Temperature dependence of the thermophysical properties of Neodymium doped borate glasses

We have experimentally measured the temperature dependence of the thermophysical properties of Nd₂O₃ doped borate glasses using a combination of the time resolved thermal lens technique with optical interferometry, thermal relaxation calorimetry and photoluminescence methods. Thermal diffusivity, thermal conductivity, fluorescence quantum efficiency, linear thermal expansion coefficient and thermal coefficient of the electronic polarizability were determined. The results showed the ability of these techniques to perform measurements very close to the glass transition region providing the absolute values of the measured physical quantities and the glass transition temperatures. In conclusion, it was observed that thermal lens and optical interferometry are advantageous methods for measurements as a function of temperature especially when low temperature scanning rate is required.     

Excited state characteristics of the Li2B4O7 and KLiB4O7 glasses activated by Cr3+ ions

The excited state characteristics by means of the excited state absorption (ESA), optical gain and bleaching spectra have been measured for prototype glasses with Li₂B₄O₇ (LBO) and KLiB₄O₇ (KLBO) compositions activated by Cr³⁺ ions. The work addressed to search for novel attractive media for broadband lasers and amplifiers, is a completion of detailed spectroscopic evaluation described in earlier papers. One of the examined materials (KLBO), in accordance with optimistic comments given in previous work, reveals a very broad gain spectrum in the near IR, which itself is interesting in view of very few reports on glasses showing optical gain for Cr³⁺ ions in the low-field local environment. The ESA/gain/bleaching spectra, registered with equipment of improved sensitivity, have been reproduced by calculations, and detailed single configuration coordinate diagram, based on experimental data, has been created for interpretation.     

Porphyrin based hybrid borate glasses: Structure and photophysical investigation

Freebase tetra phenyl porphyrin (H₂TPP) and its derivatives in different concentration ranges (0.5–2.0 mg per 12 g of boric acid) were incorporated into borate glass matrix by melt quenching technique at 230 °C. The formed glasses were stable and in green colour. The optical absorption and emission properties are different from that observed in solutions. The absorption spectrum shows a two line pattern Soret band at 435–454 nm and Q-band at 665–701 nm. The emission spectrum shows strong S₂ → S₀ emission at 490–520 nm region and S₁ → S₀ emission at 725–810 nm. The time resolved fluorescence decay of S₁ → S₀ emission shows three exponential decay. For example, in the case of 2 mg of H₂THP doped glass the lifetimes were found to be τ₁ = 0.511 ns (26.7%), τ₂ = 10 ps (64.68%) and τ₃ = 3.965 ns (8.62%). These unusual photophysical properties were found to arise from different structural motifs of porphyrin in the glass. These structures were further modeled through reactions of porphyrin with BF₃O(C₂H₅) in solution and DFT calculations.     

Optical properties of Ce-doped oxide glasses and correlations with optical basicity

A series of Ce³⁺-doped phosphate, borate, silicate and germanate glasses were prepared and their optical properties were investigated. Experimental observations on transmission and photoluminescence spectra show obvious Nephelauxetic effect depending on the optical basicity of glasses. Especially, addition of alkaline earth oxides as a substitution of glass network former contributes to the further red shifts of excitation and emission bands due to increases in the number of less polarized non-bridging oxygen ions which increase the optical basicity of the system.     

