E.S.R. studies of radiation damage and structure in oxide glasses not containing transition group ions: A contemporary overview with illustrations from the alkali borate system

Electron spin resonance (e.s.r.) is a particularly powerful method for identifying and characterizing radiation-induced defects in vitreous materials. This paper reviews the fundamental principles and the present state of the art in applying e.s.r. techniques to achieve these ends in oxide glasses which do not contain transition group ions. A wide variety of generic defect types are discussed in some detail by means of examples from the alkali borate system. These include oxygen-associated trapped hole centers and oxygen-vacancy-associated trapped electron centers, as well as several electron and hole-type centers which are associated with interstitial cations and anions, respectively. Probable analogs in other oxide glasses are pointed out. Special emphasis is placed on the kinds of structural information which can be obtained from these studies.     

EPR and optical spectra of gamma-irradiated sodium-silicate glasses containing copper oxide

The effects of an addition of CuO on the intrinsic and induced EPR and optical absorption spectra of γ-irradiated sodium-silicate glasses melted under different redox conditions are studied. It is shown that the CuO impurity blocks the formation of radiation-induced centers associated with the intrinsic defects of glass matrix. A new paramagnetic centre appears in the sodium-silicate glasses containing CuO after γ-irradiation. This center is the hole trapped at the Cu¹⁺ ion, and its spectral parameters are different from ones of the Cu²⁺ ions obtained by chemical oxidation of copper.     

Persistent spectral hole burning studies in europium doped sodium silicate and borosilicate glasses

Spectroscopic studies confirmed the coexistence of Eu³⁺ and Eu²⁺ in sodium silicate and borosilicate glasses doped with europium. Persistent spectral hole burning was observed up to room temperature. Multiple hole burning was possible with moderate laser powers. When the glass composition was modified by adding 4–5% yttrium oxide, hole retention capability, hole burning efficiency and hole density also increased in both silicate and borosilicate glasses. Hole burning is due to a charge exchange between the Eu³⁺ and its environment. Certain defect centers, which were identified by electron spin resonance measurements, contributed to the formation of stable holes in the borosilicate glass.     

