Efficient submicron processing of metals with femtosecond UV pulses

The generation of submicron-sized holes on metal surfaces by applying femtosecond UV laser pulses was investigated. Different optical schemes based on a Schwarzschild-type reflective objective were used to reach optimized ablation quality and efficiency in different applications (hole ablation, through-hole drilling, generation of surface patterns consisting of holes, etc.). Submicron-sized holes and hole patterns were ablated onto metal surfaces and drilled through ∼5-μm-thick steel foils with 600-nm diameter on the output side. Using a special optical interferometric method, large-area surface processing of high-conductivity materials in the submicron regime was performed. Combining these techniques with the application of high-repetition-rate ultra-short UV laser sources, large-area sub-μm processing of all kinds of materials in industrial environments is possible. Received: 28 February 2002 / Accepted: 12 March 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +49-551/503599, E-mail: psimon@llg.gwdg.de     

Femtosecond pulsed-laser deposition of BaTiO<Subscript>3</Subscript>

The elemental composition and the surface morphology of thin films grown by laser ablation of barium titanate with femtosecond pulses at 620 nm laser wavelength have been systematically studied according to the experimental pulsed-laser deposition parameters : laser energy density, oxygen pressure, substrate temperature, target–substrate distance and substrate position (in- and off-axis geometry). Firstly, even at high temperature (700 °C), the deposits consist of coalesced particles up to 1-μm in size, mixed in a poorly crystallised tetragonal BaTiO₃ thin film. The particles formed in femtosecond pulsed-laser deposition induce a high surface roughness, which is observed whatever the experimental growth conditions and does not correspond to the droplets often observed during laser ablation in the nanosecond regime. As shown by plasma expansion dynamics, these particles propagate toward the substrate in the plasma plume with a low velocity, and are assumed to be produced by gas-phase reactions. Moreover, the cationic concentration evaluated through the Ba/Ti ratio strongly depends on the oxygen pressure in the ablation chamber and the angular position of the substrate along the normal to the target at laser impact. Indeed, the films appear to be enriched in the heavy element (Ba) when the substrate is located at high angular deviation. This fact is correlated to an increase in the lighter species (i.e. Ti) in the central part of the plasma plume. Received: 30 April 2002 / Accepted: 26 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +33-1/4354-2878, E-mail: millon@gps.jussieu.fr RID="**" ID="**"Also at: LSMCL, Université de Metz, 57078 Metz Cedex 3, France     

Molecular imaging by Mid-IR laser ablation mass spectrometry

Mid-IR laser ablation at atmospheric pressure (AP) produces a mixture of ions, neutrals, clusters, and particles with a size distribution extending into the nanoparticle range. Using external electric fields the ions can be extracted and sampled by a mass spectrometer. In AP infrared (IR) matrix-assisted laser desorption ionization (MALDI) experiments, the plume was shown to contain an appreciable proportion of ionic components that reflected the composition of the ablated target and enabled mass spectrometric analysis. The detected ion intensities rapidly declined with increasing distance of sampling from the ablated surface to ∼4 mm. This was rationalized in terms of ion recombination and the stopping of the plume expansion by the background gas. In laser ablation electrospray ionization (LAESI) experiments, the ablation plume was intercepted by an electrospray. The neutral particles in the plume were ionized by the charged droplets in the spray and enabled the detection of large molecules (up to 66 kDa). Maximum ion production in LAESI was observed at large (∼15 mm) spray axis to ablated surface distance indicating a radically different ion formation mechanism compared to AP IR-MALDI. The feasibility of molecular imaging by both AP IR-MALDI and LAESI was demonstrated on targets with mock patterns. Presented at the 9-th International Conference on Laser Ablation, 2007 Tenerife, Canary Islands, Spain     

Phase explosion and recoil-induced ejection in resonant-infrared laser ablation of polystyrene

We investigate the phenomenon of resonant-infrared laser ablation of polymers using polystyrene as a model material. Ablation is carried out using various mid-IR laser wavelengths that are resonant with vibrational modes of a polystyrene target. Time-resolved plume imaging coupled with etch-depth measurements and thermal calculations indicate that ablation begins after a superheated surface layer reaches a temperature of ∼1000°C and undergoes spinodal decomposition. The majority of the ablated material is then expelled by way of recoil-induced ejection as the pressure of the expanding vapor plume compresses a laser-melted area.     

