Optical absorption and emission properties of Pr and Er in lithium cesium mixed alkali borate glasses

This article presents the optical absorption and emission properties of Pr³⁺ and Er³⁺ in mixed alkali borate glasses of the type 68B₂O₃·xLi₂O·(32-x)Cs₂O (where x=8, 12, 16, 20 and 24). The variation of Judd-Ofelt intensity parameters (Ω_λ), the peak wavelength of the hypersensitive transitions, radiative transition probabilities (A_rad) and peak emission cross-sections (σ_p) with x in the glass matrix have been discussed in detail. The changes in position of hypersensitive transition and intensity parameters with x are correlated to the structural changes in the host matrix. The estimated radiative lifetimes (τ_R) of certain excited states of both Pr³⁺ and Er³⁺ in lithium cesium mixed alkali borate glasses are reported. Branching ratios (β) and integrated absorption cross-sections (Σ) for certain important transitions are presented. Peak stimulated emission cross-sections (σ_p) are calculated for the observed emission peaks of Pr³⁺ and Er³⁺ ions in this glass matrix.     

Spectroscopic investigations and luminescence spectra of Nd and Dy doped different phosphate glasses

Spectral properties of Nd³⁺ and Dy³⁺ ions in different phosphate glasses were studied and several spectroscopic parameters were reported. Covalency of rare-earth-oxygen bond was studied in these phosphate glass matrices with the variation of modifier in host glass matrix. Using Judd-Ofelt intensity parameters (Ω₂, Ω₄ and Ω₆), radiative transition probabilities (A) and radiative lifetimes (τ_R) of certain excited states of Nd³⁺ and Dy³⁺ ions are estimated in these glass matrices. From the magnitudes of branching ratios (β_R) and integrated absorption cross-sections (Σ), certain transitions of both the ions are identified for laser excitation. From the emission spectra, peak stimulated emission cross-sections (σ_P) are evaluated for the emission transitions observed in all these phosphate glass matrices for both Nd³⁺ and Dy³⁺ ions.     

Characterization of Tm doped mixed alkali borate glasses—spectroscopic investigations

The effect of mixed alkalis on the optical absorption spectra of Tm³⁺ in xNa₂O·(30−x)K₂O·70B₂O₃ glasses has been studied. The optical band gap values (E_opt) for both direct and indirect transitions have been obtained using Davis and Mott theory. Spectroscopic parameters like Racah (E¹, E² and E³), spin-orbit (ξ_4f) and Judd-Ofelt intensity parameters (, and ) have been calculated for different x values. Radiative transition probabilities (A_rad), radiative lifetimes (τ_R), branching ratios (β), integrated absorption cross sections (Σ) and multiphonon relaxation rates (W_MPR) are calculated for certain excited states of Tm³⁺ ion. The observed trends in the above parameters as a function of x in these borate glasses have been discussed keeping in view the effect of mixed alkalies in borate glasses. Certain potential lasing transitions have been identified for laser action among the various transitions of Tm³⁺ in these mixed alkali borate glasses.     

Spectral Investigations on Ho3+ Doped Mixed Alkali Chloroborate Glasses

The optical absorption and emission spectra of two different Ho³⁺ doped mixed alkali chloroborate glasses have been studied in the ultraviolet-visible near-infrared regions. Various spectroscopic parameters like Racah (E¹, E², and E³), spin orbit (ξ_4f), and configuration interaction (α) parameters have been calculated. From the measured spectral intensities of the various absorption bands of Ho³⁺ ion, the Judd–Ofelt intensity parameters (Ω₂, Ω₄, and Ω₆) have been evaluated and covalency was studied as a function of x in the glass matrices. Using these parameters, radiative transition probabilities, radiative lifetimes, branching ratios, and integrated absorption cross-sections have been calculated and reported for certain excited states of Ho³⁺ ion. From the emission spectra, stimulated emission cross-sections are determined for the emission transitions, ⁵F₄, ⁵S₂?→?⁵I₈, and ⁵F₅?→?⁵I₈ in these two mixed alkali chloroborate glasses. An attempt has been made to throw some light on the environment of Ho³⁺ ions in these glass systems by studying the variation in various spectroscopic parameters.     

