Quantitatively predicting the optical and spectroscopic properties of Nd3+-doped laser glasses

Predicting the properties of glass based on compositional and structural information is a fundamental issue with enormous practical and industrial significance for the study of laser glass. Here we address this problem and demonstrate the application of phase diagram method in predicting the spectroscopic properties of Nd³⁺-doped binary and ternary silicate, binary phosphate, and borate laser glasses from their initial congruently melting compounds. In particular, spectroscopic properties, such as effective linewidth (Δλ_eff) and fluorescence branching ratio (β) can be precisely predicted in all glass systems with an error less than 5%. Furthermore, a composition–structure–property database of Nd³⁺-doped ternary silicate glass system is established and preliminarily applied to the composition design and explanation of commercial glass. This study provides interpretable predictions of the optical and spectroscopic properties for Nd³⁺-doped laser glasses.     

Experimental and theoretical studies on NIR luminescence of titanate-germanate glasses doped with Pr3+ and Tm3+ ions

Near-infrared (NIR) luminescence of Pr³⁺ and Tm³⁺ ions in titanate-germanate glasses has been studied for laser and fiber amplifier applications. The effect of the molar ratio GeO₂:TiO₂ (from 5:1 to 1:5) on spectroscopic properties of glass systems was studied by absorption, luminescence measurements, and theoretical calculations using the Judd–Ofelt theory. It was found that independent of the TiO₂ concentration, intense NIR emissions at 1.5 and 1.8 μm were observed for glasses doped with Pr³⁺ and Tm³⁺ ions, respectively. Moreover, several spectroscopic and NIR laser parameters for Pr³⁺ and Tm³⁺ ions, such as emission bandwidth, stimulated emission cross-section, quantum efficiency, gain bandwidth, and figure of merit, were determined. The results were discussed in detail and compared to the different laser glasses. Systematic investigations indicate that Pr³⁺-doped system with GeO₂:TiO₂ = 2:1 and Tm³⁺-doped glass with GeO₂:TiO₂ = 1:2 present profit laser parameters and could be successfully applied to NIR lasers and broadband optical amplifiers.     

Enhanced NIR photoemission from Bi-doped aluminoborate glasses via topological tailoring of glass structure

Bismuth (Bi)-doped laser glasses with broadband emission are of current interest in the fields of sensing, bio-imaging, and photonics. For practical applications, it must be considered how to improve the emission efficiency, in particular, for borate glasses with wide glass-forming range, low melting point, and excellent fiberizing ability. Herein, we experimentally demonstrate that addition of GeO₂ to aluminoborate glasses can effectively enhance Bi NIR emission by more than 300 times with prolonged decay time (~500 μs) and good homogeneity, which is, to our best knowledge, seldom achieved in Bi-doped borate multi-component glasses. The addition of second glass-former GeO₂, as revealed by detailed optical and structural analysis, leads to the facile regulation on local glass structure, forcing the conversion of aluminum species from AlO₅ and AlO₆ to AlO₄ and consequently pushes the conversion of Bi³⁺ to Bi⁺ and Bi⁰ and stabilizes Bi NIR centers, which finally results in highly enhanced Bi NIR emission. We believe these results could contribute to designing Bi-activated multi-component laser glass and fibers with efficient NIR photoemission.     

Enhanced broadband NIR emission in glass–ceramic fibers containing Nd3+/Yb3+ co-doped YCa4O(BO3)3 disordered nanocrystal

Demands are increasing for ultrashort pulse laser in industrial applications, where the gain bandwidth of most optical fiber material is not wide enough, and developing a wide bandwidth gain medium is challenging. Glass–ceramic fibers containing Nd³⁺/Yb³⁺ co-doped YCa₄O(BO₃)₃ nanocrystals were fabricated by the molten core method and successive heat treatment. After a careful heat treatment, Nd³⁺/Yb³⁺ co-doped YCa₄O(BO₃)₃ nanocrystals were precipitated in the fiber core. Enhanced broadband near-infrared (NIR) emission from 850 to 1150 nm (bandwidth: ∼252 nm) was obtained in the glass–ceramic fiber compared to that of precursor fiber. These results suggest that the Nd³⁺/Yb³⁺ glass–ceramic fibers are promising for broadband NIR optical amplifications and lasers.     

