Matrix assisted pulsed laser evaporation processing of triacetate-pullulan polysaccharide thin films for drug delivery systems

We report the first successful deposition of triacetate-pullulan polysaccharide thin films by matrix assisted pulsed laser evaporation. We used a KrF* excimer laser source (λ = 248 nm, τ ≈ 20 ns) operated at a repetition rate of 10 Hz. We demonstrated by FTIR that our thin films are composed of triacetate-pullulan maintaining its chemical structure and functionality. The dependence on incident laser fluence of the induced surface morphology is analysed.     

Laser deposition of cryoglobulin blood proteins thin films by matrix assisted pulsed laser evaporation

We report the first successful deposition of type II cryoglobulin blood protein thin films by matrix assisted pulsed laser evaporation (MAPLE) using a KrF^* excimer laser source (λ = 248 nm, τ_FWHM ≈ 20 ns) operated at a repetition rate of 10 Hz. We demonstrate by AFM and FTIR that MAPLE-deposited thin films consist of starting type II cryoglobulin only, maintaining its chemical structure and biological functionality, being properly collected and processed. The dependence on incident laser fluence of the induced surface morphology is presented. The presence of type II cryoglobulin was revealed as aggregates of globular material in the MAPLE-deposited thin films and confirmed by standard cryoglobulin tests.     

Ablation characteristics of aluminum oxide and nitride ceramics during femtosecond laser micromachining

Femtosecond laser ablation of aluminum oxide (Al₂O₃) and aluminum nitride (AlN) ceramics was performed under normal atmospheric conditions (λ = 785 nm, τ_p = 185 fs, repetition rate = 1 kHz), and threshold laser fluencies for single- and multi-pulse ablation were determined. The ablation characteristics of the two ceramics showed similar trends except for surface morphologies, which revealed virtually no melting in Al₂O₃ but clear evidence of melting for AlN. Based on subsequent X-ray photoelectron spectroscopy (XPS) analyses, the chemistry of these ceramics appeared to remain the same before and after femtosecond laser ablation.     

Nanosecond and femtosecond laser spectroscopy of molecules of biological interest

This paper mainly concerns on nanosecond and femtosecond laser spectroscopy of aromatic organic compounds as neurotransmitters, and plume diagnostics of the ablated species, in order to characterize the plasma dynamics, i.e. the temporal and spatial evolution of the plume. Optical emission spectroscopy has been applied to characterize the transient species produced in the femtosecond (fs) and nanosecond (ns) regimes. The laser sources employed for optical emission spectroscopy are a frequency-doubled Nd:YAG Handy (λ = 532 nm, τ = 5 ns) and a frequency-doubled Nd:glass (λ = 527 nm, τ = 250 fs). These studies aim to detect and give information on the photoexcitation and photodissociation of these biological molecules and to compare the plasma characteristics in the two ablation regimes.     

Simulation of dynamics of phase transitions in CdTe by pulsed laser irradiation

Numerical simulation of melting and solidification processes induced in CdTe by nanosecond radiation of ruby laser (λ = 694 nm, τ = 20 and 80 ns) and KrF excimer laser (λ = 248 nm, τ = 20 ns) taking into account components diffusion in melt and their evaporation from the surface has been carried out. Cd atoms evaporation has shown to essentially affect the dynamics of phase transitions in the near-surface region. Thus, in the case of the influence of ruby laser irradiation intensive surface cooling results in the formation of nonmonotone temperature profile with maximum temperature in semiconductor volume at the distance of ∼20 nm from the surface. The melt formed under the surface extends both to the surface and to the semiconductor volume as well. As a result of cadmium telluride components evaporation and diffusion in the melt the near-surface region is enriched with tellurium. The obtained melting threshold value of irradiation energy density is in a reasonable agreement with experimental data.     

