Effect on the fluorescence branching ratio of different synergistic ligands in neodymium complex doped PMMA

A series of neodymium complexes Nd(TTA)₃L_x (where TTA = α-thenoyltrifluoroacetonato, L_x (x = 1–5) = H₂O, triophenylphosphine oxide (Tppo), 2,2-bipyridine (Bipy), 1,10-phenanthroline (Phen) and 2- (N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine (Dpbt) were synthesized and incorporated in poly(methyl methacrylate). Their absorption spectra were measured and analyzed using Judd–Ofelt theory. Near-infrared luminescent spectra were studied and the radiative properties have been stimulated. Laser parameters such as effective bandwidths (Δλ_eff), stimulated emission cross-sections (σ_e), and gain bandwidth (σ_g) had also been calculated and compared with other systems. The effect on the fluorescence branching ratio (β) in the ⁴F_3/2→⁴I_11/2 transition of different synergistic ligands had been investigated and the relation between β and Judd–Ofelt parameter Ω₂, Ω₄, Ω₆ was discussed. In conclusion, among the five neodymium complexes, Nd(TTA)₃Dpbt has the largest Ω₂ parameter (33.72 × 10^? 20 cm²), stimulated emission cross-sections, which is found promising to be a candidate for laser materials in further application.     

Spectroscopic characterization of signal gain and pump ESA in short-lengths of RE-doped tellurite fibers

We report the results of emission and amplification in Tm³⁺- and Er³⁺-fibers for signal gain in the 1460–1600 nm region, which covers a large part of S-, C- and L-bands of silica fiber optical communication networks. The paper explains the mechanism for alleviating the pump-excited absorption in Er³⁺-doped and Tm³⁺-doped tellurite fibers for maximizing the pump inversion efficiency at 980 nm using the co-dopants and via the structural modification of TeO₂ glass by incorporating a high phonon energy oxide namely, B₂O₃. The spectroscopic data and gain bandwidth of Er-doped fibers are reported in the C- and L-bands. To date the measured maximum relative gain in short fibers of 5–10 cm in length in C- and L-bands are: 30 dB and 15 dB, respectively. By comparison the internal gain in a 20 cm long Tm/Yb ion co-doped fiber pumped with a 980 nm source was 7 dB.     

Boron removal from metallurgical-grade silicon using lithium containing slag

The possibility of extracting boron impurity from metallurgical-grade silicon by lithium containing slag refining for solar cell application was investigated. The distribution coefficients of boron between CaO–SiO₂–Li₂O and CaO–SiO₂–LiF slags were examined. The boron content in the refined silicon was studied under different conditions of mass ratio of slag to silicon and refining time. The results showed that a small amount of Li₂O or LiF had significant effect on the distribution coefficients of boron. The removal of boron impurity using CaO–SiO₂–LiF system was more effective than using CaO–SiO₂–Li₂O system. Values of boron content in the refined silicon did not decrease significantly when the mass ratio exceeded 4, while it had been obviously falling with the increase in refining time. When the mass ratio of CaO–SiO₂–Li₂O slag to metallurgical-grade silicon was 4, the boron content in silicon was successfully reduced from 2.2 × 10^? 5 to 1.3 × 10^? 6 after slag refining for 2 h at 1823 K.     

Stimulated emission of Co2+-doped glass–ceramics

Pump–probe spectroscopy studies on cobalt-doped spinel-based aluminosilicate glass–ceramics of various compositions have been made in the visible part of the spectrum. Stimulated emission from the ⁴T₁(⁴P) state to the ⁴A₂ one of tetrahedral Co²⁺ ion has been observed for all glass–ceramic materials. The peak values of effective stimulated emission cross-sections for Co²⁺ ions are estimated to be 4–5 × 10⁻¹⁹ cm² depending on glass–ceramics composition and are found to be higher than in spinel single crystals.     