Quantitative prediction of the structure and luminescence properties of Nd3+ doped borate laser glasses

Although great advance has been made in glass science, predicting luminescence properties of laser glass poses a significant challenge for scientists due to the complex relationship between the composition, structure, and properties of the rare earth ions doped laser glasses. The development of high-performance laser glass usually relies on intuition and trial-and-error. Recently, with the proposal of the materials genome engineering, the “glass genome” has also attracted much attention. Here, the structure of the Nd³⁺ doped B₂O₃-Li₂O laser glasses was analyzed using Fourier transform infrared spectra and nuclear magnetic resonance, revealing that the glass contains similar glass-forming ion-centered coordination polyhedron structure groups to the neighbor congruent glassy compounds. The structure and properties of glass largely depend on the neighbor congruent glassy compounds. Therefore, the structure and luminescence properties of Nd³⁺ doped B₂O₃-Li₂O and B₂O₃-MgO-Li₂O laser glasses can be quantitatively predicted via the neighbor congruent glassy compounds. The predictive values are in good agreement with the experimental data, which indicates that our approach is an effective way to predict the structure and luminescence properties of Nd³⁺ doped borate laser glasses.     

A novel unclad Nd3+-doped polymer optical fiber

Neodymium octanoate was synthesized from neodymium oxides and dissolved in poly(methylmethacrylate) (PMMA), forming a solid solution. The investigation of the absorption spectrum of Nd³⁺-doped PMMA showed that the spectrum was similar to that of Nd³⁺-doped silica glasses. The Nd³⁺-doped PMMA was used to draw a fiber and an unclad Nd³⁺-doped PMMA optical fiber was made. The emission output of the fiber at about 585 nm was observed under green source pumping at 532 nm by optimization of the Nd³⁺ concentration and the length of the fiber. Under 1 W pumping radiation, a 60 µW output was obtained for the fiber with a Nd³⁺ concentration of 70 ppm and the length of 15 cm. © 1996 John Wiley & Sons, Inc.     

Er3+-doped antimony-silica glass and fiber for broadband optical amplification

In this paper, the synthesis, structure, and optical analysis of Er³⁺-doped antimony-silica glass system are reported. The hybridization of Si with Sb ions is found to be favorable for reducing the phonon energy of the glass system. The optical properties, including the emission intensity and bandwidth, can be simultaneously improved. Notably, the full width at half maxima (FWHM) of near-infrared emission from Er³⁺ can be broadened from 61 to 82 nm. Furthermore, the antimony-silica glass fiber is successfully prepared, and the luminescence and gain performance of the fiber are characterized. The antimony-silica glass exhibits excellent fiber-forming ability, and the obtained fiber shows excellent gain performance. The results suggest that antimony-silica glass is a promising gain material for fiber amplifier and laser.     

Investigation of Pr3+ Near-Infrared Emission in Plasmonic and Dichroic Copper Nanocomposite Glasses

Melt-quenched Pr³⁺-doped phosphate glass containing Cu⁺ and Sn²⁺ as redox couple to induce Cu nanoparticle (NP) precipitation was subjected to heat treatment to develop nanocomposite glasses with plasmonic and dichroic character. The purpose was to examine the impact of Cu NPs producing dichroism on the near-infrared (NIR) emission from Pr³⁺. The parent and isothermally heat-treated glasses (520?°C: 20, 40, 60?min) were characterized by differential scanning calorimetry, Fourier transform-infrared spectroscopy, optical extinction, and photoluminescence spectroscopy with decay dynamics. From the samples, the heat-treated for 40 and 60?min showed broad plasmonic bands alongside dichroism wherein the glasses scatter red light but transmit blue. The Pr³⁺ NIR emission encompassing ¹D₂ → ³F₄, ³F₃,¹G₄ transitions was evaluated under 445 and 590?nm excitation. An increased emission was not exhibited, whereas a quenching effect became evident for samples heat-treated for 40 and 60?min. Different interactions involving Pr³⁺ ions and Cu NPs are discussed.