Laser spectroscopy of Nd and Dy ions in lead borate glasses

The spectroscopic and laser properties of Nd³⁺ and Dy³⁺ ions in lead borate glass were studied. Luminescence spectra recorded in the near-infrared and visible ranges correspond to ⁴F_3/2-⁴I_J/2 (J=9, 11, 13) transitions of Nd³⁺ and ⁴F_9/2-⁶H_J/2 (J=11, 13, 15) transitions of Dy³⁺, respectively. Luminescence decay curves were analyzed as a function of activator concentration. Luminescence quenching is observed, which is due to Ln-Ln interaction increasing. Several spectroscopic parameters relevant to laser potential of Ln³⁺ ions (Ln=Nd, Dy) in lead borate glass were determined. The relatively large values of the quantum efficiency and the room-temperature emission cross-section for the ⁴F_3/2-⁴I_11/2 transition of Nd³⁺ at 1061 nm and the ⁴F_9/2-⁶H_13/2 transition of Dy³⁺ at 573 nm imply that Ln-doped lead borate glasses can be considered as promising solid-state materials for laser applications.     

Fluorescence and Judd-Ofelt analysis of Nd ions in oxyfluoride glass ceramics containing CaF2 nanocrystals

Judd-Ofelt analyses of Nd³⁺ ions in the oxyfluoride glasses and glass ceramics containing CaF₂ nanocrystals are performed to evaluate the intensity parameters Ω_2,4,6, spontaneous emission probability, radiative lifetime, quantum efficiency, as well as stimulated emission cross-section. The influences of Nd³⁺-doping level and heating temperature on these parameters for the ⁴F_3/2→⁴I_J (J=9/2, 11/2, and 13/2) transitions are systematically discussed. The decrease of intensity parameter Ω₂ evidences the incorporation of Nd³⁺ ions into CaF₂ nanocrystals after crystallization. With increasing of Nd³⁺-doping level, the measured lifetime and quantum efficiency gradually decrease, while the stimulated emission cross-section keeps almost unchanged. For 1.0 mol% Nd³⁺-doped sample, both the emission intensity and the measured lifetime enhance with increasing of heating temperature up to 650 °C. The results indicate that the investigated glass ceramics are potentially applicable as the 1.06 um laser host.     

Photoluminescence properties of Sm in LBTAF glasses

Room temperature visible and near infrared optical absorption and emission spectra of Sm³⁺-doped lead borate titanate aluminum fluoride (LBTAF) glasses with molar composition (50−x) PbO−30H₃BO₃−10TiO₂−10AlF₃−xSm₂O₃ (x=0.1, 0.5, 1.0 and 2.0) have been analyzed. Energy parameters for the 4f⁵ electronic configuration of Sm³⁺: LBTAF glasses have been evaluated using free-ion Hamiltonian model. The experimental oscillator strengths of absorption bands have been used to determine the J-O parameters. Fluorescence spectra were recorded by exciting the samples with 402 nm. Using the J-O parameters and luminescence data, the radiative transition probabilities (A_R), branching ratios (β_R) and stimulated emission cross-sections (σ_e) were obtained. The decay curves of ⁴G_5/2→⁶H_7/2 transition exhibit single exponential for lower concentration (0.1 mol%) and non-exponential for higher concentrations. This concentration quenching has been attributed to the energy transfer through cross-relaxation between Sm³⁺ ions. From the values of the radiative parameters, it is concluded that 1.0 mol% Sm³⁺-doped LBTAF glass may be used for laser active medium with emission wavelength at 600 nm.     

