Effect of PbO on precipitation of laser-induced gold nanoparticles inside silicate glasses

We report on three-dimensional precipitation of Au nanoparticles in gold ions-doped silicate glasses by a femtosecond laser irradiation and further annealing. Experimental results show that PbO addition plays the double roles of inhibiting hole-trapped centers generation and promoting formation and growth of gold nanoparticles. Additionally, glass containing PbO shows an increased non-linear absorption after femtosecond laser irradiation and annealing. The observed phenomena are significant for applications such as fabrications of three-dimensional multi-colored images inside transparent materials and three-dimensional optical memory, and integrated micro-optical switches.     

Preparation and optical properties of silver nanoparticles induced by a femtosecond laser irradiation

Silver nanoparticles were prepared by a focused femtosecond laser irradiation in a 5 mM AgNO₃ solution in the presence of TiO₂ sol. TEM analysis revealed that the size of silver nanoparticles was less than 20 nm. A mechanism for the precipitation of silver nanoparticles was proposed. Nonlinear absorptions and optical limiting properties of silver nanoparticles contained solution were also measured. It is observed that the composite material showed strong self-focused effect and significant optical limiting property.     

Valence state change and refractive index change induced by femtosecond laser irradiation in Sm3+ doped fluoroaluminate glass

We report femtosecond laser induced valence state and refractive index change in transparent Sm³⁺-doped fluoroaluminate glass. The effect of annealing on the induced changes was studied and the thermal stability of these changes was discussed. The results show that the femtosecond laser induced valence state change is more stable than the induced refractive index change. The observed phenomenon could be applied to design the thermally erasable or stable storage medium.     

Controllable space selective precipitation of copper nanoparticles in borosilicate glasses using ultrafast laser irradiation

Transparent glasses containing copper nanoparticles are promising materials for ultrafast all-optical switches in the THz region due to their wide range of resonant absorption frequencies, ultrafast time response, as well as large third-order nonlinear optical coefficients associated with the surface plasmon resonance (SPR) in the visible region. In this paper, three dimension controllable precipitation of copper nanoparticles inside a borosilicate glass by irradiation of femtosecond laser pulses is studied. According to the designed program, different patterns made up of copper nanoparticles can be induced inside the glass sample. Absorption spectra are used to confirm the precipitation of copper nanoparticles. The precipitated nanoparticles can be space-selectively “dissolved” by the second time femtosecond laser irradiation. The involved mechanisms are discussed.     

Nanofabrication in transparent materials with a femtosecond pulse laser

Femtosecond lasers have been applied for materials processing when high accuracy and small structure size are required. Various induced structures have been observed inside glasses after the femtosecond laser irradiation. We report the femtosecond laser induced refractive-index change, space-selective valence state change of active ions, formation of nanograting, and precipitation and distribution of nanoparticles. We systematically studied the morphology of structures that are induced in the bulk of transparent materials by the tightly focused femtosecond laser radiation. Rugby-ball-like asymmetric induced structures were observed inside Ag⁺-doped silicate glass. These structures are due to the aggregation of Ag nanoparticles at the depth of the focal point. The size of the induced structure depended on the time interval between successive femtosecond laser pulses. In the case of zinc-tellurite glass, TeO₂ rich parts were formed in the center of the focal spot, while zinc migrated to the outside. The mechanisms of the observed phenomena are discussed.     

UV assisted local crystallization in Er3+ doped oxy-fluoride glass

We report on fabrication of Er³⁺-activated LaF₃ nanocrystals in transparent glasses using an original technique, which combines both heat treatment, below glass crystallization temperature, and ultraviolet laser irradiation at 244 nm. The main advantage of this method is to control the spatial localization of the nanoparticles in the glass sample, whereas annealing solely at the crystallization temperature leads to a fully crystallized glass sample. Thermal differential analysis was used to determine the crystallization temperature of the sample. The photoluminescence spectra behaviour of Er³⁺ ions, collected from the UV-irradiated and unirradiated regions, allowed us to follow and to distinguish the structural changes in the glass network under heat treatment and ultraviolet exposure.     

Rapid synthesis of copper nanoparticles by sodium hypophosphite reduction in ethylene glycol under microwave irradiation

This paper presents a rapid method for preparation of copper metal nanoparticles by reducing CuSO₄·5H₂O with NaH₂PO₂·H₂O in ethylene glycol under microwave irradiation. The influences of the reaction parameters, such as the concentrations of reducing agent and protective polymer time of microwave irradiation, on the size and agglomeration of copper nanoparticles were investigated by X-ray powder diffraction and transmission electron microscope. Well-dispersed copper nanoparticles with diameter of about 10 nm were obtained. The use of microwave irradiation accelerated the reaction rate and benefited the dispersion and the particle size distribution of the nanoparticles.     