     

Predicting and optimizing the physical and spectroscopic properties of phosphate laser glasses using a phase diagram approach

Despite the significant technological applications of laser glasses, the quantitative prediction and optimization of their properties, particularly the spectroscopic properties, remain challenging. Here we address this problem by regarding the nearest-neighboring congruently melting compounds as the “component and structural motifs” based on the phase diagram approach. The composition–structure–property (CSP) relationships of Nd³⁺-doped ternary phosphate glasses are investigated. Spectroscopic properties are quantitatively predicted with an error of less than 10% compared to the experimental results. In particular, the fluorescence lifetime (τ_m) can be accurately calculated using the phase diagram approach, which is difficult to be predicted previously. Furthermore, the CSP databases with over 1000 compositions are established for the optimization of commercial laser glasses. This study enriches the CSP database of traditional laser glass and provides guiding significance for future research.     

Synthesis and Spectral Properties of Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>-Doped Sodium Silicophosphate Glass

Combined UV-visible and FTIR spectral studies of undoped and Nd₂O₃ –doped sodium silicophosphate glasses were carried out to characterize the optical and structural properties of such glasses. The base undoped silicophosphate glass exhibits strong UV absorption which is due to the presence of unavoidable trace iron impurities (mainly Fe³⁺ ions) present contaminated within the raw materials used for the preparation of such glasses. Nd₂O₃ –doped glasses show characteristic absorption bands extending in the entire visible region which are attributed to the contribution of Nd³⁺ ions with distinct peaks which are almost constant with the increase of dopant. This comes from the combined compact glass structure containing two glass forming units and the shielding of the rare-earth ions. Infrared absorption spectra of the studied glasses reveal characteristic IR bands due to the combination of both silicate and phosphate groups. The introduction of Nd₂O₃ within the dopant level (2 %) produces no variations in the IR vibrational bands due to the presence of the two structural silicate and phosphate groups giving compactness of the network structure. The deconvoluted spectra reveal the presence of phosphate groups in a slightly high ratio due to the high content of P₂O₅ in the composition.     

New Aluminosilicate Glasses as High-Power Laser Materials

In the past few years, aluminosilicate glasses of an extremely broad compositional range have been prepared and analyzed to scan this glass type for its potential use as high-power laser material. The tested network modifier ions included Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, Pb²⁺, Y³⁺, and La³⁺. Preliminary investigations have been conducted with Sm³⁺- and Eu³⁺-doped glasses; selected glass compositions have also been prepared with Yb³⁺ doping for laser testing. It has been found that low refractive indices/low average molecular weights/low densities of the glasses in most cases support relatively long fluorescence lifetimes of the doped ions. It was further concluded that the phonon energy of the molecular network of the glasses does not affect the fluorescence properties of the doped samples. The mechanical properties such as Young's modulus, Vickers hardness, and fracture toughness generally increase with increasing field strength of the network modifier ion for constant stoichiometric ratios of the glass components. The lowest potential thermal stress values were found for zinc and magnesium aluminosilicate glasses, which also have relatively high field strengths. Taking all these facts into account, a ternary lithium aluminosilicate and a mixed lithium magnesium aluminosilicate glass doped with Yb³⁺ have been prepared in high optical quality and tested with respect to their laser performance. The fluorescence lifetime values are somewhat lower than in well-established Yb³⁺-doped laser materials, such as fluoride phosphate glass or single crystalline calcium fluoride. Nevertheless, the aluminosilicate glasses show exceptionally high absorption and emission cross sections, smooth and very broad amplification profiles, as well as much better thermomechanical properties. Quantum efficiencies close to unity could be reached by consequently removing dissolved OH from the glass melt.     

Quantitative prediction of the glass-forming region and luminescence properties in Tm3+-doped germanate laser glasses