Trapped-electron centers in pure and doped glassy silica: A review and synthesis

This paper reviews half a century of research on radiation-induced point defects in pure and doped glassy silica and its crystalline polymorph α quartz, placing emphasis on trapped-electron centers because the vast majority of all presently known point defects in various forms of SiO₂ are of the trapped-hole variety. The experimental technique most discussed here is electron spin resonance (ESR) because it provides the best means of identifying the point defects responsible for the otherwise difficult-to-attribute optical bands. It is emphasized that defects in α quartz have been unambiguously identified by exacting analyses of the angular dependencies of their ESR spectra in terms of the g matrix of the unpaired electron spin and the matrices of this spin's hyperfine interactions with non-zero-nuclear-spin ²⁹Si and ¹⁷O nuclides in pure α quartz and/or with substitutional ²⁷Al, ³¹P, or ⁷³Ge in quartz crystals respectively doped with Al, P, or Ge. Many defects in pure and doped glassy silica can be unambiguously identified by noting the virtual identities of their spin Hamiltonian parameters with those of their far better characterized doppelgangers in α quartz. In fact, the Ge(1) trapped-electron center in irradiated Ge-doped silica glass is shown here to have a crystal-like nature(!), being virtually indistinguishable from the Ge(II) center in Ge-doped α quartz [R.J. McEachern, J.A. Weil, Phys. Rev. B 49 (1994) 6698]. Still, there are other defects occurring in glassy silica that are not found in quartz, and vice versa. Nevertheless, those defects in glasses without quartz analogues can be identified by analogies with chemically similar defects found in one or both polymorphs and/or by comparison with the vast literature of ESR of paramagnetic atoms and small molecules. Oxygen “pseudo vacancies” comprising trigonally coordinated borons paired with trigonally coordinated silicons were proposed to exist in unirradiated B₂O₃–3SiO₂ glasses in order to account for observations of γ-ray-induced trapped-electron-type B- and Si-E′ centers [D.L. Griscom et al., J. Appl. Phys. 47 (1976) 960]. Analogous Al-E′ trapped-electron centers have been elucidated in silica glasses with Al impurities [K.L. Brower, Phys. Rev. B 20 (1979) 1799]). And it has been proposed [D.L. Griscom et al., J. Appl. Phys. 47 (1976) 960] that trapping of a second electron on such oxygen pseudo vacancies accounts for the predominant ESR-silent trapped-electron centers in irradiated silica glasses containing B or Al. The present paper additionally attempts to divine the identities of some of the ESR-silent radiation-induced trapped-electron centers in silica glasses free of foreign network-forming cations. This quest led to the doorstep of the most famous ESR-silent defect of all, the twofold-coordinated silicon, which is found only in silica glasses (not in quartz) and is responsible for the UV/visible optical properties of the oxygen-deficiency center known as ODC(II). The oxygen-deficiency center called ODC(I) is associated with an absorption band at 7.6 eV and, though commonly believed to be a simple oxygen mono-vacancy, is clearly more complicated than that [e.g., A.N. Trukhin, J. Non-Cryst. Solids 352 (2006) 3002]. Certain well documented but persistently enigmatic ODC(I)?ODC(II) “interconversions” [reviewed by L. Skuja, J. Non-Cryst. Solids 239 (1998) 16] have never been explained to universal satisfaction. An innovative combined ESR/thermo-stimulated-luminescence (TSL) study of a series of pure low-OH silica glasses with oxygen deficiencies of 0.000, ~ 0.015, and ~ 0.030 vol.% [A.N. Trukhin et al., J. Non-Cryst. Solids, 353 (2007) 1560] places new constraints on all future models for ODC(II). Taking this history into account, specific redefinitions of both ODC(I) and ODC(II) are proposed here. The present review also revisits a study of X-ray-induced point defects in an ultra-low-OH, high-chlorine but otherwise ultra-high-purity silica glass [D.L. Griscom, E.J. Friebele, Phys. Rev. B34 (1986) 7524], arguing that (1) most of the reported E′_γ and E′_δ centers were created via the mechanism of dissociative electron capture at chlorine-decorated oxygen vacancies, (2) the concomitantly created interstitial chloride ions serve as ESR-silent trapped-electron traps, (3) the ESR-detected “Cl⁰” centers arise from hole trapping on O₃≡ Si–Cl units without detachment of the resulting Cl atom, and (4) those chlorine atoms that are detached by homolytic bond fission are ESR-silent. Finally, in chlorine-free, low-OH, high-purity silica glasses, up to 100% of the trapped-electron centers appear to be ESR silent and are tentatively ascribed to electron trapping in pairs below the mobility edge of the conduction band. In such cases, the sum of all trapped-hole centers has been found to decay exponentially with increasing isochronal annealing temperature in the range 100 to ~ 300 K [D.L. Griscom, Nucl. Inst. & Methods B46 (1990) 12]. Overall, this review consolidates a large amount of long-existing but often underappreciated knowledge bearing on the natures of trapped-electron centers in pure and doped glassy silica, proposes new models for some of these, and raises a number of questions that cannot be fully answered without future performance of new experiments and/or ab initio calculations.     

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.     

Molecular dynamics simulation of radiation damage in glasses

Molecular dynamics simulations of the ballistic effects arising from displacement cascades in glasses have been investigated in silica and in a SiO₂-B₂O₃-Na₂O glass. In both glasses the T-O-T′ angle (where T and T′ are network formers) diminishes, despite radiation causes opposite effects: while the ternary glass swells and silica becomes denser. We show that radiation-induced modifications of macroscopic glass properties result from structural change at medium/range, reflecting an increasing disorder and internal energy of the system. A local thermal quenching model is proposed to account for the effects of ballistic collisions. The core of a displacement cascade is heated by the passage of the projectile, then rapidly quenched, leading to a process that mimics a local thermal quenching. The observed changes in both the mechanical and structural properties of glasses eventually reach saturation at 2 10¹⁸ α/g as the accumulated energy increases. The passage of a single projectile is sufficient to reach the maximum degree of damage, confirming the hypothesis postulated in the swelling model proposed by J.A.C. Marples.     

Synthesis and properties of cerium aluminosilicophosphate glasses

Cerium oxide is commonly added to silicate glasses as an optical property modifier. In particular, UV absorption, decoloration via redox coupling, and resistance to radiation-induced darkening are influenced by the addition of this rare-earth oxide. However, the limited solubility and visible color of rare-earth oxides in silicate glasses prevent any further beneficial enhancement of properties which might result from increasing the CeO₂ content. In contrast, rare-earth oxides are extremely soluble in phosphate glasses; for example, a binary cerium phosphate glass can incorporate up to 40 mol% CeO₂. Moreover, since the UV absorption edge of the phosphate network is blue-shifted compared to the silicate network, the effect of the Ce³⁺ absorption band tail on yellow coloration can be minimized.In this study, glasses in the cerium aluminosilicophosphate system were synthesized and a variety of physical and optical properties were measured including: density, refractive index, glass transition temperature, hardness, fracture toughness, and the location of the UV absorption edge. At ～9 mol% CeO₂, these cerium aluminosilicophosphate glasses exhibit similar coloration to commercially available silicate glasses which contain ～0.4 mol% CeO₂. Semi-quantitative photoemission analysis of the Ce oxidation states showed insignificant differences in the Ce³⁺/Ce⁴⁺ ratio between the phosphate and silicate glass systems.     

