Analyses of surface coloration on TiO2 film irradiated with excimer laser

TiO₂ film of around 850 nm in thickness was deposited on a soda-lime glass by PVD sputtering and irradiated using one pulse of krypton-fluorine (KrF) excimer laser (wavelength of 248 nm and pulse duration of 25 ns) with varying fluence. The color of the irradiated area became darker with increasing laser fluence. Irradiated surfaces were characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy and atomic force microscopy. Surface undergoes thermal annealing at low laser fluence of 400 and 590 mJ/cm². Microcracks at medium laser fluence of 1000 mJ/cm² are attributed to surface melting and solidification. Hydrodynamic ablation is proposed to explain the formation of micropores and networks at higher laser fluence of 1100 and 1200 mJ/cm². The darkening effect is explained in terms of trapping of light in the surface defects formed rather than anatase to rutile phase transformation as reported by others. Controlled darkening of TiO₂ film might be used for adjustable filters.     

Nanosecond pulse laser melting investigation by IR radiometry and reflection-based methods

Experimental system for nanosecond laser melting investigation was developed containing three independent noncontact methods: infrared radiometry, time-resolved reflectivity of He-Ne laser and sample surface reflected KrF heating laser pulse. The system was applied to the investigation of laser melting of Cu, Mo, Ni, Si, Sn, Ti, steel ?SN 15330 and stainless steel ?SN 17246 samples. For metallic samples the IR radiometry signal was transformed to temperature. Obtained surface temperature and reflectivity spectra in nanosecond time scale (10-1000 ns) for wide range of energy densities (100-5500 mJ cm⁻²) are presented. Interesting evolutions were found. Melting thresholds and melting durations were determined from the measured curves. The applicability of the methods is evaluated.     

Laser surface treatment of screen-printed carbon nanotube emitters for enhanced field emission

This paper investigates the surface treatment of screen-printed carbon nanotube (CNT) emitters using a 248 nm (KrF) excimer laser. The field emission characteristics of the CNT emitters are measured following irradiation using laser fluences ranging from 80 to 400 mJ/cm². The results show that the turn-on electric field, the current density, and the distribution of the emission sites are highly dependent on the value of the laser fluence and are optimized at a fluence of 150 mJ/cm². Two distinct laser fluence regimes are identified. In the low fluence regime, i.e. 80-150 mJ/cm², the surface treatment process is dominated by a photo ablation mechanism, which results in the gradual removal of the binding material from the cathode surface and leads to an improvement in the emission characteristics of the CNT cathodes with an increasing fluence. However, in the high fluence regime, i.e. 150-400 mJ/cm², the thermal ablation mechanism dominates; resulting in a removal of the CNTs from the cathode surface and a subsequent degradation in the emission characteristics.     

Preparation of the La0.8Sr0.2MnO3 films on STO and LAO substrates by excimer laser-assisted metal organic deposition using the KrF laser

La_0.8Sr_0.2MnO₃ films were prepared on SrTiO₃ (STO) and LaAlO₃ (LAO) substrates using excimer laser-assisted metal organic deposition (ELAMOD). For the LAO substrate, no epitaxial La_0.8Sr_0.2MnO₃ film was obtained by laser irradiation in the fluence range from 60 to 110 mJ/cm² with heating at 500 °C. On the other hand, an epitaxial La_0.8Sr_0.2MnO₃ film on the STO substrate was formed by laser irradiation in the fluence range from 60 to 100 mJ/cm² with heating at 500 °C. To optimize the electrical properties for an IR sensor, the effects of the laser fluence, the irradiation time and the film thickness on the temperature dependence of the resistance and temperature coefficient of resistance (TCR: defined as 1/R·(dR/dT)) of the LSMO films were investigated. An LSMO film on the STO substrate that showed the maximum TCR of 3.9% at 265 K was obtained by the ELAMOD process using the KrF laser.     

Deposition of aluminum nitride thin film on Si(1 1 1) by KrF excimer laser and its characterizations

We present the deposition of aluminum nitride (AlN) thin film by KrF excimer laser sputtering and the study of the effects of substrate temperature and laser fluences. Deposition rate of AlN thin film at 0.3 Å/pulse has been achieved with laser fluence of 1500 mJ/cm² and at substrate temperature of 250 K, and this shows the enhancement of the deposition rate at low substrate temperature. Surface morphology of the deposited films is characterized by atomic force microscopy (AFM). In addition, the electrical performance of the MIS devices with AlN thin films prepared in this experiment has been characterized.     

