KrF excimer laser ablation of thin Cr film on glass substrate

Received: 5 October 1998 / Accepted: 14 December 1998 / Published online: 24 February 1999     

Sub-500-nm patterning of glass by nanosecond KrF excimer laser ablation

The surface of flint glass of type F2 is patterned by nanosecond KrF excimer laser ablation. Strong UV absorption provides a comparatively low ablation threshold and precise ablation contours. By using a two-grating interferometer, periodic surface patterns with 330 nm period and 100 nm modulation depth are obtained. This method enables the fabrication of 7 mm×13 mm wide grating areas with perfectly aligned grooves without the need of high-precision sample positioning. By double exposure, crossed gratings with adjustable depths in the two orthogonal directions can be generated.     

Microstructure control of low-resistivity tin-doped indium oxide films grown by photoreaction of nanoparticles using a KrF excimer laser at room temperature

A tin-doped indium oxide (ITO) film on a SiO₂ substrate was prepared by photo-irradiation of spin-coated nanoparticles using a Xe excimer lamp and a KrF excimer laser. The effects of the excimer lamp and the excimer laser on the resistivity, mobility, and carrier concentration of the film were investigated. To better understand how to control the microstructure of the film, we investigated the effect of thickness on the resistivity of a film prepared by the two-step process, and found that the resistivity was higher in a thicker film. Using two-step irradiation plus one-step KrF irradiation in N₂ at room temperature, we produced an ITO film with lowest resistivity of any in this study. The electrical resistivity of this film was 5.94×10⁻⁴ Ω cm. On the other hand, when using a simple thermal process, the resistivity of a film sintered at 500°C in N₂ was 4.10×10⁻³ Ω cm. The differences in resistivity are discussed on the basis of the microstructure of the films using atomic force microscopy and Hall measurements.     

Characterization of boron carbon nitride film modified by excimer laser annealing

Boron carbon nitride (BCN) shows promise as a field emitter material because of its mechanical hardness, chemical inertness, and low electron affinity. This study investigated the modification of a BCN film with an amorphous area using KrF excimer laser (wavelength: 248 nm, photon energy: 5.0 eV) annealing without substrate heating. This achieved significant variation in characteristics, such as an increase in bandgap energy and decrease in electron affinity. Laser annealing reduced electron affinity from 0.7 to 0.3 eV. The results indicate that the modification of the BCN film by KrF excimer laser annealing achieves characteristics similar to hexagonal BN (h-BN) film without losing the desirable properties of the BCN film, such as physical stability.     

Textured thin films grown at room temperature by laser ablation

Thin films of SrFe₁₂O₁₉, BaFe₁₂O₁₉, Pb_0.76La_{0.16 0.08}Zr_0.53Ti_0.47O₃and Sr_0.3Ba_0.7Nb₂O₆ were grown on monocrystalline silicon substrates by pulsed laser deposition using a 20-ns Nd:YAG laser (1064 nm). The deposited thin films were analyzed by X-ray diffraction in the grazing incidence configuration. The analysis showed evidence of textured growth even though the films were grown at room temperature. Emission spectroscopy was used to establish the time of flight of the species within the plasma plume. Velocities of the order of 10⁶ cm/s were obtained. The high kinetic energy of the species is thought to be responsible for the film texture, as it is released in the substrate–film system, favoring a preferential growth. For all the ablated ceramics, singly ionized species were shown to expand at higher velocities than neutrals. For ions, no consistency in the mass–speed relation was obtained, suggesting both the presence of electric fields during the plasma formation and an evaporation of the target that depends on the vapor pressure of the elements. In this way species that are firstly evaporated will be attracted strongly by fast electrons, allowing heavy ions to acquire higher velocities than lighter ones. PACS 81.15.Fg; 52.38.Mf; 68.55.Jk; 52.38.Kd; 52.70.Kz     

Synthesis of boron nitride multi-walled nanotubes by laser ablation technique

Carbon nanotubes are known as prospective material for the optoelectronics, vacuum electronics, non-linear optics and for the composite material synthesis. Boron nitride nanotubes (BNNTs) were obtained only recently. It is expected that these nanotubes possess the unique properties. BN is much more chemically inert than carbon. Its oxidation temperature is above 1000°C as the graphite is totally oxidized already at 650°C. BNNTs are wide-gap semiconductors with the 6 eV gap. In case of the introducing of the carbon atoms into the BN nanotube wall its bandgap may be varied in wide range. This property is important for the UV optics.     

