Studies of the optical properties of sodium copolyphosphate glasses

A number of samples of glassy sodium polyphosphate and copolyphosphates of sodium — cobalt, sodium — copper, sodium — nickel, sodium-manganese and sodium — calcium were prepared and their optical properties were investigated. The ultraviolet and visible spectra of these glasses were recorded at the room temperature. It was found that the fundamental absorption edge of these glasses usually occurs in the ultraviolet — visible region. The optical absorption edges (E₀) were calculated by using the relation h ν = B (hν − E₀)² where B is constant. The linear variation of (hν)^1/2 with hν where is the absorption coefficient and hν is the incident photon energy, is taken as evidence of non-direct interband transitions. The E₀ values obtained for copolyphosphate glasses appeared to depend on the size of the counter cation. The infrared spectra of all these glasses appeared to be almost the same, indicating the presence of characteristic P --- O --- P linkages of linear polyphosphate chains and two non bridging oxygen atoms bonded to phosphorus atoms O --- P --- O (PO₂) units in the polyphosphate tetrahedra.     

Structure and properties of the pure and Pr-doped Ge25Ga5Se70 and Ge30Ga5Se65 glasses

The Ge₂₅Ga₅Se₇₀ and Ge₃₀Ga₅Se₆₅ pure and Pr³⁺-doped glasses were prepared by direct synthesis from elements and PrCl₃. It was found that up to 1 mol% PrCl₃ can be introduced in the Ge₂₅Ga₅Se₇₀ and Ge₃₀Ga₅Se₆₅ glasses. Both types of glasses with overstoichiometric and substoichiometric content of Se were homogeneous and of black color. The optical energy gap is E^opt_g=2.10 eV, and the glass transition temperature is T_g=543 K for Ge₂₅Ga₅Se₇₀ and T_g=633 K for Ge₃₀Ga₅Se₆₅. The long-wavelength absorption edge is near 14 μm and it corresponds to multiphonon processes. Doping by Pr³⁺ ions creates absorption bands in transmission spectra, which can be assigned to the electron transitions from the ground ³H₄ level to the higher energy levels of Pr³⁺ ions ³H₅, ³H₆, ³F₂, ³F₃ and ³F₄, respectively. By excitation with YAG:Nd laser line (1064 nm), two intense luminescence bands (1343 and 1601 nm) were excited. The first band can be ascribed to electron transitions between ¹G₄ and ³H₅ energy levels of Pr³⁺ ions. Full width at half of maximum (FWHM) of the intensity of luminescence was found to be 70 nm for (Ge₂₅Ga₅Se₇₀)_1 − x(PrCl₃)_x and (Ge₃₀Ga₅Se₆₅)_1 − x(PrCl₃)_x glasses. The FWHM in selenide glasses is lower than in halide and sulphide glasses. The second luminescence band (1601 nm) can be probably ascribed to the transitions between ³F₃ and ³H₄ energy levels of Pr³⁺ ions. The absorption and luminescence spectra of Pr³⁺ ions in studied glasses are slightly influenced by stoichiometry of glassy matrix. The Raman spectra of studied glasses were deconvoluted and assignment of Raman bands to individual vibration modes of basic structural units was suggested. The structure of studied glasses is mainly formed by corner-sharing and edge-sharing GeSe₄ tetrahedra. The vibration modes of Ga-containing structural units were not found, they are apparently overlapping with Ge-containing structural units due to small difference between atomic weights of Ge and Ga. In the glasses with substoichiometry of Se, the Ge–Ge bonds of Ge₂Se₆ structural units were found. In Se-rich glasses the Se–Se vibration modes were found. In all studied glasses also ‘wrong' bonds between like atoms were found in small amounts. Maximum phonon energy of studied glasses is 320 cm⁻¹.     

Spectroscopy of transition metal ions in inorganic glasses

Transition metal (TM) ions have been used as colouring agents in the glass industry for a long time. Recently, great attention has been paid to the TM ion doped glasses for the development of new lasers or luminescence materials. The absorption spectra of TM ions in different kinds of glasses have been studied extensively, but little work has been done for fluorescence and relaxation spectra. In this paper emphasis is laid on analysing the influence of chemical bond characteristics of the base glass on the spectra and the site structure of transition metal ions in glasses. Recent experimental results about the luminescence characteristics of low valence ions (such as Ti³⁺, Cr³⁺, V²⁺, Mn²⁺, Cu⁺, Mo³⁺) in glasses are also reported.     

