New stable fluoroindate glasses

doi:10.1016/S0167-2738(01)00895-5

Solid State Ionics

Volume 144, Issues 1–2, 1 September 2001, Pages 117-121

https://doi.org/10.1016/S0167-2738(01)00895-5 Get rights and content

Abstract

Potential applications of fluoride glasses are centered upon passive and active optical fibers. In various cases, phonon energy is a sensitive factor for the efficiency of the optical components. Because of their lower phonon energy, fluoroindate glasses offer some advantages over fluorozirconate glasses. However, the fiber-drawing ability and the resistance against devitrification are higher in InF₃-based glasses. New compositions have been investigated in order to extend IR transmission and enhance thermal stability. Various compositions are reported in the multicomponent system containing In, Ga, Y, Zn, Sr, Ba and Na. A typical composition is 30% InF₃-10% YF₃-25% BaF₂-5% SrF₂-10% NaF-10% ZnF₂-10% GaF₃. This InYBSNZnGa glass has a good stability exemplified by the value of the stability factors: T_x−T_g=108 K, S=4.1 K. Glass transition temperature, T_g=309 °C. Thermal, optical and physical properties of these glasses are reported and the effects of materials purity and processing on these properties are discussed. These glasses corrode less in aqueous solutions than other fluoride glasses.

Introduction

Heavy metal fluoride glasses are promising materials with potential applications for infrared transmission [1], [2], [3], active devices such as fiber lasers and optical amplifiers [4] and for ionic conduction [5]. Main development focusses on fluorozirconate glasses that have been extensively studied [6] and may be drawn into low loss fibres. In some cases, there are some advantages in using glasses exhibiting low phonon energies, especially for laser transitions that are sensitive to the host vibrational energy. This is the case for the 1.3-μm emission of the Pr³⁺ [7] ion. Fluoroindates, which are transparent in the infrared at longer wavelengths than fluorozirconates, also have lower phonon energy: 510 cm⁻¹ for fluoroindate glasses compared to 580 cm⁻¹ for the standard ZBLAN glass based on the fluorides of Zr, Ba, La, Al and Na. In recent years, fluoroindate glasses have attracted much interest for this reason [7]. Since they were first reported [8], glass-forming regions have been studied in various fluoride systems based on InF₃ [9], [10], [11].

The aim of this work is to define the glass compositions stable enough to give thick samples, preforms, and hopefully, optical fibers. For this purpose, new fluorides have been incorporated into glass composition and the evolution of the glass stability with respect to composition has been studied. A special emphasis was put on the substitution of gallium for indium. The influence of the GaF₃ content on some physical properties is reported.

Section snippets

Experimental

Several samples were prepared by the conventional method described in Ref. [7]. Starting materials were In₂O₃ (99.9%), Y₂O₃ (99.9%), Ga₂O₃ (99.9%), BaF₂ (>99%), SrF₂ (>97%), NaF (>97%) and ZnF₂ (>99%). The batches (about 6 g) were melted in a platinum crucible after weighing and mixing the various components. After a clear melt was obtained, liquid was poured into brass moulds held at a temperature 10 to 20 K below the glass transition temperature T_g—typically 280 °C. Finally, the samples were

Results

In order to identify the optimum compositions, we look for the maximum values of the thermal stability range ΔT and the stability criterion S. The starting composition for this study, expressed in mol%, is a quinternary glass [14]: 45InF₃-5YF₃-35BaF₂-5SrF₂-10NaF for which ΔT=84 K and S=1.2 K.

