Effects induced by 4.7 eV UV laser irradiation on pure silica core multimode optical fibers investigated by in situ optical absorption measurements

We investigated by in situ optical absorption measurements the effects induced by 4.7 eV UV laser irradiation on pure silica core optical fibers. Laser irradiation with 100 MW cm^? 2 laser intensity generates in the fiber E′ centers which partially decay after irradiation due to their reaction with diffusing H₂. An absorption band peaked at 5.3 eV is observed to grow in the post-irradiation stage with a kinetics anti-correlated to the decay of the 5.8 eV band of the E′ centers. The defect absorbing at 5.3 eV is proposed to be formed by trapping on pre-existing precursors of hydrogen atoms made available by breaking of H₂ on E′. We also show by repeated irradiation experiments that the 5.3 eV-absorbing center is photochemically destroyed by 4.7 eV laser light, and we estimate the cross section of this process. Possible structural models for this defect are discussed.     

Optical properties of Ge–Se–Te wedge-shaped films by using only transmission spectra

Amorphous Ge₁₀Se_90?xTe_x (with x = 0, 5, 10 and 15 at.%) thin films were prepared by thermal evaporation method. The optical transmission spectra of these films were measured in the wavelength range of 500–2500 nm in order to drive the refractive index and the absorption coefficient of these films. Applying the analytical expressions proposed by Swanepoel, enabling the calculations of optical constants of thin films with non-uniform thickness with high accuracy. Furthermore, the dispersion of the refractive index is discussed in terms of the single-oscillator Wemple and DiDomenico model. It was found that, the mechanism of the optical absorption follows the rule of the allowed non-direct transition. The optical band gab, E_g, and the oscillator energy, E_o, decrease while the dispersion energy, E_d, increases by increasing Te content. The relationship between the obtained results and the chemical compositions of the Ge₁₀Se_90?xTe_x thin films were discussed in terms of the chemical bond approach, the excess of Se–Se homopolar bonds and the cohesive energy (CE).     

Structure and optical properties of amorphous GeSx films prepared by PLD

Amorphous GeS_x (x = 2, 4, 6) films were prepared by the pulsed laser deposition (PLD) technique. The optical band gaps (E_g^opt) and refractive indices of the films were obtained from the optical absorption spectra and transmission spectra, respectively. The short-wave absorption edges of the films were described using the ‘non-direct transition’ model proposed by Tauc. The dispersion of the refractive index was analyzed in terms of the single-oscillator Wemple–Di Domenico model. The structural units of the films were characterized using Raman spectroscopy. In addition to the basic structural units of edge-sharing and corner-sharing [GeS₄] tetrahedra, there are S–S homopolar bonds in S-rich GeS₄ and GeS₆ films while Ge–Ge bonds exist in stoichiometric GeS₂ film. The results show that the index of refraction decreases while E_g^opt increases with the sulphur content in the GeS_x films. The changes of E_g^opt were discussed in relation to the structure of GeS_x films, which were confirmed by the Raman spectra analysis.     

Optical studies of aromatic polyazomethine thin films

Optical transmission and fundamental reflectivity spectra of aromatic polyazomethine thin films, obtained by vacuum evaporation via the polycondensation process have been investigated in the wide spectral range 0.49–6.2 eV. As initial monomers, terephaldehyde (TPA) and one of four different amines, i.e. paraphenylene-diamine (PPDA), 7,2-diamino-fluorene, 1,1′-biphenyl-3,3′,4,4′-tetramine and 3-amino-4-(1-naphthyldiazenyl)phenylamine (fat brown RR) have been used, respectively. Amorphous character of these films was confirmed by the results of X-ray diffraction and AFM investigations. Absorption coefficient of the films has been obtained and the edge of absorption seems to be similar to the absorption edge typical for amorphous semiconductors, what allowed to obtain the Urbach energy and E_T parameter. The energy gaps of the films, following the Tauc relation, are found to change from 2.05 to 2.4 eV, depending on the length of conjugated part of the polymer chain. Absorption bands above the absorption edge, observed for different polyazomethine films are connected with their chemical structure and possible electronic transitions.     

Radiation processes in oxygen-deficient silica glasses: Is ODC(I) a precursor of E′-center?

