Synthesis of Ni-doped InTaO4 nanocrystallites by reactive pulsed laser ablation for application to visible-light-operating photocatalysts

Ni-doped InTaO₄ nanocrystallites were synthesized by a reactive pulsed laser ablation process, aiming at visible-light-operating photocatalysts. The third harmonics beam of a Nd:YAG laser was focused onto a sintered In_0.9Ni_0.1TaO_4−δ target in mixture background gases (O₂ + He). The deposited species were columnar-structured porous films consisting of primary nanocrystallites. The mean diameter of the primary nanocrystallites was 4 nm. Optical absorption characteristics, especially in low absorbance (sub-band) regions, were evaluated by photoacoustic spectroscopy. Absorption in the sub-band region decreased drastically with increasing O₂ partial pressures. It is inferred that oxygen deficiencies are suppressed, because of enough oxygen vapors in the reactive background gases. An absorption band around 420 nm appeared obviously in O₂ partial pressures above 5%, in the Ni-doped InTaO₄ nanocrystallites. The visible region absorption band is presumably attributed to the Ni 3d-eg orbitals. In contrast, pure InTaO₄ nanocrystallites showed a sharp band edge, without the visible absorption band.     

Characteristic properties of Y2SiO5:Ce thin films grown with PLD

Three different gases (nitrogen (N₂), oxygen (O₂) and argon (Ar)) were used as background gases during the growth of pulsed laser deposition (PLD) Y₂SiO₅:Ce thin films. A Krypton fluoride laser (KrF), 248 nm was used for the PLD of the films on silicon (Si) (1 0 0) substrates. The effect of the background gases on the surface morphology, crystal growth and luminescent properties were investigated. All the experimental parameters, the gas pressure (455 mT), the substrate temperature (600 °C), the pulse frequency (8 Hz), the number of pulses (4000) and the laser fluence (1.6±0.2) J/cm² were kept constant. The only parameter that was changed during the deposition was the ambient gas species. The surface morphology and average particle sizes were monitored with scanning electron microscopy (SEM) and atomic force microscopy (AFM). X-ray diffraction (XRD) and Auger electron spectroscopy (AES) were used to determine the crystal structure and composition, respectively. Cathodo- (CL) and photoluminescence (PL) were used to measure the luminescent intensities for the different phosphor thin films. The nature of the particles, ablated on the substrate, is related to the collisions between the ejected particles and the ambient gas particles. The CL and PL intensities also depend on the particle sizes. A 144 h (coulomb dose of 1.4×10⁴ C cm⁻²) electron degradation study on the thin films ablated in the Ar gas environment resulted in a decrease in the main CL intensity peak at 440 nm and to the development of a new very broad luminescent peak spectra ranging from 400 to 850 nm due to the growth of a SiO₂ layer on the surface.     

Mass and kinetic energy distribution of the species generated by laser ablation of La<Subscript>0.6</Subscript>Ca<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript>

The mass distributions of the species generated by laser ablation from a La_0.6Ca_0.4MnO₃ target using laser irradiation wavelengths of 193 nm, 266 nm and 308 nm have been investigated with and without a synchronized gas pulse of N₂O. The kinetic energies of the species are measured using an electrostatic deflection energy analyzer, while the mass distributions of the species were analyzed with a quadrupole mass filter. In vacuum (pressure 10⁻⁷ mbar), the ablation plume consists of metal atoms and ions such as La, Ca, Mn, O, LaO, as well as multiatomic species, e.g. LaMnO⁺. The LaO⁺ diatomic species are by far the most intense diatomic species in the plume, while CaO and MnO are only detected in small amounts. The interaction of a reactive N₂O gas pulse with the ablation plume leads to an increase in plume reactivity, which is desired when thin manganite films are grown, in order to incorporate the necessary amount of oxygen into the film. The N₂O gas pulse appears to have a significant influence on the oxidation of the Mn species in the plume, and on the creation of negative ions, such as LaO⁻,O⁻ and O₂⁻.     