The glass-forming ability increases when InF₃ is replaced by ZnF₂ and GaF₃, which also have a glass-forming ability. In the first step, 5% and 10% ZnF₂ were incorporated in the base glass. Corresponding

Discussion

The methodology used in this work is based on the confusion principle. This principle expresses that glass stability increases as the number of the glass components increases. As an example, a binary glass may be prone to devitrification while composition adjustments in a ternary system will lead to a more stable glass. The starting point of this study was the ternary InF₃–YF₃–BaF₂ system [14]. Then, additional fluorides were incorporated into glass composition according to the sequence:

In	Y	Ba
In	Y

Conclusion

In this work, we have optimized the composition of the InF₃-based glasses to enhance thermal stability. The stability parameter S is larger than in the starting glass and the thermal stability range T_x−T_g of this new glass is 109 K. This work confirms that increasing the number of components may enhance glass-forming ability. Glass samples as thick as 8 mm may be prepared in these multicomponent systems. For some applications such as optical fibers or bulk optics, glass stability should be

References (16)

R.S. Quimby
J.M. Réau et al.
Mater. Chem. Phys.
(1989)
M. Poulain
C.J. Simmons et al.
G. Mazé
M. Poulain
J. Non-Cryst. Solids
(1993)
S. Mitachi et al.
Electron. Lett.
(1981)
B. Jaquier et al.
J. Non-Cryst. Solids
(1993)

There are more references available in the full text version of this article.

Cited by (16)