Germanate laser glasses have received much attention as a promising host materials for mid-infrared fiber lasers in recent years because of the outstanding infrared transparency, low phonon energy, and high rare earth solubility of such glasses. However, the development of high-performance germanate laser glasses is usually based on intuition and a trial-and-error method, which can involve long experimental periods and high costs, and thus, this approach is highly inefficient. Recently, with proposals for materials genome engineering, the concept of the “glass genome” has grown of interest to us. Herein, the structures of Tm³⁺-doped germanate laser glasses (BaO–GeO₂ and BaO–La₂O₃–GeO₂) were investigated by Fourier transform infrared spectra (FTIR) and Raman spectra analyses, which revealed that the resulting glass contains similar structural groups to the neighboring congruently melted glassy compounds (NCMGCs) in the composition diagram. What is more, the structure and properties of the resulting laser glasses largely depend on NCMGCs. Then, the glass-forming region, physical properties, and luminescence properties were calculated via the use of NCMGCs in Tm³⁺-doped BaO–GeO₂ binary and BaO–La₂O₃–GeO₂ ternary laser glass systems. The calculated results were in good agreement with the experimental results, thus demonstrating that our approach is practical for predicting the glass-forming region, physical properties, and luminescence properties in Tm³⁺-doped BaO–GeO₂ binary and BaO–La₂O₃–GeO₂ ternary laser glass systems. This work may provide an effective method to develop Tm³⁺-doped germanate laser glasses rapidly and at low cost.     

Tunable luminescence from bismuth‐doped phosphate laser glass by engineering photonic glass structure

Because of ultra‐broadband near‐infrared (NIR) emission bismuth‐activated glasses and fibers offer a new promising platform for novel photonic devices such as new type of optical amplifiers and broadly tunable fiber lasers. Yet, challenge remains to manipulate the NIR emission behavior of bismuth (Bi) in photonic glasses for efficient Bismuth‐doped fiber and fiber lasers. Here, by engineering phosphorus and aluminum's topology, broadly tunable NIR emission has been realized in Bismuth‐doped phosphate laser glass. Structural and optical analyses on ²⁷Al magic‐angle spinning nuclear magnetic resonance (MAS NMR), ³¹P MAS NMR, fourier transform infrared (FTIR) and static emission spectra suggest that polymerization of glass network can be improved by proper addition of aluminum into the system, which can be evidenced by partial conversion of Q² to Q³ species of phosphorus and the shift of P–O–P asymmetric stretching vibration toward lower frequency, and this turns out beneficial to Bi NIR emission. Embedding aluminum tetrahedra into phosphorus glass network can reduce the local crystal field around bismuth and therefore lead to the blueshift of Bi emission. This work presents new insights into the luminescent behavior of Bi ions in phosphate glass and it helps the design and fabrication of Bismuth‐doped glasses and fibers in future.     

Optical properties of Er3+ and Yb3+/Er3+-doped NaF-Na2SO4-Al(PO3)3 fluoro-sulfo-phosphate glasses

Fluoro-sulfo-phosphate (FPS) glass is of current interest as potential material for laser application due to its good glass-forming ability, thermal, and chemical stability as well as the complicated local environment for incorporated species. Herein, the physical and luminescent properties of Er³⁺ and Yb³⁺/Er³⁺-doped FPS glasses vs S/F ratio are investigated comprehensively. The low melting temperature (750°C) leads to fewer ingredients evaporation and easier operation. The sulfate addition depolymerizes the structure of FPS glasses, leading to either monotonic or nonmonotonic variations of physical properties, while no deterioration in thermal and limited one in chemical stability is caused. The addition of sulfate also modifies the local structure around optical active species and thus, leading to higher emission cross section (1.52 × 10⁻²⁰ cm²), effective linewidth (68.4 nm), figure of merit (5.61 × 10⁻²³ s cm²), gain bandwidth (102.44 × 10⁻²⁷ cm³), and energy-transfer microparameters (51.87 × 10⁻³⁹ cm⁶/s), implying high possibility to serve as 1.5 μm laser application.     

1.53 µm luminescence properties of Er3+-doped K–Sr–Al phosphate glasses

Trivalent erbium (Er³⁺)-doped K–Sr–Al phosphate glasses were prepared and studied their spectroscopic properties as a function of Er₂O₃ concentration. Judd–Ofelt analysis has been carried out for 1.0 mol% Er₂O₃-doped phosphate glass and in turn radiative properties have been evaluated for the excited levels of Er³⁺ ion. The radiative lifetime for the ⁴I_13/2 level was found to be higher for the present glass when compared to other Er³⁺-doped glasses. The Er³⁺-doped glasses exhibit intense near infrared emission at 1.53 µm corresponds to ⁴I_13/2→⁴I_15/2 transition as well as green emission at 546 nm corresponding to ⁴S_3/2→⁴I_15/2 under 980 nm and 488 nm excitations, respectively. The emission cross-section spectrum for 1.0 mol% of Er₂O₃-doped glass has been evaluated using McCumber theory. The gain cross-section has been evaluated as a function of population inversion, which revealed that the lasing action would be achieved at 1.53 µm for a population inversion about 40%. Decay curves for the ⁴I_13/2 level were measured and lifetimes have been determined for the studied glasses. The results indicate that the present glasses could be useful for laser as well as optical amplifiers at 1.53 µm.     