Spectroscopic and optical properties of Nd doped fluorine containing alkali and alkaline earth zinc-aluminophosphate optical glasses

Nd³⁺ doped fluorine containing zinc-aluminophosphate glasses have been prepared with alkali and alkaline earth content to understand the effect of network modifiers on radiative process. The physical and optical properties of these glasses have been evaluated. The Judd-Ofelt model for the intensity analysis of induced electric dipole transitions has been applied to the measured oscillator strengths of the absorption bands to determine the three phenomenological intensity parameters Ω₂, Ω₄ and Ω₆ for each glass. Using these parameters, transition probability (A), total transition probability (A_T), branching ratios (β_R) radiative life times (τ_R) and integrated cross-section (σ_a) for the stimulated emission have been theoretically calculated for certain excited Nd³⁺ fluorescent levels. From the obtained results the conclusion is made about the possibility of using these glasses as laser material.     

Co-reduction synthesis of new LnxSb2−xS3 (Ln: Nd, Lu, Ho) nanomaterials and investigation of their physical properties

New Ln_xSb_2−xS₃ (Ln: Lu³⁺, Ho³⁺, Nd³⁺)-based nanomaterials were synthesized by a co-reduction method. Powder XRD patterns indicate that the Ln_xSb_2−xS₃ crystals (Ln=Lu³⁺, Ho³⁺, x=0.00−0.1 and Ln=Nd³⁺, x=0.00−0.08) are isostructural with Sb₂S₃. SEM images show that doping of Lu³⁺ and Ho³⁺ ions in the lattice of Sb₂S₃ results in nanorods while that in Nd³⁺ leads to nanoflowers. UV-vis absorption and emission spectroscopy reveal mainly electronic transitions of the Ln³⁺ ions in case of Ho³⁺ and Nd³⁺ doped nanomaterials. Emission spectra show intense transitions from excited to ground state of Ln³⁺. Emission spectra of doped materials, in addition to the characteristic red emission peaks of Sb₂S₃, show other emission bands originating from f-f transitions of the Ho³⁺ ions. TGA curves indicated that Sb₂S₃ has the highest thermal stability. The electrical conductance of Ln-doped Sb₂S₃ is higher than undoped Sb₂S₃, and increase with temperature.     

Mixed alkali effect in borate glasses—EPR and optical absorption studies in xNa2O–(30−x)K2O–70B2O3 glasses doped with Mn2+

The mixed alkali borate xNa₂O–(30−x)K₂O–70B₂O₃ (5≤x≤25) glasses doped with 1 mol% of manganese ions were investigated using EPR and optical absorption techniques as a function of alkali content to look for ‘mixed alkali effect’ (MAE) on the spectral properties of the glasses. The EPR spectra of all the investigated samples exhibit resonance signals which are characteristic of the Mn²⁺ ions. The resonance signal at g≅2.02 exhibits a six line hyperfine structure. In addition to this, a prominent peak with g≅4.64, with a shoulder around g≅4.05 and 2.98, was also observed. From the observed EPR spectrum, the spin-Hamiltonian parameters g and A have been evaluated. It is interesting to note that some of the EPR parameters do show MAE. It is found that the ionic character increases with x and reaches a maximum around x=20 and thereafter it decreases showing the MAE. The number of spins participating in resonance (N) at g≅2.02 decreases with x and reaches a minimum around x=20 and thereafter it increases showing the MAE. It is also observed that the zero-field splitting parameter (D) increases with x, reaches a maximum around x=15 and thereafter decreases showing the MAE. The optical absorption spectrum exhibits a broad band around ∼20,000 cm⁻¹ which has been assigned to the transition ⁶A_1g(S)→⁴T_1g(G). From ultraviolet absorption edges, the optical bandgap energies and Urbach energies were evaluated. It is interesting to note that the Urbach energies for these glasses decrease with x and reach a minimum around x=15. The optical band gaps obtained in the present work lie in the range 3.28–3.40 eV for both the direct and indirect transitions. The physical parameters of all the glasses were also evaluated with respect to the composition.     

