Synergistic oxidation of toluene through bimetal/cordierite monolithic catalysts with ozone.

Toluene treatment has received extensive attention, and ozone synergistic catalytic oxidation was thought to be a potential method to degrade VOCs (violate organic compounds) due to its low reaction temperature and high catalytic efficiency. A series of bimetal/Cord monolithic catalysts were prepared by impregnation with cordierite, including MnxCu5-x/Cord, MnxCo5-x/Cord and CuxCo5-x/Cord (x = 1, 2, 3, 4). Analysis of textural properties, structures and morphology characteristics on the prepared catalysts were conducted to evaluate their performance on toluene conversion. Effects of active component ratio, ozone addition and space velocity on the catalytic oxidation of toluene were investigated. Results showed that MnxCo5-x/Cord was the best among the three bimetal catalysts, and toluene conversion and mineralization rates reached 100 and 96% under the condition of Mn2Co3/Cord with 3.0 g/m3 O3 at the space velocity of 12,000 h-1. Ozone addition in the catalytic oxidation of toluene by MnxCo5-x/Cord could efficiently avoid the 40% reduction of the specific surface area of catalysts, because it could lower the optimal temperature from 300 to 100 °C. (Co/Mn)(Co/Mn)2O4 diffraction peaks in XRD spectra indicated all the four MnxCo1-x/Cord catalysts had a spinel structure, and diffraction peak intensity of spinel reached the largest at the ratio of Mn:Co = 2:3. Toluene conversion rate increased with rising ozone concentration because intermediate products generated by toluene degradation might react with excess ozone to generate free radicals like ·OH, which would improve the toluene mineralization rate of Mn2Co3/Cord catalyst. This study would provide a theoretical support for its industrial application.

Beam-shaped femtosecond laser printing of quasi-capsule-shaped holographic terahertz metasurfaces.

Terahertz (THz) metasurfaces have opened up a new avenue for the THz wavefront modulation. However, high-efficient and low-cost fabrication of THz metasurfaces remains a great challenge today. Here, quasi-capsule-shaped polarization-multiplexed holographic THz metasurfaces were printed by a beam-shaped femtosecond laser. The laser beam was spatially modulated by holograms of optimized cylindrical lens loaded on a spatial light modulator (SLM). The size of quasi-capsule apertures can be exquisitely and flexibly controlled by adjusting the focal length in holograms, pulse energy, and pulse number. Based on near-field diffraction and Burch encoding, an array of 100 × 100 basic unit apertures were initially designed, and a polarization-multiplexed THz metasurface was finally printed with a dimension of 8 mm × 8 mm. The function of polarization multiplexing was demonstrated, by which two kinds of images were reconstructed in response to X and Y-polarization THz waves, respectively. The present work highlights a great leap in fabrication method for THz metasurfaces and hopefully stimulates the development of miniaturized and integrated THz systems.

Tunable color generation in CdTe-doped silicate glass enabled by ultrashort laser pulses: interior coloring and multilevel encryption.

The launch of the big data era puts forward challenges for information security. Herein, a new kind of silicate glass system co-doped with CdO and ZnTe, capable of achieving the controllable generation of intrinsic color centers (brown and green) and tiny nuclei of CdTe via direct laser writing (DLW), is developed. The controlled growth of CdTe QDs thermally, leads to a permanent color of orange at the cost of accelerated aging of the color centers of brown and green. On the one hand, going beyond traditional 2D surface coloration, the high transparency of the studied bulk medium makes 3D volumetric interior coloration possible. On the other hand, by encoding ciphertext into the tiny nuclei of CdTe, a strategy of color encryption and heat decryption is established, which brings about the merits of expanded storage capacity and improved information security. The demonstration application confirmed the user-defined multiscale interior coloration and an unprecedented multidimensional color-encryption scheme with a high-security level. The present work highlights a great leap in transparent materials for color encryption and hopefully stimulates the development of new color division multiplexing encryptions.

Femtosecond laser nanoprinting of anisotropic plasmonic surfaces: coloration and anticounterfeiting.

An anisotropic plasmonic surface of nanoellipsoid arrays is successfully fabricated on an Au film using slit-shaping-based femtosecond laser nanoprinting. The size and orientation of the nanoellipsoid can be exquisitely and flexibly controlled by adjusting the width and direction of the slit and the laser pulse energy. By dark-field optical micro-spectroscopy, anisotropic plasmonic color rendering as well as resonant light scattering from the lateral and vertical modes are experimentally and theoretically investigated in the visible spectral range. In addition, prospective use in the fields of steganographic encryption and multidimensional optical multiplexing is also proposed.

