Fabrication of submicron gratings in fused silica by F<Subscript>2</Subscript>-laser ablation

Submicron surface-relief gratings were fabricated on fused silica by F₂-laser ablation with nanosecond duration pulses from a high-resolution 157-nm optical processing system. A 157 nm wavelength projection mask was prepared by ArF-laser ablation to form a 20-μm period grating of equal lines and spaces. A 25-fold demagnification of the mask by a Schwarzschild objective generated gratings of an 830-nm period and a 250 nm modulation depth, as characterized by SEM, AFM and HeNe-laser beam diffraction. Received: 24 April 2002 / Accepted: 25 April 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +49-551/503 599, E-mail: jihle@llg.gwdg.de     

A high-sensitivity in situ optical diagnostic technique for laser cleaning of transparent substrates

A differential optical transmission technique has been used to monitor in situ the efficiency of laser cleaning for the removal of sub-micrometer-sized particles on substrates transparent at the monitoring wavelength. This technique has been applied to the removal of sub-micrometer polystyrene particles on polyimide substrates using laser pulses of 30 ps duration at 292 nm while probing the material transmission at 633 nm. The sensitivity achieved -1/10⁴ for the transmission changes induced upon single-pulse laser exposure – allows us to monitor the removal of just a few sub-micron-sized particles from the probed region inside the irradiated area. Received: 2 October 2002 / Accepted: 7 October 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +33-3/87844082, E-mail: nchaoui@iut.univ-metz.fr RID="**" ID="**"Present address: Laboratoire de Chimie et Applications, Institut Universitaire de Technologie de Metz, Département Chimie, Rue Victor Demange, 57500 Saint-Avold, France     

Angular laser cleaning for effective removal of particles. from a solid surface

Laser removal of small particles from a metal surface is carried out by changing the incident angle of the laser beam. It has been found that a dramatic improvement of cleaning efficiency in terms of area and energy is observed when using the laser at glancing angle of incidence as compared to perpendicular. Furthermore substrate damage is greatly reduced and probably eliminated at glancing angles. The process mechanism is discussed by considering the adhesion and the laser-induced cleaning forces for different incident angles. It is shown that there are different laser–matter interactions operating. Received: 25 April 2000 / Accepted: 9 May 2000 / Published online: 5 October 2000     

KrF excimer laser dry and steam cleaning of silicon surfaces with metallic particulate contaminants

KrF excimer laser-assisted dry and steam cleaning of single-crystal silicon wafers contaminated with three different types of metallic particles was studied. The laser fluence used was 0.3 J/cm². In the dry process, for samples cleaned with 100 laser pulses the cleaning efficiency was 91, 71 and 59% for Au, Cu and W particles, respectively, whilst in steam cleaning the efficiency is about 100% after 5 laser pulses, independently of the type of contaminant. The effects of laser irradiation on the Si surface are investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Laser processing at 0.3 J/cm² does not deteriorate the Si-wafer surface, either in dry or steam cleaning. However, the measured XPS intensity coming from the metallic component is greater on the cleaned surfaces than in the initial condition. Quantification of the XPS results, assuming a stratified overlayer model for the detected species and accounting for the presence of the metallic particles on the surface, showed that the obtained results can be explained by the formation of a fractional metallic monolayer on the cleaned surfaces, due to partial vaporisation of small particles initially present on the sample surface. This contamination of the substrate could be considered excessive for some applications and it shows that the process requires careful optimisation for the required efficiency to be achieved without degradation of the substrate. Received: 14 January 2001 / Accepted: 19 February 2001 / Published online: 20 June 2001     

Influence of laser fluence and irradiation timing of F2 laser on ablation properties of fused silica in F2-KrF excimer laser multi-wavelength excitation process

A collinear irradiation system of F₂ and KrF excimer lasers for high-quality and high-efficiency ablation of hard materials by the F₂ and KrF excimer lasers’ multi-wavelength excitation process has been developed. This system achieves well-defined micropatterning of fused silica with little thermal influence and little debris deposition. In addition, the dependence of ablation rate on various conditions such as laser fluence, irradiation timing of each laser beam, and pulse number is examined to investigate the role of the F₂ laser in this process. The multi-wavelength excitation effect is strongly affected by the irradiation timing, and an extremely high ablation rate of over 30 nm/pulse is obtained between -10 ns and 10 ns of the delay time of F₂ laser irradiation. The KrF excimer laser ablation threshold decreases and its effective absorption coefficient increases with increasing F₂ laser fluence. Moreover, the ablation rate shows a linear increase with the logarithm of KrF excimer laser fluence when the F₂ laser is simultaneously irradiated, while single KrF excimer laser ablation shows a nonlinear increase. The ablation mechanism is discussed based on these results. Received: 16 July 2001 / Accepted: 27 July 2001 / Published online: 2 October 2001     

