Glasses were prepared in systems based on two stoichiometric sulfides that were selected from Ga2S3, GeS2, and Sb2S3, with the incorporation of excess sulfur and CsCl. We investigated the fundamental properties, including glass transition, density, and optical absorption, and their variations with the incorporation of excess sulfur and CsCl into the pseudo two-component sulfide glasses. The incorporation of CsCl into the GeS2–Sb2S3 glasses shifted the absorption edge at the short-wavelength side to the long-wavelength direction, particularly for glasses with more amount of GeS2 than SbS3/2. In both cases of CsCl incorporation into the Ga2S3–GeS2 glass and Ga2S3–Sb2S3 glass systems, the absorption edges shifted to the short-wavelength direction regardless of the compositions. Ag photodoping behaviors were investigated for the bulk sulfide glasses with excess sulfur and CsCl. The results are discussed based on the diffusion of silver in the glass network that is modified by the incorporation.

Li+ for Na+ ion-exchange-induced phase separation in borosilicate glass was investigated. A glass with a composition, 70SiO2·15B2O3·15Na2O, was prepared. The glass was transparent, and macroscopically no phase separation was observed because the immiscibility temperature for the composition was lower than the glass transition temperature. Substitution of Li+ for Na+ at the surface domain of the glass induced phase separation in the domain and subsequent heat treatment evolved interconnected silica-rich and alkali borate-rich phases through the phase separation. However, the parts in which ion exchange did not occur kept homogeneous and transparent. This phenomenon is explainable by the fact that the immiscibility temperature for the Li+-substituted composition of the original glass elevated up to a temperature higher than the ion exchange and heat treatment temperatures. The borate-rich phases leached by acid treatment for the phase-separated glass. Through these processes, we obtained monolithic glasses consisting of porous domains, and homogeneous and transparent parts.

Emission properties of Er3+ in Ga2S3–GeS2–Sb2S3 glasses at the mid-infrared region were investigated from the viewpoint of their dependence on the concentration of the active ion and the glass composition. In the Judd–Ofelt analysis, no variation in omega parameters were observed when GeS2 was replaced by Ga2S3, while Ω2 increased as Sb2S3 was replaced by Ga2S3. This is due to the structural similarity and difference between the glass network units, GaS4 and GeS4 tetrahedra, and SbS3 pyramid. Clear mid-infrared emissions were observed at 2750 and 4300 nm assigned to the 4I11/2 → 4I13/2 and 4I9/2 → 4I11/2 transitions, respectively. The lifetime of the initial level of the 4.3 μm emission, 4I9/2, rapidly decreased with the Er3+ concentration because of the cross relaxation of this level, which can take place even at considerably low Er3+ concentration. The cross-relaxation processes were suppressed by the increase in the content of Ga2S3 because the solubility of Er3+ ions in the glasses increases with the Ga2S3 content.

To fabricate graded-index optical elements by silver staining, we investigated the behavior of ion incorporation in aluminoborosilicate glasses, in which the contents of Al2O3 and Na2O were the same (in mol%). The amount of silver incorporated into the aluminoborosilicate glasses by the staining at 320 °C for 12 h was 5 to 10 times larger than that incorporated into the soda-lime silicate and borosilicate glasses. The diffusion depth of the incorporated silver ions was approximately 80 μm, which was also much deeper than that of the soda-lime silicate and borosilicate glasses. The coloration of the glasses was suppressed, particularly for the glass with the low content of Na2O. The concentration of the incorporated silver ions at the glass surface was 2 × 1021 atom/cm3 for the 37.5SiO2·25Al2O3·25Na2O·12.5B2O3 glass, corresponding to the replacement of sodium ions (20%). The refractive indices near the stained surfaces increased by 0.04 to 0.06. These values were comparable with those of the soda-lime silicate and borosilicate glasses.

Copper(I) chloride and bromide nanoparticle-dispersed glasses were prepared by means of a conventional copper staining. The staining was performed by the following process: copper stain was applied on the surfaces of Cl−- or Br−-ion-containing borosilicate glasses, and the glasses were heat-treated at 510 °C for various times. Typical exciton bands observed in the absorption spectra of the glasses after the heat treatment indicated that CuCl and CuBr particles were formed in the surface region of the glasses. The average sizes of the CuCl and CuBr particles in the glasses heat-treated for 48 h were estimated at 4.8 and 2.7 nm, respectively. The nanoparticles were also characterized by x-ray diffraction and transmission electron microscopy. Depth profiles of Cu and CuBr concentration in the glass heat-treated for 48 h were measured. Copper decreased in concentration monotonously with depth, reaching up to 60 μm, while the CuBr concentration had a maximum at about 25 μm in depth.

The valence and coordination structure of implanted Cu and Br ions were investigated by x-ray absorption fine structure spectroscopy in (2.4 MeV 6 × 1016 Br2+ ions cm−2+ 2 MeV 6 × 1016 Cu+ ions cm−2)-implanted silica glass. It was found that the implanted Cu and Br atoms were coordinated by oxygen atoms and silicon atoms, respectively, in as-implanted glass. After heating at 600 °C, at least two-thirds of the Cu atoms were coordinated by Br atoms without the formation of crystals. The γCuBr crystal was formed after heating to 1100 °C. It was deduced that the coordination structure of Cu and Br atoms depends on defects as well as thermochemical stability and mass transport processes.