EPR,optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

Antimony phosphate glasses (SbPO) doped with 3 and 6 mol% of Cr³⁺ were studied by Electron Paramagnetic Resonance (EPR), UV–VIS optical absorption and luminescence spectroscopy. The EPR spectra of Cr³⁺-doped glasses showed two principal resonance signals with effective g values at g = 5.11 and g = 1.97. UV–VIS optical absorption spectra of SbPO:Cr³⁺ presented four characteristics bands at 457, 641, 675, and 705 nm related to the transitions from ⁴A₂(F) to ⁴T₁(F), ⁴T₂(F), ²T₁(G), and ²E(G), respectively, of Cr³⁺ ions in octahedral symmetry. Optical absorption spectra of SbPO:Cr³⁺ allowed evaluating the crystalline field Dq, Racah parameters (B and C) and Dq/B. The calculated value of Dq/B = 2.48 indicates that Cr³⁺ ions in SbPO glasses are in strong ligand field sites. The optical band gap for SbPO and SbPO:Cr³⁺ were evaluated from the UV optical absorption edges. Luminescence measurements of pure and Cr³⁺-doped glasses excited with 350 nm revealed weak emission bands from 400 to 600 nm due to the ³P₁ → ¹S₀ electronic transition from Sb³⁺ ions. Cr³⁺-doped glasses excited with 415 nm presented Cr³⁺ characteristic luminescence spectra composed by two broad bands, one band centered at 645 nm (²E → ⁴A₂) and another intense band from 700 to 850 nm (⁴T₂ → ⁴A₂).     

Thermal precipitation of silver nanoparticles and thermoluminescence in tellurite glasses

Silver metal and/or oxide precipitation of nanoparticles in thermally treated Ag-doped tellurite glasses was studied by optical absorption (OA) and transmission electron microscopy (TEM). The Lorentzian adjusted silver nanoparticles plasma resonance OA band was compared to the Drude model approach. The silver nanoparticles size distribution on the surface rather than in the bulk was determined by TEM. A model for the metallic silver precipitation is proposed. The characterization of the formation of silver nanoparticles was carried out with differential thermal analysis (DTA) to determine the glass transition temperature (Tg) and of crystallization (Tc). Previously γ-irradiated samples exhibited thermoluminescence (TL) peaks and the defect centers TeOHC, NBOHC and TeEC were identified by electron paramagnetic resonance (EPR), but no Ag⁰ signal was detected. The silver nanoparticles are known to introduce desired third-order optical nonlinearities in the composites, at wavelengths close to the characteristic surface-plasmon resonance of the metal precipitates. An increase of the glass density and refractive index with increasing AgNO₃ content was observed.     

Spectroscopic properties of Sm-containing yttrium-aluminoborate glasses and analogous huntite-like polycrystals

Sm_xY_1–xAl₃(BO₃)₄ polycrystals with huntite structure and glasses of system (mol %) 12.5 (Sm_xY_1–x)₂O₃–37.5Al₂O₃–50B₂O₃ with identical composition have been synthesized by solid state reaction and by melting process, respectively in order to compare light-emission and nonradiative energy transfer mechanisms in the two systems. The data have been analyzed to determine the concentration-dependent quantum yield of the Sm³⁺ luminescence as well as multipolarity and macro- and microparameters of the Sm–Sm interaction. The results show that the structure of the huntite cation lattice is preserved by passing from polycrystals to glasses, with an increase in the Sm–Sm minimum distance from 0.59 to 0.67 nm. At activator concentration ≤1 × 10²⁰ cm⁻³, the luminescence quantum yield in glass is higher than in polycrystals. The result turns out to be related to the partial substitution in glass by BO₄ groups of the trigonal BO₃ groups, which are responsible in crystalline Sm_xY_1–xAl₃(BO₃)₄ for efficient intracenter non-radiative energy exchange from the metastable excited ⁴G_5/2 state to phonon excitations.     

Spectroscopic and structural investigations of Er doped zinc bismuth borate glasses

Erbium doped glasses having composition 20ZnO·xBi₂O₃·(79.5 − x)B₂O₃ (15 ≤ x ≤ 35, x in mol%) were prepared by melt-quench technique. The spectroscopic properties were investigated using optical absorption and fluorescence spectra. The Judd–Ofelt intensity parameters, Ω_λ (λ = 2, 4, 6) were determined from the spectral intensities of absorption bands in order to calculate the radiative transition probability (A_R), radiative life time (τ_R), branching ratio (β_R) for various excited luminescent states. Using the emission spectra, full width at half maximum (FWHM), stimulated emission cross-section (σ_e) and figure of merit (FOM) were evaluated. The high values of Judd–Ofelt parameters indicate a substantial mixing of other electronic configuration into the 4f^N configuration by the random crystal field in the glasses. All the intensity parameters (Ω_λ) decrease with increase in Bi₂O₃ content and the effect is found to be most pronounced for Ω₂ values. The structural investigations of the glasses were carried out by recording the IR transmission spectra. A correlation between the network forming units with the multi-phonon relaxation rate and hence with the possibility of radiative quantum efficiency has been made. In addition, various physical and optical parameters have been determined from the measured density and refractive index values.     