Bacterially synthesized tellurium nanostructures for broadband ultrafast nonlinear optical applications.

Elementary tellurium is currently of great interest as an element with potential promise in nano-technology applications because of the recent discovery regarding its three two-dimensional phases and the existence of Weyl nodes around its Femi level. Here, we report on the unique nano-photonic properties of elemental tellurium particles [Te(0)], as harvest from a culture of a tellurium-oxyanion respiring bacteria. The bacterially-formed nano-crystals prove effective in the photonic applications tested compared to the chemically-formed nano-materials, suggesting a unique and environmentally friendly route of synthesis. Nonlinear optical measurements of this material reveal the strong saturable absorption and nonlinear optical extinctions induced by Mie scattering over broad temporal and wavelength ranges. In both cases, Te-nanoparticles exhibit superior optical nonlinearity compared to graphene. We demonstrate that biological tellurium can be used for a variety of photonic applications which include their proof-of-concept for employment as ultrafast mode-lockers and all-optical switches.

Recording, erasing, and rewriting of ripples on metal surfaces by ultrashort laser pulses.

Recording, erasing, and rewriting of ripples are achieved by applying femtosecond laser pulses on tungsten surfaces. Ripples oriented perpendicular to the polarization direction of the writing beam can be recorded on a metal surface by exposing the sample to a series of linearly polarized pulses. When applying the second series of pulses with varied polarization direction on the same place, the original ripples can be erased, and new ripples are rewritten with the orientation perpendicular to the polarization of the second group of pulses. The simulation shows that when original ripples exist, laser intensity is focused above the grooves with polarization parallel to original ripples, which can erase the ripples. However, when the polarization is perpendicular to the existing ripples, laser intensity is almost confined in the grooves, which accelerates the formation of ripples.

Ultrashort pulsed laser induced heating-nanoscale measurement of the internal temperature of dielectrics using black-body radiation.

The nanoscale measurement of temperature in the bulk of dielectrics initiated by a single ultrashort laser pulse was first investigated by black-body radiation. A structureless broad continuum emission has been recorded at an interval delay of 2 ns with a temporal gate of 2 ns and spectral resolution of about 0.137 nm, which provides the highest temporal and spectral precision ever. The temporally resolved emission spectrum was proved to be black-body radiation in nature, and temperature was obtained by fitting the radiation with the Planckian formula. Pulse energy was varied from 110 to 270 µJ at 600 fs and a pulse duration of 0.83 ns was also used. The temperature exhibited a small variation with an increasing pulse energy at 600 fs. However, due to the energy transfer from heated electrons to lattice, the temperature was sharply increased at pulse duration of 0.83 ns. It was estimated that heat accumulation started at 0.42-0.47 MHz for a laser pulse at 600 fs, while it was 0.25 MHz for a laser pulse at 0.83 ns.

Low chromatic Fresnel lens for broadband attosecond XUV pulse applications.

Fresnel zone plates show a great potential in achieving high spatial resolution imaging or focusing for XUV and soft/hard X-ray radiation, however they are usually strictly monochromatic due to strong chromatic dispersion and thus do not support broad radiation spectra, preventing their application to attosecond XUV pulses. Here we report on the design and theoretical simulations based on the design of an achromatic hybrid optics combining both, a refractive and diffractive lens in one optical element. We are able to show by calculation that the chromatic dispersion along the optical axis can be greatly reduced compared to a standard Fresnel zone plate while preserving the temporal structure of the attosecond XUV pulses at focus.

Ultrafast properties of femtosecond-laser-ablated GaAs and its application to terahertz optoelectronics.

We report on the first terahertz (THz) emitter based on femtosecond-laser-ablated gallium arsenide (GaAs), demonstrating a 65% enhancement in THz emission at high optical power compared to the nonablated device. Counter-intuitively, the ablated device shows significantly lower photocurrent and carrier mobility. We understand this behavior in terms of n-doping, shorter carrier lifetime, and enhanced photoabsorption arising from the ablation process. Our results show that laser ablation allows for efficient and cost-effective optoelectronic THz devices via the manipulation of fundamental properties of materials.

Novel carbazole derivatives with quinoline ring: synthesis, electronic transition, and two-photon absorption three-dimensional optical data storage.