Interaction of gamma rays with some sodium phosphate glasses containing cobalt

Undoped and cobalt-doped sodium phosphate glasses of various compositions and with varying cobalt contents were prepared. UV-visible absorption spectra were measured before and after successive gamma irradiation. Experimental results indicated that the undoped base glass reveals strong ultraviolet absorption which is related to the presence of unavoidable trace iron impurities in the raw materials. Cobalt-doped glasses show characteristic visible absorption bands which are related to the presence of Co²⁺ ions mostly in the tetra-coordination state. The generated induced color centers in the UV and visible regions by gamma irradiation are characterized in relation to intrinsic defects from the host base sodium phosphate glass and the extrinsic defects from both trace iron impurities and added doped cobalt ions. Infrared absorption measurements were carried out for some selected samples to identify the structural building groups in the studied glasses. Cobalt ions showed a shielding behavior towards the effects of progressive gamma irradiation especially in the visible spectral region.     

Chemical annealing of oxygen hole centers in bulk glasses

Chemical annealing of the oxygen hole centers in bulk glasses by using hydrogen (or deuterium) has been extensively reported in the literature. Hydrogen chemically anneals these defect centers by reacting with them to form hydroxyl species. We have here presented a reaction-diffusion model to predict the chemical annealing rates of these defect centers in bulk glasses. The model considers diffusion of hydrogen (or its isotopes, e.g., deuterium) through the glass and its simultaneous reaction with the oxygen hole defect centers, resulting in the formation of the hydroxyl species in the glass. The predictions from the model are in excellent agreement with the experimental data presented in [J. Appl. Phys. 60 (12) (1986) 4325]. The model also establishes the precise connection between the dependence of effective hydrogen diffusivity on its intrinsic diffusivity, temperature, hydrogen and defect concentration. We also discuss methods for understanding chemical annealing behavior at high temperatures, where hydrogen not only reacts with the oxygen hole centers, but also with the silica matrix. For the case where hydrogen interaction with the silica matrix is the dominant reaction, a reaction-diffusion model is presented and the equilibrium constant (between 500 and 900 °C) for the reaction is estimated by comparing the predictions from the model with the hydroxyl profiles reported in [Appl. Phys. Lett. 47 (3) (1985) 328; J. Appl. Phys. 61 (12) (1987) 5447].     

Physical properties of barium borate glasses determined over a wide range of compositions

Barium borate glasses are reported over an extended glass-forming range from R=0.2 (16.7 mol% BaO) to R=2.0 (66.7 mol% BaO), where R is the molar ratio of barium oxide to boron oxide. The density, T_g (glass transition temperature), T_x (glass recrystallization temperature), and optical cutoffs were determined. These data were compared with structural models for the glasses based on nuclear magnetic resonance results of Greenblatt and Bray. The barium borate data were also compared with similar studies of lithium and lead borate glasses. Key results observed include: (1) the density trends are understandable in terms of the abundance of the basic borate groups with the fraction of tetrahedral borons being the most important single factor, and (2) the T_gs are anomalously high when compared to either the alkali or lead borate systems.     

Sensitivity of the photo-darkening effect in CuAsSe glasses

When CuAsSe glasses are irradiated, they exhibit higher concentrations of darkening than AsSe glasses. Since darkening depends on the composition, the darkening centers in CuAsSe glasses to be of the same kind as those in AsSe glasses, i.e. arsenic clusters. Concerning the kinetics of erasing, it was found that the activation energy and the rate constant of erasing in CuAsSe are almost equal to those in AsSe glasses, but for the kinetics of darkening, it was found that the activation energy of darkening is equal to that of AsSe but α₀, which is proportional to the number of latent darkening centers, and the darkening rate constant k₁ are about twice as high as the corresponding constants of AsSe glasses. This may be the reason for the greater darkening in CuAsSe glasses. The high value of α₀ was attributed to the generation of more AsAs bonds on the addition of Cu to the AsSe glass network. The high value of k₁ was attributed to the increase in efficiency of photo-decomposition because of the many impurity levels in the band gap and also because of the narrow optical energy gap in the CuAsSe glasses.     

