Spectroscopic and photoluminescence characteristics of Dy ions in lead containing sodium fluoroborate glasses for laser materials

Lead containing calcium zinc sodium fluoroborate (LCZSFB) glasses doped with different concentrations of trivalent dysprosium ions were prepared and investigated by the XRD, FTIR, optical absorption, photoluminescence and decay curve analysis. The experimentally determined oscillator strengths have been determined by measuring the areas under the absorption peaks and the Judd–Ofelt (J–O) intensity parameters were calculated using the least squares fit method. From the evaluated J–O parameters the radiative transition probability rates, radiative lifetimes and branching ratios were calculated for ⁴F_9/2 excited level. Room temperature photoluminescence spectra for different concentrations of Dy³⁺-doped LCZSFB glasses were obtained by exciting the glass samples at 386 nm. The intensity of Dy³⁺ emission spectra increases with increasing concentration of 0.1, 0.25, 0.5 and 1.0 mol% and beyond 1.0 mol% the concentration quenching is observed. The measuring branching ratios are reasonably high for transitions ⁴F_9/2→⁶H_15/2 and ⁶H_13/2, suggesting that the emission at 484 and 576 nm, respectively, can give rise to lasing action in the visible region. From the visible emission spectra, yellow–blue (Y/B) intensity ratios and chromaticity color coordinates were also estimated. The lifetimes of ⁴F_9/2 metastable state for the samples with different concentrations were also measured and 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.     

Fluorescence characteristics of Dy ions in calcium fluoroborate glasses

Calcium fluoroborate (CFB) glasses doped with different concentrations of trivalent dysprosium ions were prepared and investigated by the FTIR, optical absorption, photoluminescence and decay analysis. Free-ion Hamiltonian model and Judd-Ofelt theory have been used to analyze the energy level scheme and the spectral intensities of Dy³⁺ ions in CFB glasses. From the emission spectra it is observed that the samples emit intense light yellowish color which is nearer to white light. Chromaticity color coordinates have been calculated and the dominant emission wavelength has also been indicated. Decay curves of ⁴F_9/2 level for the samples with different concentrations have been analyzed using the Inokuti-Hirayama model and the energy transfer and non-radiative decay rates have been determined.     

Spectral studies of Erbium doped heavy metal borophosphate glass systems

The ternary lead bismuth magnesium borophosphate glass system (LBMBPE) with molar concentrations of (50-x) PbO-xBi₂O₃-25MgHPO₄-24B₂O₃-1Er₂O₃ (x=10, 20, 30 and 40) was prepared using Melt quenching technique. The amorphous nature of these glass samples were confirmed with XRD studies, The spectral data from the optical absorption studies was employed to compute the spectroscopic parameters such as Racah coefficients (E¹, E² and E³), spin-orbit coupling (ξ_4f), configuration interaction factor (α) and Judd-Ofelt intensity parameters (Ω_λ, λ=2, 4 and 6). The IR spectra exhibit the presence of vibrational modes of phosphates, borate radicals, bismuth, lead and magnesium ions. The Judd-Ofelt parameterization indicates the covalency and vibrationonic frequencies of the ligands with rare earth ions. The radiative parameters such as radiative transition probabilities (A), the total radiative transitional probabilities (A_T), radiative life times (τ_R), branching ratios (β) and absorption cross sections (∑) were computed for certain lasing levels. The effect of compositional changes on the optical band gap is also reported. The glass systems thus developed indicate their potential lasing candidature.     

Absorption and emission spectral studies of Sm and Dy doped alkali fluoroborate glasses

Absorption and photoluminescence spectra of Sm³⁺ and Dy³⁺ doped alkali fluoroborate glasses of the composition 90.5% B₂O₃+4% AlF₃+5% MF+0.5% LnF₃ (M=Li, Na, K and Ln=Sm, Dy) have been reported. On excitation, with , the Sm³⁺ glasses are found to be orange fluorescent in color and richness of that color is high in the Na+ glass, compared to Li⁺ and K⁺ glasses. Similarly, on excitation with , the Dy³⁺ glasses are fluorescent yellow in color and that color is richer in the K⁺ glass.     

Composition dependent structural and optical properties of Sm-doped sodium borate and sodium fluoroborate glasses

Sodium borate and fluoroborate glasses doped with trivalent samarium (Sm³⁺) were prepared and their detailed spectroscopic analysis was carried out. The FTIR spectra reveal that, the glasses contain BO₃, BO₄, non-bridging oxygen and strong OH⁻ bonds. From the optical absorption spectra, Judd-Ofelt intensity parameters (Ω_λ, λ=2, 4 and 6) have been evaluated and are in turn used to predict radiative properties such as radiative transition probability (A), stimulated emission cross section () and branching ratios (β_R) for the excited levels of Sm³⁺ ions in sodium borate and sodium fluoroborate glasses. The dependence of the spectral characteristics of Sm³⁺ ions due to compositional changes have been examined and reported. The value is found to decrease with the decrease in the sodium content in the glass. The decay from the ⁴G_5/2 level is found to be non-exponential indicating a cross-relaxation among the Sm³⁺ ions.     

