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.     

Growth process of nanostructured silver films pulsed laser ablated in high-pressure inert gas

The growth process of silver thin films deposited by pulsed laser ablation in a controlled inert gas atmosphere was investigated. A pure silver target was ablated in Ar atmosphere, at pressures ranging between 10 and 100 Pa, higher than usually adopted for thin film deposition, at different numbers of laser shots. All of the other experimental conditions such as the laser (KrF, wavelength 248 nm), the fluence of 2.0 J cm⁻², the target to substrate distance of 35 mm, and the temperature (295 K) of the substrates were kept fixed. The morphological properties of the films were investigated by transmission and scanning electron microscopies (TEM, SEM). Film formation results from coalescence on the substrate of near-spherical silver clusters landing as isolated particles with size in the few nanometers range. From a visual inspection of TEM pictures of the films deposited under different conditions, well-separated stages of film growth are identified.     

F2 laser induced oxidation of inorganic material

Transparent SiO₂ thin films were selectively fabricated on Si wafer by 157 nm F₂ laser in N₂/O₂ gas atmosphere. The F₂ laser photochemically produced active O(¹D) atoms from O₂ molecules in the gas atmosphere; strong oxidation reaction could be induced to fabricate SiO₂ thin films only on the irradiated areas of Si wafer. The oxidation reaction was sensitive to the single pulse fluence of F₂ laser. The irradiated areas were swelled and the height was approximately 500-1000 nm at the 205-mJ/cm² single pulse fluence for 60 min laser irradiation. The fabricated thin films were analytically identified to be SiO₂ by the Fourier-transform IR spectroscopy. The SiO₂ thin films could be also removed by subsequent chemical etching to fabricate micro-holes 50 nm in depth on Si wafer for microfabrication.     

Morphology and composition on Al surface irradiated by femtosecond laser pulses

We study the surface chemicals and structures of aluminum plates irradiated by scanning femtosecond laser pulses in air for a wide range of laser fluence from 0.38 to 33.6 J/cm². X-ray photoelectron spectroscopy and X-ray diffraction analyses indicate clearly that crystalline anorthic Al(OH)₃ is formed under femtosecond laser pulse irradiation. Besides aluminum hydroxide, crystalline Al₂O₃ is also found in the samples irradiated at high laser fluence. Field emission scanning electron microscopy demonstrates that the surfaces of the samples irradiated with low laser fluence are colloidal-like and that nanoparticles with a few nanometers in size are embedded in glue-like substances. For high laser fluence irradiated samples, the surfaces are highly porous and covered by nanoparticles with uniform size of less than 20 nm.     

Surface modification of a WTi thin film on Si substrate by nanosecond laser pulses

Interaction of a nanosecond transversely excited atmospheric (TEA) CO₂ laser, operating at 10.6 μm, with tungsten-titanium thin film (190 nm) deposited on silicon of n-type (1 0 0) orientation, was studied. Multi-pulse irradiation was performed in air atmosphere with laser energy densities in the range 24-49 J/cm². The energy absorbed from the laser beam was mainly converted to thermal energy, which generated a series of effects. The following morphological changes were observed: (i) partial ablation/exfoliation of the WTi thin film, (ii) partial modification of the silicon substrate with formation of polygonal grains, (iii) appearance of hydrodynamic features including nano-globules. Torch-like plumes started appearing in front of the target after several laser pulses.     

Laser fluence, repetition rate and pulse duration effects on paint ablation

The efficiency (mm³/(J pulse)) of laser ablation of paint was investigated with nanosecond pulsed Nd:YAG lasers (λ = 532 nm) as a function of the following laser beam parameters: pulse repetition rate (1-10,000 Hz), laser fluence (0.1-5 J/cm²) and pulse duration (5 ns and 100 ns). In our study, the best ablation efficiency (η ≅ 0.3 mm³/J) was obtained with the highest repetition rate (10 kHz) at the fluence F = 1.5 J/cm². This ablation efficiency can be associated with heat accumulation at high repetition rate, which leads to the ablation threshold decrease. Despite the low thermal diffusivity and the low optical absorption of the paint (thermal confinement regime), the ablation threshold fluence was found to depend on the pulse duration. At high laser fluence, the ablation efficiency was lower for 5 ns pulse duration than for the one of 100 ns. This difference in efficiency is probably due to a high absorption of the laser beam by the ejected matter or the plasma at high laser intensity. Accumulation of particles at high repetition rate laser ablation and surface shielding was studied by high speed imaging.     