Spectroscopic investigations and physical properties of Mn doped mixed alkali zinc borate glasses

Spectroscopic investigations on Mn²⁺ doped 20ZnO + xLi₂O + (30−x)Na₂O + 50B₂O₃ (5 ≤ x ≤ 25) (ZLNB) glasses reveal the non-linear behavior in their physical and structural properties. FT-IR spectra of ZLNB glasses reveal diborate units in the borate network. EPR spectra exhibit characteristic resonance signals of Mn²⁺ ions. A well resolved six line hyperfine structure around g = 2.02 corresponds to the sites of Type II, and a weak broad shoulder around g = 2.7 followed by an unresolved intense signal at g = 4.25 corresponding to sites of Type I are observed for their respective transitions. A large value of zero-field splitting parameter (D) is observed and it behaves non-linearly, reaches a maximum at x = 15 mol% with increase in Li₂O content. Δg values reveal the ionic nature of glass systems. Optical absorption spectra suggest the distorted octahedral site symmetry of Mn²⁺ ions in the host. Mixed alkali effect is evident in bandgap and Urbach energies.     

Influence of MO/MF2 modifiers (M = Ca,Sr, Ba) on spectroscopic properties of Eu3+ ions in germanate and borate glasses

Series of Eu³⁺-doped lead-free germanate and borate glasses were synthesized. The MO glass modifiers (M = Ca, Sr or Ba) were partially or totally substituted by MF₂ in chemical composition. In contrast to samples modified by CaO/CaF₂ or SrO/SrF₂, the germanate glass samples containing BaO and/or BaF₂ are fully amorphous, while the lead-free borate glasses are fully amorphous, independently from glass modifiers. Effect of glass modifiers on spectroscopic properties of Eu³⁺ were systematically investigated.For that reason, excitation and emission spectra of Eu³⁺ ions in examined systems were registered. Based on the emission spectra, ratio of integrated luminescence intensity of the ⁵D₀ → ⁷F₂ transition to that of the ⁵D₀ → ⁷F₁ transition (R factor) was calculated. Moreover, the luminescence decay curves were collected and the luminescence lifetimes of the ⁵D₀ excited state of Eu³⁺ ions were determined in function of MF₂ concentration.     

Spectroscopic properties of Pr3+ and Er3+ ions in lead-free borate glasses modified by BaF2

Lead-free oxyfluoride borate glasses singly doped with Pr³⁺ and Er³⁺ were prepared and next investigated using absorption and luminescence spectroscopy. In the studied glass system, barium oxide was substituted by BaF₂. Two luminescence bands of Pr³⁺ located at visible spectral region are observed, which correspond to ³P₀–³H₄ (blue) and ¹D₂–³H₄ (reddish orange) transitions, respectively. The luminescence bands due to ¹D₂–³H₄ transition of Pr³⁺ are shifted to shorter wavelengths, when BaO was substituted by BaF₂. Near-infrared luminescence spectra of Er³⁺ ions in lead-free borate glasses modified by BaF₂ correspond to ⁴I_13/2–⁴I_15/2 transition. Their spectral linewidths increase with increasing BaF₂ concentration. The changes in measured lifetimes of rare earth ions are well correlated with the bonding parameters calculated from the optical absorption spectra.     