Plasma characterization and room temperature growth of carbon nanotubes and nano-onions by excimer laser ablation

The deposition of carbon nanotubes and carbon nano-onions at room temperature using excimer laser radiation to ablate mixed graphite-metal targets is described. Our deposition conditions are in contrast to other investigations on the pulsed laser deposition of carbon nanotubes that have employed high temperatures and high pressures. We find that the formation of these carbon nanostructures is dependent on the ambient gas employed during ablation. In the presence of O₂ gas, carbon nanotubes and nano-onions are produced, while inert atmospheres such as Ar yield amorphous carbon. High-resolution, in situ, time-resolved emission spectroscopy has been used to track the evolution of species (C₂, C₃, Ni/Co) in the ablation plume. Spectral fits on low and high-resolution spectra reveal that the vibrational-rotational temperatures for C₂ produced in O₂ remain at ∼5000 K for nearly 20 μs but drop rapidly in Ar. Details of the formation of carbon nanotubes and nano-onions, and in situ time-resolved optical emission spectroscopy are described.     

Low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation

The low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation has been studied. Two fabrication methods are presented. One is photoenhanced direct nitridation of a silicon surface with NH₃ for very thin gate insulators, and the other is photo-enhanced deposition of silicon nitride films with Si₂H₆ and NH₃ gases for stable passivation films. The ArF excimer laser irradiation dissociates the NH3 gas producing NH and NH₂ radicals which proved effective in instigating the nitridation reaction. The quality of both films has been much improved and the growth temperature has been lowered by using laser irradiation. These photo-enhanced processes seem to be promising ULSI techniques because they do not depend on high temperatures and are free from possible reactor contamination.     

Depth-profile investigations of triterpenoid varnishes by KrF excimer laser ablation and laser-induced breakdown spectroscopy

The ablation properties of aged triterpenoid dammar and mastic films were investigated using a Krypton Fluoride excimer laser (248 nm, 25 ns). Ablation rate variations between surface and bulk layers indicated changes of the ablation mechanisms across the depth profiles of the films. In particular, after removal of the uppermost surface varnish layers there was a reduction of the ablation step in the bulk that was in line with a significant reduction of carbon dimer emission beneath the surface layers as detected by laser-induced breakdown spectroscopy. The results are explicable by the generation of condensation, cross-linking and oxidative gradients across the depth profile of triterpenoid varnish films during the aging degradation process, which were recently quantified and established on the molecular level.     

Surface wettability of silicon substrates enhanced by laser ablation

Laser–ablation techniques have been widely applied for removing material from a solid surface using a laser–beam irradiating apparatus. This paper presents a surface–texturing technique to create rough patterns on a silicon substrate using a pulsed Nd:YAG laser system. The different degrees of microstructure and surface roughness were adjusted by the laser fluence and laser pulse duration. A scanning electron microscope (SEM) and a 3D confocal laser–scanning microscope are used to measure the surface micrograph and roughness of the patterns, respectively. The contact angle variations between droplets on the textured surface were measured using an FTA 188 video contact angle analyzer. The results indicate that increasing the values of laser fluence and laser pulse duration pushes more molten slag piled around these patterns to create micro-sized craters and leads to an increase in the crater height and surface roughness. A typical example of a droplet on a laser–textured surface shows that the droplet spreads very quickly and almost disappears within 0.5167 s, compared to a contact angle of 47.9° on an untextured surface. This processing technique can also be applied to fabricating Si solar panels to increase the absorption efficiency of light.     