A study of NOX production in air heated by laser discharges: Effect of energy, wavelength, multiple discharges and pressure

An experimental study on the production of NO_X in air heated under the action of a concentrated laser beam is presented. In this experiment laser induced plasma was produced in air in a closed Teflon chamber of inner volume 1600 cm³ by focusing a laser beam with either the wavelength of 1064 or 532 nm from a Q-switched Nd:YAG laser. The NO_X production was measured by chemiluminescence method and the possible effect of wavelengths, multiple discharges, and pressure on the yield of NO_X was studied. The results show that within the studied plasma energy range of 26–253 mJ for 532 nm beam and 16–610 mJ for 1064 nm beam, the NO_X production scales linearly with the dissipated plasma energy. For a given energy, 532 nm beam produces more NO_X in air at atmospheric pressure than the 1064 nm beam. In an attempt to see the possible influence of multiple discharges on the production of NO_X, discharges were created using 2–8 pulses with a repetition rate of 10 pulses per second in stationary air at atmospheric pressure. The results indicate that a certain amount of the NO_X created by a given pulse is destroyed by the subsequent pulses. In order to study the pressure dependence of the NO_X production, the pressure was varied from 16 to 100 kPa in the chamber and it was found that the NO_X production efficiency scales linearly with pressure.     

A laser dry etch process for smooth continuous relief structures in InP

A laser induced etch process is described which uses a pulsed 248 nm KrF excimer laser and Cl₂ atmosphere for the fabrication of monolithic continuously curved reliefs in InP substrate. In a bakeable processing chamber with low base pressure a wide range of laser fluences is available for damage-free etching. Especially, by photothermal heating far above the melting point, mirrorlike smooth surfaces are obtained. The etch rate characteristics are correlated to the maximum surface temperature reached during the laser pulse. The etch rate is independent of pressure and gas flux in the ranges 0.1–10 mbar and 20–300 sccm, respectively. It increases, however, with the background substrate temperature. Etch rates of up to 3.6 nm/pulse or 4.3 lm/min are possible at 20 Hz pulse repetition rate without visible surface damage. The process exhibits a smooth increase of the etch rate from 1 to 3 nm/pulse between 200 and 300 mJ/cm², which could be used for making curved reliefs by optical transmission variations on the projection mask.     

K<Subscript><Emphasis Type="Italic">α</Emphasis></Subscript> x-ray emission characterization of 100 Hz, 15 mJ femtosecond laser system with high contrast ratio

We report K _α x-ray production with a high energy (110 mJ per pulse at 800 nm before compression/15 mJ at 400 nm after compression), high repetition rate (100 Hz), and high pulse contrast (better than 10⁻⁹ at 400 nm) laser system. To develop laser-based x-ray sources for biomedical imaging requires to use high-energy and high-power ultrafast laser system where compression is achieved under vacuum. Using this type of laser system, we demonstrate long-term stability of the x-ray yield, conversion efficiency higher than 1.5×10⁻⁵ with a Mo target, and the x-ray spot size close to the optical focal spot. This high-repetition K _α x-ray source can be very useful for x-ray phase-contrast imaging. S. Fourmaux and C. Serbanescu contributed equally to this work.     

Catalyst-free synthesis of vertically-aligned ZnO nanowires by?nanoparticle-assisted pulsed laser deposition

Vertically aligned ZnO nanowires have been successfully synthesized on c-cut sapphire substrates by a catalyst-free nanoparticle-assisted pulsed-laser ablation deposition (NAPLD) in Ar and N₂ background gases. In NAPLD, the nanoparticles formed in the background gas by laser ablation are used for the growth of the nanowires. The surface density of the nanowires can be controlled by varying the density of nanoparticles, which is in turn achieved by varying ablation laser parameters such as the energy and the repetition rate. When single ZnO nanowire synthesized in a N₂ background gas was excited by 355 nm laser-pulse with a pulse-width of 8 ns, stimulated emission was clearly observed, indicating high quality of the nanowire.     

Nanosecond and femtosecond ablation of La0.6Ca0.4CoO3: a comparison between plume dynamics and composition of the films

Thin films of La_0.6Ca_0.4CoO₃ were grown by pulsed laser ablation with nanosecond and femtosecond pulses. The films deposited with femtosecond pulses (248 nm, 500 fs pulse duration) exhibit a higher surface roughness and deficiency in the cobalt content compared to the films deposited with nanosecond pulses (248 nm, 20 ns pulse duration). The origin of these pronounced differences between the films grown by ns and fs ablation has been studied in detail by time-resolved optical emission spectroscopy and imaging. The plumes generated by nanosecond and femtosecond ablation were analyzed in vacuum and in a background pressure of 60 Pa of oxygen. The ns-induced plume in vacuum exhibits a spherical shape, while for femtosecond ablation the plume is more elongated along the expansion direction, but with similar velocities for ns and fs laser ablation. In the case of ablation in the background gas similar velocities of the plume species are observed for fs and ns laser ablation. The different film compositions are therefore not related to different kinetic energies and different distributions of various species in the plasma plume which has been identified as the origin of the deficiency of species for other materials.     

