Chemistry Platform for the Ultrafast Continuous Synthesis of High-Quality III-V Quantum Dots.

A chemistry platform for the fast continuous synthesis of III-V quantum dots is demonstrated. III-nitride QDs are prepared by using short residence times (less than 30 s) in a one-step continuous process with supercritical solvents. GaN QDs prepared via this route exhibit strong UV photoluminescence with a structuring of the emission signal at low temperature (5 K), confirming their high quality. An example of metal site substitution is given with the synthesis of Inx Ga1-x N solid solution. A continuous bandgap shift towards lower energies is demonstrated when increasing the indium content with strong photoluminescence signals from UV to visible. The chemistry platform proposed could be easily extrapolated to binary and ternary III phosphides or arsenides with the homologous V source.

Optical Emission Detector Based on Plasma Discharge Generation at the Tip of a Multimaterial Fiber.

Experimental development of a compact optical emission detector based on the assembly of a polymer-metal and a standard silica fiber is presented in this paper. This device is exploited in a proof-of-principle experiment for gas detection application by means of plasma spectroscopy in the visible-Near Infrared spectral region. A multimode fiber (MMF) is associated with a functional hollow dual-electrodes elongated structure fabricated by the direct preform-to-fiber homothetic co-drawing. A potential of 1.5 kV is applied between the two electrodes embedded inside the composite cladding, which generates an atmospheric pressure dc glow discharge at the tip of the fiber bundle. The emitted light is then collected by the MMF for optical diagnostics. Probing of different atmospheres is presented at the end of this study.

Sub-diffraction-limited fluorescent patterns by tightly focusing polarized femtosecond vortex beams in a silver-containing glass.

We report that the shape and size of fluorescent patterns can be controlled by the focused laser intensity distribution, which depends on irradiation conditions as well as on the spin and orbital angular momenta being carried by light, inducing the formation of silver cluster patterns in a silver-containing zinc phosphate glass. In particular, we demonstrate that sub-diffraction-limited inner structures of fluorescent patterns can be generated by direct laser writing (DLW) with tightly focused femtosecond laser vortex beams as Laguerre-Gauss modes (LG0l) with linear and left-handed circular polarizations. We believe this technique, further combined with dual-color DLW, can be useful and powerful for developing structured light enabled nanostructures.

Patterning linear and nonlinear optical properties of photosensitive glasses by femtosecond structured light.

We report on structured light-induced femtosecond direct laser writing (DLW) under tight focusing in non-commercial silver-containing zinc phosphate glass, which leads to original patterns of fluorescent silver clusters. These fluorescence topologies show unique features of frustrated diffusion of charged species, giving rise to distorted silver cluster spatial distributions. Fluorescence and second harmonic generation correlative microscopy demonstrate the realization of structured light-induced direct laser poling, resulting from a laser-induced permanent and stable electric field buried inside the modified glass. Thus, structured light-induced DLW remarkably enables both linear and nonlinear patterning. This work highlights the interest of optical phase engineering to obtain nontrivial beam profiles and subsequent photo-induced patterns that cannot be reached under Gaussian beam irradiation.

Dual-color control and inhibition of direct laser writing in silver-containing phosphate glasses.

We report on dual-color control of femtosecond direct laser writing (DLW) in a noncommercial silver-containing zinc phosphate glass, thanks to an additional illumination with a cw (continuous wave) UV laser, either after the femtosecond irradiation or simultaneously. By tuning the cw UV power, we demonstrate the tunable control and inhibition of the production efficiency of laser-induced fluorescent silver clusters, leading up to 100% inhibition for simultaneous co-illumination when the laser writing is performed close enough to the permanent structuring threshold. The role of the cw UV illumination is discussed in terms of inhibition of the silver cluster precursors or of dissolution of the laser-induced silver clusters. These results show the ability of laser writing inhibition in our photosensitive silver-containing phosphate glass, which is a necessary step to further develop super-resolution laser writing approaches, such as STED-like DLW, either of fluorescent silver clusters or of silver metallic nanoparticles with plasmonic properties.

Enhancement of nanograting formation assisted by silver ions in a sodium gallophosphate glass.

