Compositional dependence of the optical properties of novel Ga–Sb–S–XI (XI = PbI2, CsI,AgI) infrared chalcogenide glasses

A novel family of Ga₂S₃–Sb₂S₃–XI (XI = PbI₂, CsI, AgI) was investigated to understand the role of metal halides and exploit new chalco‐halide glasses for infrared optics. The dependence of the thermal properties, infrared optical properties, and structural information of the novel family on different metal–iodines was investigated. Results showed that metal halides increase the glass stability but decrease the glass network connectivity. The compositional dependence of the short‐wave cut‐off edge is associated with the electronegativity difference between the cations and anions of the metal halides. Raman study showed that the metal–iodine modified the glass structure mainly through the iodide content, and the cations dissolved in the glass network mostly as charge compensators for the aperiodic network. For the glasses in the series Ga₂S₃–Sb₂S₃–XI–Dy³⁺, Dy³⁺ emission increased in the PbI₂‐ and CsI‐doped glasses but decreased in the AgI‐doped glass due to the combined effect of dysprosium and oxygen. For all that, these novel glasses are highly promised for use in infrared optics.     

Correlation Between Crystallization Behavior and Network Structure in GeS2–Ga2S3–CsI Chalcogenide Glasses

Diagram of the phase transformation behavior of GeS₂–Ga₂S₃–CsI glasses is realized in this article and the structure‐property dependence of the chalcogenide glasses is elucidated using differential scanning calorimetry and Raman spectroscopy. We observe the compositional threshold of crystallization behavior locates at x = 6–7 mol% in (100?x)(0.8GeS₂–0.2Ga₂S₃)–xCsI glasses, which is confirmed by the thermodynamic studies. Structural motifs are derived from the Raman result that [Ge(Ga)S₄], [S₂GeI₂], [S₃GaI], and [S₃Ga–GaS₃] were identified to exist in this glass network. Combined with the information of structural threshold, local arrangement of these structural motifs is proposed to explain all the experimental observations, which provides a new way to understand the correlation between crystallization behavior and network structure in chalcogenide glasses.     

Ga–Sb–S Chalcogenide Glasses for Mid‐Infrared Applications

In this study, a novel chalcogenide glass system, Ga–Sb–S, is reported. The glass‐forming ability, the physical properties, and the structure are investigated; and the potential applications of the glasses are evaluated. The compositions consisting of ~3%–10% Ga, ~29%–37% Sb, and ~57%–63% S can form glasses. The glasses have a wide transparent window of ~0.8–14 μm, high linear refractive indices of ~2.62–2.70 (@10 μm), high third‐order nonlinear refractive indices of ~12.4 × 10^?14 cm²/W (@ 1.55 μm), low phonon energy, and large rare earth solubility. These favorable properties make them promising materials for mid‐infrared applications such as thermal imaging, nonlinear optics, and lasers.     

The Effect of PbS on Crystallization Behavior of GeS2‐Ga2S3‐Based Chalcogenide Glasses

Glass‐ceramics of PbS‐doped 80GeS₂·20Ga₂S₃ were fabricated by heat treatments of base glasses at T_g+30°C for different durations. They exhibited improved mechanical properties such as hardness and resistance to crack propagation, and meanwhile retained their excellent infrared transmission. X‐ray diffraction and Raman results indicated that Ga₂S₃ and GeS₂ crystals were precipitated inside glassy matrix. The crystallization kinetics of base glass was investigated using differential scanning calorimetry under nonisothermal conditions. Compared with the previous work concerning on 80GeS₂·20Ga₂S₃ glass, there exists some different features of crystallization behavior. Such variation is discussed and correlated with the network structure and crystallization kinetics in this glass system.     

Dy3+‐Doped Selenide Chalcogenide Glasses: Influence of Dy3+ Dopant‐Additive and Containment

