Ultrafast-Laser-Induced Tailoring of Crystal-in-Glass Waveguides by Precision Partial Remelting.

Space-selective laser-induced crystallization of glass enables direct femtosecond laser writing of crystal-in-glass channel waveguides having nearly single-crystal structure and consisting of functional phases with favorable nonlinear optical or electrooptical properties. They are regarded as promising components for novel integrated optical circuits. However, femtosecond-laser-written continuous crystalline tracks typically have an asymmetric and strongly elongated cross-section, which causes a multimode character of light guiding and substantial coupling losses. Here, we investigated the conditions of partial remelting of laser-written LaBGeO5 crystalline tracks in lanthanum borogermanate glass by the same femtosecond laser beam which had been used for their writing. Exposure to femtosecond laser pulses at 200 kHz repetition rate provided cumulative heating of the sample in the vicinity of the beam waist sufficient to provide space-selective melting of crystalline LaBGeO5. To form a smoother temperature field, the beam waist was moved along the helical or flat sinusoidal path along the track. The sinusoidal path was shown to be favorable for tailoring the improved cross-section of the crystalline lines by partial remelting. At optimized laser processing parameters, most of the track was vitrified, and the residual part of the crystalline cross-section had an aspect ratio of about 1:1. Thermal-induced stress emerging during the tailoring procedure was efficiently eliminated by fine post-annealing. The proposed technique suggests a new way to control the morphology of laser-written crystal-in-glass waveguides by tailoring their cross-section, which is expected to improve the mode structure of the guided light.

Effect of Pulse Repetition Rate on Ultrafast Laser-Induced Modification of Sodium Germanate Glass.

We report an unexpected pulse repetition rate effect on ultrafast-laser modification of sodium germanate glass with the composition 22Na2O 78GeO2. While at a lower pulse repetition rate (~≤250 kHz), the inscription of nanogratings possessing form birefringence is observed under series of 105-106 pulses, a higher pulse repetition rate launches peripheral microcrystallization with precipitation of the Na2Ge4O9 phase around the laser-exposed area due to the thermal effect of femtosecond pulses via cumulative heating. Depending on the pulse energy, the repetition rate ranges corresponding to nanograting formation and microcrystallization can overlap or be separated from each other. Regardless of crystallization, the unusual growth of optical retardance in the nanogratings with the pulse repetition rate starting from a certain threshold has been revealed instead of a gradual decrease in retardance with the pulse repetition rate earlier reported for some other glasses. The repetition rate threshold of the retardance growth is shown to be inversely related to the pulse energy and to vary from ~70 to 200 kHz in the studied energy range. This effect can be presumably assigned to the chemical composition shift due to the thermal diffusion of sodium cations occurring at higher pulse repetition rates when the thermal effect of the ultrashort laser pulses becomes noticeable.

One-Stage Femtosecond Laser-Assisted Deposition of Gold Micropatterns on Dielectric Substrate.

In this study, a simple one-stage laser-assisted metallization technique based on laser-induced backside wet etching and laser-induced chemical liquid-phase deposition is proposed. It allows for the fabrication of gold micropatterns inside the laser-written trace on a glass substrate. The reduction and deposition of gold inside and outside the laser-ablated channel were confirmed. The presence of Au nanoparticles on the surface of the laser-written micropattern is revealed by atomic force microscopy. The specific resistivity of the gold trace formed by ultrafast light-assisted metal micropatterning on a dielectric glass substrate is estimated as 0.04 ± 0.02 mΩ·cm. The obtained results empower the method of the selective laser-assisted deposition of metals on dielectrics and are of interest for the development of microelectronic components and catalysts, heaters, and sensors for lab-on-a-chip devices.

Defect-assisted photocatalytic activity of glass-embedded gallium oxide nanocrystals.