Line patterning with large refractive index changes in the deep inside of glass by nanosecond pulsed YAG laser irradiation

Nanosecond (∼100 ns) pulsed (10 Hz) Nd:YAG laser operating at the wavelength (λ) of 1064 nm with pulse energies of 0.16-1.24 mJ/cm² has irradiated 10Sm₂O₃·40BaO·50B₂O₃ glass. It is demonstrated for the first time that the structural modification resulting the large decease (∼3.5%) in the refractive index is induced by the irradiation of YAG laser with λ=1064 nm. The lines with refractive index changes are written in the deep inside of 100-1000 μm depths by scanning laser. The line width is 1-13 μm, depending on laser pulse energy and focused beam position. It is proposed that the samarium atom heat processing is a novel technique for inducing structural modification (refractive index change) in the deep interior of glass.     

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.     

Beyond the pulse-area theorem: Role of the absorption and the dispersion in the propagation of weak ultrashort resonant pulses

We present here some fundamental but yet underlooked features of the propagation of weak ultrashort pulses (with Δ_dτ << 1, where Δ_d is the Doppler width and τ is the pulse duration) in resonant atomic media. We show that the pulse area behaviour and the pulse spectrum at resonance are governed by the usual optical depth (α₀L, where α₀ is the absorption coefficient at resonance and L the length of the medium), whereas the pertinent parameter that governs the severity of the dispersion effects and the distortion of the pulse is the dispersion parameter e_disp = (α₀L)Δ_dτ that we introduce. Paradoxical effect such as distortionless propagation (e.g. e_disp << 1) with vanishing pulse area (when α₀L >> 1) can then explained within this formalism.     

Laser synthesis of semiconductor nanostructures with narrow band gap

Semiconductor nanostructures with narrow band gap were synthesized by means of laser chemical vapor deposition (LCVD) of elements from iron carbonyl vapors [Fe(CO)₅] under the action of Ar⁺ laser radiation (λ_L = 488 nm) on the Si substrate surface. The temperature dependence of the specific conductivity of these nanostructures in the form of thin films demonstrated typical semiconductor tendency and gave the possibility to calculate the band gap for intrinsic conductivity (E_g) and the band gap assigned for impurities (E_i), which were depended upon film thickness and applied electrical field. Analysis of deposited films with scanning electron microscopy (SEM) and atomic force microscopy (AFM) demonstrated their cluster structure with average size not more than 100 nm. Semiconductor properties of deposited nanostructures were stipulated with iron oxides in different oxidized phases according to X-ray photoelectron spectroscopy (XPS) analysis.These deposited nanostructures were irradiated with Q-switched YAG laser (λ_L = 1064 nm) at power density about 6 × 10⁷ W/cm². This irradiation resulted in the crystallization process of deposited films on the Si substrate surface. The crystallization process resulted in the synthesis of iron carbide-silicide (FeSi_2−xC_x) layer with semiconductor properties too. The width of the band gap E_g of the synthesized layer of iron carbide-silicide was less than for deposited films based on iron oxides Fe₂O_3−x (0 ≤ x ≤ 1).     

Pulsed-laser deposition of smooth thin films of Er, Pr and Nd doped glasses

Thin films of complex oxides have been obtained by pulsed-laser deposition (PLD) from glass targets belonging to the system Li₂O-Al₂O₃-P₂O₅-(RE)₂O₃, with RE = Nd, Pr, Er. The films were deposited on quartz, silicon and ITO/glass substrates using a F₂ laser (λ = 157 nm, ι ≈ 20 ns) for ablation in vacuum. The structural, morphological and optical properties of the oxide films were investigated through IR and UV-VIS spectroscopy, Atomic Force Microscopy (AFM), Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy (SEM-EDX) and Spectroscopic Ellipsometry. The laser wavelength was found to be the key parameter to obtain thin films with very smooth surface. In this way new possibilities are opened to grow multilayer structures for photonic applications.     