Ultrafast modification of elements distribution and local luminescence properties in glass

The success in construction of three-dimensional micro optical components or devices inside transparent materials is highly dependent on the ability to modify materials’ local structure. Especially, the realization of space-selective manipulation of element distribution is highly desirable since most of optical parameters such as refractive index and luminescence are closely related to element distribution. Up to present, the only way to control selective element distribution is local melting of glass. Here, we reported, for the first time to our knowledge, the success in realization of space-selective manipulation of element distribution in glassy state region (i.e., un-melted region) inside glass with the irradiation of high repetition rate femtosecond laser. Confocal fluorescence spectra and micro-Raman spectra show that the luminescence distribution of Cu⁺ ions and the glass network structure can be controlled with femtosecond laser irradiation, revealing the potential applications of this technique in the fabrication of functional waveguides and integrated optical devices.     

Aerosol synthesis and reactive behavior of faceted aluminum nanocrystals

We show a low temperature gas-phase synthesis route to produce faceted aluminum crystals in the aerosol phase. Use of triisobutylaluminum whose decomposition temperature is below the melting point of elemental aluminum enabled us to grow nanocrystals from its vapor. TEM shows both polyhedral crystalline and spherical particle morphologies, but with the addition of an annealing furnace one can significantly enhance the production of just the polyhedral particles. The results on surface passivation with oxygen suggest that these nanocrystals are less pyrophoric than the corresponding spherical aluminum nanoparticles, and combustion tests show an increase in energy release compared to commercial nanoaluminum.     

Role of bromine on the thermal and optical properties of photo-thermo-refractive glass

Photo-thermo-refractive (PTR) glass is a photosensitive silicate glass doped with cerium, silver, and fluorine. The precipitation of a minor crystalline phase after UV-exposure and thermal treatment induces a refractive index change, which is large enough to create diffractive optical elements. In this work we present a first attempt to understand the role of bromine on thermal and optical properties of PTR glass. We reveal that at least 75% of the concentration of bromine of commercial PTR glass is necessary to produce photo-induced crystallization. We also show that an increase of the bromine concentration will increase the mean refractive index of virgin PTR glass. Further thermal treatments induce a decrease of the mean refractive index of PTR glass. This decrease is finally shown to be larger in UV-exposed glass if photo-induced crystallization is present. We also show that bromine concentration will decrease water concentration in PTR glass and have an impact on the losses in visible. We demonstrate that the higher the bromine concentration, the higher the shift of the silver containing particles absorption band. In addition, if bromine concentration is high enough to produce photosensitivity, an increase of scattering due to the crystallization process is observed.     

Surface analysis of different oriented GaAs substrates annealed under bismuth flow

Several orientations of GaAs substrates, including (1 0 0), (4 1 1), (1 1 1) and (5 1 1) have been annealed in a metalorganic vapour phase epitaxy (MOVPE) horizontal reactor at different annealing temperatures and under different trimethyl-bismuth (TMBi) flux. Surface morphology of the annealed GaAs substrates was investigated by means of scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show islands formation on all the studied samples. The density and size of Bi islands vary greatly with annealing temperature and TMBi flow. For different substrate orientations, the activation energies were deduced from Arrhenius plot of island density. Except for (5 1 1) oriented GaAs, all the studied orientations show the same activation energy of 1.8 eV. For low annealing temperature 420 °C, and under different Bi flux, each oriented substrate shows a specific behaviour. For higher temperatures 700 °C and above Bi islands are totally removed and the substrates are smooth. Surface change of (1 0 0) oriented GaAs substrate was in situ monitored by laser reflectometry.     

Effect of thickness and heat treatment on the crystallite size and dislocation density of nanostructured zinc oxide thin films

The zinc oxide thin films were deposited by the sol–gel method on the glass microscope slide substrates. The microstructure of films was determined as a function of film thickness as well as annealing temperature using X-ray line broadening technique and applying whole powder pattern modeling (WPPM). This investigation showed that the film thickness has no significant effect on the grain size, whereas the dislocation density decreases with the film thickness. On the other hand with the rise of annealing temperature the dislocation density decreases, but the crystallite size becomes larger.     

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.     

Study on Ag doping in congruent lithium niobate crystal

Ag doped congruent lithium niobate crystal has been demonstrated as a promising photorefractive material for holographic recording applications. In this paper, the effects of Ag doping on the lattice structure and the optical properties were investigated by XRD, Raman spectroscopy and optical absorption characterization. The Ag ion was proposed to occupy Li-sites and results in lattice deformation. The band gap became narrower and an absorption band at near 500 nm was created with Ag doping. High temperature annealing and UV irradiation were performed to further understand the Ag doping effects.     