Broadband near-infrared emission from Bi–Er–Tm Co-doped germanate glasses

Bi–Er–Tm co-doped germanate glasses and Bi, Er, Tm singly doped glasses were prepared and characterized through absorption spectra, NIR emission spectra and decay lifetime. A super broadband near-infrared emission from 1000 nm to 1600 nm, covering the whole O, E, S, C, and L bands, was observed in the Bi–Er–Tm co-doped samples due to the result of the overlapping of the Bi related emission band (centered at 1300 nm), the emission from Er^{3+ 4}I_13/2 → ⁴I_15/2 transition (centered at 1534 nm) as well as the emission from Tm^{3+ 3}H₄ → ³F₄ transition (centered at 1440 nm), which is essential for broadly tunable laser sources and broadband optical amplifiers. The energy transfer process was also discussed at the end of the paper.     

Spectroscopic properties and energy transfer in Yb3+–Ho3+ co-doped germanate glass emitting at 2.0 μm

A new kind of germanate glass co-doped with Yb³⁺–Ho3⁺ was prepared. The J-O parameters were calculated to be Ω₂ = (6.59 ± 0.21) × 10^? 20 cm², Ω₄ = (2.77 ± 0.36) × 10^? 20 cm², and Ω₆ = (1.90 ± 0.25) × 10^? 20 cm². The little overlap between the absorption cross section and stimulated emission cross section indicates a non-resonant energy transfer process. The calculation demonstrates that the energy transfer between Yb³⁺ and Ho³⁺ is one-phonon assisted in a great measure. The gain coefficient of Ho³⁺ at 2.0 μm was also calculated. The fluorescence measurement shows the Yb³⁺ co-doping enhances the 2.0 μm emission remarkably.     

Emissions of 1.20 and 1.38 μm from Ho3+-doped lithium–barium–bismuth–lead oxide glass for optical amplifications

Efficient infrared emissions at 1.20 μm [⁵I₆ → ⁵I₈ transition] and 1.38 μm [(⁵ F₄, ⁵ S₂) → ⁵I₅ transition] from Ho³⁺-doped lithium–barium–bismuth–lead (LBBP) glass were observed. The stimulated emission cross-sections were calculated to be 0.29 × 10^?20 and 0.25 × 10^?20 cm² for 1.20 and 1.38 μm emissions, respectively. Judd-Ofelt characteristic parameters Ω₂, Ω₄ and Ω₆ for Ho³⁺ in LBBP glass were calculated to be 6.72 × 10^?20, 2.35 × 10^?20 and 0.61 × 10^?20 cm², respectively, which indicates a strong asymmetry and a covalent environment between the Ho³⁺ ions and the ligands in this glass. The optical amplifications operating at these relatively unexplored wavelength regions were evaluated and discussed.     

Photoluminescence properties of Sm3+-doped SFB glasses for efficient visible lasers

The photoluminescence properties of different concentrations of Sm³⁺ ions doped sodium fluoroborate (SFB) glasses of composition Na₂O–LaF₃–CaF₂–AlF₃–B₂O₃–SmF₃ have been investigated. The energy level analysis is carried out using free-ion Hamiltonian model. The Judd–Ofelt intensity parameters are used to evaluate the laser characteristic parameters such as spontaneous transition probability, radiative lifetime and fluorescence branching ratio for ⁴G_5/2 → ⁶H_J (J = 5/2, 7/2, 9/2 and 11/2) emission transitions of Sm³⁺ ion. The principal photoluminescence transitions of interest are identified by recording the emission spectra for different Sm³⁺ ion concentrations and measuring their emission cross-sections, integrated absorption cross-sections and optical gain parameters. The decay profiles from the ⁴G_7/2 excited manifold state to its lower lying energy levels have been recorded by monitoring the excitation and emission wavelengths at 402 and 600 nm, respectively. The dependence of effective fluorescence lifetime on the Sm³⁺ concentration is also discussed.     