Spectroscopic properties of Yb in heavy metal contained fluorophosphate glasses

A new series of 20Bi(PO₃)₃–10Sr(PO₃)₂–35BaF₂–35MgF₂ doped with Yb³⁺ is introduced for fiber and waveguide laser applications. The stimulated emission cross-section σ_emi, which was found to be 1.37 pm² at the lasing wavelength of 996 nm, is the highest one among fluorophosphate glasses. It has been found that an extremely high gain coefficient of G = 1.65 ms pm⁴ and high quantum efficiency of η = 93% for 1 wt.% Yb₂O₃ doped systems. The various concentration effects on laser performance properties including minimum pumping intensity I_min, the minimum fraction of excited ions β_min and the saturation pumping intensity I_sat are analyzed as a function of Yb₂O₃ concentration. Those results obtained in current system had advantage over some fluorophosphate glasses reported.     

Infrared spectra of zinc doped lead borate glasses

The infrared spectra of zinc-doped lead borate glasses (10–30 mol% ZnO) were measured over a continuous spectral range (400–4000 cm⁻¹) in an attempt to study their structure systematically. No boroxol ring formation was observed in the structure of these glasses. The formation of Zn in tetrahedral coordination was not observed. The conversion of three-fold to four-fold coordinated boron took place.     

Composition dependence of electrical properties of ZnF2-MO-TeO2 glasses

Dielectric constant (ε′), loss (tan δ), a.c. conductivity (σ) of ZnF₂-MO-TeO₂ glasses with varying concentrations of MO (P₂O₅, As₂O₃ and Bi₂O₃) were measured as a function of frequency and temperature over moderately wide ranges. From the analysis of these studies along with IR spectra and DTA results of these glasses, the structural changes in the systems with the concentration of metal oxides are discussed.     

Composition and concentration dependence of spectroscopic properties of Nd-doped tellurite and metaborate glasses

The spectroscopic properties of tellurite glasses of composition (in mol%) TNKNd: (70 − x)TeO₂-15Nb₂O₅-15K₂O-xNd₂O₃ (x = 0.1, 1.0, 1.5, 2.0 and 2.5) and TNLNd10: 69TeO₂-15Nb₂O₅-15Li₂O-1.0Nd₂O₃ and lithium metaborate glass of composition LBNNd10: 89LiBO₂-10Nb₂O₅-1.0Nd₂O₃ have been investigated using absorption and emission spectra and decay curve analysis. An energy level analysis has been carried out considering the experimental energy positions of the absorption and emission bands, using the free-ion Hamiltonian model. The spectral intensities have been calculated by using the Judd-Ofelt theory and in turn the radiative properties such as radiative transition probabilities, emission cross-sections, branching ratios and radiative lifetimes have been estimated. The decay curves at the lower concentrations are exponential while they show a non-exponential behavior at higher concentrations (?1.0 mol%) due to energy transfer processes. The effective lifetimes for the ⁴F_3/2 level are found to decrease with increase in Nd₂O₃ concentration for all the glasses under investigation. The non-exponential decay curves have been well-fitted to the Yokota-Tanimoto model with S = 6, indicating that the nature of energy transfer is of dipole-dipole type and energy migration also plays an important role. The results obtained have been compared with Nd³⁺-doped phosphate, fluorophosphate, lead borate, tellurite, germanate and silicate glasses and Nd³⁺-doped YAG ceramic and Ca₂Nb₂O₇ crystals.     

Optical properties of (1-x-y)B2O3-xLi2O-yMCI2 (M=Cd, Zn) glasses

Optical absorption and transmission spectra of (1-x-y)B₂O₃-xLi₂O-yMCI₂ (M=Cd, Zn) glasses of varying compositions were recorded in the UV-visible region. From the spectra, various optical parameters such as optical energy gap (E _opt), refractive index (n), optical dielectric constant (ɛ′), width of the tail of localized states in the forbidden gap (ΔE), ratio of carrier concentration to the effective mass (N/m*) and the constantB were evaluated. The effects of composition of glasses on these parameters are discussed.     