The use of glassceramics in photocatalysis is an attractive option for the realization of smart optical fibers and self-cleaning windows. Here we present the photocatalytic activity of germanosilicate glasses embedding Ga2O3 nanocrystals prepared by batch melting and glass heat treatment. The powdered material is used for UV-assisted degradation of rhodamine in water. The kinetics show changes after repeated experiments. In the first cycle, the apparent rate is governed by a second-order reaction with a Gaussian-like shape, whereas the second cycle follows a first-order reaction. The modification appears to be correlated with perturbations in the defect population. Photoluminescence has been used to monitor the evolution of such defects. Kinetic data on photoreactions and defect formation have been modelled in a combined frame in which the defect concentration determines the photocatalytic activity. The results prove the photocatalytic ability of the studied glassceramics. Moreover, the general validity of the kinetic model can be of interest for other systems in which the photocatalytic response depends on photoreactive species concentration.

Hollow Channel Formation inside Sodium Aluminoborate Glass by Femtosecond Laser Writing and Distilled Water Etching.

Recently, the effect of nanograting formation was demonstrated for binary sodium borate glass with the possibility of data storage with an enhanced level of security. The obvious disadvantage of such glass is poor chemical stability, which limits real applications. In this paper, we show that the introduction of Al2O3 allows preserving the possibility of nanograting formation with a significant increase of chemical resistance and thus to preserve optical memory applications. On the other hand, the possibility of selective etching of laser-written tracks by means of distilled water is revealed, which was not demonstrated for other types of glasses. The dependence of retardance of nanogratings form birefringence on laser writing parameters is established and discussed. Structural features of laser-modified microdomains are studied via Raman spectroscopy which revealed an increase of three-coordinated boron content. A possible mechanism of selective etching is discussed.

Data on the femtosecond laser-induced formation of tracks in silver-containing zinc phosphate glass.

Direct femtosecond laser writing of tracks in the volume of silver-containing zinc phosphate glass is investigated. Tracks were written by the femtosecond laser irradiation with the wavelength of 1030 nm, the pulse duration of 180 fs and a scanning speed of 1 mm/s. The data shows the effect of the pulse repetition rate (10, 100 and 500 kHz) and the pulse energy (60-120 nJ) on the microstructure and optical properties of the laser-written tracks. The data was collected by optical microscopy in the brightfield and fluorescence mode. Moreover, the data shows the dependence of the width and height of the laser-written tracks on the pulse energy and pulse repetition rate.

Glass: Home of the Periodic Table.

Glass is the most common material around us, and humankind uses it every day for more than 5000 years. However, from the chemical point of view, glass is the only material that could represent almost all elements of the Periodic Table inside itself, showing the effect of the Periodic Law on properties of the final material. In this paper, we show the most remarkable examples demonstrating that glass can rightfully be called "home" for all chemical elements providing different properties depending on its composition. We gave a new look at the Periodic Table and described how a small number of glass-forming components creates unique glass structure which could enclose almost all remaining elements including transition and noble metals, lanthanides and actinides as modifying components providing an inconceivable number of discoveries in material science. Moreover, we reviewed a series of studies on the direct femtosecond laser writing in glasses which paves the way for a redistribution of chemical elements in the spatially confined nanosized zone in glass volume providing unique properties of laser-induced structures. Finally, for the first time, we reproduce the Periodic Table in birefringence colors in the bulk of silica glass using a direct laser writing technique. This image of 3.6 × 2.4 mm size can withstand temperature up to 900°C, humidity, electromagnetic fields, powerful cosmic and reactor radiation and other environmental factors and demonstrates both the art of direct laser writing and symbolic role of glass as the safest and eternal home for the Periodic Table.

Multiwalled Carbon Nanotubes and the Electrocatalytic Activity of Gluconobacter oxydans as the Basis of a Biosensor.

This paper considers the effect of multiwalled carbon nanotubes (MWCNTs) on the parameters of Gluconobacter oxydans microbial biosensors. MWCNTs were shown not to affect the structural integrity of microbial cells and their respiratory activity. The positive results from using MWCNTs were due to a decrease in the impedance of the electrode. The total impedance of the system decreased significantly, from 9000 kOhm (G. oxydans/chitosan composite) to 600 kOhm (G. oxydans/MWCNTs/chitosan). Modification of the amperometric biosensor with nanotubes led to an increase in the maximal signal from 65 to 869 nA for glucose and from 181 to 1048 nA for ethanol. The biosensor sensitivity also increased 4- and 5-fold, respectively, for each of the substrates. However, the addition of MWCNTs reduced the affinity of respiratory chain enzymes to their substrates (both sugars and alcohols). Moreover, the minimal detection limits were not reduced despite a sensitivity increase. The use of MWCNTs thus improved only some microbial biosensor parameters.