Fluoride glass-based optical fibers
2024, Specialty Optical Fibers: Materials, Fabrication Technology, and Applications
Starting with fiber optic communication, the original application of fluoride fibers and the efforts to obtain low-loss fibers are described, including the development of fluoride glass materials, advances in glass melting techniques, and improvements in fabrication techniques of fiber preforms and fibers. Then, it is followed by a description of applications of the existing fluoride fibers, such as fiber lasers, fiber amplifiers, supercontinuum sources, and sensors. Finally, a summary of fluoride fiber applications is presented, and an outlook is given on obtaining low-loss fluoride fibers.
Interactions of yttrium and lanthanum fluorides with other fluorides
2022, Journal of Fluorine Chemistry
Citation Excerpt :
Rare earth fluorides are precursors of metal production by calciothermic reduction. Yttrium and lanthanum fluorides are important components of fluoride glasses [19–21] and fluorine solid electrolytes [22–25]. Solid-state laser topics require the production of materials based on rare-earth fluoride compounds in the form of single crystals [3,26].
Both yttrium and lanthanum fluorides are amphoteric compounds according to the Lewis acid and base theory, and this factor defines YF₃ and LaF₃ chemical behavior. In the present paper, we discuss interactions of yttrium and lanthanum fluoride with other metal fluorides (binary systems YF₃-MF_n and LaF₃- MF_n), using our own experimental data along with literature publications and suggesting the “cation cumulative moment M versus cation electronegativity X” diagram (M is the ratio of the cation charge to its ionic radius). Two areas of compound formation have been suggested in the said diagram for both groups of systems. These areas include well-known compounds in YF₃-MF_n and LaF₃- MF_n systems that are formed with fluorides of alkaline elements on the one hand, and compounds with numerous fluorides of tetravalent (Zr, Hf, Mo, Sn, Pt) and pentavalent (As, Sb) elements on the other hand. During the transition from yttrium to lanthanum, the number of compounds decreases. In particular, compounds disappear in systems with difluorides Ca, Sr, Ba and Pb. This is explained both by the weakening of the acidity of lanthanum fluoride compared to yttrium fluoride and by an increase in the ionic radius of the cation, which leads to a change in the preferred coordination numbers in crystal structures. We predict the existence of numerous compounds of yttrium fluoride with fluorides of pentavalent elements and suggest carefully checking formation of compounds in the YF₃ systems with small trivalent cation fluorides.
Spectroscopic properties of tellurite glasses co-doped with Er3+ and Yb3+
2015, Journal of Luminescence
Spectroscopic characterization of Er³⁺/Yb³⁺ co-doped tellurite glasses 70.8TeO₂–5Al₂O₃–13K₂O–(11−x)–BaO–0.2Er₂O₃–xYb₂O₃, where x=0, 0.4, 0.8, 1.2 and 2 mol% has been carried out through X-ray diffraction, Raman, absorption and luminescence spectra. The Judd–Ofelt intensity parameters were calculated for 0.2 mol% Er³⁺-doped glass and are used to evaluate radiative properties such as transition probabilities, branching ratios and radiative lifetime. The emission cross-section of the ⁴I_13/2→⁴I_15/2 transition has been calculated from the absorption data using McCumber׳s theory. The emission intensity of both, visible and infrared signals as a function of Yb₂O₃, have been studied under 980 nm and 375 nm laser excitation. The physical mechanisms responsible for both, visible and infrared signals in the tellurite samples have been explained in terms of the energy transfer and excited state absorption process. The FWHM of the ⁴I_13/2→⁴I_15/2 transition as a function of Yb₂O₃ mol% and distance (δ) between the laser focusing point and the end-face of the glass has been reported. It was observed both, experimentally and numerically, a change in the FWHM with variations of δ less than 8 mm. The latter was attributed to the radiation trapping effect.
Structural and luminescence properties of Sm3+ ions in zinc fluorophosphate glasses
2013, Optical Materials
Citation Excerpt :
A large ΔT (ΔT > 100 °C) value indicates that crystallization occurs at a temperature close to melting temperature. Therefore, the glasses possessing high thermal stability are the best candidates for blowing, molding or rod/fiber drawing due to the correspondingly small chance of crystallization problems [19]. The value of ΔT for PKAZLFSm10 glass is found to be 113 °C which indicates that it may be suitable for fiber drawing.
Sm³⁺-doped zinc fluorophosphate (PKAZLFSm) glasses have been prepared by conventional melt quenching technique and are characterized through thermal, Raman, absorption, emission and decay rate analysis. The Judd–Ofelt (JO) theory has been used to derive the spectroscopic properties of Sm³⁺:PKAZLFSm glasses. The decay rates for the ⁴G_5/2 level of Sm³⁺ ions have been measured and are found to be single exponential at lower concentration (⩽0.1 mol% Sm₂O₃) and turns into non-exponential at higher concentrations (⩾0.5 mol% Sm₂O₃) due to energy transfer through cross-relaxation. The experimental lifetimes for ⁴G_5/2 level of Sm³⁺ ions are found to decrease from 3.2 to 0.5 ms when the concentration increased from 0.01 to 4.0 mol% Sm₂O₃ due to energy transfer among Sm³⁺ ions. In order to know the nature of the energy transfer mechanism, the non-exponential decay rates are well fitted to Inokuti–Hirayama model for S = 6, indicating that the energy transfer process is of dipole–dipole type. The results obtained for the ⁴G_5/2 → ⁶H_7/2 transition indicate that the Sm³⁺:PKAZLFSm10 glass can be very much useful for the development of visible lasers in the reddish orange spectral region.
Fluoride materials for optical applications: Single crystals, ceramics, glasses, and glass-ceramics
2011, Journal of Fluorine Chemistry
Preparation and properties of rare-earth containing oxide fluoride glasses
2007, Journal of Fluorine Chemistry
The preparation of the rare earth containing oxide fluoride glasses LnF₃ (Ln; Y through Lu)–BaF₂–AlF₃–GeO₂ in which the nominal content of LnF₃ reached 60 mol% in maximum and their basic properties such as density, refractive index and glass transition temperature were investigated and summarized in detail. Especially, in order to discuss the local structure around the rare earth ion in the glass, the Judd–Ofelt analysis (discussion with Ω parameters) of the HoF₃–BaF₂–AlF₃–GeO₂ glasses was carried out. The unique fluorescent behavior and the magnetic properties of LnF₃–BaF₂–AlF₃–GeO₂ glasses (Ln = Tb and/or Sm) were also studied.

View all citing articles on Scopus

View full text

Article preview

Solid State Ionics

Abstract

Introduction

Section snippets

Experimental

Results

Discussion

Conclusion

References (16)

Mater. Chem. Phys.

J. Non-Cryst. Solids

Electron. Lett.

J. Non-Cryst. Solids

Cited by (16)

Fluoride glass-based optical fibers

Interactions of yttrium and lanthanum fluorides with other fluorides

Spectroscopic properties of tellurite glasses co-doped with Er<sup>3+</sup> and Yb<sup>3+</sup>

Structural and luminescence properties of Sm<sup>3+</sup> ions in zinc fluorophosphate glasses

Fluoride materials for optical applications: Single crystals, ceramics, glasses, and glass-ceramics

Preparation and properties of rare-earth containing oxide fluoride glasses