Optical and electronic polarizability investigation of Nd-doped soda-lime silicate glasses

This paper reports on different physical and optical properties of Nd³⁺-doped soda-lime silicate glass. The glasses containing Nd³⁺ in (65−x)SiO₂:25Na₂O:10CaO:xNd₂O₃ (where x=0.0-5.0 mol%) have been prepared by the melt-quenching method. In order to understand the role of Nd₂O₃ in these glasses the density, molar volume, refractive index and optical absorption were investigated. The results show that the density and molar volume of the glasses increase with an increase in Nd₂O₃ concentration and consequently generate more non-bridging oxygen (NBOs) into glass matrix. The optical absorption spectra were measured in the wavelength range from 300 to 700 nm and the optical band gaps were determined. It was found that the optical band gap decreases with an increase in Nd₂O₃ concentration. On the basis of the measured values of density and refractive index, the Nd³⁺ ion concentration in glasses, the polarizability of oxide ions and optical basicity were theoretically determined.     

Optical absorption and photoluminescence studies of Eu-doped phosphate and fluorophosphate glasses

Phosphate (P₂O₅+K₂O+BaO+Al₂O₃+Eu₂O₃) and fluorophosphate (P₂O₅+K₂O+BaO+BaF₂+Al₂O₃+Eu₂O₃) glasses with different Eu³⁺ ion concentrations have been prepared and characterized through optical absorption, photoluminescence and decay times. An intense red luminescence is observed from the ⁵D₀ emitting level of Eu³⁺ ions in these glasses. The relative luminescence intensity ratio of ⁵D₀→⁷F₂→⁵D₀→⁷F₁ transitions has been evaluated to estimate the local site symmetry around the Eu³⁺ ions. The emission spectra of these glasses show a complete removal of degeneracy for the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions. Second and fourth rank crystal-field (CF) parameters have been calculated together with the CF strength parameter by assuming the C_2v symmetry for the Eu³⁺ ions in both the phosphate and fluorophosphate glasses. Judd-Ofelt parameters have been evaluated from the luminescence intensity ratios of ⁵D₀→⁷F_J (J=2, 4 and 6) to ⁵D₀→⁷F₁ transitions. These parameters have been used to derive radiative properties such as transition probabilities, branching ratios, radiative lifetimes and peak stimulated emission cross-sections for the ⁵D₀→⁷F_J transitions. Decay curves of the ⁵D₀ level of Eu³⁺ ions in these two Eu³⁺:glass systems have been measured by monitoring the ⁵D₀→⁷F₂ transition (611 nm) at room temperature. The experimental lifetime of the ⁵D₀ level in the title glasses is found to be higher than Eu³⁺-doped niobium phosphate glasses. The analysis indicates that the lifetime of the ⁵D₀ level is found to be less sensitive to the Eu³⁺ ion concentration and addition of BaF₂ has no significant effect on the optical properties of Eu³⁺-doped phosphate glasses.     

Physical, structural, and luminescence studies of Nd3+ doped MgO-ZnO borate glass

A series of borate glass of the system xNd₂O₃-5MgO-20ZnO-(75 ? x)B₂O₃, where x = 0.5, 1.0,1.5, 2.0, and 2.5 was successfully fabricated using melt quench method. The properties of the glass were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR), absorption and luminescence spectra. The upconversion properties of Nd³⁺ doped borate glass were observed by using 574 nm excitation wavelength corresponding to ⁴ I _15/2 → ² H _114/2 transition. The emission bands centered at 460, 500 and 620 nm which corresponding to the Nd³⁺ transitions, ⁴ F _7/2 → ⁴ I _15/2, ² H _11/2 → ⁴ I _15/2, and ⁴ F _9/2 → ⁴ I _15/2 respectively were observed at room temperature. The presence of Nd³⁺ in borate based glass could intensify the upconversion luminescence spectra as it can potentially be used as host materials for upconversion lasers.     