Pulsed-laser crystallization and epitaxial growth of metal-organic films of Ca-doped LaMnO3 on STO and LSAT substrates

Ca-doped LaMnO₃ (LCMO) thin films have been successfully prepared on SrTiO₃ (STO) and [(LaAlO₃)_0.3-(SrAlTaO₆)_0.7] (LSAT) substrates using the excimer laser assisted metal-organic deposition (ELAMOD) process. The crystallization and the epitaxial growth of the amorphous metal-organic LCMO thin films have been achieved using a KrF excimer laser irradiation while the substrates were kept at constant temperature of 500 °C. Epitaxial films were obtained using laser fluence in the interval of 50-120 mJ/cm². The microstructure of the LCMO films was studied using cross-section transmission electron microscopy. High quality of LCMO films having smooth surfaces and sharp interfaces were obtained on both the STO and the LSAT substrates. The effect of the laser fluence on the temperature coefficient of resistance (TCR) was investigated. The largest values of TCR of the LCMO grown on the LSAT and the STO substrates of 8.3% K⁻¹ and 7.46% K⁻¹ were obtained at different laser fluence of 80 mJ/cm² and 70 mJ/cm², respectively.     

High-resolution electron microscopy study of SiGeC thin films grown on Si(1 0 0) by laser-assisted techniques

PLIE was used for rapid crystallisation of a-SiGeC films deposited by LCVD on Si(1 0 0) substrates. HRTEM study of thin films grown with several laser energies shows that the combination of the two laser techniques gives an almost completely crystallised alloy, even for the lowest laser fluence. Island formation is observed below a certain threshold of fluence (about 450 mJ/cm²). In the case of the lowest energy (100 mJ/cm²) the material was partially crystallised (with the crystalline material being the predominant state), to a nanocrystalline alloy with a considerable amount of epitaxialy grown grains and with grain sizes of several tens of nanometers. Above the threshold of 450 mJ/cm² a rather smooth thin film is grown. The crystallisation is almost complete and the alloy is grown in an almost perfect epitaxial way.     

Time-resolved measurements during backside dry etching of fused silica

The laser-induced backside dry etching (LIBDE) investigated in this study makes use of a thin metal film deposited at the backside of a transparent sample to achieve etching of the sample surface. For the time-resolved measurements at LIBDE fused silica samples coated with 125 nm tin were used and the reflected and the transmitted laser intensities were recorded with a temporal resolution of about 1 ns during the etching with a ∼30 ns KrF excimer laser pulse. The laser beam absorption as well as characteristic changes of the reflection of the target surface was calculated in dependence on the laser fluence in the range of 250-2500 mJ/cm² and the pulse number from the temporal variations of the reflection and the transmission. The decrease of the time of a characteristic drop in the reflectivity, which can be explained by the ablation of the metal film, correlates with the developed thermal model. However, the very high absorption after the film ablation probably results in very high temperatures near the surface and presumably in the formation of an absorbing plasma. This plasma may contribute to the etching and the surface modification of the substrate. After the first pulse a remaining absorption of the sample was measured that can be discussed by the redeposition of portions of the ablated metal film or can come from the surface modification in the fused silica sample. These near-surface modifications permit laser etching with the second laser pulse, too.     

Indium tin oxide sol-gel precursor conversion process using the third harmonics of Nd:YAG laser

We use the third harmonics of Nd:YAG laser (λ = 355 nm) for simultaneous precursor conversion and dopant activation on sol-gel ITO thin films at a laser fluence range of 700-1000 mJ/cm². A minimum resistivity of 5.37 × 10⁻² Ω-cm with a corresponding carrier concentration of 6 × 10¹⁹ cm⁻³ is achieved at laser irradiation fluence of 900 mJ/cm². X-ray photoelectron analysis reveals that extremely high tin concentration of 19.4 at.% and above is presented in the laser-cured ITO thin films compared with 8.7 at.% in the 500 °C thermally cured counterpart. These excess tin-ions form complex defects, which contribute no free carriers but act as scattering centers, causing inferior electrical properties of the laser-cured films in comparison with the thermally cured ones.     

Influence on the laser induced backside dry etching of thickness and material of the absorber, laser spot size and multipulse irradiation

Laser induced backside dry etching method (LIBDE) was developed - analogously to the well-known laser induced backside wet etching (LIBWE) technique - for the micromachining of transparent materials. In this procedure, the absorbing liquid applied during LIBWE was replaced with solid metal layers. Fused silica plates were used as transparent targets. These were coated with 15-120 nm thick layers of different metals (silver, aluminium and copper). The absorbing films were irradiated by a nanosecond KrF excimer laser beam through the quartz plate. The applied fluence was varied in the 150-2000 mJ/cm² range, while the irradiated area was between 0.35 and 3.6 mm². At fluences above the threshold values, it was found that the metal layers were removed from the irradiated spots and the fused silica was etched at the same time. In our experiments, we investigated the dependence of the main parameters (etch rate and threshold) of LIBDE on the absorption of the different metal layers (silver, copper, aluminium), on the size of the irradiated area, on the film thickness and on the number of processing laser pulses.     