Author Correction: Single shot laser writing with sub-nanosecond and nanosecond bursts of femtosecond pulses.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

Multilevel data writing in nanoporous glass by a few femtosecond laser pulses.

Multidimensional data recording inside nanoporous high-silica glass by a femtosecond laser beam has been investigated. It is shown that three femtosecond laser pulses at pulse repetition rates up to 1 MHz are sufficient for recording 3 bits of information inside nanoporous glass, which is an order of magnitude lower than the number of pulses required for data writing in silica glass and provides a corresponding gain in the data writing speed. Multilayer data recording and reading were demonstrated providing the storage density corresponding to the capacity of 25 GB in the optical compact disc form factor. An outstanding thermal stability of the proposed optical data storage is confirmed by the 24 h long heat treatment at 700°C, which could not damage the recorded data.

Single shot laser writing with sub-nanosecond and nanosecond bursts of femtosecond pulses.

A method is proposed for efficient laser modification of fused silica and sapphire by means of a burst of femtosecond pulses having time separation in the range 10-3000 ps. Modification enhancement with the pulse separation increase in the burst was observed on the tens picoseconds scale. It is proposed that accumulated transient tensile strain in the excitation region plays a crucial role in modification by a sub-nanosecond burst.

Augmented excitation cross section of gadolinium ions in nanostructured glasses.

In this Letter, we present detailed absorption and emission data on nanostructured germanosilicate glasses and glass ceramics containing Ga2O3 nanophases and doped with Gd ions. The results show that these systems are suitable hosts for the enhancement of the excitation cross section of rare earth ions via energy transfer from the gallium oxide nanophase with a related quantum yield of 21%. The role of matrix composition and nanostructure morphology on the Gd emission is discussed.

Donor-Acceptor Control in Grown-in-Glass Gallium Oxide Nanocrystals by Crystallization-driven Heterovalent Doping.

Incorporation of doping ions in nanocrystals is a strategy for providing nanophases with functions directly related to ion features. At the nanoscale, however, doping can also activate more complex effects mediated by perturbation of the nanophase size and structure. Here, we report a paradigmatic case in which we modify grown-in-glass γ-Ga2 O3 nanophases by nickel or titanium doping of the starting glass, so as to control the concentration of oxygen and gallium vacancies responsible for the light emission. Optical absorption and luminescence show that Ni2+ and Ti4+ ions enter into the nanophase, but differential scanning calorimetry and X-ray diffraction indicate that Ni and Ti also work as modifiers of nanocrystal growth. As a result, doping influences nanocrystal size and concentration, which in turn dictate the number of donors and acceptors per nanocrystal. Finally, the chain of effects turns out to control both the intensity and spectral distribution of the light emission.

Light-emitting Ga-oxide nanocrystals in glass: a new paradigm for low-cost and robust UV-to-visible solar-blind converters and UV emitters.

Wide-bandgap nanocrystals are an inexhaustible source of tuneable functions potentially addressing most of the demand for new light emitting systems. However, the implementation of nanocrystal properties in real devices is not straightforward if a robust and stable optical component is required as a final result. The achievement of efficient light emission from dense dispersions of Ga-oxide nanocrystals in UV-grade glass can be a breakthrough in this regard. Such a result would permit the fabrication of low cost UV-to-visible converters for monitoring UV-emitting events on a large-scale - from invisible hydrogen flames to corona dispersions. From this perspective, γ-Ga2O3 nanocrystals are developed by phase separation in Ga-alkali-germanosilicate glasses, obtaining optical materials based on a UV transparent matrix. Band-to-band UV-excitation of light emission from donor-acceptor pair (DAP) recombination is investigated for the first time in embedded γ-Ga2O3. The analysis of the decay kinetics gives unprecedented evidence that nanosized confinement of DAP recombination can force a nanophase to the efficient response of exactly balanced DAPs. The results, including a proof of concept of UV-to-visible viewer, definitely demonstrate the feasibility of workable glass-based fully inorganic nanostructured materials with emission properties borrowed from Ga2O3 single-crystals and tailored by the nanocrystal size.