Formation of periodic structures by laser ablation of metals in liquids

Experimental results are presented on ablation of metals (W, Cu, brass and bronze) in a liquid environment (e.g., ethanol or water) by irradiation with either a pulsed copper vapor laser (0.51 μm) or a pulsed Nd:YAG laser (1.06 μm). The target material is ejected into surrounding liquid in the form of nanoparticles. In a certain range of laser parameters (fluence and number of laser shots) the surface of the solid target is composed of micro-cones having a regular structure. The distance between neighboring micro-cones in the structure depends on the laser spot size. The structures allow the observation of up-conversion of the laser frequency due to generation of the second harmonics in the eye retina.     

Characterization of Ag and Au nanoparticles created by nanosecond pulsed laser ablation in double distilled water

Pulsed laser ablation of Ag and Au targets, immersed in double-distilled water is used to synthesize metallic nanoparticles (NPs). The targets are irradiated for 20 min by laser pulses at different wavelengths—the fundamental and the second harmonic (SHG) (λ = 1064 and 532 nm, respectively) of a Nd:YAG laser system. The ablation process is performed at a repetition rate of 10 Hz and with pulse duration of 15 ns. Two boundary values of the laser fluence for each wavelength under the experimental conditions chosen were used—it varied from several J/cm² to tens of J/cm². Only as-prepared samples were measured not later than two hours after fabrication. The NPs shape and size distribution were evaluated from transmission electron microscopy (TEM) images. The suspensions obtained were investigated by optical transmission spectroscopy in the near UV and in the visible region in order to get information about these parameters. Spherical shape of the NPs at the low laser fluence and appearance of aggregation and building of nanowires at the SHG and high laser fluence was seen. Dependence of the mean particle size at the SHG on the laser fluence was established. Comments on the results obtained have been also presented.     

Laser sintering of Cu paste film printed on polyimide substrate

We here show that highly conductive copper films are obtainable from Cu paste by laser sintering. The Cu paste synthesized using an organo-metallic compound was screen-printed onto polyimide substrate and the printed films were scanned by an ultraviolet laser beam at 355 nm under nitrogen atmosphere. Very compact microstructure was observed throughout the whole thickness and the sintered films were mechanically robust. Although Cu is known susceptible to oxidation, no Cu oxides were incorporated into the film during laser sintering. An electrical resistivity of 1.86 × 10⁻⁵ Ω cm was obtained. This resistivity is several orders of magnitude lower than those reported for the copper nanoparticle paste thermally sintered under N₂ or H₂ atmosphere.     

Femtosecond laser micromilling of Si wafers

Femtosecond laser micromilling of silicon is investigated using a regeneratively amplified 775 nm Ti:Sapphire laser with a pulse duration of 150 fs operating at 1 kHz repetition rate. The morphological observation and topological analysis of craters fabricated by single-shot laser irradiation indicated that the material removal is thermal in nature and there are two distinct ablation regimes of low fluence and higher fluence with logarithmical relations between the ablation depth and the laser fluence. Crater patterns were categorized into four characteristic groups and their formation mechanisms were investigated. Femtosecond laser micromilling of pockets in silicon was performed. The effect of process parameters such as pulse energy, translation speed, and the number of passes on the material removal rate and the formation of cone-shaped microstructures were investigated. The results indicate that the microstructuring mechanism has a strong dependence on the polarization, the number of passes and laser fluence. The optimal laser fluence range for Si micromilling was found to be 2-8 J/cm² and the milling efficiency attains its maximum between 10 and 20 J/cm².     

KrF laser ablation of a polyethersulfone film: Effect of pulse duration on structure formation

Polyethersulfone (PES) films were processed with KrF laser irradiation of different pulse durations (τ). Scanning electron microscopy (SEM) and Raman spectroscopy were employed for the examination of the morphology and chemical composition of the irradiated surfaces, respectively. During ablation with 500 fs and 5 ps pulses, localized deformations (beads), micro-ripple and conical structures were observed on the surface depending on the irradiation fluence (F) and the number of pulses (N). In addition, the number density of the structures is affected by the irradiation parameters (τ, F, N). Furthermore, at longer pulse durations (τ = 30 ns), conical structures appear at lower laser fluence values, which are converted into columnar structures upon irradiation at higher fluences. The Raman spectra collected from the top of the structures following irradiation at different pulse durations revealed graphitization of the ns laser treated areas, in contrast to those processed with ultra-short laser pulses.     

