Electro-optical characterization of Ge–Se–Te glasses

Chalcogenide bulk glasses Ge₂₀Se_80−xTe_x for x(0,15) have been prepared by systematic replacement of Se by Te. Selected glasses have been doped with Ho, Er and Pr, and samples have been characterized by transmission spectroscopy, measurements of dc electrical conductivity and low-temperature photoluminescence. Absorption coefficients have been derived from measured transmittance and estimated reflectance. Arrhenius plots of dc electrical conductivity, in the measured temperature range 300–460 K, are characterized by single activation energies roughly equal to the half of the optical gap. Activation energies deduced from Arrhenius plots reveal a systematic decrease with increasing Te content. Similarly, both absorption and low-temperature photoluminescence spectra reveal shifts of absorption edge and/or dominant luminescence band to longer wavelength due to Te → Se substitution. Samples doped with Ho and Er exhibit a strong luminescence at 1200 and 1540 nm due to ⁵I₆ → ⁵I₈ and ⁴I_13/2 → ⁴I_15/2 transitions of Ho³⁺ and Er³⁺ ions, respectively. Pr doped samples exhibit only a relatively weak luminescence peak at 1590 nm, which we tentatively assign to ³F₃ → ³H₄ transition of Pr³⁺ ions. Absorption of the base glass luminescence at 1460 and 1520 nm has been observed at low temperature on samples doped with Pr and Er, respectively.     

Energy transfer studies of Ce:Eu system in phosphate glasses

The preparation of sodium phosphate glasses singly and doubly doped with rare earth ions Ce³⁺ and Eu³⁺ by melt quench method is described. The spectroscopic characterizations of the samples are done using absorption, excitation and emission spectra. The nonradiative energy transfer between trivalent cerium and europium is achieved through the phosphate lattice and the results are incorporated. The main reason of quenching of Ce³⁺ ions and the mechanism of energy transfer is mainly electric dipole-dipole in nature for Ce³⁺:Eu³⁺ system.     

Optical properties of PbSe quantum dots doped in borosilicate glass

PbSe quantum dots (QDs) were synthesized in borosilicate glass and their optical properties were investigated. The typical quantum confinement effects were clearly observed from the absorption when the average radii of the QDs changed from 1.7 to 3.1 nm. Photoluminescence from PbSe QDs was achieved in 1.1–2.2 μm wavelength region that covers the entire fiber-optic telecommunication window. Borosilicate glasses containing controlled size of PbSe QDs provide potentials for the fiber-optic amplifiers.     

Structural study of sol-gel silicate glasses by IR and Raman spectroscopies

A study of the structure and bonding configuration of sol-gel silicate glasses by Raman and infrared spectroscopies is presented. Moreover, a review of the Raman lines and infrared bands assignment, the identification of the non-bridging silicon-oxygen groups and the ring structures are also demonstrated. The evolution of the changes of the bonding configuration in the composition and the stabilization temperature of the bioactive glasses is discussed in terms of the structural and textural characteristics of the glasses. Raman and infrared analyses contribute to the improvement in understanding of the local symmetry for sol-gel silicate glasses. infrared spectroscopy has allowed to identify the vibration bands of the hydroxyl groups associated with various configurations of the terminal silanol bonds on the glass surface and the free molecular water in the glass matrix. Raman analysis has provided an alternative method of quantifying the network connectivity grade and predicting the textural properties of the sol-gel silicate glasses.     

Effect of X-ray irradiation on solarization and crystallization of photosensitive glasses containing Ce, Sb, Sn and Ag

The effect of X-ray irradiation on the solarization and crystallization of a lithium silicate glass was investigated in this research. The results showed that the X-ray power has a significant effect on the amount of solarization, and the crystallization temperature of the glass. Applying an X-ray power of 2400 W on glass containing the photosensitive elements of Ce, Sb, Sn and Ag led to reduction of the DTA crystallization peak temperature from 704 to 590 °C. UV spectroscopy showed that solarization of irradiated glasses containing Ce, Sb and Sn ions was responsible for formation of Ag clusters and reduction of crystallization temperature of glasses. Microstructural analysis also showed that the solarized glasses had a finer microstructure relative to that of the non-irradiated one. These differences attributed to changes in crystallization mechanism observed in the non-irradiated glass.     