Er3+-doped germanate glasses for active waveguides prepared by Ag+/K+ ↔ Na+ ion-exchange

Planar waveguides were prepared by Ag⁺/K⁺ ? Na⁺ ion-exchange on Er⁺³-doped GeO₂–ZnO–Na₂O–Li₂O glasses obtained by a melting–casting method. Optical parameters of the waveguides were measured at 543.5, 632.8, and 1550 nm by m-line technique as a function of the Ag⁺ ion-exchange time. The optimized planar waveguides show an effective diffusion depth (d) of 2.95 μm and well confined propagating TE₀ and TM₀ modes at 1550 nm. Spectroscopic properties as photoluminescence emission and emission decay time were evaluated for the erbium-doped planar waveguide, indicating that Ag⁺ ? Na⁺ ion-exchange enhance the photoluminescence emissions in the green and infrared regions from erbium ions. The glass system studied is promising to be applied as optical amplifiers in the C-telecom band. Green emission sensitized by Ag⁺ was also observed.     

2 μm spectroscopic investigation of Tm3+-doped tellurite glass fiber

TmF₃ doped TeO₂–ZnO–La₂O₃ (TZL) glasses and fibers have been prepared by the conventional melt-quenching and suction casting methods, respectively. 2 μm emission properties and energy transfer mechanisms of the TZL glasses and fibers have been analyzed and discussed. The oscillator strength, Judd–Ofelt parameters, radiative transition probability and radiative lifetime of Tm³⁺ have been calculated based on the absorption spectra and Judd–Ofelt theory. The maximum emission cross-section of Tm³⁺ is 6.9 × 10^?21 cm² near 2 μm. Emission spectra have been obtained from both TZL fibers and bulk glass when excited with a 794 nm pump. The results of 2 μm emission spectra indicate that the line width of Tm³⁺ measured in fibers is narrower than that in the bulk glass sample. The peak position of the emission spectra shifts to longer wavelength with increment of the fiber length.     

Spectroscopic properties and energy transfer in Ga2O3– Bi2O3–PbO–GeO2 glasses codoped with Tm3+ and Ho3+

This paper reports on the spectroscopic properties and energy transfer in Ga₂O₃–Bi₂O₃–PbO–GeO₂ glasses doped with Tm³⁺ and/or Ho³⁺. From the optical absorption spectra of Tm³⁺, Judd–Ofelt intensity parameters, radiative transitions probabilities, fluorescence branching ratios, and radiative lifetimes have been calculated using Judd–Ofelt theory. The measured differential scanning calorimetry result shows that the glass exhibits excellent stability against devitrification with ΔT = 129 °C. The measured luminescence spectra show that the ³H₄ → ³F₄ transition of Tm³⁺ upon 808 nm laser diode excitation possess a broad full width at half-maximum of ∼126 nm. The maximum value calculated stimulated emission cross-section and the measured lifetime of ³H₄ level from the 1.47-μm transition are ∼4.73 × 10⁻²¹ cm² and ∼0.239 ms, respectively. It is noticed that codoping of Ho³⁺ could significantly enhanced the ratio of the intensity of 1.47–1.80 μm by energy transfer via Tm³⁺: ³F₄ → Ho³⁺: ⁵I₇.     

1.5 μm Emission and infrared-to-visible frequency upconversion in Er+3/Yb+3-doped phosphoniobate glasses

Sodium phosphoniobate glasses with the composition (mol%) 75NaPO₃–25Nb₂O₅ and containing 2 mol% Yb³⁺ and x mol% Er³⁺ (0.01 ⩽ x ⩽ 2) were prepared using the conventional melting/casting process. Er³⁺ emission at 1.5 μm and infrared-to-visible upconversion emission, upon excitation at 976 nm, are evaluated as a function of the Er³⁺ concentration. For the lowest Er³⁺ content, 1.5 μm emission quantum efficiency was 90%. Increasing the Er³⁺ concentration up to 2 mol%, the emission quantum efficiency was observed to decrease to 37% due to concentration quenching. The green and red upconversion emission intensity ratio was studied as a function of Yb³⁺ co-doping and the Er³⁺–Er³⁺ energy transfer processes.     