Projection-patterned etching of silicon in chlorine atmosphere with a KrF excimer laser

The formation of relief features in silicon by a one-step process that avoids resist patterning has been achieved by laser-projection-patterned etching in a chlorine atmosphere. Etching is performed with a pulsed KrF excimer laser (λ=248 nm, τ=15 ns) and deep UV projection optics having an optical resolution of 2 μm. Etching takes place in two steps. Between laser pulses, the silicon surface is covered with a monolayer of chemisorbed chlorine atoms (one Cl per Si). During the laser pulse, surface transient heating at temperatures in excess of 1250 K results in the desorption of the reaction products (mainly SiCl₂). At laser energy densities that induce surface melting, this desorption results in a saturated etch. rate of 0.06 nm per pulse, corresponding to the removal of about 0.5 Si monolayer per pulse. At densities below the melting threshold, reduced thermal and possibly a small amount of photochemical etching result in lower etch rates. Projection of a resolution test photomask onto the silicon surface shows that the size of etched features differs from the size of the projected features and strongly depends on the laser energy density. As a result of the heat spread in silicon and of the highly nonlinear character of the etching reaction, etched features smaller than the irradiated area are obtained at all fluences in the range 350–700 mJ/cm². Etched lines having a width down to about 1.3 μm were produced. Proximity effects due to heat spread were also evidenced for small projected features (<4 μm). The characteristics of the etched patterns are compared with those obtained for GaAs etching in chlorinated gases with the same experimental set-up. Significant differences in pattern resolution for Si and GaAs etching are observed. This variation in resolution is believed to result from the fact that Si has a greater thermal diffusivity than GaAs.     

等离子体增强脉冲激光沉积o-BN薄膜

利用等离子体增强脉冲激光沉积系统在Si（100）基底上沉积出了高质量的o-BN薄膜,利用红外光谱（FTIR）、X射线衍射谱（XRD）和原子力显微镜照片对o-BN薄膜进行了表征.通过红外光谱（FTIR）得到o-BN薄膜的红外峰特征峰值为1189cm^-1,1585cm^-1和1450cm^-1;由XRD谱得到o-BN薄膜的（111）,（020）,（021）,（310）和（243）各晶面的衍射峰, 特别是（310）和（243）晶面的衍射峰非常强;通过原子力显微镜照片清楚看到BN薄膜具有尖状突起的表面形貌. 关键词： 等离子体增强脉冲激光沉积 氮化硼薄膜 X射线衍射谱     

Millimeter-long nanofibers of PMMA spun at super-high speed by ablation with a single pulse of a KrF excimer laser

A new form of matter removal in laser ablation is reported. Polymethylmethacrylate (PMMA) nanofibers are obtained when a PMMA target is irradiated with a single pulse of a KrF excimer laser, whose beam is sharply imaged on a square of side the order of 140 μm, so that a strong intensity gradient is produced. The fluence threshold at which fibers appear, 3 J/cm², is much larger than the ablation threshold, approximately 0.8–1 J/cm². Above this fluence, the melt depth is then large enough and the temperature profile is such that explosive boiling is obtained. The model suggests an expulsion of energetic droplets from the intense pressure of the plume to the exterior of the spot. For the transient melt of a polymeric viscoelastic liquid resulting from UV-laser excitation, such droplets provide the heads of the jets pulled from the melt bath, giving rise, after solidification, to nanofibers. The speed of fiber spinning is extremely high (∼800 m/s) and unusual properties of the laser-produced nanofibers may be expected. Received: 16 April 2002 / Accepted: 17 April 2002 / Published online: 19 July 2002     

Optical studies on the deposition of carbon nitride films by laser ablation

2 radicals when the 355 and 1064 nm outputs of a Nd:YAG laser were applied. While for the 532 nm ablation, a relatively higher concentration of excited atomic carbon was obtained. Different Raman and FTIR spectral features were observed from the deposited films with different ablation wavelengths. The 532 nm laser ablation is proposed for the synthesis of high quality carbon nitride films. Received: 16 October 1996 / Accepted: 11 April 1997     

Pulsed laser ablation and deposition of silicon

A KrF laser was used to ablate a polycrystalline Si target for deposition of Si on MgO and GaAs substrates at room temperature. The deposition was performed in 10⁻⁸ mbar, with two types of laser beams: a homogeneous beam being imaged onto the target (2.9 J/cm²), and a non-homogeneous which is nearly focused (2 J/cm², 6.5 J/cm²). In both cases, the beam was scanned over an area of 1 cm². For the homogenous beam, we observed only a limited number of droplets (<0.1 μm). A high number of micron-sized (<5 μm) droplets were observed on the film by the higher fluence nonhomogeneous laser beam. Raman spectroscopy showed that the micron-sized droplets are crystalline while the film is amorphous. The generation of the large droplets is most likely related to the cone structures formed on the ablated target. We also compared cone formation on a polycrystalline Si target and a single crystalline Si wafer, using multiple laser pulses onto a single spot.     