Laser-induced spark for simultaneous ignition and fuel-to-air ratio measurements

This work investigates the use of laser-induced gas breakdown for simultaneously igniting and measuring fuel-to-air ratio of CH₄–air and H₂–air combustible mixtures. The fuel-to-air ratio is determined using the measured spectral peak ratio I_o,Hα/I_o,OI. Sparks are produced using a single-mode, Q-switched Nd–YAG laser. The laser produces a beam of 6 mm in diameter at the wavelength of 1064 nm and pulse duration of 5.5 ns. The beam optics is designed to have mainly a beam splitter and a focusing lens. The beam splitter is coated to reflect the laser beam and transmit emission lines with wavelengths from 600 to 900 nm which are then collected by a fiberoptic cable and detected by an imaging spectrometer–detector assembly. The results showed a linear dependence of the spectral peak ratio on the equivalence ratio that can be generally expressed by φ=a(I_o,Hα/I_o,OI)+b, where a and b are the parameters that depend on the gas pressure. Using the least-square curve fitting technique to fit the experimental data, a calibration curve for calculating the equivalence ratio as a function of the ratio of (I_o,Hα/I_o,OI) was generated.     

Investigating gate metal induced reduction of surface donor density in GaN/AlGaN/GaN heterostructure by electroreflectance spectroscopy

The internal field of GaN/AlGaN/GaN heterostructure on Si-substrate was investigated by varying the thickness of an undoped-GaN capping layer using electroreflectance spectroscopy. The four samples investigated are AlGaN/GaN heterostructure without a GaN cap layer (reference sample) and three other samples with GaN/AlGaN/GaN heterostructures in which the different thickness of GaN cap layer (2.7 nm, 7.5 nm, and 12.4 nm) has been considered. The sheet carrier density (n_s) of a two-dimensional electron gas has decreased significantly from 4.66 × 10¹² cm⁻² to 2.15 × 10¹² cm⁻² upon deposition of a GaN capping layer (12.4 nm) over the reference structure. Through the analysis of internal fields in each GaN capping and AlGaN barrier layers, it has been concluded that the undiminished surface donor states (n_s) of a reference structure and the reduced n_s caused by the Au gate metal are approximately 5.66 × 10¹² cm⁻² and 1.08 × 10¹² cm⁻², respectively.     

Structural characterization and optoelectronic properties of GaN thin films on Si(111) substrates using pulsed laser deposition assisted by gas discharge

GaN films have been grown on Si(111) substrates with a thin AlN buffer layer using pulsed laser deposition (PLD) assisted by gas discharge. The crystalline quality, surface morphology and optoelectronic properties of the deposited films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL) spectroscopy, and room-temperature Van der Pauw–Hall measurements. The influence of the deposition temperature in the range 637–1037 K on the crystallinity of GaN films, the laser incident energy in the range 150–250 mJ/pulse on the surface morphology and the optoelectronic properties were systematically studied. The XRD analysis shows that the crystalline quality of the GaN films improves with increasing deposition temperature to 937 K, but further increase of the deposition temperature to 1037 K leads to the degradation of the crystalline quality. AFM results show that the surface roughness of the GaN films can be decreased with increasing laser incident energy to 220 mJ/pulse. Further increase of the laser incident energy to 250 mJ/pulse leads to an increase in the surface roughness. The optoelectronic properties of GaN films were also improved by increasing the laser incident energy to 220 mJ/pulse. GaN films which have a n-type carrier concentration of 1.26×10¹⁷ cm^-3 and a mobility of 158.1 cm²/Vs can be deposited at a substrate temperature of 937 K, a deposition pressure of 20 Pa and a laser incident energy of 220 mJ/pulse. Their room-temperature PL spectra exhibit a strong band-edge emission at 365 nm. PACS 81.15.Fg; 81.05.Ea; 78.20.-e; 73.61.Ey; 78.66.Fd     

Development of ultra-short pulse VUV laser system for nanoscale processing

We have developed intense vacuum ultraviolet (VUV) radiation sources for advanced material processing, such as photochemical surface reactions and precise processing on a nanometer scale. We have constructed a new VUV laser system to generate sub-picosecond pulses at the wavelength of 126 nm. A seed VUV pulse was generated in Xe as the 7th harmonic of a 882-nm Ti:sapphire laser. The optimum conversion was achieved at the pressure of 1.2 Torr. The seed pulse will be amplified by the Ar₂^*\mathrm{Ar}_{2}^{*} media generated by an optical-field-induced ionization Ar plasma produced by the Ti:sapphire laser. We have obtained a gain coefficient of g=0.16 cm⁻¹. Our developing system will provide VUV ultra-short pulses with sub-μJ energy at a repetition rate of 1 kHz.     