The accumulation of radiation-induced defects under non-destructive X-ray and destructive cathodoexcitation was studied in pure silica KS-4V glasses possessing an absorption band at 7.6 eV. The correspondence between the existence of this band and the creation of the E′-center by radiation was checked. Detection of induced defects was accomplished by measurement of the luminescence during irradiation, post irradiation afterglow or phosphorescence, induced optical absorption, and thermally stimulated luminescence. In all samples, these observed phenomena associated with charge trapping and recombination on the oxygen-deficient luminescence center. Others centers of luminescence were not significant contributors. In some samples, the intensity of the 7.6 eV absorption band was deliberately increased by treatment in hydrogen at 1200 C for 100 h. The intensity of luminescence in hydrogen-treated samples was smaller because of the known quenching effect of hydrogen on the luminescence of oxygen-deficient centers. The optical absorption method does not reveal an induced absorption band for the E′-center in the hydrogen-free samples with different levels of oxygen deficiency. Therefore, we did not detect the transformation of the defect responsible for the 7.6 eV absorption band or the ODC(I) defect into the E′-center. In the hydrogen-treated sample, the absorption of the E′-center was detected. The E′-centers creation in the hydrogen-treated sample was associated with precursors created by hydrogen treatment (≡Si–O–H and ≡Si–H) in the glass network. The destructive e-beam irradiation reveals an increase with dose of the ODC luminescence intensity in the sample exhibiting a small 7.6 eV band. That means that the corresponding luminescence centers are created. Optical absorption measurements in that case reveal the presence of E′-centers and a broad band at 7.6 eV. A compaction of the irradiated volume was detected. Therefore, we conclude that the E′-center is produced by heavy damage to the glass network or by the presence of precursors.     

Observation of HfO2 thin films by deep UV spectroscopic ellipsometry

Deep UV spectroscopic ellipsometry (SE) is used for structure change observations in thin hafnia (HfO₂) layers deposited by p-MOCVD on silicon substrate. The absorption edge E_g and most of the critical point transitions in HfO₂ are above 6 eV, which makes the extension to Deep UV SE (5–9 eV) very suitable. The phase mixture changes as function of thickness and deposition process temperature, deduced from SE correspond well to XRD and Angle Resolved (AR)-XPS spectroscopy observations. From the absorption spectra at 4.5 eV, defects such as oxygen vacancies are detected, whereas from XPS spectra the estimation of the O/Hf ratio follows the same trend. Deep UV SE reveals differences in the dielectric function with orthorhombic/monoclinic phase mixtures essentially with peaks at 7.5 and 8.5 eV. Quantum confinement originated from the grain size of the films and the excitonic origin of the 6 eV feature are discussed.     

Temperature dependence of the generation and decay of E′ centers induced in silica by 4.7 eV laser radiation

We report a study of the generation of silicon dangling bonds (E′ centers) induced in fused silica by 4.7 eV laser irradiation in the 10 < T < 475 K temperature range, carried out by in situ optical absorption spectroscopy. The generation of the defects, occurring by transformation of pre-existing precursors, results to be a thermally activated process, quenched below 150 K and with a 0.044 eV activation energy. At T > 200 K the induced defects undergo a post-irradiation decay due to their reaction with mobile H₂. The interplay between generation and annealing gives rise to a bell-shaped temperature dependence of the concentration of induced E′ centers, peaking at 250 K.     

Electrical characterizations of silver chalcogenide glasses

We present a study of the electrical properties of silver chalcogenide glasses ‘40AgI’–30Ag₂S–30GeS₂, 45AgI–27.5Ag₂S–27.5GeS₂ and 50AgI–25Ag₂S–25GeS₂ in the 77–400 K temperature and the 20 Hz to 1 MHz frequency ranges. In our temperature range, a large variation of the real permittivity is observed, in relation with an electrodes polarization effect. As the amount of silver iodide increases in the Ag₂S–GeS₂ matrix, the glass transition temperature and the activation energies decrease, the electrical conductivity increases and reaches 4 Ω⁻¹ m⁻¹ at room temperature for the glass with 50% AgI. The study of the conductivity shows a behavior due to a high ionic conductivity, thermally activated with E_dc = 0.21 eV, E₁ = 0.075 eV (40AgI–30Ag₂S–30GeS₂, 45AgI–27.5Ag₂S–27.5GeS₂), E_dc = 0.17 eV, E₁ = 0.055 eV for 50AgI–25Ag₂S–25GeS₂. For these glasses, we have seen three conductivity regimes. The first two terms are thermally activated. The third term cannot be actually clearly identified because either it is thermally activated with a very low activation energy and frequency dependent, or it is almost non-thermally activated and frequency dependent.     