Stark splitting of the ground state of Er in fluorozirconate glass at low temperature

Optical properties of Er³⁺-doped ZBLAN glass matrix have been studied by luminescence spectroscopy under 488 nm excitation. The spectrum of the ⁴S_3/2⁴I_15/2 transition, carried out at temperature T = 2 K, shows a new line in the lowest energy region. This new line, centered at 17 996 cm⁻¹, was attributed to the lower transition between the Stark components of the ⁴S_3/2⁴I_15/2 transition. Measurements from T = 2 K to room temperature show the disappearance of this new line. From the results we estimate the splitting of 415 cm⁻¹ for the ground state and 100 cm⁻¹ for the ⁴S_3/2 excited multiplet. The experimental result allows us to assign the positions of the eight Stark components of the ground state multiplet of the Er³⁺ in the ZBLAN glass matrix.     

Absorption and photoluminescence of PbS QDs in glasses

Optical properties of PbS quantum dots (QDs) precipitated inside the oxide glass matrix were investigated. Photoluminescence (PL) from the PbS QDs showed peak wavelengths located at 1170–1680 nm with widths of 150–550 nm. Radii of QDs in glasses were 2.3–4.7 nm depending upon the thermal treatment. Peak wavelengths of PL bands shifted as much as 70 nm as the temperatures and excitation irradiances increased. Calculated effective local temperatures indicated that these shifts of PL spectra were associated with local heating induced by the temperatures and laser beam.     

Peculiarities of photoluminescence excited by 157 nm wavelength F2 excimer laser in fused and unfused silicon dioxide

Photoluminescence (PL) spectra and kinetics of high purity amorphous silicon dioxide with ultra low hydroxyl content is studied under the excitation by F₂ excimer laser (157 nm wavelength) pulses. Materials synthesized in the SPCVD plasma chemical process are studied before and after fusion. Two bands are found in the PL spectra: one centered at 2.6–2.9 eV (a blue band) and the other at 4.4 eV (a UV band). Luminescence intensity of unfused material is found to increase significantly with exposure time starting from a very small level, whereas in fused counterpart it does not depend on irradiation time. Both bands show complicated decay kinetics, to which add exponential and hyperbolic functions. The UV band of the unfused material is characterized by decay with exponential time constant τ  4.5 ns and hyperbolic function t⁻ⁿ, where n = 1.5 ± 0.4. For the blue band the hyperbolic decay kinetics with n  1.5 extends to several milliseconds, gradually transforming to the exponential one with τ = 11 ± 0.5 ms. In fused glass relative contribution of the fast component to the UV band is small whereas for the blue one it is great, that allows one to more accurately determine the hyperbolic law factor n = 1.1 ± 0.1 typical for tunneling recombination. Simultaneous intracenter and recombination luminescence, the later occurring with the participation of laser radiation induced defects, add particular features to the decay kinetics. Spectra of the above luminescence processes are different. A less sharp position of bands is associated with the recombination luminescence. The origin of the observed PL features we attribute to the presence of oxygen deficient centers in glass network in the form of twofold coordinated silicon. Such centers being affected by network irregularities can be responsible for the recombination PL component. A great variety of network irregularities is responsible for centers’ structural inequivalence, which causes a non-uniform broadening of PL spectral and kinetic parameters.     