Electron structure and electron dynamics at InSb(111)2×2 semiconductor surface

The conduction band electronic structure and the electron dynamics of the clean InSb(111)2×2 surface have been studied by laser based pump-and-probe photoemission. The results are compared to earlier studies of the InSb(110) surface. It is found that both the energy location and the time dependence of the photoexcited structures are very similar for the two surfaces. This indicates that the dominant part of the photoemission signal in the conduction band region is due to excitations of electrons in the bulk region and that the surface electronic states play a minor role. The fast decay of the excited state, τ∼12 ps, indicates that diffusion of hot electrons into the bulk is an important mechanism. Received: 9 May 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +46-0824/913-1, E-mail: gm@matphys.kth.se     

Mechanisms of small clusters production by short and ultra-short laser ablation

The mechanisms involved into the formation of clusters by pulsed laser ablation are studied both numerically and experimentally. To facilitate the model validation by comparison with experimental results, the time and length scales of the simulation are considerably increased. This increase is achieved by using a combination of molecular dynamics (MD) and the direct simulation Monte Carlo (DSMC) methods. The combined MD-DSMC model is then used to compare the relative contribution of the two channels of the cluster production by laser ablation: (i) direct cluster ejection upon the laser-material interaction, and (ii) collisional sticking and aggregation in the ablated gas flow. Calculation results demonstrate that both of these mechanisms play a role. The initial cluster ejection provides cluster precursors thus eliminating the three-body collision bottleneck in the cluster growth process. The presence of clusters thus facilitates the following collisional condensation and evaporation processes. The rates of these processes become considerable, leading to the modification of not only the plume cluster composition, but also the dynamics of the plume expansion. Calculation results explain several recent experimental findings.     

Characterization of laser-ablated and chemically reduced silver colloids in aqueous solution by UV/VIS spectroscopy and STM/SEM microscopy

Silver colloids in aqueous solution were studied by different scanning microscopy techniques and UV/VIS spectroscopy. The silver colloids were produced either by chemical reduction or by nanosecond laser ablation from a solid silver foil in water. Variation of laser power and ablation time leads to solutions of metal clusters of different sizes in water. We characterized the electronic absorption of the clusters by UV/VIS spectroscopy. STM (scanning tunneling microscope) imaging of the metal colloids shows atomic resolution of rod- or tenon-like silver clusters up to 10-nm length formed by laser ablation. Our scanning electron microscope measurements, however, show that much larger silver colloids up to 5-μm length are also formed, which are not visible in the STM due to their roughness. We correlate them with the long-wavelength tail of the multimodal UV/VIS spectrum. The silver colloids obtained by chemical reduction are generally larger and their electronic spectra are red-shifted compared to the laser-ablated clusters. Irradiation of the colloid solution with nanosecond laser pulses of appropriate fluence at 532 nm and 355 nm initially reduced the colloid size. Longer irradiation at 355 nm, however, leads to the formation of larger colloids again. There seems to be a critical lower particle size, where silver clusters in aqueous solution become unstable and start to coagulate. Received: 24 June 2002 / Revised version: 25 July 2002 / Published online: 25 October 2002 RID="*" ID="*"This work is part of the thesis of H. M?ltgen RID="**" ID="**"Corresponding author. Fax: +49-211/811-5195, E-mail: kleinermanns@uni-duesseldorf.de     

Ablation with a single micropatterned KrF laser pulse: quantitative evidence of transient liquid microflow driven by the plume pressure gradient at the surface of polyesters

A microscopic flow of a transient liquid film produced by KrF laser ablation is evidenced on targets of PET and PEN. Experiments were done by using single pulses of the excimer laser beam micropatterned with the aid of submicron projection optics and grating masks. The samples of various crystalline states, ablated with a grating-forming beam (period Λ=3.7 μm), were precisely measured by atomic force microscopy, in order to evidence any deviation from the ablation behavior predicted by the current theory (combination of ablation curve and beam profile). This was confirmed by comparing various behaviors dependent on the polymer nature (PC, PET and PEN). PC is a normally ablating polymer in the sense that the ablated profile can be predicted with previous theory neglecting liquid-flow effects. This case is called ‘dry’ ablation and PC is used as a reference material. But, for some particular samples like crystalline PET, it is revealed that during ablation a film of transient liquid, composed of various components, which are discussed, can flow under the transient action of the gradient of the pressure of the ablation plume and resolidify at the border of the spot after the end of the pulse. This mechanism is further supported by a hydrodynamics theoretical model in which a laser-induced viscosity drop and the gradient of the plume pressure play an important role. The volume of displaced liquid increases with fluence (0.5 to 2 J/cm²) and satisfactory quantitative agreement is obtained with the present model. The same experiment done on the same PET polymer but prepared in the amorphous state does not show microflow, and such an amorphous sample behaves like the reference PC (‘dry’ ablation). The reasons for this surprising result are discussed. Received: 31 October 2002 / Accepted: 4 November 2002 / Published online: 22 January 2003 RID="*" ID="*"Present address: ST Microelectronics, Crolles, France RID="**" ID="**"Corresponding author. Fax: +33-556/84-6645, E-mail: s.lazare@lpcm.u-bordeaux1.fr     