This work reports on process‐induced impurities in rare‐earth ion: Dy³⁺‐doped selenide chalcogenide glasses, which are significant materials for active photonic devices in the mid‐infrared region. In particular, the effect of contamination from the silica glass ampoule containment used in chalcogenide glass synthesis is studied. Heat‐treating Dy‐foil‐only, and DyCl₃‐only, separately, within evacuated silica glass ampoules gives direct evidence of silica ampoule corrosion by the rare‐earth additives. The presence of [Ga₂Se₃] associated with [Dy] on the silica glass ampoule that has been contact with the chalcogenide glass during glass melting, is reported for the first time. Studies of 0–3000 ppmw Dy³⁺‐doped Ge_16.5As₉Ga₁₀Se_64.5 glasses show that Dy‐foil is better than DyCl₃ as the Dy³⁺ additive in Ge‐As‐Ga‐Se glass in aspects of avoiding bulk crystallization, improving glass surface quality and lowering optical loss. However, some limited Dy/Si/O related contamination is observed on the surfaces of Dy‐foil‐doped chalcogenide glasses, as found for DyCl₃‐doped chalcogenide glasses, reported in our previous work. The surface contamination indicates the production of Dy₂O₃ and/or [≡Si‐O‐Dy=]‐containing particles during chalcogenide glass melting, which are potential light‐scattering centers in chalcogenide bulk glass and heterogeneous nucleation agents for α‐Ga₂Se₃ crystals.     

Ga-Sb-S-I chalcohalide glasses and fibers for mid-infrared applications

In this work, environment friendly Ga-Sb-S-I chalcohalide glasses and fibers are developed for mid-infrared applications. The developed Ga₈Sb₃₂S_60-xI_x (x = 0-10) glasses have a transmission window of ~0.7-14 µm, linear refractive indices (n₀) of ~ 2.690-2.751 at 1.55 µm, nonlinear refractive indices (n₂) of ~10.5-12.4 × 10⁻¹⁴ cm²/W at 1.55 µm, and zero dispersion wavelengths (λ₀) of ~4.94-5.25 µm. The developed Ga₈Sb₃₂S₅₅I₅/Ga₈Sb₃₁S₅₆I₅ (core/cladding) fiber can transmit infrared light from below 2 µm to ~8 µm, and shows the minimum loss of ~1.2 dB/m at ~6 µm. The wide transmission window, high optical nonlinearity and superior thermal stability against crystallization of the glasses, and the good 2-8 µm transmission property of the fiber make these materials promising for mid-infrared applications such as thermal imaging, nonlinear optics, and laser transmission.     

Chalcogenide glasses with embedded ZnS nanocrystals: Potential mid‐infrared laser host for divalent transition metal ions

Chalcogenide glasses (ChGs) containing II‐VI chalcogenide (ChG) nanocrystals such as ZnS/Se have recently been intensively studied as promising mid‐infrared nonlinear optics and laser materials, yet preparation of pure‐phase II‐VI nanocrystals embedded in ChGs via controlled crystallization is still very challenging. In this study, a new system of ChGs and glass ceramics (GCs), viz., (100?x)As₂S₃–xZnSe (x = 0 ~ 30 mol%), is synthesized, and its physical and optical properties including density, molar volume, microhardness, glass transition temperature, glass network structure, transmission, and refractive index are comprehensively characterized. Significantly, it is initially demonstrated that pure ZnS nanocrystals can be precipitated in GCs simply by a thermal treatment process. The composition and thermal treatment temperature dependencies of crystallization are studied using X‐ray diffraction spectroscopy, and the morphology of the nanocrystals by high‐resolution transmission electron microscope. The ChG GCs with embedded ZnS nanocrystals retaining good transparency can be a potential host laser material for divalent transition metals (e.g., Cr²⁺/Fe²⁺, etc.), and thus used for ultrabroadband tunable continuous or ultra‐short‐pulsed mid‐infrared fiber lasers.     

Thermal and optical properties of La2O3–Ga2O3– (Nb2O5 or Ta2O5) ternary glasses

La₂O₃–Ga₂O₃–M₂O₅ (M = Nb or Ta) ternary glasses were fabricated using an aerodynamic levitation technique, and their glass‐forming regions and thermal and optical properties were investigated. Incorporation of adequate amounts of Nb₂O₅ and Ta₂O₅ drastically improved the thermal stabilities of the glasses against crystallization. Optical transmittance measurements revealed that all the glasses were transparent over a wide wavelength range from the ultraviolet to the mid‐infrared. The refractive indices of the glasses increased and the Abbe number decreased upon substituting Ga₂O₃ with Nb₂O₅, and the decrease in the Abbe number was significantly suppressed when Ta₂O₅ was incorporated into the glass. As a result, excellent compatibility between high refractive index and lower wavelength dispersion was realized in La₂O₃–Ga₂O₃–Ta₂O₅ glasses. Analysis based on the single‐oscillator Drude–Voigt model provided more systematical information and revealed that this compatibility was due to an increase in the electron density of the glass.     