Luminescence and defects of Yb3+-doped sol–gel silica glasses

The optical properties of Yb-doped sol–gel silica glasses were studied by optical absorption and radio-luminescence (RL) measurements, that revealed the typical absorption and emission pattern of Yb³⁺ ions. Moreover, RL bands in the 1.5–3.5 eV interval were also observed, and related to defects of the silica matrix. The RL intensity temperature dependence, investigated in the 10–320 K interval, evidenced the presence of the SiO₂ self-trapped exciton emission at 2.2 eV, whose intensity was rapidly quenched by temperature increasing. At variance, the Yb³⁺ emission intensity increased markedly by temperature increasing. This phenomenon is interpreted by considering a competitive role of point defects in free carrier trapping, evidenced by parallel wavelength resolved thermally stimulated luminescence measurements.     

Laser spectroscopy of Nd3+-doped PbO–Bi2O3–Ga2O3–BaO glasses

We present spectroscopic results of PbO–Bi₂O₃–Ga₂O₃–BaO glass doped with different concentration of Nd₂O₃. These glasses have high refractive index (∼2.4) and large spectral transmission window. Measurements of absorption, emission and fluorescence lifetime are presented. From the calculations of the Judd–Ofelt parameters the radiative lifetimes, branching ratios and quantum efficiency of ⁴F_3/2 level are calculated. The highest emission intensity was measured for the sample doped with 0.5 wt% of Nd₂O₃ with emission cross-section of 2.6 × 10⁻²⁰ cm², at 1069 nm, fluorescence lifetime of 110 μs, quantum efficiency of 82% and effective linewidth of 34 nm. The results point out this glass system as good candidate to be used in the development of photonic devices operating in the near infrared spectral range.     

Spectroscopic properties of the 1.8 μm emission of Tm3+/Yb3+ codoped TeO2–ZnO–Bi2O3 glasses with efficient energy transfer

Tm³⁺-doped and Tm³⁺/Yb³⁺-codoped TeO₂–ZnO–Bi₂O₃ (TZB) glasses are prepared by melt-quenching method. The Judd-Ofelt intensity parameters (Ω_t t = 2, 4, 6), radiative transition rate, and radiative lifetime of Tm³⁺ are calculated based on the absorption spectra. The 1.8 μm emission of the samples is investigated under 980 nm laser excitation. The absorption, emission cross-sections, and gain coefficient of Tm³⁺:³F₄ → ³H₆ are calculated. The energy transfer processes of Yb³⁺–Yb³⁺ and Yb³⁺–Tm³⁺ are analyzed, the results show that the Yb³⁺ ions can transfer their energy to Tm³⁺ ions with large energy transfer coefficient, and a maximum efficiency of 79%.     

Network structure of multi-component sodium borosilicate glasses by neutron diffraction

Neutron diffraction structure study has been performed on multi-component sodium borosilicate based waste glasses with the composition of (65 − x)SiO_2. · xB₂O₃ · 25Na₂O · 5BaO · 5ZrO₂, x = 5–15 mol%. The maximum momentum transfer of the experimental structure factor was 30 Å⁻¹, which made available to determine the distribution function with high r-space resolution. Reverse Monte Carlo modelling was applied to calculate several partial atomic pair correlation functions, nearest neighbor distances and coordination numbers have been revealed. The characteristic features of Si–O and Si–Si distributions are similar for all glassy samples, suggesting that the Si–O network consisting of tetrahedral SiO₄ units is highly stable even in the multi-component glasses. The B–O correlations proved to be fairly complex, two distinct first neighbor distances are present at 1.40 Å and 1.60 Å, the latter equals the Si–O distance. Coordination number distribution analyzes has revealed 3 and four-coordinated boron atoms. The O–O distribution suggests a network configuration consisting of boron rich and silicon rich regions. Our findings are consistent with a structure model where the boron rich network contains mostly trigonal BO₃ units, and the silicon rich network is formed by a mixed continuous network of ^[4]Si–O–Si^[4] with several different ^[4]B–O–Si^[4] and ^[3]B–O–Si^[4] linkages.     