Study of thermal and optical properties of the Ge-Te-CdI2/ZnI2 far infrared transmitting glasses

A systematic series of (100 ? x)(GeTe_4.3) ? xCdI₂/ZnI₂ far infrared transmitting glasses were prepared by traditional melt-quenching method. ZnI₂ (20 mol%) can be introduced in the glassy matrix, while only 10 mol% CdI₂ can be incorporated in the Ge-Te-CdI₂ glass system. Based on differential thermal analysis (DTA) data, most of the glass samples have good thermal stability. A maximum ΔT value of 115 °C was obtained for the glass composition 90(GeTe_4.3)–10ZnI₂. The allowed indirect transition optical band gap was calculated according to the classical Tauc equation. It is found that the indirect optical band gap decreased from 0.619 to 0.569 eV with the CdI₂ addition and increased from 0.628 to 0.677 eV with the ZnI₂ addition. According to infrared transmission spectra, the Ge-Te-CdI₂/ZnI₂ glasses show wide IR transparency.     

Effect of laser irradiation on thermal and optical properties of selenium–tellurium alloy

The crystallization parameters such as glass transition temperature (T_g), onset crystallization temperature (T_c), peak crystallization temperature (T_p) and enthalpy released (ΔH_C) of the bulk Se–Te chalcogenide glass has been studied by using Differential Scanning Calorimeter (DSC), under non-isothermal condition at a heating rate of 20 K/min. The values of T_g, T_c, T_p and ΔH_C with and without laser irradiation for different exposure time have been studied. The optical absorption of pristine and laser irradiated thermally evaporated Se–Te films has been measured. The films shows indirect allowed interband transition that is influenced by the laser irradiation. The optical energy gap has been found to decrease from 1.61 to 1.38 eV with increasing irradiation time from 5 to 20 min. The results have been analyzed on the basis of laser irradiation-induced defects in the film.     

Thermal and optical properties of CuO–BaO–B2O3–P2O5 glasses

CuO-doped barium borophosphate glasses in a series of xCuO–(45 − x)BaO–10B₂O₃–45P₂O₅ in molar ratio with x = 0–15 mol% were prepared by a melt-quenching technique. All the glasses had excellent thermal stability against crystallization. Glass transition temperature, thermal expansion coefficient and molar volume decrease with increasing CuO concentration. The linear relationship between the absorption coefficient and CuO concentration exists for a peak wavelength in the transitions of ²A_1g → ²B_1g, ²B_2g → ²B_1g, ²E_g → ²B_1g. The relationship between the properties and glass structure evaluated by Raman spectroscopy is discussed.     

Compositional dependence of optical parameters in Se–Bi–Te–Ag thin films

Compositional dependence of optical parameters in thermally evaporated amorphous Se_80.5Bi_1.5Te_18 ? yAg_y (for y = 0, 1.0, 1.5 and 2.0 at.%) quaternary thin films has been studied using well established Swanepoel method. The optical properties like, refractive index (n), extinction coefficient (k), absorption coefficient (α) and optical band gap (E_g) have been determined from the transmission spectra in the spectral range from 500 to 2500 nm. The optical band gap (E_g) has been estimated by using Tauc's extrapolation method and is found to increase with an increase in the Ag concentration. Present study shows that the refractive index, extinction coefficient and optical band gap increase with the increasing Ag content which is in agreement with the earlier studies. While the increase in the refractive index with Ag content over the entire spectral range can be attributed to the increased polarizability of larger Ag atomic radius (153 pm) compared to the Te atomic radius (135 pm), the increase in the optical band gap with increasing Ag concentration is correlated to an increase in the cohesive energy and decrease in the electronegativity of the films under study. The dielectric constant and optical conductivity (σ) of the thin films under study are also found to increase with the Ag concentration.     