Mechanisms of fluorescence enhancement in rare earth sol-gel glass containing Al

Analysis of glasses containing Eu and Tb dopants yields new insights about the role of Al³⁺ co-doping in improving fluorescence yield of glasses containing rare earth (RE) dopants. Our work suggests that Al co-doping enhances fluorescence by two important mechanisms. (1) At low Al:RE ratio the site symmetry is lowered, allowing more admixture of opposite parity wavefunctions and increased transition probability. (2) At high Al:RE ratio, the highest frequency phonons are of lower energy; so nonradiative decay rates are reduced. In addition, a new technique - post-annealing immersion - is introduced, which allows the study of RE location in the sol-gel matrix. Al co-doping is observed to increase the tendency for RE ions to reside on pore surfaces.     

In situ-monitored enhancement and quenching effect of Cu nanoclusters on Sm3+ photoluminescence in glass

An assessment of the influence of heat treatment temperature and retention time on the optical properties of a Cu⁺ and Sm³⁺ co-doped phosphate glass of interest to photonic applications is reported. Particularly, the enhancement of the orange-red photoluminescence (PL) from Sm³⁺ ions has been realized in the glass through the development of non-plasmonic Cu clusters. It was exposed during an in situ isothermal treatment wherein optical absorption and PL were monitored together in real time. Following the PL increase, a drop in the Sm³⁺ emission intensity was produced concurring with the appearance of Cu nanoparticles (NPs) exhibiting the surface plasmon resonance. Hence, the connection between energy donor (sensitizing) effects of small Cu clusters and the energy acceptor (quenching) character of Cu NPs is supported. It is the first time to the author's knowledge that the enhancement of Sm³⁺ luminescence via Cu clusters embedded in glass is indicated.     

Luminescence properties of Tb doped and Tm/Tb/Sm co-doped glasses for LED applications

Tb³⁺ ions doped and Tm/Tb/Sm co-doped glasses for light-emitting-diodes (LED) applications have been synthesized by melt quenching method. Their photoluminescence properties were studied by emission and excitation spectra. The ⁵D₃ and ⁵D₄ emission of Tb³⁺ can be varied by adjusting Tb³⁺ concentrations and the compositions of glass matrix. Blue, green and reddish orange emission bands were observed in the emission spectra of Tm/Tb/Sm co-doped glasses. The combination of these emission bands allows the realization of white light when the glasses are excited by near ultraviolet light. In addition, the relative intensity ratios of respective emission lines are dependent on the composition of glasses and the excitation wavelength.     

EPR and optical absorption studies of Fe ions in sodium borophosphate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectral investigations have been carried out on Fe³⁺ ions doped sodium borophosphate glasses (NaH₂PO₄-B₂O₃-Fe₂O₃). The EPR spectra exhibit resonance signals with effective g values at g=2.02, g=4.2 and g=6.4. The resonance signal at g=4.2 is due to isolated Fe³⁺ ions in site with rhombic symmetry whereas the g=2.02 resonance is due to Fe³⁺ ions coupled by exchange interaction in a distorted octahedral environment. The EPR spectra at different temperatures (123-295 K) have also been studied. The intensity of the resonance signals decreases with increase in temperature whereas linewidth is found to be independent of temperature. The paramagnetic susceptibility (χ) was calculated from the EPR data at various temperatures and the Curie constant (C) and paramagnetic Curie temperature (θ_p) have been evaluated from the 1/χ versus T graph. The optical absorption spectrum exhibits bands characteristic of Fe³⁺ ions in octahedral symmetry. The crystal field parameter (Dq) and the Racah interelectronic repulsion parameters (B and C) have also been evaluated and discussed.     

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.     

Spectroscopic properties of Sm3+ ions in lead fluorophosphate glasses

The Sm³⁺-doped lead fluorophosphate glasses of composition 44P₂O₅–17K₂O–9Al₂O₃–(24?x)PbF₂–6Na₂O–xSm₂O₃, where x=0.01, 0.05, 0.1, 0.5, 1.0 and 2.0 mol%, have been prepared by conventional melt quenching technique and are characterized through differential thermal analysis, Raman, absorption and emission spectra and decay rate measurements. Free-ion Hamiltonian model for energy level analysis and Judd–Ofelt theory for spectral intensities have been used to analyze the spectroscopic properties of Sm³⁺ ions in lead fluorophosphate 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 turn 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 2.54 to 0.92 ms when the concentration increased from 0.01 to 2.0 mol% Sm₂O₃ due to energy transfer. 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, which indicates that the energy transfer process is of dipole–dipole type.     