Synthesis of functionally graded bioactive glass-apatite multistructures on Ti substrates by pulsed laser deposition

Functionally graded glass-apatite multistructures were synthesized by pulsed laser deposition on Ti substrates. We used sintered targets of hydroxyapatite Ca₁₀(PO₄)₆(OH)₂, or bioglasses in the system SiO₂-Na₂O-K₂O-CaO-MgO-P₂O₅ with SiO₂ content of either 57 wt.% (6P57) or 61 wt.% (6P61). A UV KrF* (λ = 248 nm, τ > 7 ns) excimer laser source was used for the multipulse laser ablation of the targets. The hydroxyapatite thin films were obtained in H₂O vapors, while the bioglass layers were deposited in O₂. Thin films of 6P61 were deposited in direct contact with Ti, because Ti and this glass have similar thermal expansion behaviors, which ensure good bioglass adhesion to the substrate. This glass, however, is not bioactive, so yet more depositions of 6P57 bioglass and/or hydroxyapatite thin films were performed. All structures with hydroxyapatite overcoating were post-treated in a flux of water vapors. The obtained multistructures were characterized by various techniques. X-ray investigations of the coatings found small amounts of crystalline hydroxyapatite in the outer layers. The scanning electron microscopy analyses revealed homogeneous coatings with good adhesion to the Ti substrate. Our studies showed that the multistructures we had obtained were compatible with further use in biomimetic metallic implants with glass-apatite coating applications.     

Multilayered metal oxide thin film gas sensors obtained by conventional and RF plasma-assisted laser ablation

Multilayered thin films of In₂O₃ and SnO₂ have been deposited by conventional and RF plasma-assisted reactive pulsed laser ablation, with the aim to evaluate their behaviour as toxic gas sensors. The depositions have been carried out by a frequency doubled Nd-YAG laser (λ = 532 nm, τ = 7 ns) on Si(1 0 0) substrates, in O₂ atmosphere. The thin films have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrical resistance measurements. A comparison of the electrical response of the simple (indium oxide, tin oxide) and multilayered oxides to toxic gas (nitric oxide, NO) has been performed. The influence on the structural and electrical properties of the deposition parameters, such as substrate temperature and RF power is reported.     

Microstructuring of fused silica by laser-induced backside wet etching using picosecond laser pulses

The laser-induced backside wet etching (LIBWE) is an advanced laser processing method used for structuring transparent materials. LIBWE with nanosecond laser pulses has been successfully demonstrated for various materials, e.g. oxides (fused silica, sapphire) or fluorides (CaF₂, MgF₂), and applied for the fabrication of microstructures. In the present study, LIBWE of fused silica with mode-locked picosecond (t_p = 10 ps) lasers at UV wavelengths (λ₁ = 355 nm and λ₂ = 266 nm) using a (pyrene) toluene solution was demonstrated for the first time. The influence of the experimental parameters, such as laser fluence, pulse number, and absorbing liquid, on the etch rate and the resulting surface morphology were investigated. The etch rate grew linearly with the laser fluence in the low and in the high fluence range with different slopes. Incubation at low pulse numbers as well as a nearly constant etch rate after a specific pulse number for example were observed. Additionally, the etch rate depended on the absorbing liquid used; whereas the higher absorption of the admixture of pyrene in the used toluene enhances the etch rate and decreases the threshold fluence. With a λ₁ = 266 nm laser set-up, an exceptionally smooth surface in the etch pits was achieved. For both wavelengths (λ₁ = 266 nm and λ₂ = 355 nm), LIPSS (laser-induced periodic surface structures) formation was observed, especially at laser fluences near the thresholds of 170 and 120 mJ/cm², respectively.     

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.     

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.     

Polycaprolactone biopolymer thin films obtained by matrix assisted pulsed laser evaporation

We report the successful deposition of polycaprolactone polymer by MAPLE using a KrF* excimer laser (λ = 248 nm, τ = 7 ns). According to FTIR spectra the deposited films have similar chemical structure to the dropcast material. The fluence plays a key role in optimizing the performances of MAPLE-synthesized polycaprolactone structures. We demonstrated that MAPLE allows for controlling the morphology of films to the level required in targeted drug delivery of pharmacologic agents.     