Structural and optical properties of 6CaO·6SrO·7Al2O3 thin films derived by sol-gel dip coating process

The nanostructured 6CaO·6SrO·7Al₂O₃ (C6S6A7) thin films with cubic structure using calcium, strontium metals, aluminium isopropoxide and ethylene glycol monomethyl ether as stating materials has been fabricated via sol-gel route. Based on hydrolysis of Ca²⁺, Sr²⁺ and Al³⁺ in the sol-gel processing using ethylene glycol monomethyl ether as solvent have been employed as the precursor material. The films were coated on soda lime float glass by the dip coating technique and annealed at 450 °C in air atmosphere. The structure, morphology and composition of the films were investigated by Fourier transformed infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy indicating that the films were composed of C6S6A7 nanoparticles with cubic structure. The spectral transmittance of the films was measured in the wavelength range of 200-1100 nm using an UV-visible spectrometer. It has been found that the optical properties of the films significantly affected by precursor chemistry and annealing temperature due to the improvement of the crystallinity of the films with increasing annealing temperature and became stable when the annealing temperature is higher than 450 °C. The C6S6A7 films annealed at 450 °C had high transparency about 80% in wide visible range.     

Effect of calcination temperature on the textural properties of 3 mol% yttria-stabilized zirconia powders

Zirconia-based ceramics have been commonly used in many different technological fields. This kind of materials have consequently received a great deal of attention. The main goal of this study was to investigate the effect of the calcination temperature on the morphological and textural properties of 3 mol% yttria-stabilized zirconia powders (3YSZ). Scanning electronic microscopy (SEM), nitrogen adsorption isotherms, thermogravimetry-differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy have been used with such an aim. Once the 3YSZ powders were dried at 100 °C they were subjected to calcination at 300, 500 or 700 °C. The calcination temperature noticeably influences the surface and textural properties of the 3YSZ powders. Textural parameters appear to be closely related to the removal of the alcohol used in the sol-gel synthesis procedure. The largest values of specific surface area and pore volumes correspond to samples prepared at 100 and 500 °C (i.e., 161 and 62 m²/g). In the first case, this fact is attributable to the removal of residual water and alcohol occluded within the powder particles whereas in the second case it may be due to the elimination of gases produced during the calcination stage.     

Fluorescence of copper, manganese and antimony ions in phosphate glass host

The paper presents a study based on luminescence characteristics of phosphate glasses containing Cu²⁺, Mn⁴⁺ and Sb³⁺. The glass samples obtained by a wet chemical route belong to Li₂O–BaO–Al₂O₃–La₂O₃–P₂O₅ oxide system. The oxide composition of the glass samples is calculated to obtain a vitreous network composed of metaphosphate chains bonded by modifier ions (Li⁺, Ba²⁺ and La³⁺) and fluorescent ions. The absorption spectra of the samples were acquired in the UV domain in order to establish the excitation wavelength for each fluorescent ion. The absorption peaks of Sb³⁺ ion are ranged at 285 nm and 250 nm, Mn²⁺ ion at 280 nm and 365 nm, Cu²⁺ ion at 295 nm and 313 nm. The luminescence peaks of Cu²⁺, Mn⁴⁺ and Sb³⁺ ions are found in the visible domain at different wavelengths, depending on the oxidation state and coordination symmetry of each fluorescent ion. The fluorescence of Sb³⁺ ion has a strong signal at 450 nm and a weak one at 465 nm, Mn²⁺ ion shows a fluorescence peak at 600 nm and the pair Cu²⁺/Cu⁺ ions reveals a fluorescence emission at 460 nm.     

Structural peculiarities, and electrical and optical properties of 70TeO2·30PbCl2 glasses doped with Pr, prepared in Pt or Au crucibles

The influence of crucibles (Au or Pt) on the structure, electrical, dielectric and optical properties of 70TeO₂·30PbCl₂ glasses doped with Pr³⁺ added as a metal, chloride, or oxide, in concentrations of 500–1500 wt-ppm, is reported. The dc conductivity of ‘pure’ glasses prepared in Au crucibles is two orders of magnitude higher than that of those prepared in Pt crucibles. Upon doping, the dc conductivity of glasses prepared in Pt and Au crucibles increases or decreases, respectively. The static relative permittivity is equal to 33 ± 2. In the range of 640–700 nm, six photoluminescence (PL) peaks were observed, at 641.5, 647.1, 652.4, 660.8, 662.9, and 664.5 nm. In the range of 200–1200 cm⁻¹, seven Raman scattering (RS) peaks were observed at 184, 217, 321, 468, 654, 735 cm⁻¹, and a small peak at 650 cm⁻¹. Both spectra were deconvoluted using symmetrical Gaussian functions. Relative intensities of PL and RS bands depend on the concentration and chemical form of Pr³⁺ and on the material of the crucible. However, positions of these bands are independent of these conditions.     