Near infrared fluorescence and energy transfer in Ce/Nd Co-doped CaxSr1−xS

Novel near infrared (NIR) phosphors Ca_xSr_1−xS:Ce³⁺,Nd³⁺ were synthesized by a solid state reaction. The NIR emission was realized through an efficient absorption by the allowed 4f-5d transition of Ce³⁺ and efficient energy transfer to Nd³⁺ via well-matched energy levels. Ce³⁺ and Nd³⁺ content in CaS/SrS was optimized. It was found that CaS:Ce³⁺,Nd³⁺ gave much stronger NIR emission than that of SrS:Ce³⁺,Nd³⁺. Further studies on Ca_xSr_1−xS:Ce³⁺,Nd³⁺ indicated that both visible emission of Ce³⁺ and NIR emission of Nd³⁺ were observably affected by Ca/Sr ratio. The energy transfer efficiency, which can be estimated from fluorescence lifetime of Ce³⁺, increased from 52% to 74% for the Ca_xSr_1−xS:Ce³⁺,Nd³⁺ (x=0 to 1) series, accompanied with a shift of maximal emission wavelength of Ce³⁺ from 482 to 505 nm. The results showed that overlap between emission spectrum of Ce³⁺ and excitation spectrum of Nd³⁺ plays an important role in the energy transfer efficiency, and Ce³⁺ emitting in green or blue-greenish region sensitized the Nd³⁺ NIR fluorescence emission more efficiently than that in blue region.     

Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Bi(PO4)3 phosphors

A series of orange reddish emitting phosphors Eu³⁺-doped Sr₃Bi(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence (PL) properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Bi(PO₄)₃:Eu³⁺ phosphors invariably exhibit five peaks assigned to the ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The luminescence intensity was enhanced with increasing Eu³⁺ content and the emission reached the maximum intensity at x=0.05 in Sr₃Bi(PO₄)₃:xEu³⁺. The energy transfer behavior in the phosphors was discussed. The Commission Internationale de lEclairage (CIE) chromaticity coordinates, the quantum efficiencies, and the decay curves of the entitled phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Bi(PO₄)₃ phosphors are promising orange reddish-emitting phosphors pumped by near-UV light.     

Sensitized red luminescence from Bi co-doped Eu: ZnO-B2O3 glasses

Photoluminescence properties of Bi³⁺ co-doped Eu³⁺ containing zinc borate glasses have been investigated and the results are reported here. Bright red emission due to a dominant electric dipole transition ⁵D₀→⁷F₂ of the Eu³⁺ ions has been observed from these glasses. The nature of Stark components from the measured fluorescence transitions of Eu³⁺ ions reveal that the rare earth ions could take the lattice sites of C_s or lower point symmetry in the zinc borate glass hosts. The significant enhancement of Eu³⁺ emission intensity by 346 nm excitation (¹S₀→³P₁ of Bi³⁺ ions) elucidates the sensitization effect of co-dopant. The energy transfer mechanism between sensitizer (Bi³⁺) and activator (Eu³⁺) ions has been explained.     

Effect of composition on the spontaneous emission probabilities, stimulated emission cross-sections and local environment of Tm in TeO2-WO3 glass

Effect of composition on the structure, spontaneous and stimulated emission probabilities of various 1.0 mol% Tm₂O₃ doped (1−x)TeO₂+(x)WO₃ glasses were investigated using Raman spectroscopy, ultraviolet-visible-near-infrared (UV/VIS/NIR) absorption and luminescence measurements.Absorption measurements in the UV/VIS/NIR region were used to determine spontaneous emission probabilities for the 4f-4f transitions of Tm³⁺ ions. Six absorption bands corresponding to the absorption of the ¹G₄, ³F₂, ³F₃ and ³F₄, ³H₅ and ³H₄ levels from the ³H₆ ground level were observed. Integrated absorption cross-section of each band except that of ³H₅ level was found to vary with the glass composition. Luminescence spectra of the samples were measured upon 457.9 nm excitation. Three emission bands centered at 476 nm (¹G₄→³H₆ transition), 651 nm (¹G₄→³H₄ transition) and 800 nm (¹G₄→³H₅ transition) were observed. Spontaneous emission cross-sections together with the luminescence spectra measured upon 457.9 nm excitation were used to determine the stimulated emission cross-sections of these emissions.The effect of glass composition on the Judd-Ofelt parameters and therefore on the spontaneous and the stimulated emission cross-sections for the metastable levels of Tm³⁺ ions were discussed in detail. The effect of temperature on the stimulated emission cross-sections for the emissions observed upon 457.9 nm excitation was also discussed.     