Femtosecond and nanosecond laser damage thresholds of doped and undoped triazenepolymer thin films

The influence of pulse duration on the laser-induced damage in undoped or infrared-absorbing-dye doped thin triazenepolymer films on glass substrates has been investigated for single, near-infrared (800 nm) Ti:sapphire laser pulses with durations ranging from 130 fs up to 540 fs and complementarily for infrared (1064 nm) Nd:YAG ns-laser single-pulse irradiation. The triazenepolymer material has been developed for high resolution ablation with irradiation at 308 nm. Post-irradiation optical microscopy observations have been used to determine quantitatively the threshold fluence for permanent laser damage. In contrast to our previous studies on a triazenepolymer with different composition [J. Bonse, S.M. Wiggins, J. Solis, T. Lippert, Appl. Surf. Sci. 247 (2005) 440], a significant dependence of the damage threshold on the pulse duration is found in the sub-picosecond regime with values ranging from ∼500 mJ/cm² (130 fs) up to ∼1500 mJ/cm² (540 fs). Other parameters such as the film thickness (50 nm and 1.1 μm samples) or the doping level show no significant influence on the material behavior upon irradiation. The results for fs- and ns-laser pulse irradiation are compared and analyzed in terms of existent ablation models.     

Crystallisation of TiO2 thin films induced by excimer laser irradiation

Titanium dioxide thin films have been deposited by reactive magnetron sputtering on glass substrate and subsequently irradiated by UV radiation using a KrF excimer laser. In this work, we have study the influence of the laser fluence (F) ranging between 0.05 and 0.40 mJ/cm² on the constitution and microstructure of the deposited films. Irradiated thin films are characterized by profilometry, scanning electron microscopy and X-ray diffraction. As deposited films are amorphous, while irradiated films present an anatase structure. The crystallinity of the films strongly varies as a function of F with maximum for F = 0.125 J/cm². In addition to the modification of their constitution, the irradiated areas present a strongly modified microstructure with appearance of nanoscale features. The physico-chemical mechanisms of these structural modifications are discussed based on the theory of nucleation.     

Ultra fast melting process in femtosecond laser crystallization of thin a-Si layer

In this paper, we investigated the mechanism of crystallization induced by femtosecond laser irradiation for an amorphous Si (a-Si) thin layer on a crystalline Si (c-Si) substrate. The fundamental, SHG, THG wavelength of a Ti:Sapphire laser was used for the crystallization process. To investigate the processed areas we performed Laser Scanning Microscopy (LSM), Transmission Electron Microscopy (TEM) and Imaging Pump-Probe measurements. Except for 267 nm femtosecond laser irradiation, the crystallization occurred well. The threshold fluences for the crystallization using 800 nm and 400 nm femtosecond laser irradiations were 100 mJ/cm² and 30 mJ/cm², respectively. TEM observation revealed that the crystallization occurred by epitaxial growth from the boundary surface between the a-Si layer and c-Si substrate. The melting depths estimated by Imaging Pump-Probe measurements became shallower when the shorter wavelength was used.     

Fixation of bioactive calcium alkali phosphate on Ti6Al4V implant material with femtosecond laser pulses

Bone implants made of metal, often titanium or the titanium alloy Ti6Al4V, need to be surface treated to become bioactive. This enables the formation of a firm and durable connection of the prosthesis with the living bone. We present a new method to uniformly cover Ti6Al4V with a thin layer of ceramics that imitates bone material. These calcium alkali phosphates, called GB14 and Ca10, are applied to the metal by dip coating of metal plates into an aqueous slurry containing the fine ceramic powder. The dried samples are illuminated with the 790 nm radiation of a pulsed femtosecond laser. If the laser fluence is set to a value just below the ablation threshold of the ceramic (ca. 0.4 J/cm²) the 30 fs laser pulses penetrate the partly transparent ceramic layer of 20-40 μm thickness. The remaining laser fluence at the ceramic-metal interface is still high enough to generate a thin metal melt layer leading to the ceramic fixation on the metal. The laser processing step is only possible because Ti6Al4V has a lower ablation threshold (between 0.1 and 0.15 J/cm²) than the ceramic material. After laser treatment in a fluence range between 0.1 and 0.4 J/cm², only the particles in contact with the metal withstand a post-laser treatment (ultrasonic cleaning). The non-irradiated rest of the layer is washed off. In this work, we present results of a successful ceramic fixation extending over larger areas. This is fundamental for future applications of arbitrarily shaped implants.     