Structure of Cu ions in (Cl+Cu)-, (Br+Cu)-, (I+Cu)-, (S+Cu)- and (Se+Cu)-ion implanted silica glasses has been studied by x-ray absorption and optical absorption spectroscopies. Cu ions formed Cu-O bonds in the as-implanted glasses, due to the homogeneous distribution of Cu ions and the low local concentration of halogen and chalcogen ions in silica glass. Heat treatment at about 600°C caused the formation of bonds between Cu ions and halogen/chalcogen ions without forming Cu halide or chalcogenide crystals. It was deduced that the formation of these bonds was controlled by the diffusion of Cu ions in silica glass. On the other hands, it was inferred that the formation of Cu halide and chalcogenide crystals was controlled not only by the diffusion of halogen/chalcogen ions but also by the diffusion of matrix ions.

Coordination structures of implanted Fe, Co, and Ni ions were studied in 1.78–2.00-MeV 5 × 1016 ions/cm2-implanted silica glasses by x-ray absorption and optical absorption spectroscopies. It was found from x-ray absorption spectra that the implanted Fe, Co, and Ni ions are coordinated by ca.3 oxygen atoms. The implanted ions dispersed in glass matrix and did not form crystals. The valence of the implanted ions was about 1.5. The Fe–O, Co–O, and Ni–O interatomic distances were 190, 191, and 192 pm, respectively. In addition, it was found from optical absorption spectra that one-fifth of implanted Co ions were present as Co2+ ions in tetrahedral symmetry.

180 keV Mn+ ions were implanted in silica glass at doses ranging from 1×1016 to 2×1017 ions/cm2 at room temperature. The coordination structure of implanted Mn atoms was studied by X-ray absorption spectroscopy. It was found that Mn atoms were mainly coordinated by O atoms in silica glasses as-implanted at doses lower than 5×1016Mn+ions/cm2. The Mn-O bond distance was 2.07 Å and the coordination number was 4.3 in average. Mn atoms were mainly coordinated by Mn and O atoms in the glasses as-implanted at doses higher than 1×1017 Mn+ions/cm2. In all the glasses, Mn atoms which are coordinated by O atoms were present as divalent state. After heating at 700 °C in air, Mn atoms were present as trivalent state and tended to form oxide crystals.

We report on the third-order nonlinear optical responses of V2O5 films prepared by pyrolysis of spin-coated films of vanadium 2-ethylhexanoate. Temporal behavior of third-order optical nonlinearity of the spin-coated V2O5 films was examined at a wavelength of 532 nm by the degenerate four-wave mixing (DFWM) technique using a mode locked Nd/YAG laser (35 ps fwhm). Fast relaxation with a lifetime of 25 ps and slow relaxation with a lifetime of 150 ps were observed. The nonlinear transmission experiment on the spin-coated V2O5 films using the same laser source showed that the transmittance decreased with increasing intensity of the incident light. The intensity-dependent absorption coefficients (β) were roughly estimated to be 3.5×10−5 cm/W. Transient absorption properties of the V2O5 film were measured by use of the second and third harmonics of a Q switched Nd/YAG laser (10 ns fwhm). The results observed for the nonlinear transmission and the transient absorption suggest that induced absorption would contribute to the third-order optical nonlinearity of the V2O5 films with fast response times, and also suggest that the V2O5 films have potentiality for use as optical power limiting materials.

Coordination state of gold atoms implanted in silica glass to an energy of 1.5 MeV and a dose of 1 × 1017 ions/cm2 has been studied by x-ray absorption fine structure spectroscopy. It was found that most of the gold atoms form gold clusters in which the nearest neighboring Au–Au interatomic distance is shorter by 0.05 °A than that in bulk gold. The contraction of Au–Au interatomic distance of gold clusters in silica glass is less than that reported in the previous studies on gold clusters within the other substrates. Gold atoms are coordinated by about four gold atoms in average. In addition, it was found that Au–O bonds are formed at the gold clusters/silica glass interface. It was deduced that the formation of Au–O bond at the gold clusters/silica glass interface depresses the contraction of Au–Au interatomic distance.

The local structure and crystallization behavior of Nd15Fe77Bx (x = 2−14) melt-spun alloys were studied by Nd L3 extended x-ray absorption fine structure (EXAFS). The conventional x-ray powder diffractometry studies showed that the Nd–Fe–B melt-spun ribbons had the amorphous structure regardless of the boron content. EXAFS studies of the local structure around the Nd atom confirmed that the Nd–Fe–B melt-spun alloys had the amorphous structure and virtually the same nearest neighbor distance from the Nd atom. The amorphous alloys were heated by a differential scanning calorimetry in order to investigate the variation in the local structure during the crystallization process by EXAFS measurements. Although no appreciable difference was found in the nearest neighbor distance of the Nd atom between the amorphous alloys and the crystallized alloys, the small variation in the nearest neighbor distance during the crystallization process was detected by EXAFS measurements.

The structure of ultrafine gold particles embedded in silica glass by ion implantation has been studied by x-ray absorption fine structure spectroscopy. It is found that the Au–Au interatomic distance in the particles is very similar to that in bulk gold within 0.01 Å. Mean-square relative displacement in the particles is 1.2–1.3 times larger than that in bulk gold.

Degenerate four-wave mixing experiments have been performed for Au colloid-doped glasses prepared by melting and sputtering methods. The nonlinear optical properties of the glasses are discussed from viewpoint of the concentration of the Au colloid particles and the thickness of the glasses. We also discuss the dependence of the nonlinear properties on the pulse duration of laser for the measurements, and a very slow relaxation.