Local order and non-linear optical properties in bulk nanostructured niobiosilicate glasses

This communication presents and discusses an experimental proof of the correlation among local structure and second harmonic generation (SHG) in bulk nanostructured potassium niobiosilicate (KNS) glasses. In particular, SHG shows a maximum in correspondence of the early stages of nanostructuring, that are characterized by the segregation within the amorphous matrix of nanosized inhomogeneities. EXAFS experiments indicate that these inhomogeneities are determined by the maximum size reached by the niobium second coordination shell combined with the sudden inclusion of potassium atoms in it. Such rearrangement at the local level determines the maximum fluctuation of the bulk glass refractive index and in turn its maximum SHG activity.     

Fluorescence enhancement of europium complex co-doped with terbium complex in a poly(methyl methacrylate) matrix

The enhanced fluorescence of Eu(DBM)₃Phen(DBM: dibenzoylmethide; Phen: phenanthroline) by Tb(DBM)₃Phen in a poly(methyl methacrylate) (PMMA) has been studied. A combinatorial methodology was adopted to allow rapid optimization of the fluorescence enhancement conditions of thin-film samples in arrays of microwells. Based on Eu(DBM)₃Phen doped PMMA, three material libraries were generated in order to compare the effects of species identity and Tb(DBM)₃Phen content to the effect of other complexes containing enhancing ions (La³⁺, Gd³⁺, Dy³⁺, Y³⁺, Ce³⁺) on the luminescence efficiency of the Eu³⁺ complex in PMMA. The fluorescence enhancement of Eu(DBM)₃Phen in PMMA is considered to originate from intramolecular and intermolecular energy transfer processes.     

Spectroscopic and structural properties of Cr in silicate glasses: Cr does not probe the average glass structure

Cr³⁺-containing alkali, alkaline earth and mixed alkali-alkaline earth silicate glasses have been investigated using Cr K-edge extended x-ray absorption fine structure (EXAFS) and optical absorption spectroscopy. The local environment of Cr³⁺ appears similar in all glasses regarding EXAFS analysis, in particular for Cr-O distance (1.99 Å). By contrast, optical absorption spectra show variations of crystal field values and disorder effects with the nature of the modifier cation, revealing that some differences exist in the local surrounding of Cr³⁺ in glasses. In addition, in mixed alkali-alkaline earth glasses optical absorption parameters remain close to the values found in binary silicate glasses with the same alkali, which reveals a preference for alkalis in the surrounding of Cr³⁺. As a whole, these data show that Cr³⁺ is not probing the average glass structure and demonstrate its heterogeneous distribution at a local scale.     

Second harmonic generation studies of intrinsic and extrinsic relaxation dynamics in poly(methy1 methacrylate)

Second harmonic generation (SHG) is used to monitor the reorientation a dopant chromophore in slightly entangled poly(methy1 methacrylate) (PMMA). The effect of charge and temperature on both the decay and the much less studied onset modes of SHG signal at temperatures above the glass transition has been examined. At variance with the theoretical predictions, it is shown that the onset and the decay times are not coincident. An isothermal experiment above the glass transition shows a lengthening of relaxation time of the decay mode due to successive poling process, which is ascribed to charge memory effects. In contrast, the latter do not affect the onset characteristic time. The effect of temperature above the glass transition on dopant rotation and polymer relaxations has been also examined. As temperature increases the relaxation times of both the onset and the decay modes decrease. If the surface charge and the charge memory effect are erased, the decay time compares quite well with the structural relaxation time. Differently, the onset time exhibits a partial decoupling.     