Spatially selective Au nanoparticle growth in laser-quality glass controlled by UV-induced phosphate-chain cross-linkage.

Herein we describe how UV excitation of localized electronic states in phosphate glasses can activate structural rearrangements that influence the kinetics of Au nanoparticle (NP) thermal growth in Au-doped glass. The results suggest a novel strategy to address the problem of controlling nano-assembly processes of metal NP patterns in fully inorganic and chemically stable hard materials, such as laser-quality glasses. We show that the mechanism is promoted by opening and subsequent cross-linkage of phosphate chains under UV excitation of non-bridging groups in the amorphous network of the glass, with a consequent modification of Au diffusion and metal NP growth. Importantly, the micro-Raman mapping of the UV-induced modifications demonstrates that the process is restricted within the beam waist region of the focused UV laser beam. This fact is consistent with the need for more than one excitation event, close in time and in space, in order to promote structural cross-linkage and Au diffusion confinement. The stability of the photo-induced modifications makes it possible to design new metal patterning approaches for the fabrication of three-dimensional metal structures in laser-quality materials for high-power nonlinear applications.

Native amorphous nanoheterogeneity in gallium germanosilicates as a tool for driving Ga2O3 nanocrystal formation in glass for optical devices.

Nanoparticles in amorphous oxides are a powerful tool for embedding a wide range of functions in optical glasses, which are still the best solutions in several applications in the ever growing field of photonics. However, the control of the nanoparticle size inside the host material is often a challenging task, even more challenging when detrimental effects on light transmittance have to be avoided. Here we show how the process of phase separation and subsequent nanocrystallization of a Ga-oxide phase can be controlled in germanosilicates - prototypal systems in optical telecommunications - starting from a Ga-modified glass composition designed to favour uniform liquid-liquid phase separation in the melt. Small angle neutron scattering data demonstrate that nanosized structuring occurs in the amorphous as-quenched glass and gives rise to initially smaller nanoparticles, by heating, as in a secondary phase separation. By further heating, the nanophase evolves with an increase of nanoparticle gyration radius, from a few nm to a saturation value of about 10 nm, through an initial growing process followed by an Ostwald ripening mechanism. Nanoparticles finally crystallize, as indicated by transmission electron microscopy and X-ray diffraction, as γ-Ga(2)O(3)- a metastable gallium oxide polymorph. Infrared reflectance and photoluminescence, together with the optical absorption of Ni ions used as a probe, give an indication of the underlying interrelated processes of the structural change in the glass and in the segregated phase. As a result, our data give for the first time a rationale for designing Ga-modified germanosilicates at the nanoscale, with the perspective of a detailed nanostructuring control.

A wind tunnel test of newly developed personal bioaerosol samplers.

In this study the performance of two newly developed personal bioaerosol samplers was evaluated. The two test samplers are cyclone-based personal samplers that incorporate a recirculating liquid film. The performance evaluations focused on the physical efficiencies that a personal bioaerosol sampler could provide, including aspiration, collection, and capture efficiencies. The evaluation tests were carried out in a wind tunnel, and the test personal samplers were mounted on the chest of a full-size manikin placed in the test chamber of the wind tunnel. Monodisperse fluorescent aerosols ranging from 0.5 to 20 microm were used to challenge the samplers. Two wind speeds of 0.5 and 2.0 m/sec were employed as the test wind speeds in this study. The test results indicated that the aspiration efficiency of the two test samplers closely agreed with the ACGIH inhalable convention within the size range of the test aerosols. The aspiration efficiency was found to be independent of the sampling orientation. The collection efficiency acquired from these two samplers showed that the 50% cutoff diameters were both around 0.6 microm. However the wall loss of these two test samplers increased as the aerosol size increased, and the wall loss of PAS-4 was considerably higher than that of PAS-5, especially in the aerosol size larger than 5 microm, which resulted in PAS-4 having a relatively lower capture efficiency than PAS-5. Overall, the PAS-5 is considered a better personal bioaerosol sampler than the PAS-4.