Magneto‐optical effects of Ge‐Ga‐Sb(In)‐S chalcogenide glasses with diamagnetic responses

The Faraday effects of Ge‐Ga‐Sb(In)‐S serial chalcogenide glasses were investigated at the wavelengths of 635, 808, 980, and 1319 nm, respectively. The compositional dependences were analyzed and associated influencing factors including the absorption edge, the concentration of Sb³⁺/In³⁺ ions, and the wavelength dispersion of refraction index were discussed. 80GeS₂·20Sb₂S₃ composition glass was found to have the largest Verdet constant (V=0.253, 0.219, 0.149, and 0.065 min·G^?1·cm^?1 for wavelengths 635, 808, 980, and 1319 nm, respectively) in these glasses, which is larger than that of commercial diamagnetic glasses (Schott, SF 6, V=0.069 min·G^?1·cm^?1@633 nm, for example). Sb³⁺ ions with high polarizability possessing s²‐sp electron jumps involving ¹S₀→¹P₁, ³P_0,1,2 transitions are responsible for large Verdet constant, and Becquerel rule is proved to be an effective guidance for estimating the Verdet constant and further optimizing the compositions in chalcogenide glasses.     

First Identification of Rare‐Earth Oxide Nucleation in Chalcogenide Glasses and Implications for Fabrication of Mid‐Infrared Active Fibers

Gallium (Ga) helps solubilize rare‐earth ions in chalcogenide glasses, but has been found to form the dominant crystallizing selenide phase in bulk glass in our previous work. Here, the crystallization behavior is compared of as‐annealed 0–3000 ppmw Dy³⁺‐doped Ge–As–Ga–Se glasses with different Ga levels: Ge_16.5As_(19?x)Ga_xSe_64.5 (at.%), for x = 3 and 10, named Ga₃ and Ga₁₀ glass series, respectively. X‐ray diffraction and high‐resolution transmission electron microscopy are employed to examine crystals in the bulk of the as‐prepared glasses, and the crystalline phase is proved to be the same: Ge‐modified, face centered cubic α‐Ga₂Se₃. Light scattering of polished glass samples is monitored using Fourier transform spectroscopy. When Ga is decreased from 10 to 3 at.%, the bulk crystallization is dramatically reduced and the optical scattering loss decreases. Surface defects, with a rough topology observed for both series of as‐prepared chalcogenide glasses, are demonstrated to comprise Dy, Si, and [O]. For the first time, evidence for the proposed nucleation agent Dy₂O₃ is found inside the bulk of as‐prepared glass. This is an important result because rare‐earth ions bound in a high phonon–energy oxide local environment are, as a consequence, inactive mid‐infrared fluorophores because they undergo preferential nonradiative decay of excited states.     

Effect of glass composition on the physical properties and luminescence of Pr3+ ion-doped chalcogenide glasses

In this work, Pr³⁺ ion-doped Ge₂₀Ga_15−xSb_xSe₆₅ (x = 0, 5, 10, in mol%), Ge₂₀Sb_15−yIn_ySe₆₅ (y = 5, 10, in mol%), Ge₂₀Ga_15−zIn_zSe₆₅ (z = 0, 5, 10, in mol%), and Ge₂₀Ga₅Sb₁₀Se₆₀I₅ glasses were prepared. The structural units, thermal properties, and optical properties of these glasses were analyzed. In addition, a comprehensive comparison study of the effects of metal ions (Sb, Ga, and In), S/Se ratio, and I content on the mid-infrared (MIR) luminescence of Pr³⁺ ions was conducted. Under a 1.55-μm laser pump, 0.2 mol% of Pr³⁺ ion-doped chalcogenide glasses performed strong photoluminescence in the wavelength range of 3.5-5.5 μm. Results indicated that the Sb-containing glass performed the strongest emission intensity among the studied glasses. Moreover, halogen element I can reduce the phonon energy of the matrix, which is beneficial to the luminescence of Pr³⁺ ions and provide significant possibilities for developing MIR lasers and amplifiers.     