Optical properties of oxide glasses containing transition metals: Case of titanium- and chromium-containing glasses

One of the major driving forces for the development of new glasses is the demand for high optical non-linearity with reduced cost and a higher damage resistance. Oxide glasses with large non-linear refractive index and non-linear absorption coefficient are promising materials for fiber telecommunication and for non-linear optical devices such as ultrafast optical switches, power limiters, real time holography, self-focusing, white-light continuum generation and photonic applications. To get insight into the optical absorption in amorphous materials, studies are still needed for revealing the nature of photoelectronic excitations in these materials by comparison with that in crystals which have been understood firmly based on band theory. Although the IR absorption loss in oxide glasses is larger than of fluorides, low light scattering loss is expected in these oxide glasses because they have lower glass transition temperature. In addition, small concentration of dopant such as alkaline metal and alkaline earth metal elements gives rise to the structural relaxation of the frozen-in density fluctuations even below glass transition temperature T_g, adding to the reduction of T_g as well. A review of the fundamentals and recent research advances in optical properties of oxide glasses containing chromium or titanium is presented.     

Microhardness study of (1-x-y)(B2O3)-x(Li2O)-y(MCI2), (M=Cd, Zn) glasses

Results of microhardness measurements on (1-x-y)(B₂O₃)-x(Li₂O)-y(MCI₂), (M=Cd, Zn) glasses, in the applied load range 25–500 g, are presented. The microhardness was found to decrease with increase in load up to 50 g, then it increased and finally attained a practically constant value with increase in load. The effects of composition of the glasses on microhardness are discussed.     

Optical absorption of Nd, Sm and Dy in bismuth borate glasses with large radiative transition probabilities

This paper reports on the optical properties of Nd³⁺, Sm³⁺ and Dy³⁺ in bismuth borate glasses, with Bi₂O₃ content varying from 30 to 60 mol%. The variation of the optical properties with composition plays a dominant role in determining a good laser host material. The variation of the Judd–Ofelt intensity parameters Ω_t (t=2,4,6) and the radiative transition probabilities and the hypersensitive band positions, with composition, have been discussed in detail. The changes in position and intensity parameters of the transitions in the optical absorption spectra are correlated to the structural changes in the host glass matrix. The variation of Ω₂ with Bi₂O₃ content has been attributed to changes in the asymmetry of the ligand field at the rare earth ion site and to the changes in their rare earth–oxygen (R–O) covalency, whereas the variation of Ω₆ strongly depends on nephlauxetic effect. The shift of the hypersensitive band shows that the covalency of the R–O bond increases with increase of Bi₂O₃ content, due to increased interaction between the rare earth ions and the non-bridging oxygens. The radiative transition probabilities of the rare earth ions are large in bismuth borate glasses, suggesting their suitability for laser applications.     

Study on optical weak absorption of borate crystals

Borate crystal is an important type of nonlinear optical crystals used in frequency conversion in all-solid-state lasers. Especially, LiB₃O₅ (LBO), CsB₃O₅ (CBO) and CsLiB₆O₁₀ (CLBO) are the most advanced. Although these borate crystals are all constructed by the same anionic group-(B₃O₇)⁵⁻, they show different nonlinear optical properties. In this study, bulk weak absorption values of three borate crystals have been studied at 1064 nm by a photothermal common-path interferometer. The bulk weak absorption values of them along [1 0 0], [0 1 0] and [0 0 1] directions were obtained, respectively, to be approximately 17.5 ppm cm⁻¹, 15 ppm cm⁻¹ and 20 ppm cm⁻¹ (LBO); 80 ppm cm⁻¹, 100 ppm cm⁻¹ and 40 ppm cm⁻¹ (CBO); 600 ppm cm⁻¹, 600 ppm cm⁻¹ and 150 ppm cm⁻¹ (CLBO) at 1064 nm. The results showed an obvious discrepancy of the values of these crystals along three axis directions. A correlation between the bulk weak absorption property and crystal intrinsic structure was then discussed. It is found that the bulk weak absorption values strongly depend on the interstitial area surrounded by the B–O frames. The interstitial area is larger, the bulk weak absorption value is higher.