On determining the spot size for laser fluence measurements

Energy fluence, defined as pulse energy over irradiated area, is a key parameter of pulsed laser processing. Nevertheless, most of the authors using this term routinely do not realize the problems related to the accurate measurement of the spot size. In the present paper we are aiming to approach this problem by ablating crystalline Si wafers with pulses of a commercial KrF excimer laser (λ = 248 nm, τ = 15 ns) both in vacuum and at ambient atmosphere. For any pulse energy, the size of the ablated area monotonously increases with increasing number of pulses. The difference in the ablated area could be as high as a factor of three when 2000 consecutive pulses impinge on the surface. The existence and extent of the gradual lowering of multi-pulse ablation threshold queries the applicability of routinely used procedure of dividing the pulse energy with the size of the ablated area exposed into either carbon-paper or a piece of Si with one or a few pulses when determining the fluence. A more quantitative way is proposed allowing comparison of results originating from different laboratories.     

Application of the laser ablation for conservation of historical paper documents

Laser ablation was applied for surface cleaning and spectroscopic diagnostics of historical paper documents and model samples in the framework of the conservation projects. During cleaning the spectra of ablation products were recorded by means of the LIBS technique which allowed for nearly non-destructive identification of surface layers such as contaminants, substrate and pigments. For consecutive laser pulses a strong decrease of band intensities of the emission lines of Ca, Na, K, Al and Fe ascribed to contaminants were observed. The effect was used for monitoring of the cleaning progress of stained paper. For surface cleaning and spectra excitation the Q-switched Nd:YAG laser of 6 ns pulsewidth operating at wavelengths of 266, 355, 532, and 1064 nm and of fluence selected from the range 0.3-0.9 J/cm² was applied. The ablation parameters were optimized in agreement with the literature and the results were confirmed by surface studies and testing of the mechanical and chemical properties, and also by the response to the ageing process of the paper substrate. In case of the model paper irradiated in the UV range at 266 and 355 nm a visual inspection revealed local damages of the cellulose fibers accompanied by a decrease of the mechanical strength of the substrate. The effect was more pronounced after artificial ageing. The best results were obtained for samples irradiated at 532 nm and at laser fluence below the damage threshold of 0.6 J/cm², which is in agreement with literature.     

Effect of spot size on cone formation in a XeCl laser ablation of polyethersulfone films

Radiation from the UV excimer lasers, with the fluence above the ablation threshold, can etch the polymer surfaces by photoablation. In some cases different microstructures may appear on the surface during the laser ablation. In this paper the effect of the laser spot size on the cone formation on polyethersulfone films has been investigated. The experiments have been performed with a XeCl laser at the wavelength of 308 nm and at the fluences of 70 and 100 mJ/cm² at air. For the investigation of the effect of the laser spot size on cone formation, the samples were irradiated at two different laser spot sizes of w₁ and w₂ = 0.1 w₁. The morphology of the processed surface was studied by scanning electron microscopy (SEM). It has shown that the shape, size and density of cones change with the change of the laser spot size. Also, the number of pulses and the pulse repetition rate which are needed for threshold of cone formation are affected by the laser beam spot size on the surface.     

Evolution of InP surfaces under low fluence pulsed UV irradiation

An InP wafer was irradiated in air by a series of UV pulses from a nitrogen laser with fluences of 120 mJ/cm² and 80 mJ/cm². These fluences are below the single-pulse ablation threshold of InP. Over the studied region the distribution of the radiation intensity was uniform. The number of pulses varied from 50 to 6000. The evolution of the surface morphology and structure was characterized by atomic force microscopy, optical microscopy and Raman spectroscopy. The relationship between mound size and the number of pulses starts out following a power law, but saturates for a sufficiently high number of pulses. The crossover point is a function of fluence. A similar relation exists for the surface roughness. Raman spectroscopic investigations showed little change in local crystalline structure of the processed surface layer.     