Effective sensitization of Eu3+ ions on Eu3+/Nd3+ co-doped multicomponent borosilicate glasses for visible and NIR luminescence applications

Eu³⁺/Nd³⁺ co-doped multicomponent borosilicate glasses (ND1E: 10BaO +10ZnF₂+10K₂O +20SiO₂+(49-x) B₂O₃+1Nd₂O₃+xEu₂O₃) were prepared by conventional melting and rapid quench technique to evaluate the effect of Eu³⁺ ions in the Nd³⁺ doped glasses. Thermal stability, structural and spectroscopic characteristics of the ND1E glasses were investigated by using DSC, XRD, FTIR, Optical absorption, excitation and emission measurements. The Judd – Ofelt (JO) analysis is implemented to the absorption spectrum of the prepared glassy matrix in order to identify their potential applicability in lasing devices. Enhancement of ⁷F₀ → ⁵L₆ band (394 nm) with the increasing concentration of Eu³⁺ ion in the Nd³⁺ excitation spectra (λ_emi = 1060 nm) reveals the possibility of obtaining the characteristic fluorescence spectra of Nd³⁺ ion with the typical excitation wavelengths (Nd³⁺ = 584 nm and Eu³⁺ = 394 nm) of both rare earth ions and it is further verified from the emission spectrum. This interesting luminescence effect of showing excellent visible and NIR emission under 394 nm excitation mainly attributes the energy transfer mechanism between the RE³⁺ ions and the reason underlying this effect is discussed in detail with the help of partial energy level diagram. Energy transfer efficiency between the Eu³⁺ and Nd³⁺ ions were evaluated by using the radiative lifetimes of the prepared glasses. Also, a comparison of radiative properties and lasing characteristics of Eu³⁺/Nd³⁺ co-doped glasses with other Nd³⁺ glasses are reported. The emission intensities were characterized using CIE chromaticity diagram and the observed CIE coordinates shows a shift towards reddish – orange region with the increase in Eu³⁺ concentration. The quantum efficiency of the prepared glasses was determined experimentally. The obtained results suggest that the ND1E glassy system can be considered as a potential candidate for visible and NIR luminescence applications.     

Structural,luminescence and NMR studies on Nd3+-doped sodium–calcium-borate glasses for lasing applications

In this work, Neodymium (Nd³⁺) -doped borate glasses were synthesised by melt-quenching method and their structural as well as optical properties were analysed through XRD, Raman, NMR, DSC, UV–Visible, luminescence and decay studies for the possible application as laser gain medium. DSC and XRD results revealed that the glasses have high transition temperature and are in amorphous nature, respectively. The vibrational characteristics of the host matrices as well as the effect of Nd³⁺ incorporation were analysed by using Raman spectra, which exhibit majorly borate groups as supported by NMR results. The band gap energy of the glasses decreases with an increase in Nd³⁺ concentration. Using Judd-Oflet theory the characteristic intensity parameters (Ω_λ, λ = 2, 4 and 6) were calculated and further used for calculating the various radiative parameters from the emission spectra. The emission cross-section (σ_em) was estimated as high as 1.15 × 10⁻²⁰ cm² from the Füchtbauer–Landenburg (FL) equation for the dominant ⁴F_3/2→⁴I_11/2 (1056 nm) transition. The effect of Nd³⁺ concentration on the lifetime of the ⁴F_3/2 luminescent level was analysed from the decay curve analyses. From which, the corresponding quantum efficiency (η) was estimated and found as high as 54%. The investigated result suggests the prepared glasses can be utilized as gain medium to generate laser at around 1.05 μm.     