一种新型稀土配合物Tb(m-benzoicacid)3的发光特性的研究

研究了一种新型稀土配合物发光材料 ,对苯甲酸铽Tb(m benzoicacid) 3 的发光特性。以这种材料为掺杂剂 ,聚乙烯咔唑 (PVK)为基质材料制备了薄膜器件。通过对光谱的研究 ,发现在掺杂体系中 ,PVK与Tb(m benzoicacid) 3 之间存在有效的能量传递 ,能量传递效率与铽配合物的掺杂浓度有关 ,随着Tb配合物的掺杂浓度的增加 ,Tb的特征发光在掺杂体系中所占比重也相应增加 ,而PVK的发光相对明显减弱 ,当Tb(m benzoicacid) 3 :PVK的质量比高于 2 0 %时 ,整个体系的发光变为以Tb的发光为主 ,而PVK的发光基本猝灭了。以PVK :Tb(m benzoicacid) 3 掺杂体系为发光层 ,八羟基喹啉铝 (Alq)为电子传输层 ,制备了双层电致发光器件 ,器件的结构为ITO/PVK :Tb(m benzoicacid) 3 /Alq/LiF/Al,该器件的电致发光为三价铽离子的特征发光 ,在 2 1V的电压下 ,亮度可达 311nt。     

Compositional-dependent lead borate based glasses doped with Eu ions: Synthesis and spectroscopic properties

New multicomponent lead borate based glasses with various PbO/B₂O₃ weight ratio were prepared. The glass samples were analyzed in detail by using Raman and IR absorption spectroscopy. Optical properties of Eu³⁺ ions have been investigated in lead borate based systems, in which PbO/B₂O₃ weight ratios were changed from 1:2 to 8:1 in glass composition. The values of the phonon energy of the host and ⁵D₀ lifetime of Eu³⁺ decrease, whereas absorption and emission intensities, as well as bonding parameter increase with increasing PbO concentration. Additionally, spectral lines are shifted in direction to the lower frequency region. Non-monotonic dependence of the fluorescence intensity ratio R (⁵D₀-⁷F₂/⁵D₀-⁷F₁) upon PbO/B₂O₃ content has been observed in contrast to bonding parameter that is also non-linear but monotonic. Some structural and spectroscopic aspects for Eu-doped lead borate based glasses are presented.     

Investigation on luminescence properties of Nd ions in alkaline-earth titanium phosphate glasses

Nd³⁺ ions doped alkaline-earth titanium phosphate glasses were prepared by using the conventional melt quenching method. Absorption spectra were recorded and oscillator strengths of the transitions were calculated using area under the absorption bands. The energy level analysis was carried out by using free-ion Hamiltonian model. The three host dependent Judd-Ofelt intensity parameters, Ω_λ (λ = 2, 4, and 6) were used to elucidate the structure of glassy matrix around Nd³⁺ ion as well as to determine the ⁴F_3/2 metastable state radiative properties such as radiative transition probabilities, branching ratios and radiative lifetimes. The decay curves of all the three glasses show single exponential behavior. The discrepancy between the experimental and calculated lifetimes of emitting level was attributed to multiphonon relaxation. The achieved high quantum efficiencies for the ⁴F_3/2 level indicate efficient laser emission at 1.06 μm in these glass systems.     

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.     

Composition dependent structural and optical properties of Sm doped boro-tellurite glasses

Boro-tellurite glasses with the composition (69-x)H₃BO₃+xTeO₂+15MgCO₃+15K₂CO₃+1Sm₂O₃ (where x=0, 10, 20, 30 and 40 wt%) doped with trivalent samarium have been prepared and their structural and spectroscopic behavior were studied and reported. The FTIR spectra reveal the presence of BO₃ and BO₄ non-bridging oxygen as well as strong OH⁻ bonds in the prepared glasses. Through the optical absorption spectra, Judd-Ofelt intensity parameters (Ω_λ, λ=2, 4 and 6) have been evaluated and the same is in turn used to predict radiative properties such as radiative transition probability (A), stimulated emission cross-section () and branching ratios (β_R) for the excited levels of Sm³⁺ ions corresponding to ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2, ⁴G_5/2→⁶H_9/2 and ⁴G_5/2→⁶H_11/2 transitions. Structural and spectral dependence of the Sm³⁺ ions due to the compositional changes have been examined and reported. The lifetime of the ⁴G_5/2 level is found to be non-exponential for all the prepared glasses indicating a cross-relaxation among the Sm³⁺ ions. The structural and spectroscopic results corresponding to compositional changes have been compared with the similar studies and reported.     

The anisotropy of fluorescence in ring units

The time dependence of the anisotropy of fluorescence after an impulsive excitation in the ring unit (resembling the B850 ring of the purple bacterium Rhodopseudomonas acidophila) is calculated. Fast fluctuations of the environment are simulated by dynamic disorder and slow fluctuations by static disorder. Both types of disorder are taken into account simultaneously. Without dynamic disorder modest degrees of static disorder are sufficient to cause the experimentally found initial drop of the anisotropy on a sub-100 fs time scale. Two different models of the spectral density J(ω) of phonons have been often used in the literature to describe influence of the bath. The spectral density J(ω) enters the non-Markovian dynamical equations for the one exciton density matrix (entering the time dependence of the anisotropy of fluorescence). The spectral density J(ω) with high-energy tail leads to faster anisotropy decay.