Transversely pumped laser using F 3 + and F2 mixed color centers in a LiF crystal at room temperature

A stable laser with F₃⁺ and F₂ mixed color centers in LiF crystal is constructed using a transversely pumped cavity at room temperature. The mixed color center laser is pumped with a nitrogen-laser-pumped dye laser. A pulse output of the laser is 0.23 mJ. The pulse widths of the F₃⁺ and F₂ color center lasers are about 12 and 8.5 ns, respectively. The optical–optical conversion efficiency is about 5.0%. The divergence of the F₃⁺ color center laser beam is about 2.2 mrad and that of the F₂ color center laser beam about 3.5 mrad. The polarization of the mixed color center laser is about 0.97. The output of the F₃⁺ color center laser extends from 515 to 575 nm and peaks at 540 nm, while that of the F₂ color center laser extends from 633 to 705 nm and peaks at 667 nm.     

THz radiation generation via the interaction of two‐colour ultra‐short laser pulses with SO2 and NH3 gases

In this work, using a two‐dimensional particle‐in‐cell Monte Carlo collision computation method, terahertz (THz) radiation generation via the interaction of two‐colour, ultra‐short, high‐power laser pulses with the polyatomic molecular gases sulphur dioxide (SO₂) and ammonia (NH₃) is examined. The influence of SO₂ and NH₃ pressures and two‐colour laser pulse parameters, i.e., pulse shape, pulse duration, and beam waist, on the THz radiation generation is studied. It is shown that the THz signal generation from SO₂ and NH₃ increases with the background gas pressure. It is seen that the THz emission intensity for both gases at higher laser pulse durations is higher. Moreover, for these polyatomic gases, the plasma current density increases with increase in the laser pulse beam waist. A more powerful THz radiation intensity with a larger time to peak of the plasma current density is observed for SO₂ compared to NH₃. In addition, many THz signals with small intensities are observed for both polyatomic gases. It is seen that for both SO₂ and NH₃ the generated THz spectral intensity is higher at higher gas pressures.     

Manifestation of hexagonal-like structure in the second-order nonlinear effects in the GaN nanocrystallites

Contribution of the hexagonal-like structural components to the photoinduced second harmonic generation (SHG) in GaN large-sized nanocrystallites (with sizes about the 10–30 nm) incorporated into the polyvinylalcohol photopolymer matrices is revealed. The SHG measurements were done using pulsed Nd:YAG laser beam (λ=1.06 μm; pulse duration τ=15–50 ps, laser power about 30 MW) as a fundamental ones and a picosecond nitrogen pulsed laser (P=10 MW; λ=0.377 μm; pulse time duration τ=10–25 ps) as a photoinducing one. We have found that with increasing pumping power density the SHG output signal increases and achieves its maximum value for the power density about 2.6 GW/cm² per pulse. The maximal output photoinduced SHG signal was achieved for parallel directions of the pumping and fundamental beam polarizations. The maximal values of the second-order nonlinear susceptibilities were equal to about 1.09 pm/V. We have observed an increase of the output SHG below 30 K and for pump-probe delaying time about 18 ps. Substantial contribution to the SHG of wurtzite-like (hexagonal) structural fragments is shown.     

Photoacoustic spectroscopy detection and extraction of discharge feature gases in transformer oil based on 1.5 μ tunable fiber laser

Information from the analysis of gasses dissolved in insulating oils is valuable for early a transformer maintenance. By means of dissolved gas analysis (DGA), it is possible to distinguish faults such as partial discharge (corona), overheating (pyrolysis) and arcing in a great variety of oil-filled equipment. Tunable fiber laser-based second harmonic photoacoustic spectroscopy offers a fast and good-noise-immunity technique for the quantitative analysis of trace gases in transformer oil. In this work, the discharge feature gases, such as C₂H₂, CH₄, CO₂ and H₂O, were measured with a tunable laser photoacoustic spectrometer at the 1530.3709 nm transition line, as a typical application of precise measurement of multi-gas, a proposed BSS model based on overcomplete ICA basis and five-point-sampling method based on a created weight-truncation-constraint equation was used to remove noise so that several fault gases can be extracted with a higher detection accuracy and a method detection limit. Experiment shows that within 0.15 nm band near 1530.3709 nm, the four-gas contents have been detected and extracted and the detection accuracy has been improved from available scanning spacing of 0.03 nm to available extracting spacing of 0.0011 nm. At room temperature and atmospheric pressure, this can achieve simultaneous detection for multiple feature gases in discharged transformer oil using laser source with a limited waveband.     