Catalytic growth and characterization of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

β-Ga₂O₃ nanowires have been synthesized using Ga metal and H₂O vapor at 800 °C in the presence of Ni catalyst on the substrate. Remarkable reduction of the diameter and increase of the length of the Ga₂O₃ nanowires are achieved by separation of Ga metal and H₂O vapor before they reach the substrate. Transmission electron microscopy analyses indicate that the β-Ga₂O₃ nanowires possess a single-crystalline structure. Photoluminescence measurements show two broad emission bands centered at 290 nm and 390 nm at room temperature. Received: 27 June 2002 / Accepted: 7 October 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +886-6/234-4496, E-mail: wujj@mail.ncku.edu.tw     

VUV F<Subscript>2</Subscript> laser ablation of sodium chloride

We report an investigation of the ablation of NaCl crystals at the 157-nm wavelength of the F₂ laser where there is very strong excitonic absorption. Probe-beam deflection and etch-rate measurements show that the interaction is characterised by a low ablation threshold (∼80 mJ cm^-2) and a capability for controllable material removal at the nanometer level. Scanning electron microscopy of the exposed surfaces show this to be microscopically smooth but with fine cracks present. It is demonstrated that micron-scale features can be formed in NaCl using 157-nm laser ablation, a result attributed to the strongly localised optical and thermal nature of the interaction. The results are discussed within the framework of a thermal vaporisation model. Received: 29 May 2002 / Accepted: 17 July 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1482/465606, E-mail: p.e.dyer@hull.ac.uk     

Determination of an optimal five-gas combination in a sealed-off CO<Subscript>2</Subscript> laser

For obtaining the maximal output power, five lasing gas mixtures (CO₂, N₂, He, Xe and H₂) in a sealed-off CO₂ laser are optimized by applying a genetic algorithm and solving CO₂ laser kinetics equations. A comparison of numerical simulations shows that the optimal pressures of CO₂ and N₂ are 1.15 Torr and 7.32 Torr, respectively. Accordingly, the maximum laser power of 124 W is obtained by utilizing the optimal gas combination and an optimized resonator with a length of 1.2 m. Received: 14 August 2002 / Published online: 22 January 2003 The project supported by Zhejiang Provincial Natural Science Foundation of China (No. 602098). RID="*" ID="*"Corresponding author. Fax: +86-571/8832-0369, E-mail: chengch@mail.hz.zj.cn     

Photoluminescence behavior of pulsed laser deposited ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin-film phosphors grown on various substrates

ZnGa₂O₄ thin-film phosphors have been grown on Si(100), Al₂O₃(0001) and MgO(100) substrates using pulsed laser deposition. The structural characterization was carried out on a series of ZnGa₂O₄ films grown on various substrates under various substrate temperatures and oxygen pressures. The films grown on these substrates not only have different crystallinity and surface morphology, but also different Zn/Ga composition ratio. The crystallinity and photoluminescence (PL) of the ZnGa₂O₄ films are highly dependent on the deposition conditions, in particular the stoichiometry ratio of Zn/Ga and the kind of substrate. The variation of Zn/Ga in the films also depends on not only the oxygen pressure but also the substrate temperature during deposition. The PL properties of pulsed laser deposited ZnGa₂O₄ thin films have indicated that Al₂O₃(0001) and MgO(100) are promising substrates for the growth of high-quality ZnGa₂O₄ thin films and that the luminescence brightness depends on the substrate. The luminescence spectra show a broad band extending from 350 to 600 nm and peaking at 460 nm. Received: 11 July 2002 / Accepted: 31 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +82-51-6206356, E-mail: jhjeong@pknu.ac.kr     

Ultrahigh-efficiency TEM<Subscript>00</Subscript> diode-side-pumped Nd:YVO<Subscript>4</Subscript> laser

