhanced dramatically when the SiO 2 concentration is optimized. Owing to the confinement effect of phase-separation network structure on active ions, the upconversion (UC) luminescence efficiency of the designed glass is 150 times higher than that of traditional FS glasses and even seven times higher than that of ZBLAN (ZrF 4 -BaF 2 -LaF 3 -AlF 3 -NaF) glass, which is the most commonly used material for UC fiber lasing applications. These intriguing properties of the glass indicate that phase-separation engineering not only provides a powerful solution to conquer the conventional contradiction between thermodynamic stability and luminescence efficiency but also offers significant opportunities for manufacturing a wide range of optical composites with multiple functions.

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“…Moreover, for glasses consisting of two or three different kinds of glass formers, the glass networks remain virtually dominated by one type of topological structures, for example, formation of certain types of B-O-P and B-O-Si linkages of medium range scale (5-20 Å) [20] Hence, the mixed-former-glasses still suffer from limited site-to-site variations for the dopants. [25][26][27] As a comparison, PL properties of the REs, for example, Er 3+ which possess 4f-4f electronic transitions that are shielded by 5p shells from the outer chemical environment and thus insensitive to the local chemical environment, [28] were also examined in the newly developed PG glass. The new method is termed "melt-in-melt" to highlight the key step in the glass preparation and further details are provided in Figure 1.…”

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confidence: 99%

Topological Engineering of Photoluminescence Properties of Bismuth‐ or Erbium‐Doped Phosphosilicate Glass of Arbitrary P₂O₅ to SiO₂ Ratio

Chu

Zhang

et al. 2018

Advanced Optical Materials

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research to applied industrial and social applications including but certainly not limited to window glasses, windscreens, kitchen cooktops, microscope and telescope lens, and optics, and so on, owing to such unmatched and outstanding properties as ease of large-scale and complex shape production as well as chemical and mechanical durability. [1] However, glasses, usually made by the traditional melt-quenching method viz., cooling a viscous liquid fast enough to avoid crystallization (known as supercooling), [2] are seriously constrained to those that entail an acceptable degree of glass-forming ability unless otherwise being made under extremely harsh conditions (e.g., superfast cooling or high-energy irradiation, etc.) that are not readily available to ordinary glass-making labs and factories. [3] This leads to a significantly limited range of available constituents and functions of the obtained glasses. For example, spectroscopic features of active dopants (e.g., rare-earth (REs) ions, transition, and main group metals) are closely associated with their chemical states and the surrounding chemical environments provided by the glass host; hence, it is possible to induce new photoluminescence (PL) functions such as ultrabroadband and enhanced up-/down-conversion emissions via proper doping, post thermal, and magnetic treatments or A new method is reported to achieve the manufacture of glass of arbitrary ratio of SiO 2 /P 2 O 5 which cannot be made by conventional melt-quenching method. The new method is termed "melt-in-melt" which encapsulates the key step in the glass manufacturing process, i.e. one molten glass is poured into another molten glass with a stirring at high temperatures. Because of near unlimited possibilities in designing new glass compositions, there is a correspondingly great degree of freedom in the topological engineering of the glass structure, which in turn strongly influences the photoluminescence (PL) properties of active dopants. As a proof concept, bismuth and erbium are selected as the indicator dopants for emphasizing the real advantages of the new method as an effective means to tailoring the PL properties of the doped glasses. The micro structure and element distribution within the fabricated glasses are comprehensively characterized by high-resolution scanning electron microscopy, micro-Raman and high-performance X-ray fluorescence spectroscopy. Phase separation occurring at both nano-and meso-scale is observed. Apart from the developed glasses being themselves promising broadband emission phosphors, the new glass-making method may extend the possible applications of glass for important photonic applications (e.g. optical sensing, lighting, display, optical amplification and lasing etc.).

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Bane to boon: intrinsic defect sensitized photoluminescence from Mn²⁺ or rare-earth ion doped fluorosilicate photonic glasses

Abstract: Defects present ubiquitously in glasses exert a strong influence on the optical qualities and performances of glass, a phenomenon that has not been well studied to date.

Cited by 21 publications

References 42 publications

Physico‐chemical properties of international simple glass (ISG) nuclear waste simulants: Luminescence baseline study

Physico‐chemical properties of international simple glass (ISG) nuclear waste simulants: Luminescence baseline study

Phase‐Separation Engineering of Glass for Drastic Enhancement of Upconversion Luminescence

Topological Engineering of Photoluminescence Properties of Bismuth‐ or Erbium‐Doped Phosphosilicate Glass of Arbitrary P₂O₅ to SiO₂ Ratio

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Bane to boon: intrinsic defect sensitized photoluminescence from Mn2+ or rare-earth ion doped fluorosilicate photonic glasses

Abstract: Defects present ubiquitously in glasses exert a strong influence on the optical qualities and performances of glass, a phenomenon that has not been well studied to date.

Cited by 21 publications

References 42 publications

Physico‐chemical properties of international simple glass (ISG) nuclear waste simulants: Luminescence baseline study

Physico‐chemical properties of international simple glass (ISG) nuclear waste simulants: Luminescence baseline study

Phase‐Separation Engineering of Glass for Drastic Enhancement of Upconversion Luminescence

Topological Engineering of Photoluminescence Properties of Bismuth‐ or Erbium‐Doped Phosphosilicate Glass of Arbitrary P2O5 to SiO2 Ratio

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Bane to boon: intrinsic defect sensitized photoluminescence from Mn²⁺ or rare-earth ion doped fluorosilicate photonic glasses

Topological Engineering of Photoluminescence Properties of Bismuth‐ or Erbium‐Doped Phosphosilicate Glass of Arbitrary P₂O₅ to SiO₂ Ratio