Filling boron nitride nanotubes with metals

The authors’ endeavors over the last few years with respect to boron nitride (BN) nanotube metal filling are reviewed. Mo clusters of 1–2 nm in size and FeNi Invar alloy (Fe ∼60 at. %; Ni ∼40 at. %) or Co nanorods of 20–70 nm in diameter were embedded into BN nanotube channels via a newly developed two-stage process, in which multi-walled C nanotubes served as templates for the BN multi-walled nanotube synthesis. During cluster filling, low-surface-tension and melting-point Mo oxide first filled a C nanotube through the open tube ends, followed by fragmentation of this filling into discrete clusters via O₂ outflow and C→BN conversion within tubular shells at high temperature. During nanorod filling, C nanotubes containing FeNi or Co nanoparticles at the tube tips were first synthesized by plasma-assisted chemical vapor deposition on FeNi Invar alloy or Co substrates, respectively, and, then, the nanomaterial was heated to the melting points of the corresponding metals in a flow of B₂O₃ and N₂ gases. During this second stage, simultaneous filling of nanotubes with a FeNi or Co melt through capillarity and chemical modification of C tubular shells to form BN nanotubes occurred. The synthesized nanocomposites were analyzed by scanning and high-resolution transmission electron microscopy, electron diffraction, electron-energy-loss spectroscopy and energy-dispersive X-ray spectroscopy. The nanostructures are presumed to function as ‘nanocables’ having conducting metallic cores (FeNi, Co, Mo) and insulating nanotubular shields (BN) with the additional benefit of excellent environmental stability. Received: 10 October 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

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     

Exciton dispersion in silicon nanostructures formed by intense,ultra-fast electronic excitation

The intense, ultra-fast electronic excitation of clean silicon (100)–(2×1) surfaces leads to the formation of silicon nanostructures embedded in silicon, which photoluminesce in the yellow-green (∼2-eV band gap). The silicon surfaces were irradiated with slow, highly charged ions (e.g. Xe⁴⁴⁺ and Au⁵³⁺) to produce the ultra-fast electronic excitation. The observation of excitonic features in the luminescence from these nanostructures has recently been reported. In this paper we report the dispersion of the excitonic features with laser excitation energy. A phonon-scattering process is proposed to explain the observed dispersion. Received: 2 October 2001 / Accepted: 18 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +1-925/423-7040, E-mail: Hamza1@llnl.gov RID="**" ID="**"Present address: University of California, Lawrence Berkeley National Laboratory, Berkeley, CA 94 720, USA     

High-resolution electron microscopy of individual metallofullerene molecules on the dipole orientations in peapods

Electron microscopy with atomic sensitivity enables us to obtain a direct image of the intra-molecular structure of metallofullerenes encapsulated inside single-walled carbon nanotubes. By a comparison of high-resolution images with a simulation to extract the relative atom positions for encaged metal atoms in each molecule, the distribution of the molecular orientations and interactions between adjacent molecules in metallofullerene peapods have been statistically analyzed. The results are suggestive of strong interactions between fullerene–fullerene and fullerene–tube in peapods at room temperature. Received: 10 October 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/61-6310, E-mail: suenaga-kazu@aist.go.jp     

Properties of an ultrashort-pumped near-IR high gain dye amplifier

An ultra-short-pumped optical dye amplifier operating in the near-IR (720 nm) has been developed. We present an experimental study of the input–output characteristics of this simple device in a traveling wave collinear configuration. In essence, the combined effects of the ultrafast nature of the anisotropy induced by the exciting laser pulse along with the short transit time across the length of the cell allow for optimal output conditions given the number of molecules in the active volume. Two distinct amplifying regimes have been observed depending on photon density. Typical gain values of 10⁴ of the narrow bandwidth (∼9 nm) subpicosecond output signal were measured. The 8-mm² beam cross section enables this photon amplifier to be utilized in time-gated imaging applications. Received: 12 December 2001 / Revised version: 13 May 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +1-819/564-5442, E-mail: Daniel.Houde@Usherbrooke.ca     