Excitation of thermoluminescence in Eu doped Ba0.12Sr0.88SO4 nanophosphor by low energy argon ions

In the present paper thermoluminescence properties of argon ions irradiated barium strontium mixed sulphate phosphor are reported. The Ba_0.12Sr_0.88SO₄ phosphor was prepared by chemical co-precipitation method. The X-ray diffraction study of prepared sample suggests orthorhombic structure with average grain size of 37 nm. The samples were irradiated with 1.2 MeV Argon ions at fluences varying between 10¹¹-10¹⁵ ions/cm². The argon ions penetrate to the depth of 1.89 μm and lose their energy mainly via electronic stopping. Due to ion irradiation, a large number of defects in the sample are formed. Thermoluminescence (TL) glow curves were recorded for each of the ion fluence. These curves exhibit one broad peak with maximum intensity at 498 K composed of three overlapping peaks. This indicates that different sets of traps are being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The peaks were observed due to formation of trap levels by ion irradiation and subsequently activation of traps on thermal stimulation. The TL response of the nanophosphor is linear in the dose range 59 kGy-590 MGy. Kinetic parameters associated with the prominent peaks were calculated using glow curve deconvolution (GCD) and verified by different glow curve shape and sample heating rate methods.     

Pulsed laser ablation of borax target in vacuum and hydrogen DC glow discharges

The aim of our experiment was to produce a material with BH bonds for applications in hydrogen storage and generation. By using KrF excimer laser (λ = 248 nm) ablation of borax (Na₂B₄O₇) target, thin films were deposited on KBr and silicon substrates. Ablation was performed both in vacuum and in hydrogen atmosphere. DC glow discharge technique was utilized to enhance hydrogen gas ionization. Experiments were performed using laser fluence from 5 to 20 J/cm². Films were deposited under gas pressure of 1 × 10⁻⁵ to 5 × 10⁻² mbar and substrate temperatures of 130-450 °C. Scanning electron microscopy analysis of films showed presence of circular particulates. Film thickness, roughness and particulates number increased with increase in laser fluence. Energy dispersive X-ray spectroscopy analysis shows that sodium content in the particulates is higher than in the target. This effect is discussed in terms of atomic arrangements (both at surface and bulk) in systems where ionic and covalent bonds are present and by looking at the increased surface/bulk ratio of the particulates with respect to the deposited films. The Fourier transform infrared spectroscopy measurements showed presence of BO stretching and BOB bending bonds. Possible reasons for absence of BH bonds are attributed to binding enthalpy of the competing molecules.     

Properties of conductive polymer films deposited by infrared laser ablation

Thin films of the conducting polymer poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) were deposited by resonant infrared laser vapor deposition (RIR-LVD). The PEDOT:PSS was frozen in various matrix solutions and deposited using a tunable, mid-infrared free-electron laser (FEL). The films so produced exhibited morphologies and conductivities that were highly dependent on the solvent matrix and laser irradiation wavelength used. When deposited from a native solution (1.3% by weight in water), as in matrix-assisted pulsed laser evaporation (MAPLE), films were rough and electrically insulating. When the matrix included other organic “co-matrices” that were doped into the solution prior to freezing, however, the resulting films were smooth and exhibited good electrical conductivity (0.2 S/cm), but only when irradiated at certain wavelengths. These results highlight the importance of the matrix/solute and matrix/laser interactions in the ablation process.     

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.     

Laser backwriting process on glass via ablation of metal targets

Ablation of metal targets onto pyrex glass substrates, using a Q-switched Nd:YAG laser working at 355 nm, was used to study the potential of a laser backwriting process for the fabrication of optical waveguides via an index of refraction change. Metal foils of stainless steel, aluminum, copper, brass and gold have been used as blanks and irradiated by focusing the laser beam through a cylindrical lens under continuous movement in a direction perpendicular to the irradiation. An horizontal setup was found suitable to improve the effect of the plume in the sample. Results were obtained for two different configurations. Transversal profiles were analysed using a contact profilometer, comparing results obtained for the different configurations, traverse speeds and metal targets used. Two ablation regimes were identified, which are related to a critical laser fluence value of 2.7 J/cm². Surface micrographs obtained by scanning electron microscopy are discussed, together with the characteristics of the structures attained, taking into account the optical and thermal properties of the ablated metal blanks.