Evaluation of the guided random parameterization method for critical cooling rate calculations

We focus on a recently suggested approach to the calculation of critical cooling rates for glass formation. It is a “random parameterization” method that is guided by a limited number of isothermal scanning calorimetry experiments. However, several assumptions have been made in its derivation that may not mirror the actual crystallization behavior of most supercooled liquids, which may jeopardize the estimation of glass forming ability. We evaluate those assumptions and the applicability of the method is tested for lithium disilicate glass (which displays moderate internal nucleation rates) and dibarium titanium silicate glass (which displays very high internal nucleation rates, similar to those of metallic glasses). Both glasses nucleate homogeneously and exhibit polymorphic crystallization. Our calculations show that some overlooked variables, such as the sample geometry, nucleation induction-times, surface crystallization and the breakdown of the Stokes–Einstein/Eyring equation, have significant roles on the calculated time–temperature–transformation curves during heating experiments. We demonstrate that the proposed random parameterization method can only be used when a glass forming liquid that undergoes internal crystallization is cooled from above its liquidus to various test temperatures. If the sample undergoes predominant surface crystallization or if it is heated to the test temperature several corrections must be made.     

Equilibrium concentration of oxygen rich and deficient defect centers in germanosilicate glasses

Equilibrium concentrations of oxygen rich and deficient defect centers are calculated as a function of temperature and glass redox condition for germanosilicate glasses. We have here used the approach of Silin and Lace [J. Non-Cryst. Solids 149 (1992) 54-61] but extended it to include the case of binary system of germanosilicate glasses. A set of 23 reactions is identified as the possible pathway for formation of different defect centers. Each of these reactions are represented by forward and backward steps with Arrhenius kinetics and their activation energies are estimated based on the relevant bond energies of the involved species. Equilibrium concentrations are determined by setting rates of each of these reactions equal to zero. Typical results are presented for glasses which are: (i) stoichiometric, (ii) glasses with excess oxygen levels of 10¹⁶ to 10²⁰ cm⁻³, and (iii) glasses which are oxygen deficient by 10¹⁶ to 10¹⁸ cm⁻³.     

X-ray scattering studies of the short and medium range ordering in AsxTe1−x glasses

The structures of As_xTe_1−x(x = 0.2, 0.4, and 0.5) glasses are studied using the differential X-ray anomalous scattering technique. The partial distribution functions have also been obtained for the stoichiometric As₂Te₃ glass, giving information on the medium range ordering. All the glasses show chemical disorder to differing extents, the As₂Te₃ glass being the most disordered. The Te coordination number undergoes a change at x=0.4 where it is 2.5 compared with 2 for AsTe. This change indicates the existence of about 50% of threefold Te sites in the stoichiometric glass, as well as in the Te-rich glasses. Some of the physical properties of the glasses may be explained based on these results.     

Effect of cooling on the optical properties and crystallization of UV-exposed photo-thermo-refractive glass

Photo-thermo-refractive (PTR) glass is a multi-component silicate glass that undergoes a refractive index change after UV-exposure and thermal treatment. This photo-thermo-refractivity is due to the precipitation of sodium fluoride nano-crystals; thus the glass remains highly transparent in the visible and near-IR regions. Up to now, most studies focused on the influence of temperature and duration of thermal treatment on the PTR glass properties, but no attention was given to the cooling step after thermal treatment. In this paper, the influence of cooling on crystallization and resulting optical properties of UV-exposed PTR glass is studied. We show that cooling between the nucleation and growth treatments is a mandatory step to achieve the full benefits of the first heat-treatment, i.e., a large number of small crystals. We also show that the main part of the refractive index change occurs on the cooling path after pre-nucleation. Non-isothermal DSC study associated with in situ pre-nucleation treatment shows that pre-nucleation enhances crystallization only if the temperature is decreased below T_g before the second (development) treatment. Using high temperature photometric measurements of the absorption spectra of UV-exposed PTR glasses, we tentatively associate that effect with the presence of liquid drops of a silver containing phase during regular pre-nucleation treatment. This fact explains the necessity to cool such drops below their melting point to obtain nucleation centers for efficient precipitation of NaF nano-crystals.     