Evaluation of physical sampling efficiency for cyclone-based personal bioaerosol samplers in moving air environments.

The need to determine occupational exposure to bioaerosols has notably increased in the past decade, especially for microbiology-related workplaces and laboratories. Recently, two new cyclone-based personal bioaerosol samplers were developed by the National Institute for Occupational Safety and Health (NIOSH) in the USA and the Research Center for Toxicology and Hygienic Regulation of Biopreparations (RCT & HRB) in Russia to monitor bioaerosol exposure in the workplace. Here, a series of wind tunnel experiments were carried out to evaluate the physical sampling performance of these two samplers in moving air conditions, which could provide information for personal biological monitoring in a moving air environment. The experiments were conducted in a small wind tunnel facility using three wind speeds (0.5, 1.0 and 2.0 m s(-1)) and three sampling orientations (0°, 90°, and 180°) with respect to the wind direction. Monodispersed particles ranging from 0.5 to 10 µm were employed as the test aerosols. The evaluation of the physical sampling performance was focused on the aspiration efficiency and capture efficiency of the two samplers. The test results showed that the orientation-averaged aspiration efficiencies of the two samplers closely agreed with the American Conference of Governmental Industrial Hygienists (ACGIH) inhalable convention within the particle sizes used in the evaluation tests, and the effect of the wind speed on the aspiration efficiency was found negligible. The capture efficiencies of these two samplers ranged from 70% to 80%. These data offer important information on the insight into the physical sampling characteristics of the two test samplers.

Microfluorescence analysis of nanostructuring inhomogeneity in optical fibers with embedded gallium oxide nanocrystals.

A spectroscopic protocol is proposed to implement confocal microfluorescence imaging to the analysis of microinhomogeneity in the nanocrystallization of the core of fibers belonging to a new kind of broadband fiber amplifier based on glass with embedded nanocrystals. Nanocrystallization, crucial for achieving an adequate light emission efficiency of transition metal ions in these materials, has to be as homogeneous as possible in the fiber to assure optical amplification. This requirement calls for a sensitive method for monitoring nanostructuring in oxide glasses. Here we show that mapping microfluorescence excited at 633 nm by a He-Ne laser may give a useful tool in this regard, thanks to quasi-resonant excitation of coordination defects typical of germanosilicate materials, such as nonbridging oxygens and charged Ge-O-Ge sites, whose fluorescence are shown to undergo spectral modifications when nanocrystals form into the glass. The method has been positively checked on prototypes of optical fibers--preventively characterized by means of scanning electron microscopy and energy dispersive spectroscopy--fabricated from preforms of Ni-doped Li2O-Na2O-Sb2O3-Ga2O3-GeO2-SiO2 glass in silica cladding and subjected to heat treatment to activate gallium oxide nanocrystal growth. The method indeed enables not only the mapping of the crystallization degree but also the identification of drawing-induced defects in the fiber cladding.

Performance evaluation of two personal bioaerosol samplers.

In this study, the performance of two newly developed personal bioaerosol samplers for monitoring the level of environmental and occupational airborne microorganisms was evaluated. These new personal bioaerosol samplers were designed based on a swirling cyclone with recirculating liquid film. The performance evaluation included collection efficiency tests using inert aerosols, the bioaerosol survival test using viable airborne microorganism, and the evaluation of using non-aqueous collection liquid for long-period sampling. The test results showed that these two newly developed personal bioaerosol samplers are capable of doing high efficiency, aerosol sampling (the cutoff diameters are around 0.7 µm for both samplers), and have proven to provide acceptable survival for the collected bioaerosols. By using an appropriate non-aqueous collection liquid, these two personal bioaerosol samplers should be able to permit continuous, long-period bioaerosol sampling with considerable viability for the captured bioaerosols.