Femtosecond pulsed laser deposition of diamond-like carbon films: The effect of double laser pulses

The bonding structure of carbon films prepared by pulsed laser deposition is determined by the plasma properties especially the change of the kinetic energy. Using double laser pulses the ablation process and the characteristics of the generated plasma can be controlled by the setting of the delay between the pulses. In our experiments, amorphous carbon films have been deposited in vacuum onto Si substrates by double pulses from a Ti:sapphire laser (180 fs, λ = 800 nm, at 1 kHz) and a KrF laser system (500 fs, λ = 248 nm, at 5 Hz). The intensities have been varied in the range of 3.4 × 10¹² to 2 × 10¹³ W/cm². The morphology and the main properties of the thin layers were investigated as a function of the time delay between the two ablating pulses (0-116.8 ps) and as a function of the irradiated area on the target surface. Atomic force microscopy, spectroscopic ellipsometry and Raman-spectroscopy were used to characterize the films. It was demonstrated that the change of the delay and the spot size results in the modification of the thickness distribution of the layers, and the carbon sp²/sp³ bonding ratio.     

Preparation and characterization of pulsed laser deposition (PLD) SiC films

Si K-edge XAFS was used to characterize a stoichiometric SiC film prepared by pulsed KrF laser deposition. The film was deposited on a p-type Si(1 0 0) wafer at a substrate temperature of 250 °C in high vacuum with a laser fluence of ∼5 J/cm². The results reveal that the film contains mainly a SiC phase with an amorphous structure in which the Si atoms are bonded to C atoms in its first shell similar to that of crystalline SiC powder but with significant disorder.     

Effect of pulse width and fluence of femtosecond laser on the size of nanobump array

Conical nanobump arrays were generated on gold thin film processed by interfering femtosecond laser. The transition of the height and diameter as functions of fluence and pulse width was investigated. When the fluence was 87 mJ/cm², the height and diameter were not so different at 350 fs or shorter pulse width. They decreased at longer pulse width, and no bump could be generated over 1.6 ps. The results suggest the decrease of size is due to the diffusion of electron to not-excited region, and due to heat conduction to not heated region or substrate, or change of absorbance of laser. At long pulse width of 2.4 ps and relatively higher fluence of 190 mJ/cm², nanobump had liquid-like structure as a stop motion of a water drop.     

Preparation of palladium film by coating photolysis process using KrF or ArF excimer laser

The preparation of palladium (Pd) films has been investigated using KrF or ArF laser irradiation on a Pd acetate (PdAc) coated substrate. A crystalline Pd film could be obtained by KrF laser irradiation (fluence = 15-40 mJ/cm²) but PdAc was found to remain in the film. An increase in the substrate temperature to 423 K decreased the inclusion of the unreacted precursor and produced a better crystallinity. An amorphous and uniform Pd film composed of very fine particles was found to be formed by this process under reduced pressure, which is probably due to the preferential ablation of the crystalline nuclei. ArF laser irradiation is more effective for decomposing the PdAc and for producing a Pd film with a better crystallinity and no (or smaller) organic inclusion.     

Diamond-like phase formation in an amorphous carbon films prepared by periodic pulsed laser deposition and laser irradiation method

Diamond-like carbon (DLC) films were fabricated by pulsed laser ablation of a liquid target. During deposition process the growing films were exited by a laser beam irradiation. The films were deposited onto the fused silica using 248 nm KrF eximer laser at room temperature and 10⁻³ mbar pressure. Film irradiation was carried out by the same KrF laser operating periodically between the deposition and excitation regimes. Deposited DLC films were characterized by Raman scattering spectroscopy. The results obtained suggested that laser irradiation intensity has noticeable influence on the structure and hybridization of carbon atoms deposited. For materials deposited at moderate irradiation intensities a very high and sharp peak appeared at 1332 cm⁻¹, characteristic of diamond crystals. At higher irradiation intensities the graphitization of the amorphous films was observed. Thus, at optimal energy density the individual sp³-hybridized carbon phase was deposited inside the amorphous carbon structure. Surface morphology for DLC has been analyzed using atomic force microscopy (AFM) indicating that more regular diamond cluster formation at optimal additional laser illumination conditions (∼20 mJ per impulse) is possible.