We investigated the influence of silver ions during the direct femtosecond laser-induced formation of nanogratings (NGs) at the surface of a tailored sodium gallophosphate glass. We observed that the silver ions had a remarkable influence because the silver-containing glass showed (1) lower fluence thresholds for the formation of the NGs; (2) much smoother NG shapes; and (3) a bifunctional behavior because fluorescence from laser-induced silver clusters occurs prior to the formation of the NGs. We demonstrate for the first time, to our knowledge, the formation of NGs assisted by noble metal ions, such as ions playing a kind of catalytic-like role that enhances and improves the NG formation and its incubation process. Our innovative approach provides promising potential for further improvements in processes for NG formation.

Examination of femtosecond laser matter interaction in multipulse regime for surface nanopatterning of vitreous substrates.

The paper presents our results on laser micro- and nanostructuring of sodium aluminosilicate glass for the permanent storage purposes and photonics applications. Surface structuring is realized by fs laser irradiation followed by the subsequent etching in a potassium hydroxide (10M@80 °C) for 1 to 10 minutes. As the energy deposited is lower than the damage and/or ablation threshold, the chemical etching permits to produce small craters in the laser modified region. The laser parameters dependent interaction regimes are revealed by microscopic analysis (SEM and AFM). The influence of etching time on craters formation is investigated under different incident energies, number of pulses and polarization states.

Optical and structural characterization of femtosecond laser written micro-structures in germanate glass.

We report on direct femtosecond laser writing in zinc barium gallo-germanate glasses. A combination of spectroscopic techniques allows to progress in the understanding of the mechanisms taking place depending on the energy. In the first regime (type I, isotropic local index change) up to 0.5 µJ, the main occurrence is the generation of charge traps inspected by luminescence, together with separation of charges detected by polarized second harmonic generation measurements. At higher pulse energies notably at the threshold corresponding to 0.8 µJ or in the second regime (type II modifications corresponding to nanograting formation energy domain), the main occurrence is a chemical change and re-organization of the network evidenced by the appearance of molecular O2 seen in the Raman spectra. In addition, the polarization dependence of the second harmonic generation in type II indicates that the organization of nanogratings may be perturbed by the laser-imprinted electric field.

Toward low-loss mid-infrared Ga2O3-BaO-GeO2 optical fibers.

The development of efficient and compact photonic systems in support of mid-infrared integrated optics is currently facing several challenges. To date, most mid-infrared glass-based devices are employing fluoride or chalcogenide glasses (FCGs). Although the commercialization of FCGs-based optical devices has rapidly grown during the last decade, their development is rather cumbersome due to either poor crystallization and hygroscopicity resilience or poor mechanical-thermal properties of the FCGs. To overcome these issues, the parallel development of heavy-metal oxide optical fiber from the barium-germanium-gallium oxide vitreous system (BGG) has revealed a promising alternative. However, over 30 years of fiber fabrication optimization, the final missing step of drawing BGG fibers with acceptable losses for meters-long active and passive optical devices had not yet been reached. In this article, we first identify the three most important factors that prevent the fabrication of low-loss BGG fibers i.e., surface quality, volumic striae and glass thermal-darkening. Each of the three factors is then addressed in setting up a protocol enabling the fabrication of low-loss optical fibers from gallium-rich BGG glass compositions. Accordingly, to the best of our knowledge, we report the lowest losses ever measured in a BGG glass fiber i.e., down to 200 dB km-1 at 1350 nm.

Three-dimensional direct femtosecond laser writing of second-order nonlinearities in glass.

We demonstrate that direct femtosecond laser writing in silver-containing zinc and gallium phosphate glass enables generation of three-dimensional (3D) optical second-order nonlinear microstructures having an χ(2) value about 2.5 times that of quartz. The proposed physical model involves photo-reduction, photo-dissociation, and migration of silver species within the glass matrix. 3D laser-written second-order nonlinear structures could become a new class of nonlinear optical components.

Spatial beam reshaping and large-band nonlinear conversion in rectangular-core phosphate glass fibers.

Here we present the ability of Nd3+-doped zinc-phosphate glasses to be shaped into rectangular core fibers. At first, the physico-chemical properties of the developed P2O5-based materials are investigated for different concentrations of neodymium oxide and core and cladding glass compositions are selected for further fiber development. A modified stack-and-draw technique is used to produce multimode large rectangular-core optical fibers. Self-guided nonlinear effects acting as spatial beam reshaping processes occurring in these newly-developed photonic structures lead to the generation of spectral broadenings in the visible and near-infrared spectral domains.