Spectroscopic properties of Tm3+ doped TeO2-R2O-La2O3 glasses for 1.47 μm optical amplifiers

Upon excitation at 808 nm laser diode, an intense 1.47 μm infrared fluorescence has been observed with a broad full width at half maximum (FWHM) of about 124 nm for the Tm³⁺-doped TeO₂-K₂O-La₂O₃ glass. The Judd–Ofelt parameters found for this glass are: Ω₂ = 5.26 × 10^?20 cm², Ω₄ = 1.57 × 10^?20 cm² and Ω₆ = 1.44 × 10^?20 cm². The calculated emission cross-sections of the 1.47 μm transition are 3.57 × 10^?21 cm², respectively. It is noted that the gain bandwidth, σ_e × FWHM, of the glass is about 440 × 10^?28 cm³, which is significantly higher than that in ZBLAN and Gallate glasses, a high gain of 35.5 dB at 1470 nm can be obtained in a TKL glass fiber. TeO₂-R₂O (R = Li, Na, K)-La₂O₃ glasses has been considered to be more useful as a host for broadband optical fiber amplifier.     

Hydrogen and oxygen concentration analysis of porous silicon

Elastic recoil detection and Rutherford backscattering spectrometry combined with the nuclear reaction analysis method have been applied for the determination of oxygen, hydrogen and carbon concentration depth profiles of aged p⁺-type porous Si layers of different low and medium porosities. The plan view and cross-section scanning electron microscopy images have provided with information about both the diameter and silicon skeleton structure of the pores. The concentration depth profiles reveal the existence of a non-homogeneous subsurface porous film several hundred nanometers thick for all the studied samples. Differences in the atomic composition among low and medium porosity layers and the possible origin of various impurities are discussed. The maximum H content in PSi has been observed at the depth of 200–600 nm, while the highest oxygen concentration is typical of 200 nm thick subsurface layers. The highest obtained ratio of H/Si atomic concentrations reaches the value of 2 for the PSi samples with porosity P of 66%, comparing to N_H/N_Si = 0.27 in the case of P = 25% PSi.     

Improved method for preparation of anhydrous silica by microwave irradiation with spectroscopic characterization and toxicity assay

Amorphous anhydrous silica SiO_{2 (mw)} (99.99%) is successfully synthesized through microwave irradiation technique and time of reaction is reduced up to 1 h. The dehydration phase study of Si–water, Si–OH, Si–O–Si networking, elemental analysis and surface morphology was carried out by FTIR, FTNIR, SEM and EDAX spectroscopic techniques. The broad absorption stretching and bending of Si–OH and H₂O at 3695.38–2832.96 cm^? 1, 1638 cm^? 1 and 1191.20–1017.14 cm^? 1 completely disappeared and appearance of new bands at 946.93 and 797.63 cm^? 1 confirmed the amorphous anhydrous silica with Si–O–Si networking. The SEM images of SiO_{2 (mwc)} described the smooth and fine particle texture and confirmed 99.99% Si–O–Si networking of anhydrous silica. The 99.99% purity was verified by EDAX spectra which exhibited sharp signals only for oxygen and silicon. Toxicity against Monomorium minimum and Tribolium castaneum with 100% mortality and LT₅₀ 91 min and 7.5 h respectively is being reported. It can be used for long storage of grains in the future.     

Pr3 +–Yb3 +‐codoped lanthanum fluorozirconate glasses and waveguides for visible laser emission

Pr^3 +–Yb^3 +‐codoped fluoride glass waveguides have been synthesized by Physical Vapor Deposition (PVD). A study of the evaporation of ternary mixture of rare earth fluorides LaF₃–PrF₃–YbF₃ has been necessary to control the doping of the evaporated glass. Optical and spectroscopic studies have been performed in both bulk and waveguide configuration. Red, orange, green and blue emissions in Pr^3 +–Yb^3 +-codoped lanthanum flurozirconate glasses called ZLAG have been investigated, by exciting in the blue or in the infra-red at 980 nm. Bulk samples with different dopant concentrations (0.25–3 mol% for Pr^3 + and 0–5 mol% for Yb^3 +) have been studied in order to optimize the Pr^3 + emission. It has been shown than the luminescence is similar in bulk and waveguide upon excitation at 980 nm.