Mid‐IR transparent TeO2‐TiO2‐La2O3 glass and its crystallization behavior for photonic applications

In this report, effect of enhanced rare earth (La₂O₃) concentration on substitution of TeO₂ within ternary TeO₂‐TiO₂‐La₂O₃ (TTL) glass system has been studied with respect to its thermal, structural, mechanical, optical, and crystallization properties with an aim to achieve glass and glass‐ceramics having rare‐earth‐rich crystalline phase for nonlinear optical and infrared photonic applications. DSC analysis (10°C/min) demonstrates a progressive increase in glass‐transition temperature (T_g) from 359 to 452°C with the increase in La₂O₃ content. Continuous glass network modification with transformation of [TeO₄] to [TeO₃/TeO₃₊₁] units is evidenced from Raman spectra which is corroborated with XPS studies. While mechanical properties demonstrate enhancement of cross‐linking density in the network. These glasses exhibit optical transmission window extended from 0.4 to 6 μm with calculated zero dispersion wavelength (λ_ZDW) varying from 2.41 to 2.28 μm depending upon La₂O₃ content. Crystallization kinetics of TTL10 (80TeO₂‐10TiO₂‐10La₂O₃ in mol%) glass has been studied via established models. Activation energy (E_a) has been evaluated and dimensionality of crystal growth (m) suggests formation of surface crystals. Glass‐ceramic with crystalline phase of La₂Te₆O₁₅ has been realized in heat‐treated TTL10 glass samples (at 450°C). As predicted from DSC analysis, FESEM study unveils the formation of surface crystallized glass‐ceramics.     

Investigation of the Ga-Sb-S chalcogenide glass with low thermo-optic coefficient as an acousto-optic material

In this study, two series of Ga_xSb_40-xS₆₀ (x = 4, 6, 8, 10 mol%) and Ga_ySb₃₆S_64-y (y = 3, 5, 6 mol%) glasses were prepared and the relationship between their compositional and acousto-optic (AO) properties was investigated systematically for the first time. In the Ga_ySb₃₆S_64-y system, the AO figure of merit (M₂) increased as the Ga increased, and the maximum M₂ of the Ga₆Sb₃₆S₅₈ glass was 455.78 × 10^?18 s³/g, which is ～301 times greater than that of fused silica and ～2.5 times greater than that of As₂S₃ chalcogenide (ChG) glass at 1550 nm. However, its thermo-optic coefficients (dn/dT) varied greatly (32.1 × 10^?6 °C^?1–57.2 × 10^?6 °C^?1), and acoustic attenuations (α) at 10 MHz were high, from 5.446 dB/cm to 7.274 dB/cm. In the Ga_xSb_40-xS₆₀ glass system, the M₂ value and α at different ultrasonic frequencies gradually decreased with the improvement of Ga. Compared with the Ga_ySb₃₆S_64-y system, the Ga_xSb_40-xS₆₀ glass system had lower α (at 10 MHz) and dn/dT, which are 5.001 dB/cm–5.563 dB/cm and 17.3 × 10^?6 °C^?1–55.6 × 10^?6 °C^?1, respectively. These results provide a significant reference for the further development of novel ChG glasses and help expand their application fields.     

Ce3+‐ and Dy3+‐Doped Oxyfluoride Borosilicate Glasses with Near White Luminescence

A series of Ce³⁺/Dy³⁺‐doped oxyfluoride borosilicate glasses prepared by melt‐quenching method are investigated for light‐emitting diodes applications. These glasses are studied via X‐ray diffraction (XRD), optical absorption, photoluminescence (PL), color coordinate, and Fourier transform infrared (FT‐IR) spectra. We find that the absorption and emission bands of Ce³⁺ ions move to the longer wavelengths with increasing Ce³⁺ concentrations and decreasing B₂O₃ and Al₂O₃ contents in the glass compositions. We also discover the emission behavior of Ce³⁺ ions is dependent on the excitation wavelengths. The glass structure variations with changing glass compositions are examined using the FT‐IR spectra. The influence of glass network structure on the luminescence of Ce³⁺/Dy³⁺ codoped glasses is studied. Furthermore, the near‐ideal white light emission (color coordinate x = 0.32, y = 0.32) from the Ce³⁺/Dy³⁺ codoped glasses excited at 350 nm UV light is realized.     

Er3+ Ions‐Doped Germano‐Gallate Oxyfluoride Glass‐Ceramics Containing BaF2 Nanocrystals

Er³⁺ ions‐doped germano‐gallate oxyfluoride glass‐ceramic containing BaF₂ nanocrystals was prepared through conventional melt quenching and subsequent thermal treatment method. X‐ray diffraction patterns and transmission electron microscope images confirmed the formation of BaF₂ nanocrystals in glass‐ceramics. Preferential incorporation of Er³⁺ ions into the BaF₂ nanocrystals were confirmed by the absorption spectra and emission spectra, and enhanced upconversion emission and infrared emission were observed. Relatively high transmittance in the mid‐infrared region indicated great potential of this germano‐gallate oxyfluoride glass‐ceramics as host materials for the efficient mid‐infrared emission from rare‐earth ions.     