Thermal History Mapping in Powder Bed Laser Sintering at the Micrometer Scale.

A thermal sensor was used to better understand parameters which influenced the interaction between a laser beam and a 0.5% Mn-doped ZnAl2.2O4 material, especially the laser defocusing parameter. The optical properties of the material depend on whether the Mn2+ ions occupy octahedral and/or tetrahedral sites depending on thermal history. A screen printing process is performed to obtain material thin films. Laser irradiation of the films was carried out (patterning 1 cm length single laser track) with different z defocusing heights. Luminescence properties around laser tracks led to the thermal history determination at the micrometer scale. It was shown that spatial thermal gradients defined at the micrometer scale perpendicularly to the borders of the laser tracks could be semiquantified for different z conditions. Laser defocusing leads to decrease thermal gradients as confirmed by thermal modeling studies.

Emission-photoactivity cross-processing of mesoporous interfacial charge transfer in Eu3+ doped titania.

Periodic mesoporous Eu(3+) doped titania materials were obtained through the EISA (Evaporation Induced Self Assembly) process. Eu(3+) ions, entrapped within the semi-crystalline walls of the highly porous framework, appear to be advantageous during the probing of surface photochemical reactions. Its emission intensity is very sensitive to the presence of physisorbed molecules, in gas or liquid phase, that reside within the pores. In particular, strong fluctuations in intensity of the (5)D(0)→(7)F(2) transition were observed under UV light exposure on the time scale of tens of seconds. The emission modulation dynamics show a strong correlation with the crystallinity of the titania matrix. Correlation of the emission with the photocatalytic activity of the semiconductor for photodegradation of an organic molecule is observed. A model is proposed to describe the involved mechanisms.

Transparent Glasses and Glass-Ceramics in the Ternary System TeO2-Nb2O5-PbF2.

Transparent fluorotellurite glasses were prepared by melt-quenching in the ternary system TeO2-Nb2O5-PbF2. The synthesis conditions were adjusted to minimize fluorine loss monitored as HF release. It was found that 10 mol% of Nb2O5 is the optimum content for PbF2 incorporation up to 35 mol% in the tellurite matrix without loss of glass forming ability. Such glass compositions exhibit a wide optical window from 380 nm to about 6 µm. Crystallization properties were carefully investigated by thermal analysis and compositions with higher PbF2 contents exhibit preferential precipitation of lead oxyfluoride Pb2OF2 at lower temperatures. The lead oxyfluoride crystallization mechanism is also governed by a volume nucleation, barely reported in tellurite glasses. Eu3+ doping of these glass compositions also promotes a more efficient nucleation step under suitable heat-treatments, resulting in transparent Eu3+-doped glass-ceramics whereas undoped glass-ceramics are translucent. Finally, Eu3+ spectroscopy pointed out a progressive, more symmetric surrounding around the rare earth ions with increasing PbF2 contents as well as higher quantum efficiencies. These new fluorotellurite glass compositions are promising as luminescent hosts working in the middle infrared.

Synthesis and characterization of Eu3+, Ti4+ @ ZnO organosols and nanocrystalline c-ZnTiO3 thin films aiming at high transparency and luminescence.

By exploiting colloidal properties, such as transparency, rheology and versatile chemistry, we propose to synthesize new photonic nanomaterials based on colloidal solutions and thin films. This contribution highlights our efforts to elaborate and to characterize nanostructures based on the ZnO-TiO2 system. Using a recently developed sol-gel route to synthesize new Ti4+@ZnO organosols, we were able to prepare, at relatively low temperature (400 °C) and short annealing time (15 min), highly transparent, luminescent, nanocrystalline Eu3+ doped c-ZnTiO3 thin films. The organosols and thin films were characterized with UV-visible-near infrared absorption, ellipsometry, photoluminescence spectroscopy, dynamic light scattering, x-ray diffraction and scanning electron microscopy.

Radiation-Induced Defects and Effects in Germanate and Tellurite Glasses.

This review focuses on the radiation-induced changes in germanate and tellurite glasses. These glasses have been of great interest due to their remarkable potential for photonics, in terms of extended transmission window in the mid-infrared, ability of rare-earth loading suitable with a laser, and amplification in the near- and mid-infrared or high nonlinear optical properties. Here, we summarize information about possible radiation-induced defects, mechanisms of their formation, and the influence of the glass composition on this process. Special attention is paid to laser-induced structural modification of these glasses, including possible mechanisms of the laser-glass interaction, laser-induced crystallization, and waveguide writing. It is shown that these methods can be used for photostructuring of the glass and have great potential for practical applications.