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.     

Structural distribution and rigidity of the glass network determined by EPR of Cu

The linewidth-broadening of the EPR spectra of Cu²⁺ in silicate, borate and phosphate glasses was analyzed in terms of the distribution of g_| and A_| (δ_| and δA_|) and related to the distribution of the rigidity of the network structure. X- and K-band spectra were measured for the glasses doped with ⁶³Cu²⁺ (93% abundance). The linewidth of the HFS shoulders with parallel orientation to H increased linearly with increasing m or microwave frequency. δg_| and δA_| showed a marked dependence on glass composition. For example, in Na₂O---B₂O₃ glasses, on going from x (mol% of Na₂O) being small through intermediate to large, δg_| varied from small through large to negligibly small. In contrast to these glasses δg_| was extremely large for 75PbO · 25B₂O₃ glass. The large δg_| for the Na₂O---B₂O₃ glassesof intermediate x was attributed to the coexistence of various borate groups competitively coordinating to Cu²⁺. Negligibly small δg_| for 70Na₂O · 30B₂O₃ glass and extremely large δg_| for 75PbO ·25B₂O₃ glass, both with a narrower structural distribution, reflect regidity of the glass network. The Pb---O bonding is strong enough to distort the coordination of Cu²⁺-complex. The situation is the reverse in Na₂O---B₂O₃ glasses.     

Optical properties of porous glasses doped with ZnS

The paper presents a new preparation method to form semiconductor nanoclusters inside silica porous glasses as matrices and describes investigations of the luminescence properties of the samples loaded repeatedly with ZnS nanoparticles. Silica porous glasses were obtained by leaching the two-phase sodium borosilicate glasses in acid solution. The samples consisting of two types of glasses with different pore sizes and immobilized nanosized ZnS in these matrices by a chemical deposition process were used. EDS measurements confirmed purity of the samples. The recorded absorption and photoluminescence spectra exhibit the quantum size effect due to the increasing number of the chemical deposition cycles.     

Conductivity and optical absorption of semiconducting WO3 glasses

The dc conductivity and optical properties of WO₃---B₂O₃---ZnO glasses containing up to 80% WO₃ have been measured and are analyzed using small polaron hopping theory. The thermal hopping energy E_H is estimated from the temperature dependence of the conductivity, but an accurate determination of its value is not possible due to the continuous curvature of the conductivity plots. The optical absorption is dominated by W⁵⁺ ligand field absorption in the visible and by a band edge at 3.5 eV; the absorption by the small polarons is too weak to be observed directly. The optical hopping energy E_o is determined from the thermomodulation spectra. The values obtained for E_H and E_o can be combined to give a polaron binding energy and a disorder energy both approximately equal to 0.4 eV. A similar disorder energy is obtained from an analysis of the electro-modulation spectra in the band edge region.     

Silica under hydrostatic pressure: A non continuous medium behavior

The homogeneous/inhomogeneous structure of glasses is still a debated question. Hydrostatic high pressure experiments allow us to determine if a glass behaves as an elastic continuous random network or if a nanometer scale heterogeneity has to be taken into account. In order to get information on the homogeneous/inhomogeneous structure of glasses, in situ high pressure Raman experiments are performed on silica in the elastic domain up to 4.7 GPa. A strong decrease of the Boson peak intensity is observed between 1 bar and 3 GPa. We show that this decrease does not correspond quantitatively to the effect of pressure on a homogeneous elastic medium. From the interpretation of the narrowing of the main Raman band width under pressure as a narrowing of the θ inter-tetrahedral Si–O–Si angle distribution it is shown that the decrease of the Boson peak intensity is correlated to the decrease of the intrinsic inhomogeneity of the silica glass. These results confirm the occurrence of an intrinsic inhomogeneity at a nanometer scale even in a single component glass like SiO₂ which is very important for the interpretation of the optical or mechanical properties of the glasses.     