Physicochemical and optical properties of glasses in the Ga4Ge21S50-Sb2S3 system

This paper reports on the results of an investigation into the influence of Sb₂S₃ dopants on the glass-forming ability, heat resistance, softening temperature, density, refractive index, transparent region, and impurity optical absorption of glasses of the composition 0.16GaS₂ · 0.84GeS₂. The data obtained indicate that glasses in the Ga₄Ge₂₁S₅₀-Sb₂S₃ system with a high Sb₂S₃ content are of interest as materials for use in fiber optics.     

The influence of different antimony content in Ga-As-Sb-S chalcogenide glass system: Modification of physical & spectroscopic properties and fiber forming ability

In order to improve the fiber drawing performances including the anti-crystallization in fiber drawing process and the mechanical properties, the fourth component of antimony (Sb) was introduced into Ga_0.8As_39.2S₆₀ glass, and a serial Ga_0.8As_39.2-xSb_xS₆₀ (x = 0, 1, 3,5, 7, 9 and 11) novel chalcogenide glasses doped with 3000 ppmw Dy³⁺ ions were prepared. The influences of antimony content on the physical properties, spectroscopic properties and fiber forming ability of glass were investigated. The experiment results indicate that the introduction of moderate antimony into glass effectively improves the fiber drawing performance and the spectroscopic properties of Dy³⁺ ions. The Ga_0.8As_34.2Sb₅S₆₀ composition glass possesses the best performance and it is recommended a good candidate for mid-infrared laser working medium.     

High Brightness 2.2–12 μm Mid‐Infrared Supercontinuum Generation in a Nontoxic Chalcogenide Step‐Index Fiber

An environment friendly nonlinear chalcogenide glass fiber with a Ge‐Sb‐Se core and a Ge‐Se cladding is fabricated for bright broadband mid‐infrared (MIR) supercontinuum (SC) generation. The fabricated Ge‐Sb‐Se/Ge‐Se fiber with a core diameter of 6 μm shows zero group velocity dispersion at ~4.2 μm and ~7.3 μm. By pumping the fiber with a length of 11 cm at 4.485 μm with 330 fs pulses, we achieve a SC covering the 2.2–12 μm spectral range and with an output average power of ~17 mW. This bright broadband SC source is promising for high‐resolution MIR spectroscopy.     

Coloration and Nonlinear Optical Properties of ZnTe Quantum Dots in ZnO–TeO2–P2O5 Glasses

ZnO–TeO₂–P₂O₅ glasses were prepared by melt‐quenching method. The color of the glass samples changed from colorless to pale red and dark red with increasing TeO₂ content. Coloration mechanism and nonlinear optical properties of ZnO–TeO₂–P₂O₅ glasses have been investigated. Raman spectra and transmission electron microscope measurements indicated the precipitation of ZnTe quantum dots in the glasses and ZnTe quantum dots are the origin of coloration. Z‐scan technique was used to examine the nonlinear optical properties of the glasses. The glass sample with 30 mol% TeO₂ exhibits large third‐order nonlinear optical susceptibility of 10^?11 esu.     

Near white light emission of Ce3+‐, Ho3+‐, and Sm3+‐doped oxyfluoride silicate glasses

The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐ single and co‐doped oxyfluoride silicate glasses for light emitting diodes are studied. These glasses were prepared by melt quenching method and their optical and structural properties were investigated by absorption spectra, photoluminescence spectra, Commission International de I'Eclairage chromaticity coordinates, X‐ray diffraction, and Fourier transform infrared spectra. It is found that the introduction of Al₂O₃ in glass composition can improve the emissions of Ho³⁺ and Sm³⁺. While the presence of B₂O₃ has the adverse effect and can suppress the emissions of Ho³⁺ and Sm³⁺. With substituting Na₂O for CaO in the glass compositions, CaF₂ crystals can be formed during the melt quenching process. We find the formation of CaF₂ crystals can change the emission behavior of Ho³⁺ and Sm³⁺ ions. White light emissions can be achieved in the glasses and the luminescence colors can be tuned by varying the concentrations of the doped rare‐earth ions and the composition of glass matrix. The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐doped oxyfluoride silicate glasses presented here demonstrate promising applications in the fields of light emitting diodes.