Luminescent studies of Dy ion in alkali lead tellurofluoroborate glasses

Dy³⁺-doped alkali lead tellurofluoroborate (RLTB) glasses (R=Li, Na and K) were prepared by melt quenching technique. Judd-Ofelt theory has been used to evaluate the three intensity parameters Ω₂, Ω₄ and Ω₆ from the experimental oscillator strengths. The photoluminescence spectra obtained by the excitation wavelength of 385 nm show four emission bands at 454, 483, 575 and 665 nm corresponding to the ⁴I_15/2→⁶H_15/2 and ⁴F_9/2→⁶H_J/2 (J=15/2, 13/2 and 11/2) transitions, respectively. The laser characteristic parameters like fullwidth at half maxima (FWHM), stimulated emission cross-sections (σ_e), optical gain parameters (σ_e×τ_exp) and gain bandwidth parameters (σ_e×FWHM) were determined. From the visible emission spectra, yellow to blue (Y/B) intensity ratios and chromaticity coordinates were also estimated. The lifetimes of ⁴F_9/2 metastable state were also measured and discussed.     

Thermal stability and spectroscopic properties of Er-doped lead fluorogermanate glasses

The thermal characterization and spectroscopic properties of Er³⁺-doped 0.6GeO₂-(0.4-x)PbO-xPbF₂ glasses were investigated experimentally. With the replacement of PbO by PbF₂ the thermal stability of glasses is improved and the infrared fluorescence intensity at 1530 nm is increased. The Judd-Ofelt intensity parameters, radiative transition rates, and fluorescence lifetimes of the excited ⁴I_13/2 level of Er³⁺ ions were calculated from Judd-Ofelt theory. The asymmetric ligand field around Er³⁺ ions resulted from the incorporation of PbF₂ into germanate glasses, broadens the infrared emission spectra at 1530 nm. Upconversion luminescence in the investigated glasses was observed at room temperature under the excitation of 976 nm laser diode. The glass 0.6GeO₂-0.3PbO-0.1PbF₂ exhibits the maximum upconversion emission intensity, while no frequency upconversion luminescence was observed in the 0.6GeO₂-0.4PbO glass. The quadratic dependence of the green and red emissions on excitation power indicates that two-photon absorption contributes to the visible emission under the 976-nm excitation.     

Synthesis and luminescence properties of europium doped YBa3B9O18

Europium (Eu³⁺) doped YBa₃B₉O₁₈ were synthesized by conventional solid state solidification methods. (Y_1−xEu_x)Ba₃B₉O₁₈ formed solid solutions in the range of x=0–1.0. The luminescence property measurements upon excitation in ultraviolet–visible range show well-known Eu³⁺ excitation and emission. The charge transfer excitation band of Eu³⁺ dominates the excitation spectra. The emission spectrum of Eu³⁺ ions consists mainly of several groups of lines in the 550–720 nm region, due to the transitions from the ⁵D₀ level to the levels ⁷F_J (J=0, 1, 2, 3, 4) of Eu³⁺ ions. The dependence of luminescence intensity on Eu³⁺ concentration shows no concentration quenching for fully concentrated EuBa₃B₉O₁₈. Eu³⁺ doped YBa₃B₉O₁₈ are promising phosphors for applications in displays and optical devices.