Absorption spectra of GaN: film characterization by Urbach spectral tail and the effect of electric field

The absorption tail of undoped and Si-doped GaN films was investigated at different temperatures and under applied electric field. It was found that the spectral dependence of logarithm of absorption coefficient is combined of two linear functions: ln[(hν)]=C₁+(hν−E_g)/U₁ for hν<3.42 eV and ln[(hν)]=C₂+(hν−E_g)/U₂ for 3.44<hν<3.5 eV with Urbach energies U₁=400–470 meV and U₂=10–20 meV. The influence of an electric field effect on the absorption spectra follows the Dow and Redfield theory. It was shown that the intrinsic electric field about 10⁵ V/cm exists in our samples. The implemented analysis of the absorption spectra gives the qualitative method of film characterization.     

Brillouin scattering and pockels coefficients in silicate glasses

The Brillouin spectra of binary and ternary silicate glasses were investigated and absolute values for the Pockets coefficients p₁₂ and p₄₄ and (p₁₁ – p₁₂) were calculated from the measured spectra. The results were interpreted as to the density and refractive index dependence of the Pockels coefficients in terms of the theoretical treatments by Carleton, Mueller and Sipe. From the measured p₁₂ and p₄₄ values the quantity (∂ε/∂p), the change of the dielectric constant with respect to density, was calculated and compared with (∂ε/∂) evaluated from the Lorentz-Lorenz equation, Drude equation and the Carleton model. The Lorentz-Lorenz and Drude equations overestimated the magnitude of (∂ε/∂), while the Carleton model with its two limiting cases set upper and lowe bounds to (∂ε/∂). From the (∂ε/∂) results the strain polarizability constant (λ₀) was determined and its physical significance discussed. In general, the alkali-oxide concentration dependence of the Pockels coefficients of various silicate glasses has been measured and qualitatively explained by several existing theoretical formulations.     

Synthesis, growth and characterization of a new laser upconversion crystal Ba2ErCl7

A modified method to synthesize the new laser upconversion material Ba₂ErCl₇ using Er₂O₃, BaCl₂ 2H₂O and NH₄CI is reported for the first time in this paper. Single crystals up to 5–8mm in diameter and 10–20 mm in length have been grown by Czochralski method. The transmittance spectra of Ba₂ErCl₇ single crystal has first been measured by using an HITACHI U-3500 spectrophotometer. There are three intense absorption peaks ⁴I_9/2⁴I_11/2 and ⁴I_13/2 in the infrared range which can be excited by 803nm, 980nm and 1.5μm laser diodes (LDs), respectively. The cut-off wavelength of the crystal is 230mn. Intense green luminescence can be observed when the crystal is pumped by a ED at 803nm. The formation of the defects is also discussed.     

EXAFS and XANES joint analyses for semiconducting vanadium phosphate glasses

Vanadium EXAFS spectra of 50V₂O₅-50P₂O₅ glasses with different C = V⁺⁴/V_tot have been measured. The V-O distances increase by ΔR₁ = (0.03 ± 0.02) Å to ΔR₂ = (0.07 ± 0.03) Å going from a glass with C = 0.64 to C = 0.84 and from C = 0.51 to C = 0.84, respectively. The EXAFS data show a basically similar structure of the vanadium sites for both the V⁴⁺ and V⁵⁺ ionic states. The density of the glasses increases with C from the value d₁ = 2.81 g/cm³ for C = 0.51 to d₂ = 2.92 g/cm³ for C = 0.84 indicating a more random packing of glass units.     

Ab initio molecular dynamics simulations of oxygen-deficient centers in pure and Ge-doped silica glasses: Structure and optical properties

We have calculated the optical absorption (OA) bands of oxygen-deficient centers (ODC(I) type) in pure and germanium (Ge)-doped silica using the density functional theory-plane waves (DFT-PW) method connected to the Kubo–Greenwood formalism. A statistical approach is used in order to reproduce the complex nature of amorphous systems. This preliminary study shows that calculated locations of the OA bands of both Si-ODC and Ge-ODC accurately agree with experimental data in spite of the well-known underestimation of the gap of insulators using DFT.     