Beat the diffraction limit in 3D direct laser writing in photosensitive glass.

Three-dimensional (3D) femtosecond laser direct structuring in transparent materials is widely used for photonic applications. However, the structure size is limited by the optical diffraction. Here we report on a direct laser writing technique that produces subwavelength nanostructures independently of the experimental limiting factors. We demonstrate 3D nanostructures of arbitrary patterns with feature sizes down to 80 nm, less than one tenth of the laser processing wavelength. Its ease of implementation for novel nanostructuring, with its accompanying high precision will open new opportunities for the fabrication of nanostructures for plasmonic and photonic devices and for applications in metamaterials.

Nanoparticles (NPs) of WO3-x Compounds by Polyol Route with Enhanced Photochromic Properties.

Tungsten trioxide (WO3) is well-known as one of the most promising chromogenic compounds. It has a drastic change of coloration induced from different external stimuli and so its applications are developed as gas sensors, electrochromic panels or photochromic sensors. This paper focuses on the photochromic properties of nanoWO3, with tunable composition (with tunable oxygen sub-stoichiometry). Three reference samples with yellow, blue and black colors were prepared from polyol synthesis followed by post annealing under air, none post-annealing treatment, or a post-annealing under argon atmosphere. These three samples differ in terms of crystallographic structure (cubic system versus monoclinic system), oxygen vacancy concentration, electronic band diagram with occurrence of free or trapped electrons and their photochromic behavior. Constituting one main finding, it is shown that the photochromic behavior is highly dependent on the compound's composition/color. Rapid and important change of coloration under UV (ultraviolet) irradiation was evidenced especially on the blue compound, i.e., the photochromic coloring efficiency of this compound in terms of contrast between bleached and colored phase, as the kinetic aspect is high. The photochromism is reversible in a few hours. This hence opens a new window for the use of tungsten oxide as smart photochromic compounds.

Europium-doped mesoporous titania thin films: rare-earth locations and emission fluctuations under illumination.

Herein, Eu(III)-doped 3D mesoscopically ordered arrays of mesoporous and nanocrystalline titania are prepared and studied. The rare-earth-doped titania thin films-synthesized via evaporation-induced self-assembly (EISA)-are characterized by using environmental ellipsoporosimetry, electronic microscopy (i.e. high-resolution scanning electron microscopy, HR-SEM, and transmission electron microscopy, HR-TEM), X-ray diffraction, and luminescence spectroscopy. Structural characterizations show that high europium-ion loadings can be incorporated into the titanium-dioxide walls without destroying the mesoporous arrangement. The luminescence properties of Eu(III) are investigated by using steady-state and time-resolved spectroscopy via excitation of the Eu(III) ions through the titania host. Using Eu(III) luminescence as a probe, the europium-ion sites can be addressed with at least two different environments within the mesoporous framework, namely, a nanocrystalline environment and a glasslike one. Emission fluctuations ((5)D(0)-->(7)F(2)) are observed upon continuous UV excitation in the host matrix. These fluctuations are attributed to charge trapping and appear to be strongly dependent on the amount of europium and the level of crystallinity.

Direct laser writing of a new type of waveguides in silver containing glasses.

Direct laser writing in glasses is a growing field of research in photonics since it provides a robust and efficient way to directly address 3D material structuring. Generally, direct laser writing in glasses induces physical modifications such as refractive index changes that have been classified under three different types (Type I, II & III). In a silver-containing zinc phosphate glass, direct laser writing additionally proceeds via the formation of silver clusters at the periphery of the interaction voxel. In this paper, we introduce a novel type of refractive index modification based on the creation of the photo-induced silver clusters allowing the inscription of a new type of optical waveguides. Various waveguides as well as a 50-50 beam splitter were written inside bulk glasses and characterized. The waveguiding properties observed in the bulk of such silver-containing glass samples were further transposed to ribbon shaped fibers made of the same material. Our results pave the way for the fabrication of 3D integrated circuits and fiber sensors with original fluorescent, nonlinear optical and plasmonic properties. The universality of these new findings should further extend in any silver-containing glasses that show similar laser-induced behavior in terms of silver cluster production.