Biocompatible and bioactive coatings of Mn-doped β-tricalcium phosphate synthesized by pulsed laser deposition

The extension of pulsed laser deposition to the synthesis on Ti substrates of β-tricalcium phosphate (β-TCP) coatings doped with manganese is reported. Targets sintered from two crystalline Mn-doped β-TCP powders (with the composition Ca_2.9Mn_0.1(PO₄)₂ and Ca_2.8Mn_0.2(PO₄)₂) were ablated with an UV KrF* (λ = 248 nm, τ ∼ 7 ns) laser source. X-ray diffraction and energy dispersive X-ray spectroscopy investigations showed that the films, while prevalently amorphous, had a Ca/P ratio of about 1.50-1.52. Scanning electron microscopy analyses revealed a rather homogeneous aspect of the coatings which were molded to the relief of the chemically etched Ti substrate. Fluorescence microscopy was applied to test the proliferation of mesenchymal stem cells grown on the obtained biostructures. Our investigations found that, even 14 days after cultivation, the synthesized films were not cytotoxic. On the contrary, they showed excellent bioactivity, as demonstrated by the neat spread of the cells over the entire surface of Mn-doped β-TCP. When tested in osteoprogenitor cell culture, the Ca_2.8Mn_0.2(PO₄)₂ samples revealed a higher potential for proliferation and better viability compared with Ca_2.9Mn_0.1(PO₄)₂.     

Shallow hydroxyapatite coatings pulsed laser deposited onto Al2O3 substrates with controlled porosity: correlation of morphological characteristics with in vitro testing results

We studied the influence of porous Al₂O₃ substrates on Ce-stabilized ZrO₂-doped hydroxyapatite thin films morphology pulsed laser deposited on their top. The porosities of substrates were monitored by changing sintering temperatures and measured with a high pressure Hg porosimeter.The depositions were conducted in 50 Pa water vapors by multipulse ablation of the targets with an UV KrF* (λ = 248 nm, τ ∼ 25 ns) excimer laser. The surface morphology of synthesized nanostructures was investigated by scanning electron microscopy and atomic force microcopy. Ca/P ratio within the range 1.67-1.70 was found for hydroxyapatite coatings by energy dispersive spectroscopy.The films were further seeded with mesenchymal stem cells for in vitro tests. The cells showed good attachment and spreading uniformly covering the entire surface of samples. The complexity of film morphology which is increasing with substrate porosity was shown to have a positive influence on cultivated cells density.     

Particulate assisted growth of ZnO nanorods and microrods by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on the gallium nitride (GaN) and sapphire (Al₂O₃) substrates by pulsed laser deposition (PLD) without using any metal catalyst. The experiment was carried out at three different laser wavelengths of Nd:YAG laser (λ = 1064 nm, λ = 532 nm) and KrF excimer laser (λ = 248 nm). The ZnO films grown at λ = 532 nm revealed the presence of ZnO nanorods and microrods. The diameter of the rods varies from 250 nm to 2 μm and the length varies between 9 and 22 μm. The scanning electron microscopy (SEM) images of the rods revealed the absence of frozen balls at the tip of the ZnO rods. The growth of ZnO rods has been explained by vapor-solid (V-S) mechanism. The origin of growth of ZnO rods has been attributed to the ejection of micrometric and sub-micrometric sized particulates from the ZnO target. The ZnO films grown at λ = 1064 nm and λ = 248 nm do not show the rod like morphology. X-ray photoelectron spectroscopy (XPS) has not shown the presence of any impurity except zinc and oxygen.     

In situ monitoring the pulse CO2 laser interaction with 316-L stainless steel using acoustical signals and plasma analysis

In most laser material processing, material removal by different mechanisms is involved. Here, application of acoustic signals with thermoelastic (below threshold) and breakdown origin (above threshold) together with plasma plume analysis as a simple monitoring system of interaction process is suggested. In this research the interaction of pulse CO₂ laser with 200 ns duration and maximum energy of 1.3 J operating at 1 Hz with austenitic stainless steel (316-L) is reported. The results showed that the non-linear point of the curve can serve as a useful indicator of melting fluence threshold (in this case ≈830 J cm⁻²) with corresponding temperature calculated using plasma plume analysis. Higher acoustic amplitudes and larger plasma plume volume indicates more intense interaction. Also, analysis showed that a phase explosion process with material removal (ejecta) in the form of non-adiabatic (i.e., d_t ? α⁻¹) is at play after laser pulse is ended. Also, SEM photographs show different surface quality medication at different laser intensities, which indicates the importance of recoil momentum pressure and possibly electrons and ions densities in heat transfer. Finally, electrochemical test indicate an improved corrosion resistance for laser treated samples compared to untreated ones.