Nanosecond laser ablation and deposition of silicon

Nanosecond-pulsed KrF (248 nm, 25 ns) and Nd:YAG (1064 nm, 532 nm, 355 nm, 5 ns) lasers were used to ablate a polycrystalline Si target in a background pressure of <10⁻⁴ Pa. Si films were deposited on Si and GaAs substrates at room temperature. The surface morphology of the films was characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Round droplets from 20 nm to 5 μm were detected on the deposited films. Raman Spectroscopy indicated that the micron-sized droplets were crystalline and the films were amorphous. The dependence of the properties of the films on laser wavelengths and fluence is discussed.     

Direct fabrication of microgratings in fused quartz by laser-induced plasma-assisted ablation with a KrF excimer laser

We report precision microfabrication of fused quartz by laser ablation with a conventional UV laser for what is believed to be the first time. A high-quality micrograting structure is fabricated in fused quartz by a novel technique of laser-induced plasma-assisted ablation with a single KrF excimer laser (248 nm). The plasma generated from a metal target by laser irradiation effectively assists in ablation of the fused-quartz substrate by the same laser beam, although the laser beam is transparent to the substrate. A grating with a period of 1.06 mum is achieved by use of a phase mask. We can control the grating depth to 300 nm by changing the pulse number. This technique permits high-quality microfabrication of electronic and optoelectronic devices based on fused quartz and related silicate materials by use of a conventional UV laser.     

Foamy coating obtained by laser ablation of glass ceramic substrates at high temperature

This paper presents a study of the effect of temperature in the machining of glass ceramic cooking plates by laser ablation. A Q-switched Nd:YAG laser at its fundamental wavelength of 1064 nm with pulsewidths in the nanosecond range was used. The beam was focalized and scanned over the surface covering an area of several squared millimetres. With the same irradiance and process parameters the rise of the surface temperature some hundreds of degrees changes drastically the ablation conditions. As temperature is risen the amount of particles ejected from the interaction zone diminishes, recasting over the processed area generating a white and foamy self-layer.The size of the ejected particles and the morphology, composition and microstructure of the new layer is described. This layer could be used to change the thermal conductivity of the glass ceramic plate as well as for aesthetic purposes.     

Effect of excimer laser annealing on the silicon nanocrystals embedded in silicon-rich silicon nitride film

The investigations of silicon-rich silicon nitride film grown by plasma-enhanced chemical vapor deposition and then annealed by excimer laser have been carried out systematically. The surface roughness and the crystallization of the films have significantly been improved after the excimer laser annealing. The samples demonstrate visible photoluminescence emission under optical excitation at room temperature. It is found that the emission peak energy as well as emission intensity changes with laser annealing conditions, and the relevant mechanism is discussed in detail. Our investigation exhibits the size controllability of silicon nanocrystals embedded in the silicon nitride film, which implies promising applications in optoelectronic devices such as light-emitting diodes and solar cells.     

Pulsed laser deposition of hexagonal and cubic boron nitride films

Hexagonal and cubic boron nitride films are deposited by pulsed laser ablation from a boron nitride and a boron target using a KrF excimer laser. Hexagonal films are deposited in nitrogen as background gas or with nitrogen/argon ion bombardment at ion-to-arriving-target-atom (I/A) ratios at the substrate below 0.5. Nucleation of the cubic phase takes place exclusively with ion bombardment at I/A ratios above 1.0, which may be reduced down to 0.6 after the completion of the nucleation process. The influence of the parameters of the laser and ion beams on the properties of the hexagonal films are presented. The Vickers microhardness and the intrinsic stress of those films vary in wide ranges of 5 to 25 GPa and 1 to 16 GPa, respectively. Pulsed laser deposited hexagonal boron nitride films show good adhesion to silicon and stainless steel if they are deposited at I/A ratios below 0.5, and can be used as intermediate layers for improving the adhesion of cubic boron nitride films. So far, 0.5 7m thick, nearly phase-pure cubic boron nitride films with good adhesion have been deposited. The microstructural, mechanical, and optical properties of those layer systems are presented and discussed.