Magnetic properties of Ni:SiO<Subscript>2</Subscript> nanocomposites synthesized by a modified sol–gel method

Ni nanoparticles embedded in an amorphous SiO₂ matrix were produced by a modified sol–gel method. This method resulted in nanocomposites with a controlled size distribution and good dispersion of the metallic particles. The particle-size distributions were found to have an average radius of ∼3 nm, as inferred from transmission electron microscopy, X-ray-diffraction analysis, and magnetic measurements. Magnetic characterizations revealed that samples exhibit superparamagnetic behavior above the blocking temperature T_B, 20 K≤T_B≤40 K, and absence of a shift along the field axis on hysteresis loops measured at T≤T_B, indicating that the metallic nanoparticles are also free from an oxide layer. Received: 7 October 2002 / Accepted: 9 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +55-11/3091-6984, E-mail: rjardim@if.usp.br     

Excimer laser polymer ablation: twenty years on

Research and development in excimer laser polymer ablation has been actively pursued for some twenty years, driven by interest in the basic science as well as by numerous applications that have emerged for this high-resolution technique for material removal. This paper reviews some of the basic mechanistic aspects of the UV laser–polymer interaction as a prelude to dealing with practical matters related to polymer processing by ablation. Applications in micro-machining and potential areas for future research are briefly covered. Received: 7 October 2002 / Accepted: 8 February 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +44-1482/465-606, E-mail: p.e.dyer@hull.ac.uk     

Nonlinear electrical characteristics and dielectric properties of Ca,Ta-doped TiO<Subscript>2</Subscript> varistors

Ca,Ta-doped TiO₂ varistors with high nonlinear coefficients are obtained by a ceramic sintering. The nonlinear electrical and dielectric properties of the samples doped with 0.5mol% Ca and various concentrations of Ta (0.05∼2.0mol%) were investigated. The samples sintered at 1350 °C have nonlinear coefficients of α=5.1∼42.1 and high relative dielectric constants approach 10⁵. The effects of Ta-doping on the nonlinear and dielectric properties of the Ca,Ta-doped TiO₂ varistors are studied in greater detail. When the concentration of Ta is 0.5mol%, the sample possesses the highest nonlinear coefficient and a comparatively lower dielectric constant. The effects of Ta and the nonlinear electrical behavior of the TiO₂ system are explained by analogy to a grain-boundary atomic defect model. Received: 24 October 2001 / Accepted: 8 January 2002 / Published online: 3 May 2002 RID="*" ID="*"Corresponding author. Fax: +86-10/826-49531, E-mail: wangwanyan@yahoo.com.cn     

Pulsed laser deposition and in situ diagnostics of the process applied to shape-memory alloys

NiTi films deposited by pulsed laser ablation on Si/SiO₂ are shown to exhibit structural and functional properties related to the shape-memory effect. Film characterization suggests that relevant temperatures for the solid-to-solid transformation responsible for the shape memory are in substantial agreement with those of the bulk target material, demonstrating a good congruency of the deposition process. Besides the technological interest for this class of thin films, our findings point out the suitability of laser ablation for metal alloy deposition. An investigation based on in situ ion-mass spectroscopy and covariance mapping analysis allows us to determine the main vapor-phase processes leading to the formation of stoichiometric clusters expected to play a relevant role in assisting the growth of NiTi thin films. Received: 6 August 2001 / Accepted: 11 April 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +39-50/2214-333, E-mail: fuso@df.unipi.it     

Surface nanostructuring of silicon

Irradiation with polarized laser light of 248-nm wavelength induces the formation of periodic undulations ∼10-nm-highon flat silicon substrates. The wavelength of these periodic structures is a function of the light wavelength and the angle of incidence of the laser beam. Linear arrays of silicon nanoparticles with fairly uniform size that extended up to a millimeter were formed if the irradiation was performed using polarized light. When non-polarized laser light with the same fluence was used to illuminate an initially flat surface, non-aligned nanoparticle strings were obtained. However, if part of the irradiated area was microstructured, nanoparticle linear arrays resulted in the vicinity of the microstructured region. An analysis on the evolution of these nanostructures is presented. Nanocolumns could be grown on top of every cone of a microstructured surface upon cumulative laser irradiation with non-polarized light, reaching a height of ∼3 μm and a diameter of 100–200 nm. The mechanisms of nanocolumn origin and growth are analyzed. Received: 16 December 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +1-865/974-4115, E-mail: apedraza@utk.edu