Microstructural modification of chalcogenide glasses by femtosecond laser

With the irradiation by femtosecond (fs) laser with high repetition rate, GeS₂ micro/nano-crystalline formation and microstructural modification occurred in pseudo-binary GeS₂–In₂S₃ glass, while almost no similar change was observed in GeS₂ glass. The addition of In₂S₃ is beneficial for the precipitation of GeS₂ micro/nano-crystals. It is expected that functional micro/nano-crystals can be controllably prepared in chalcogenide glasses by fs laser irradiation through glass composition design.     

Growth of epitaxial TmFeCuO4 thin films by pulsed laser deposition

Epitaxial thin films of TmFeCuO₄ with a two-dimensional triangular lattice structure were successfully grown on yttria-stabilized-zirconia substrates by pulsed laser deposition and ex situ annealing in air. The films as-deposited below 500 °C showed no TmFeCuO₄ phase and the subsequent annealing resulted in the decomposition of film components. On the other hand, as-grown films deposited at 800 °C showed an amorphous nature. Thermal annealing converted the amorphous films into highly (0 0 1)-oriented epitaxial films. The results of scanning electron microscopic analysis suggest that the crystal growth process during thermal annealing is dominated by the regrowth of non-uniformly shaped islands to the distinct uniform islands of hexagonal base.     

Intrinsic gettering in germanium-doped Czochralski crystal silicon crystals

The intrinsic gettering (IG) of germanium-doped Czochralski (GCZ) silicon with different concentrations of germanium has been investigated in this paper. The conventional Czochralski (CZ) and the GCZ silicon samples were annealed using a one-step high temperature process followed by a sequence of low–high temperature annealing cycles. It was found that the good defect-free denude zones in the near surface of the GCZ silicon could be achieved using simply a one-step high temperature annealing process. Furthermore, the density of bulk microdefects as IG sites was higher than that in the CZ silicon, as a result of germanium enhancing oxygen precipitation during three-step annealing. Meanwhile, the experimental results showed that germanium also enhanced the out-diffusion of oxygen. Furthermore, it is believed that germanium doping can increase the ability of IG in CZ silicon wafers.     

An analytical model for combined radiative and conductive heat transfer in fiber-loaded silica aerogels

An improved analytical model for the total thermal conductivity of fiber-loaded silica aerogels was developed based on the complex refractive index, size, orientation, volume fraction and morphology of the fibers and silica aerogel. A cubic array of spherical porous secondary nanoparticles and a modified parallel-series model were proposed to model the combined solid and gaseous thermal conductivities. An anomalous diffraction theory (ADT) was used to predict the fiber extinction coefficient. Five common fiber types in the composites were studied including amorphous SiO₂ glass, silicon glass, common float glass, soda lime silica glass and borosilicate glass. The results show that the total extinction coefficient of the silica aerogel system is largest by loading with the common float glass fiber and lowest by loading with the soda lime silica glass among the five fiber types. The model provides theoretic guidelines for material designs with optimum parameters, such as the type, inclination angle, volume fraction and diameter of the fibers as well as the aerogel nanoparticle and pore sizes. The optimum fiber for improved thermal insulation should have a large spectral complex refractive index throughout the infrared region.     

The growth of Pd thin films on a 6H-SiC(0 0 0 1) substrate

Pd thin films, grown on Si-rich 6H-SiC(0 0 0 1) substrates, were studied by atomic force microscopy, electron diffraction and high-resolution transmission electron microscopy. It is concluded that the growth is successful only when all the growth process takes place at room temperature. Under these conditions a very good epitaxial growth of Pd is achieved, despite the large misfit (about 8.6%) between Pd and the substrate and the existence of a semi-amorphous layer between the thin film and the substrate. A large number of twins appear in these films.     

The temperature gradient technique (TGT) growth and optical properties of Yb-doped YAlO3 single crystal

The dark-brown colored 5 at% Yb-doped YAlO₃ (Yb:YAP) single crystal was grown successfully by temperature gradient technique (TGT) for the first time. The TGT-grown Yb:YAP crystal with the perovskite structure and excellent crystallization perfection were confirmed by the X-ray diffractions techniques. The dark-brown color of TGT-Yb:YAP crystal turned into the colorless after annealing in the air at 1200 °C for 10 h. The absorption spectra, LD-excited infrared emission and X-ray excited luminescence spectra of the air-annealed Yb:YAP single crystal were investigated at the room temperature. The results indicate that the TGT-Yb:YAP single crystals can be used for the laser and scintillation applications.