Band gap determination by absorption spectrum fitting method (ASF) and structural properties of different compositions of (60−x) V2O5–40TeO2–xSb2O3 glasses

Glasses with compositions (60?x) V₂O₅–40TeO₂–xSb₂O₃ with 0 ? x ? 10 (in mol%) have been prepared using usual melt quenching method. The position of the absorption edge and hence the values of the optical band gap was found to depend on the glass composition. Using the Tauc model, the absorption spectrum fitting method (ASF) was employed to obtain the optical band gap. This method requires only the measurement of the absorbance spectrum of the sample. For each sample, the width of the band tail was determined. Also, the density and glass transition temperature values indicate that the rigidity and packing of the samples increase with increase in Sb₂O₃ concentration.     

Complex primary crystallization kinetics of amorphous Finemet alloy

The complex primary crystallization kinetics of the amorphous Finemet soft magnetic alloys has been analyzed by non-isothermal DSC measurements. The local activation energies E_c(α) were determined by an isoconversional method without assuming the kinetic model function and its average value was about 383 kJ/mol. The nucleation activation energy E_n and growth activation energy E_g were 425 and 333 kJ/mol, respectively. And the apparent local activation energies E_c can be expressed by E_n and E_g as follows: E_c = aE_n + bE_g. The local Avrami exponents lies between 1 and 2 in a wide range of 0.2 < α < 0.9, and it indicates that dominating crystallization mechanism in the non-isothermal primary crystallization of amorphous Finemet alloy is one dimensional growth at a near-zero nucleation rate for surface crystallization. The significant variation of local Avrami exponent and local activation energy for primary crystallization with crystallized volume fraction demonstrates that the primary crystallization kinetics of amorphous Finemet alloy varies at different stages. In addition, the variable local activation energies E_c(α) and local Avrami exponents n(α) are applicable and correct in describing the primary crystallization process of the amorphous Finemet alloy according to the theoretical DSC curve simulation.     

Electrical properties of annealed a-SiC:H thin films

In the present work the dependence of electrical properties of a-SiC:H thin films on annealing temperature, T_a, has been extensively studied. From the measurements of dark dc electrical conductivity, σ_D, in the high temperature range (from 283 up to 493 K), was found that the conductivity activation energy, E_a, is invariant for T_a ⩽ 673 K and equal to 0.64 eV, whereas for T_a from 673 up to 873 K, E_a increases at about 0.2 eV reaching to a maximum value 0.85 eV at T_a = 873 K, suggesting the optimum material quality. This behavior of E_a as a function of T_a is mainly attributed to relaxation of the strain in the amorphous network, which is possibly combined with weak hydrogen emission for temperatures up to 873 K. For further increase of T_a (>873 K) the phenomenon of hydrogen emission, causes rapid decrease of E_a down to 0.24 eV at T_a = 998 K, deteriorating the material quality. These results are also supported by the measurements of dark dc electrical conductivity in the low temperature range (from 133 up to 283 K), where the dependence of the density of gap states at the Fermi level, N(E_F), on annealing temperature presents the minimum value at T_a = 873 K. The Meyer–Nelder rule was found to hold for the a-SiC:H thin films for annealing temperatures up to 873 K. Finally, the dependence of dark dc electrical conductivity at room temperature, σ_DRT, on T_a showed to reflect directly the dependence of E_a on T_a.     

Fluorine laser-induced silicon hydride Si–H groups in silica

Formation and destruction of silicon hydride (Si–H) groups in silica by F₂ laser irradiation and their vacuum ultraviolet (VUV) optical absorption was examined by infrared (IR) and VUV spectroscopy. Photoinduced creation of Si–H groups in H₂-impregnated oxygen deficient silica is accompanied by a growth of infrared absorption band at 2250 cm⁻¹ and by a strong increase of VUV transmission at 7.9 eV. Photolysis of Si–H groups by 7.9 eV photons in this glass was not detected when the irradiation was performed at temperature 80 K. However, a slight destruction of Si–H groups under 7.9 eV irradiation was observed at the room temperature. This finding gives a tentative estimate of VUV absorption cross section of Si–H groups at 7.9 eV as 4 × 10⁻²¹ cm², showing that Si–H groups do not strongly contribute to the absorption at the VUV fundamental absorption edge of silica glass.     