Ultrahigh-efficiency TEM₀₀ operation is demonstrated in a diode-pumped Nd:YVO₄ laser in a bounce amplifier geometry using a specially designed astigmatically optimised cavity configuration. Optical efficiency >68% is demonstrated and up to 27.1 W of output power for multimode operation. For single-mode TEM₀₀ operation, an output power of 23.1 W for 39.5 W of diode pumping was produced with beam propagation parameters of M_x ²=1.3 and M_y ²=1.1. Received: 10 October 2002 / Revised version: 9 December 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +44-20/7594-7744, E-mail: a.minassian@ic.ac.uk     

Electronic structure of defective lithium cobaltites Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoO<Subscript>2</Subscript>

X-ray absorption, resonant X-ray emission, and X-ray photoelectron spectroscopical methods have been applied for the study of the electronic structure of defective lithium cobaltites Li _x CoO₂ (0.6≤x≤1.0). Resonant O K α X-ray emission spectra of LiCoO₂ showed localized excitonic states due to a dd transition between occupied and unoccupied Co 3d states. On the base of measurements of Co 3s X-ray photoelectron, Co 2p, and O 1s X-ray absorption spectra, it was established that in defective cobaltites the electronic holes are localized mainly in O 2p states. An evidence of phase separation in Li _x CoO₂ has been found. It was shown that the semiconductor-to-metal transition in Li _x CoO₂ (x<0.76) at about 160 K is not accompanied by changes in the Co 3d electronic configuration which remains 3d ⁶.     

Effect of vapor attenuation in surface ablation of cobalt by pulsed UV laser

Numerical calculations based on a thermal model were presented, which describe the process of target heating and ablation of cobalt during irradiation by 30-ns laser pulses at 308 nm. The attenuation of laser by vapor has been taken into account in this model. As results of the calculations, the temperature distribution beneath the target surface and the temporal evolution of surface temperature were given. The dependence of ablation rate on laser fluence was also studied based on this model. The surface ablation of cobalt with pulsed excimer laser was investigated experimentally. Our model considering proper vapor attenuation has shown to be in good agreement with the experimental results. Received: 20 January 2000 / Accepted: 13 March 2000 / Published online: 5 July 2000     

Phase transformation during surface ablation of cobalt-cemented tungsten carbide with pulsed UV laser

Surface ablation of cobalt-cemented tungsten carbide hard metal has been carried out in this work using a 308 nm, 20 ns XeCl excimer laser. Surface microphotography and XRD, as well as an electron probe have been used to investigate the transformation of phase and microstructure as a function of the pulse-number of laser shots at a laser fluence of 2.5 J/cm². The experimental results show that the microstructure of cemented tungsten carbide is transformed from the original polygonal grains of size 3 μm to interlaced large, long grains with an increase in the number of laser shots up to 300, and finally to gross grains of size 10 μm with clear grain boundaries after 700 shots of laser irradiation. The crystalline structure of the irradiated area is partly transformed from the original WC to βWC_1-x, then to αW₂C and CW₃, and finally to W crystal. It is suggested that the undulating ‘hill–valley’ morphology may be the result of selective removal of cobalt binder from the surface layer of the hard metal. The formation of non-stoichiometric tungsten carbide may result from the escape of elemental carbon due to accumulated heating of the surface by pulsed laser irradiation. Received: 13 July 2000 / Accepted: 27 October 2000 / Published online: 10 January 2001     

Anisotropy of the dielectric permittivity of Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> measured with light-induced grating techniques

We apply, for the first time to our knowledge, photorefractive grating spectroscopy to obtain not-yet-known data on the anisotropy of the dielectric permittivity of Sn₂P₂S₆. Two independent techniques are used, one based on measurements of the amplitude of the space-charge field grating as a function of grating spacing and the other based on measurements of the grating decay time, also as a function of grating spacing. Both techniques provide close values for the anisotropy, which appears to be well pronounced, a ratio ε_xx/ε_zz≈4 is revealed for two of the three independent components of the dielectric tensor. Our data also allow us to conclude that the charge mobility is nearly isotropic in the same plane, μ_xx/μ_zz≈1. Received: 2 December 2002 / Published online: 26 March 2003 RID="*" ID="*"Corresponding author. Fax: +380-44/265-2359, E-mail: odoulov@iop.kiev.ua     