We designed carbazole unit with an extended π conjugation by employing Vilsmeier formylation reaction and Knoevenagel condensation to facilitate the functional groups of quinoline from 3- or 3,6-position of carbazole. Two compounds doped with poly(methyl methacrylate) (PMMA) films were prepared. To explore the electronic transition properties of these compounds, one-photon absorption properties were experimentally measured and theoretically calculated by using the time-dependent density functional theory. We surveyed these films by using an 800 nm Ti:sapphire 120-fs laser with two-photon absorption (TPA) fluorescence emission properties and TPA coefficients to obtain the TPA cross sections. A three-dimensional optical data storage experiment was conducted by using a TPA photoreaction with an 800 nm-fs laser on the film to obtain a seven-layer optical data storage. The experiment proves that these carbazole derivatives are well suited for two-photon 3D optical storage, thus laying the foundation for the research of multilayer high-density and ultra-high-density optical information storage materials.

Broadband ultrafast nonlinear absorption and nonlinear refraction of layered molybdenum dichalcogenide semiconductors.

A series of layered molybdenum dichalcogenides, i.e., MoX2 (X = S, Se and Te), were prepared in cyclohexyl pyrrolidinone by a liquid-phase exfoliation technique. The high quality of the two-dimensional nanostructures was verified by transmission electron microscopy and absorption spectroscopy. Open- and closed-aperture Z-scans were employed to study the nonlinear absorption and nonlinear refraction of the MoX2 dispersions, respectively. All the three-layered nanostructures exhibit prominent ultrafast saturable absorption (SA) for both femtosecond (fs) and picosecond (ps) laser pulses over a broad wavelength range from the visible to the near infrared. While the dispersions treated with low-speed centrifugation (1500 rpm) have an SA response, and the MoS2 and MoSe2 dispersions after higher speed centrifugation (10,000 rpm) possess two-photon absorption for fs pulses at 1030 nm, which is due to the significant reduction of the average thickness of the nanosheets; hence, the broadening of band gap. In addition, all dispersions show obvious nonlinear self-defocusing for ps pulses at both 1064 nm and 532 nm, resulting from the thermally-induced nonlinear refractive index. The versatile ultrafast nonlinear properties imply a huge potential of the layered MoX2 semiconductors in the development of nanophotonic devices, such as mode-lockers, optical limiters, optical switches, etc.

Optical absorption and photocurrent enhancement in semi-insulating gallium arsenide by femtosecond laser pulse surface microstructuring.

We observe an enhancement of optical absorption and photocurrent from semi-insulating gallium arsenide (SI-GaAs) irradiated by femtosecond laser pulses. The SI-GaAs wafer is treated by a regeneratively amplified Ti: Sapphire laser of 120 fs laser pulse at 800 nm wavelength. The laser ablation induced 0.74 µm periodic ripples, and its optical absorption-edge is shifted to a longer wavelength. Meanwhile, the steady photocurrent of irradiated SI-GaAs is found to enhance 50%. The electrical properties of samples are calibrated by van der Pauw method. It is found that femtosecond laser ablation causes a microscale anti-reflection coating surface which enhances the absorption and photoconductivity.

Ultrafast saturable absorption of two-dimensional MoS2 nanosheets.

Employing high-yield production of layered materials by liquid-phase exfoliation, molybdenum disulfide (MoS2) dispersions with large populations of single and few layers were prepared. Electron microscopy verified the high quality of the two-dimensional MoS2 nanostructures. Atomic force microscopy analysis revealed that ~39% of the MoS2 flakes had thicknesses of less than 5 nm. Linewidth and frequency difference of the E(1)2g and A1g Raman modes confirmed the effective reduction of flake thicknesses from the bulk MoS2 to the dispersions. Ultrafast nonlinear optical (NLO) properties were investigated using an open-aperture Z-scan technique. All experiments were performed using 100 fs pulses at 800 nm from a mode-locked Ti:sapphire laser. The MoS2 nanosheets exhibited significant saturable absorption (SA) for the femtosecond pulses, resulting in the third-order NLO susceptibility Imχ((3)) ~ 10(-15) esu, figure of merit ~10(-15) esu cm, and free-carrier absorption cross section ~10(-17) cm(2). Induced free carrier density and the relaxation time were estimated to be ~10(16) cm(-3) and ~30 fs, respectively. At the same excitation condition, the MoS2 dispersions show better SA response than the graphene dispersions.

Polarization dependence of the self-organized microgratings induced in SrTiO3 crystal by a single femtosecond laser beam.

In this paper, self-organized microgratings are fabricated in SrTiO(3) crystal just by scanning the focus of a tightly-focused linearly-polarized femtosecond laser beam to form a single line. The polarization direction of the laser beam is rotated by a λ/2 waveplate to check the effect of the polarization azimuth on the micrograting morphology. Fourier analyzing of the microscopic images of the microgratings indicates that the polarization plane azimuth of the laser beam does have influence on the microgratings in the aspects of groove orientation and groove spacing. A possible mechanism of polarization dependence is also proposed.