Facile synthesis of monodispersed α-Fe2O3 microspheres through template-free hydrothermal route

Monodisperse α-Fe₂O₃ microspheres have been selectively synthesized through a facile hydrothermal method without the assistance of any surfactant, employing FeCl₃·6H₂O and NH₄NaHPO₄ as initial materials. The products were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. α-Fe₂O₃ microspheres with average size about 250 nm were constructed by single crystalline nanoparticles with average diameter about 15 nm. The investigation on the evolution formation revealed that growth temperature was critical to control the assembly of the fresh formed nanocrystallites, and the microsphere formation was proved to be the Ostwald ripening process by tracking the structures of the products at different growth temperature. α-Fe₂O₃ microspheres showed a weak ferromagnetic behavior with a remanent magnetization of 0.208 emu g⁻¹ and a coercivity of 1,034.27 Oe at room temperature.     

The effect of sub-band gap photon illumination on the properties of GaN layers grown on Si(111) by MBE

Nanostructured GaN layers are fabricated by laser-induced etching processes based on heterostructure of n-type GaN/AlN/Si grown on n-type Si(111) substrate. The effect of varying laser power density on the morphology of GaN nanostructure layer is observed. The formation of pores over the structure varies in size and shape. The etched samples exhibit dramatic increase in photoluminescence intensity compared to the as-grown samples. The Raman spectra also display strong band at 522 cm⁻¹ for the Si(111) substrate and a small band at 301 cm⁻¹ because of the acoustic phonons of Si. Two Raman active optical phonons are assigned h-GaN at 139 and 568 cm⁻¹ due to E2 (low) and E2 (high), respectively. Surface morphology and structural properties of nanostructures are characterized using scanning electron microscopy and X-ray diffraction. Photoluminance measurement is also taken at room temperature by using He–Cd laser (λ = 325 nm). Raman scattering is investigated using Ar⁺ Laser (λ = 514 nm).     

Excimer laser deposited CuO and Cu<Subscript>2</Subscript>O films with third-order optical nonlinearities by femtosecond <Emphasis Type="Italic">z</Emphasis>-scan measurement

By controlling the oxygen pressure, single-phase CuO and Cu₂O thin films have been obtained on quartz substrates using a pulsed laser deposition technique. The structure properties and linear optical absorption of the films were characterized by X-ray diffraction and UV–VIS spectroscopy. By performing z-scan measurements using a femtosecond laser (800 nm, 50 fs), the real and imaginary parts of the third-order nonlinear susceptibility, Re χ ⁽³⁾ and Im χ ⁽³⁾, of the films were determined. Both CuO and Cu₂O films exhibited large optical nonlinearities, which is comparable to those in some representative semiconductor films such as ZnO and GaN films using femtosecond laser excitation. Compared with Cu₂O films, the CuO films showed larger third-order nonlinear optical effects under off-resonance excitation. Furthermore, the mechanisms of the optical nonlinearities in CuO and Cu₂O films are explained in the main text. It was suggested that the reasons of the difference in their nonlinear refractive effects may be related to the different electronic structure in CuO and Cu₂O materials.     

Effect of the ceramic grain size and concentration on the dynamical mechanical and dielectric behavior of poly(vinilidene fluoride)/Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> composites

Laser-induced backside wet and dry etching (LIBWE and LIBDE) methods were developed for micromachining of transparent materials. Comparison of these techniques is helpful in understanding the etching mechanism but was not realized due to complications in setting up comparable experimental conditions. In our comparative investigations we used a solid tin film for dry and molten tin droplets for wet etching of fused-silica plates. A tin–fused-silica interface was irradiated through the sample by a KrF excimer laser beam (λ=248 nm, FWHM=25 ns); the fluence was varied between 400 and 2100 mJ/cm². A significant difference between the etch depths of the two investigated methods was not found. The slopes of the lines fitted to the measured data (sl_LIBDE=0.111 nm/mJ cm⁻², sl_LIBDE=0.127 nm/mJ cm⁻²) were almost similar. Etching thresholds for LIBDE and LIBWE were approximately 650 and 520 mJ/cm², respectively. To compare the dependence of etch rates on the pulse number, target areas were irradiated at different laser fluences and pulse numbers. With increasing pulse number a linear rise of depth was found for wet etching while for dry etching the etch depth increase was nonlinear. Secondary ion mass spectroscopic investigations proved that this can be due to the reconstruction of a new thinner tin-containing surface layer after the first pulse.