F2-laser ablation patterning of dielectric layers

Spatially defined patterning of multi-layer dielectric optical systems by laser-induced ablation is demonstrated. A 49-layer high-reflectivity mirror for 193-nm light was irradiated with F₂-laser light through the CaF₂-substrate to cleanly remove the whole dielectric stack by rear-sided ablation. The 157-nm light is absorbed efficiently by dielectric layers such as SiO₂ and Al₂O₃ that are typically used for ultraviolet (UV) transmission at 193-nm and longer wavelengths. Thus it is possible to ablate highly reflective UV-laser mirrors (HR 193 nm) and to create dielectric masks that withstand high power levels at 193 nm. A single 157-nm pulse with a fluence of less than 500 mJ/cm² is sufficient to cleanly ablate the whole layer stack with sharp edges and without debris deposition. Received: 31 October 2000 / Accepted: 14 November 2000 / Published online: 10 January 2001     

Compact diode-side-pumped Nd:YVO<Subscript>4</Subscript> laser in grazing-incidence configuration

The analysis of compact CW diode-side-pumped grazing-incidence-geometry Nd:YVO₄ laser designs is presented. An output power of 5 W (λ=1064 nm) was produced at 17 W of diode pump (conversion efficiency of 30%) in single transverse TEM₀₀ mode operation at high laser beam quality (M_x ²≈1.05 and M_y ²≈1.01). The resonator geometry was analyzed by applying generalized 4×4 matrix modeling of the spatial mode size, including the impact on the laser operation of cavity astigmatism and a thermal lens in the laser slab. The simplicity and compactness of the laser cavities allow their use for technological applications. Received: 31 July 2002 / Published online: 22 January 2003 RID="*" ID="*"Corresponding author. Fax: +44-20/7594-7744, E-mail: m.damzen@ic.ac.uk     

N+BF<Subscript>2</Subscript> and N+C+BF<Subscript>2</Subscript> high-dose co-implantation in silicon

Nitrogen and boron BF₂, and nitrogen, carbon, and boron BF₂ high-dose (6×10¹⁶–3×10¹⁷ cm^-2) co-implantation were performed at energies of about 21–77 keV. Subsequent high-temperature annealing processes (600, 850, and 1200 °C) lead to the formation of three and two surface layers respectively. The outer layer mainly consists of polycrystalline silicon and some amorphous material and Si₃N₄ inclusions. The inner layer is highly defective crystalline silicon, with some inclusions of Si₃N₄ too. In the N+B-implanted sample the intermediate layer is amorphous. Co-implantation of boron with nitrogen and with nitrogen and carbon prevents the excessive diffusivity of B and leads to a lattice-parameter reduction of 0.7–1.0%. Received: 10 January 2002 / Accepted: 30 May 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +34-91/3974895; E-mail: Lucia.Barbadillo@uam.es     

High-peak-power diode-pumped passively Q-switched Nd:YVO<Subscript>4</Subscript> laser

We report on a passively Q-switched diode-pumped Nd:YVO₄ laser polarized along the a axis (corresponding to the smallest value of emission cross section at 1064 nm), generating 157-μJ pulses with 6.0-ns time duration (>20 kW peak power) and 3.6 W of average power at 1064 nm with good beam quality (M²<1.4). The selection of the polarization was performed by a novel technique relying on the birefringence of the laser crystal and on the misalignment sensitivity of the resonator. Received: 30 September 2002 / Revised version: 22 November 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +39-382/422583, E-mail: agnesi@ele.unipv.it     

Orientation ordering of N<Subscript>2</Subscript> molecules in vertically aligned CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanotubes

Arrays of vertically aligned nitrogen-doped carbon (CN _x ) nanotubes have been synthesized by decomposition of aerosol mixture of acetonitrile and ferrocene at 850°C. Nitrogen concentration in the outer shells of the CN _x nanotubes was found from X-ray photoelectron spectroscopy (XPS) data to reach ∼6%. The XPS N 1s spectra and N 1s near-edge X-ray absorption fine structure (NEXAFS) spectra identified three chemical forms of nitrogen in the CN _x nanotube arrays: pyridine-like, graphitic, and molecular nitrogen. The π ^* resonance of molecular nitrogen showed clear polarization dependence that indicates predominant orientation of N₂ molecules along the nanotubes axis. The estimated range of the polar angle distribution of the N₂ molecules orientation in the CN _x nanotube array amounts to 15°.