Waveguides fabricated by femtosecond laser exploiting both depressed cladding and stress-induced guiding core.

We report on the fabrication of stress-induced optical channel waveguides and waveguide splitters with laser-depressed cladding by femtosecond laser. The laser beam was focused into neodymium doped phosphate glass by an objective producing a destructive filament. By moving the sample along an enclosed routine in the horizontal plane followed by a minor descent less than the filament length in the vertical direction, a cylinder with rarified periphery and densified center region was fabricated. Lining up the segments in partially overlapping sequence enabled waveguiding therein. The refractive-index contrast, near- and far-field mode distribution and confocal microscope fluorescence image of the waveguide were obtained. 1-to-2, 1-to-3 and 1-to-4 splitters were also machined with adjustable splitting ratio. Compared with traditional femtosecond laser writing methods, waveguides prepared by this approach showed controllable mode conduction, strong field confinement, large numerical aperture, low propagation loss and intact core region.

Optical waveguides in TiO2 formed by He ion implantation.

We report on the formation and the optical properties of the planar and ridge optical waveguides in rutile TiO2 crystal by He+ ion implantation combined with micro-fabrication technologies. Planar optical waveguides in TiO2 are fabricated by high-energy (2.8 MeV) He+-ion implantation with a dose of 3 × 10¹6 ions/cm² and triple low energies (450, 500, 550) keV He+-ion implantation with all fluences of 2 × 10¹6 ions/cm² at room temperature. The guided modes were measured by a modal 2010 prism coupler at wavelength of 1539 nm. There are damage profiles in ion-implanted waveguides by Rutherford backscattering (RBS)/channeling measurements. The refractive-index profile of the 2.8 MeV He+-implanted waveguide was analyzed based on RCM (Reflected Calculation Method). Also ridge waveguides were fabricated by femtosecond laser ablation on 2.8 MeV ion implanted planar waveguide and Ar ion beam etching on the basis of triple keV ion implanted planar waveguide, separately. The loss of the ridge waveguide was estimated. The measured near-field intensity distributions of the planar and ridge modes are all shown.

Femtosecond laser-induced inverted microstructures inside glasses by tuning refractive index of objective's immersion liquid.

We report the formation of inverted microstructures inside glasses after femtosecond laser irradiation by tuning the refractive index contrast between the immersion liquid and the glass sample. By using water as well as 1-bromonaphthalene as immersion liquids, microstructures with similar shape but opposite directions are induced after femtosecond laser irradiation. Interestingly, the elemental distribution in the induced structures is also inverted. The simulation of laser intensity distribution along the laser propagation direction indicates that the interfacial spherical aberration effect is responsible for the inversion of microstructures and elemental distribution.

Space-selective precipitation of Ge crystalline patterns in glasses by femtosecond laser irradiation.

Crystalline Ge was induced space selectively inside a borosilicate glass by 800 nm, 250 kHz femtosecond laser irradiation. Micro-Raman spectra and x-ray diffraction analysis confirmed that the laser-induced crystals were cubic Ge. A periodic structure consisting of Ge crystalline lines was inscribed in the glass sample by continuously moving the focal point of the laser beam. Large third-order nonlinear optical properties and ultrafast response time were observed from the crystallization region owing to highly optical nonlinearity of Ge crystals. These results may find some applications in fabrication of functional optical and photonic devices, such as optical circuits.

Synthesis of ZnO nanoflowers and their wettabilities and photocatalytic properties.

By combing laser direct writing and hydrothermal growth, we demonstrate the growth of three-dimensional flowerlike ZnO nanostructures from aqueous solution. Our approach offers synthetic flexibility in controlling film architecture, coating texture and crystallite size. The wettability is studied by measurement of time-dependent contact angles in the as-grown samples. In addition, superior photocatalytic activity of the flowerlike ZnO nanostructures in the degradation of Rhodamine B is investigated as well. The influence factors and formation mechanism of the flowerlike ZnO nanostructures are also analyzed and discussed.

Redistribution of elements in glass induced by a high-repetition-rate femtosecond laser.

The redistribution of elements in a multicomponent oxyfluoride glass is induced by a 250 kHz femtosecond laser. Elemental distribution in the cross section of the modified region along the laser propagation axis is analyzed by an electron microprobe analyzer. The results indicate that the relative concentrations of network formers of the glass are higher in the central area of the modified region and lower in the periphery of the modified region compared with the unirradiated areas. However, the relative concentrations of network modifiers are as opposed to that of network formers. Fluorescence spectra confirm that the distribution of fluorescence intensity of Yb(3+) in the modified region is consistent with that of its concentration. The effects of spherical aberration of the incident beam on the elemental redistribution are also discussed.