Effect of neodymium ions on upconversion fluorescence studies of oxyfluorosilicate glasses for optoelectronic devices

Effect of Nd₂O₃ concentrations on optical properties and upconversion studies were investigated for oxyfluorosilicate glasses with composition of SiO₂-Al₂O₃-Na₂CO₃-SrF₂-CaF₂. The Judd-Ofelt (JO) intensity parameters, Ω_λ (λ = 2, 4 and 6) as well as radiative properties for the ⁴F_3/2 level of Nd³⁺ ion have been evaluated from the absorption spectra of 1.0 mol% Nd₂O₃-doped glass. For all the glass samples, the strong NIR emissions were observed at 891, 1058 and 1330 nm and have been attributed to ⁴F_3/2 → ⁴I_{9/2, 11/2, 13/2} transitions respectively. The stimulated emission cross-section for the ⁴F_3/2 → ⁴I_11/2 transition is evaluated and found to be 4.24 × 10^–20 cm². From the decay curves, experimental lifetimes (τ_exp) of the ⁴F_3/2 level have been determined and are found to be 363, 340, 205, 134, 122 and 54 μs for 0.1, 0.5, 1.0, 1.5, 2.0 and 3.0 mol% Nd³⁺ ions doped glasses, respectively. By exciting the prepared glass samples at 808 nm, the upconversion of infrared light into blue, green, yellow and red emission have also observed. These results indicate that the present glasses could be useful for opto-electric devices and solid state laser applications.     

Improved broadband near-infrared luminescence in Nd3+/Tm3+ co-doping tellurite glass with Ag NPs

The near-infrared (NIR) luminescence in S+E+O bands of tellurite glasses doped with Nd³⁺/Tm³⁺ and Ag nanoparticles (NPs) was investigated. The tellurite glasses were prepared by melt-quenching and heat-treated techniques. Under the excitation of 808 nm laser, Nd³⁺/Tm³⁺ doped tellurite glasses produced three NIR luminescence bands of 1.33, 1.47 and 1.85 μm, originating from Nd³⁺:⁴F_3/2→⁴I_13/2, Tm³⁺:³H₄→³F₄ and Tm³⁺:³F₄→³H₆ transitions respectively. Interestingly, a broadband luminescence spectrum ranging from 1280 to 1550 nm with the FWHM (full width at half maximum) about 201 nm was obtained due to the overlapping of the first two NIR bands. Further, the peak intensity of this broadband luminescence was increased by 75% after the introduction of Ag NPs with diameter in 10–20 nm. The analysis of fluorescence decay shows that compared with the enhanced local electric field, the energy transfer from Ag species to Nd³⁺ and Tm³⁺ ions plays a major role in luminescence enhancement. The findings in this work indicate that tellurite glass co-doped with Nd³⁺/Tm³⁺ and Ag NPs is a potential gain material applied in the S+E+O-band photonic devices.     

A novel Nd3+-doped MgO-Al2O3-SiO2-based transparent glass-ceramics: Toward excellent fluorescence properties

Generally, glass-ceramics have superior properties compared to their parent glasses. Here, we prepared a novel Nd³⁺-doped MgO-Al₂O₃-SiO₂-based transparent glass-ceramics with excellent fluorescence properties. The effects of Nd₂O₃ content on the structure and properties of glass-ceramics were studied, aiming to provide a key guidance for preparing this transparent glass-ceramics. The results revealed that the glass stability increased originally and then decreased with increasing Nd₂O₃ content, so did the variation of wavenumbers in infrared spectra. And these glass-ceramics are mainly composed of cordierite with residual glassy phase. The three phenomenological intensity parameters (Ω_2,4,6) and radiative properties were estimated by Judd-Ofelt theory, and the values of Ω₂ first decreased and then increased with increasing Nd₂O₃ content. Three main emission peaks ascribed to the transitions from ⁴F_3/2 to ⁴I_9/2, ⁴I_11/2, ⁴I_13/2 at 898, 1057, 1330  nm were observed, respectively. The branching ratios for ⁴F_3/2→⁴I_11/2 transition increased as the Nd₂O₃ content raised, and the fluorescence lifetimes of the ⁴F_3/2 level were found to increase first and then decrease with Nd₂O₃ content (from 181 to 726 μs). The excellent fluorescence properties indicate that this novel glass-ceramics can be used as a potential solid-state optical functional material for 1.06 μm laser emission.