NMR studies of Na2O---B2O3---SiO2 glasses of mid-alkali content

¹¹B Fourier transform spectra have been used to study the structure of Na₂O---B₂O₃---SiO₂ glasses of mid-alkali content. Based on the measurements of the fraction N₄ of four-coordinated borons, it has been found that for K = mol.% SiO₂/mol.% B₂O₃ 8 and R = mol.% Na₂O/mol.% B₂O₃ = 1, N₄ is obviously smaller than 1 rather than equal to 1 as assumed in the relevant literature. Only when R reaches a value appropriately greater than 1, can the case where N₄ = 1 occur. A structural model suggested in this paper can satisfactorily explain the fact.     

Optical absorption study on radiation damage in fluoride glasses

The effect of 1.7 MeV electrons on the coloration of fluorozirconate (ZBL) and fluorohafnate (HBL) glasses has been investigated. Irradiation can produce intense broad absorption bands at 325 nm and 253 nm in the glasses. However, the size and shape of the absorption bands in zirconate-based glass (ZBLA) which has Al³⁺ ions as network stabilizers is different from those in ZBL and HBL glass. The optical absorption bands due to self-trapped hole centers can be assigned from dichroic absorption measurements. It appears that the radiolysis damage mechanism may contribute to the coloration of these fluoride glasses.     

Reflection spectra of silicate glasses in the vacuum ultraviolet region

Reflection spectra of silicate glasses were measured in the spectral region 2–13 eV. The bands due to bridging oxygen were found at 11.6 and 10.4–9.5 eV. The bands for non-bridging oxygens were found in the region 8.8–4.9 eV. They shift to lower energy with increasing ionic radius for the low valency cations while they shift to higher energy with increasing ionic radius for the high valency cations. The correlation between the measured bands and the absorption wavelength calculated from Drude-Voigt dispersion formula is discussed.     

Photoluminescence from E band centers in amorphous and crystalline SiO2

Photoluminescence (PL) originating from intrinsic defects in neutron-irradiated crystalline (x-) SiO₂ is observed and compared with that from amorphous (a-) SiO₂. The PL and photoluminescence excitation (PLE) spectra of x-SiO₂ are qualitatively similar to those of a-SiO₂. This suggests that PL centers, similar to those found in amorphous systems, are present in ordered systems. In addition, the PL and PLE spectra a-SiO₂ and a-As₂S₃ scale with energy band gap, suggesting that the radiative processes in a-SiO₂ and semiconducting chalcogenide glasses are alike. The similarity of the PL from x-SiO₂ to that from a-SiO₂ and the scaling of the PL from a-SiO₂ and a-As₂S₃ with energy band gap strongly suggest that PL centers are unique bonding configurations which primarily depend on the chemistry of the system rather than on the degree of long range order.     

d-f and f-f transition bands of praseodymium and samarium ions in silica glasses

d-f and f-f transition bands of Pr and Sm ions in silica glasses have been studied by the absorption, excitation and emission spectra. In particular, Sm-doped silica glasses were treated with different atmospheres around the T_g temperature. The change of the valency state and the transition band shown after the treatments are discussed.     

A study of alkali resistance of CaO---Al2O3---SiO2 glasses

The alkali resistance and structure of CaO---Al₂O₃---SiO₂ glasses are studied in this paper. The change of coordination number of aluminum ions in the glasses, caused by corrosion from the cement extract aqueous solution, was determined by means of X-ray fluorescence spectra and infrared absorption spectra. The interrelationship between glass compositions, structure, and alkali resistance is discussed.     

Inferences about structure of aluminosilicates from viscosity data

Replacement of two cations of silica by two cations of alumina and one of baria in barium silicate glasses raises the strain, annealing and softening points even though the number of non-bridging oxygen atoms is unchanged. This observation is difficult to explain unless one postulates that a large moiety such as the S₈ unit (described herein) moves as a whole during any flow process in this temperature range. The dependence of the strain point on the excess baria in a series of glasses having a constant number of non-bridging oxygens and constant alumina suggests that the negative charges of the alumina sites are balanced preferentially by barium ions rather than alkali ions.