Effect of method of preparation and drying time on photophysical properties of coumarin 1 laser dye embedded in HCl catalysed sol-gel glasses

Coumarin 1 (C1) dye is impregnated in transparent sol-gel glass samples prepared by sol-gel process using three methods - (I) using HCl as catalyst and glycerol as a drying control chemical additive (DCCA), (II) using HCl as catalyst at 60 °C subsequent drying at room temperature, and (III) using HCl as catalyst at 60 °C and heated at 600 °C for 3 h. The sol-gel matrices prepared by Methods I and II are given dip treatment with methanol/distilled water (50/50 volume) for 16 h before dipping into dye solution. The effect of method and drying time of matrix on spectroscopic properties of C1 dye doped glass samples has been studied. The optical density (OD) at absorption maximum wavelength and fluorescence intensity (FI) at fluorescence maximum wavelength of all C1 dye doped samples prepared by Methods I and II decrease, where as there is no change in photophysical properties (OD/FI) is observed in samples prepared by Method III with the time of drying of the sol-gel samples. These absorption/fluorescence properties of C1 dye in sol-gel glass matrices are compared with its respective properties in methanolic solution in acidic environment.     

Theoretical study on the electronic structures and spectral properties of two series of osmium(II) complexes with different substituent groups

Two series of osmium(II) complexes with different substituent groups (-CF₃, -N(CH₃)₂) have been studied by using the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, to investigate their electronic structures, absorption, and emission properties. The influence of different substituted groups on their photophysical properties has also been explored. The lowest energy absorption and emission wavelengths calculated are in good agreement with the available experimental values. Besides, ionization potential (IP), electron affinities (EA), and reorganization energy (λ) were calculated to evaluate the charge transfer and balance properties between hole and electron. It is expected that the theoretical studies could provide valuable information for the phosphorescent osmium(II) material for use in the organic light-emitting diodes.     

Effect of Bi2O3 proportion on physical, structural and electrical properties of zinc bismuth phosphate glasses

The variation in physical, structural and electrical properties has been studied as a function of Bi₂O₃ content in 20ZnF₂-(10 + x) Bi₂O₃-(70-x) P₂O₅, 0 ≤ x ≤ 10 mol% glasses, which were prepared by melt quenching technique and characterized by differential thermal analysis (DTA). Colorless samples, which have no absorption peaks, are obtained for 10 and 12 mol% of Bi₂O₃ and the glasses are slowly becoming brownish from 15 to 20 mol% of Bi₂O₃ which exhibit two absorption peaks at ~ 370 nm, ~ 450 nm correspond to Bi° transitions ⁴S_3/2 → ²P_3/2 and ⁴S_3/2 → ²P_1/2 respectively. The decrease in ³P₁ → ¹S₀ transition of Bi³⁺ photo luminescence emission for 18 and 20 mol% of Bi₂O₃ and increase in optical absorption area shows the reduction of Bi³⁺ to Bi°. From FTIR studies it is observed that an addition of Bi₂O₃ decreases the P―O―P covalent bond by forming P―O―Bi bonds due to high polarizing nature of Bi³⁺ ions. Dielectric parameters like ε', tan δ and a.c. conductivity σ_ac are found to increase and activation energy for a.c. conduction is found to decrease with the increase in the concentration of Bi₂O₃. Density of defect energy states is found to increase for higher concentration of Bi₂O₃ and is discussed according to quantum mechanical tunneling (QMT) model.     

Effect of denaturation of DNA on the molecular organization of a fluorescent dye in ultra thin films

Acridine Orange (AO) forms H-dimer in solid state and in ultra thin films. However, H dimer of AO reduces its efficiency as a usefull material for fluorescence probe. In the present work detailed investigations has been done on the interaction of AO with different forms of DNA in order to check the effectiveness in controlling the dimeric sites of AO in the Layer by Layer (LbL) self assembled film. It was found that single stranded DNA (ssDNA) is most effective than the dsDNA and coil-shaped DNA in controlling the dimeric sites of AO in LbL film.