Silver valence and local environments in borosilicate and calcium aluminoborate waste glasses as determined from X-ray absorption spectroscopy

Silver K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data were collected and analyzed to characterize silver (Ag) environments in borosilicate and Ca-aluminoborate glass formulations developed as potential candidates for the immobilization of certain nuclear wastes. Silver is found in some nuclear waste streams and must be encapsulated in glass during waste vitrification processes. A related concern deals with phase separation within these glasses and whether colloidal silver would be present in the glass melt, which could present processing issues, or in the waste glass product. Characterization of the silver environments provides useful information for optimizing the silver incorporation ability of such glasses. Data were also gathered on four crystalline standards: Ag-foil, Ag₂O, argentojarosite (AgFe₃(SO₄)₂(OH)₆), and AgO. XANES data indicate Ag⁺ as the dominant species in the glasses. XANES and EXAFS data show that the average Ag environment in the Ca-aluminoborate glass is different compared with those in the two borosilicate glasses investigated. EXAFS analyses show that Ag in the borosilicate glasses is coordinated by two oxygens in a similar environment to that in crystalline Ag₂O, except that the associated Ag–O distances are approximately 0.10 Å longer in the glass. Silver in the Ca-aluminoborate glass may be within one highly disordered site, or possibly, several different sites, where the average Ag–O distance, coordination number, and Debye–Waller factor are larger than those determined for the borosilicate glasses. Despite their relatively high silver contents, there is no evidence from XANES or EXAFS of colloidal silver in the glasses investigated.     

Spectroscopic studies of lead arsenate glasses doped with nickel oxide

Lead arsenate glasses containing different concentrations of NiO ranging from 0 to 1 mol% (in steps of 0.2 mol%) were prepared. The samples were characterized by X-ray diffraction and differential thermal analysis. A number of studies viz., optical absorption, thermoluminescence, magnetic susceptibilities and IR spectra, have been carried out on these glasses. The bands observed in the optical absorption spectra of the glasses have been analyzed using Tanabe-Sugano diagrams for d⁸ ion; the analysis indicates the presence of Ni²⁺ ions in both tetrahedral and octahedral positions. The increase in the concentration of NiO in the glass matrix shows a gradual transformation of nickel ions from tetrahedral positions to octahedral positions in the glass network. The thermoluminescence light output of the X-ray irradiated glasses has exhibited a glow peak at 353 K (with increasing intensity with an increase in the concentration of NiO) in addition to the conventional peak due to the recombination of electron-hole centers; this glow peak is identified due to ³T₂ → ³A₂ emission transition of octahedral Ni²⁺ ions. The value of the magnetic moment evaluated from the measured magnetic susceptibility show a decreasing trend from 3.84 to 3.10 μ_B with the increase in the concentration of NiO. All these studies indicate an increasing presence of octahedral (lasing) Ni²⁺ ions in these glasses with the increase in the concentration of NiO.     

Inhomogeneous nature of UV absorption bands of bulk and surface oxygen-deficient centers in silica glasses

Photochemical and photoluminescence studies of oxygen-deficient centers stabilized in the bulk and on the surface of silica glasses clearly demonstrate the inhomogeneous nature of the absorption and luminescence spectra of oxygen-deficient centers. The conclusion is drawn that the inhomogeneity of the absorption spectra is due to the dispersion of the energy of the S₀-S₁ transition, while the inhomogeneity of the luminescence spectra is due to the dispersion of the energy barrier of intersystem crossing. The inhomogeneous nature of the oxygen-deficient centers in silica glasses is assumed to be caused by a small dispersion in the geometrical parameters of different groups of centers with similar chemical properties.     

High-speed transient currents in chalcogenide glasses

High-speed transient currents are often observed in chalcogenige glasses. We explain these effects by invoking the presence of Valence Alternation Pairs (VAPs). After an electric field is applied across the chalcogenide glass, carriers can tunnel directly from the electrodes onto the appropriately charged defect centers. This leads to the appearance of potential barriers near the contacts, resulting in a rapid decay of the current. Such a mechanism cannot occur in materials without a large concentration of negatively correlated defects.     

Physical aging and molecular mobility of amorphous polymers

The classical approaches of the slow dynamics of liquid glass formers and glasses are recalled. Actually, it is well acknowledged that several features are common to glasses and glass forming liquids. For example, the quasi universal occurrence of secondary β slow (or so-called Johari–Goldstein) relaxation and its correlation with the α relaxation process has to be included in any physical model. This ingredient is now introduced in the coupling model proposed by Ngai. However, recent experimental data, mainly dealing with physical aging, show that some aspects remain unsolved and many questions are still to be answered.