Optical properties of microcrystalline 3C–SiC:H films measured by resonant photothermal bending spectroscopy

Optical absorption coefficient spectra of hydrogenated microcrystalline cubic silicon carbide (μc-3C–SiC:H) films prepared by Hot-Wire CVD method have been estimated for the first time by resonant photothermal bending spectroscopy (resonant-PBS). The optical bandgap energy and its temperature coefficient of μc-3C–SiC:H film is found to be about 2.2 eV and 2.3 × 10⁻⁴ eV K⁻¹, respectively. The absorption coefficient spectra of localized states, which are related to grain boundaries, do not change by exposure of air and thermal annealing. The localized state of μc-3C–SiC:H has different properties for impurity incorporation compared with that of hydrogenated microcrystalline silicon (μc-Si:H) film.     

Mechanisms controlling primary crystallisation of Ga20Te80 glasses

The kinetic study of the crystallisation process of Ga₂₀Te₈₀ glass from isothermal and continuous heating calorimetric data have been performed applying a recently developed procedure. The kinetic information was complemented with X-ray diffraction measurements. With this scope, three crystallisation patterns, with three-dimensional isotropic growth have been analysed: (i) site saturation and interface controlled growth. (ii) homogeneous nucleation with interface controlled growth and (iii) homogeneous nucleation with two simultaneous modes of crystal growth (interface- and diffusion-controlled). A complex model with two simultaneous modes of three-dimensional isotropic crystal growth with decreasing homogeneous nucleation and soft impingement has been applied for modelling primary crystallisation of the Ga₂₀Te₈₀ glass. The model goes beyond the isokinetic hypothesis when coupling isothermal and continuous heating kinetic data. The apparent activation energy E_a = (2.06 ± 0.03) eV/at obtained for the primary crystallisation of the phase Te is shown to correspond to an activation energy for nucleation E_I = (2.85 ± 0.03) eV/at and an interface controlled activation energy for growth E_u = (1.90 ± 0.03) eV/at at the crystallisation onset.     

Origins of optical absorption between 4.8 and 4.9 eV in silica implanted with Si and with O ions

We have determined some of the sources of the optical absorption bands between 4.8 and 4.9 eV in Si and O-implanted silica using several ion energies to produce layers of implanted ions with constant concentrations. The concentrations of implanted ions in the implanted layers ranged from >0.015 at.% to <3 at.%. Optical absorption was measured from 2.0 to 6.5 eV. Electron paramagnetic resonance measurements were made at ∼20.3 and 33 GHz for sample temperatures ranging from 77 to 100 K for most measurements. The components identified in the spectra, based on comparison with reported parameters, were, in the Si case, due to E′ centers and peroxy radicals. In the O case they were due to E′ centers, non-bridging oxygen hole centers, peroxy radical centers, and a newly appearing state which we labeled the OS center. By comparing the changes in the absorption at 4.83 eV with the changes in the concentrations of the various electron paramagnetic resonance components and with the reports in the literature, we conclude that there are at least four oxygen related centers and one Si related center absorbing between 4.8 and 4.9 eV.     

Effect of silver doping on the electrical properties of a-Sb2Se3

This paper reports the effect of Ag-doping on electrical properties of a-Sb₂Se₃ in the temperature range 230–340 K and frequency range 5–100 kHz. The variation of transport properties with thermal doping has been studied. Ag-doping produces two homogeneous phases in the sample, which are found to be voltage dependent in the temperature range studied and frequency dependent in lower frequency region (0.1–10 kHz). Activation energy E_g and C′ [= σ₀ exp (γ/k), where γ, is the temperature coefficient of the band gap] calculated from dc conductivity has been found to vary from (0.42 ± 0.01) eV to (0.26 ± 0.01) eV and (4.11 ± 0.01) × 10⁻⁵ to (2.90 ± 0.02) × 10⁻⁶ Ω⁻¹ cm⁻¹ respectively. Ag-doping can be used to make the sample useful in device applications.