Deposition of biopolymer thin films by matrix assisted pulsed laser evaporation

We report on the successful deposition of high quality type I fibrilar collagen thin films by Matrix assisted pulsed laser evaporation (MAPLE). Thin films deposition was performed in a N₂ ambient (20 Pa) using a KrF* laser source (=248 nm,20 ns) operated at a repetition rate of 3 Hz, the incident laser energy at a value within the range (20-35)mJ , and the laser spot area was (3.5-18.5)±0.1 mm². The collagen films were deposited on double face polished 100 single crystalline Si wafers and characterized by Fourier transform infrared spectroscopy, atomic force microscopy and high-resolution transmission electron microscopy. We demonstrate that our thin films are composed of collagen, with no impurities and the roughness can be controlled by the deposition conditions. PACS 52.38.Mf; 82.35.Pq; 83.80.Lz     

Structural and optical characterization of undoped, doped, and clustered ZnO thin films obtained by PLD for gas sensing applications

The synthesis by pulsed laser deposition technique of zinc oxide thin films suitable for gas sensing applications is herein reported. The ZnO targets were irradiated by an UV KrF^* (λ = 248 nm, τ_FWHM ∼7 ns) excimer laser source, operated at 2.8 J/cm² incident fluence value, whilst the substrates consisted of SiO₂(0 0 1) wafers heated at 150 °C during the thin films growth process. The experiments were performed in an oxygen dynamic pressure of 10 Pa. Structural and optical properties of the thin films were investigated. The obtained results have demonstrated that the films are c-axis oriented. Their average transmission in the visible-infrared spectral region was found to be about 85%. The equivalent refractive indexes and extinction coefficients were very close to those of the tabulated reference values. Doping with 0.5% Au and coating with 100 pulses of Au clusters caused but a very slight decrease (with a few percent) of both transmission and refractive index values. The coatings with the most appropriate optical properties as waveguides have been selected and their behavior was tested for butane sensing.     

Matrix assisted pulsed laser evaporation of poly(d,l-lactide) thin films for controlled-release drug systems

We report the successful deposition of the porous polymer poly(d,l-lactide) by matrix assisted pulsed laser evaporation (MAPLE) using a KrF* excimer laser (248 nm, τ = 7 ns) operated at 2 Hz repetition rate. The chemical structure of the starting materials was preserved in the resulting thin films. Fluence played a key role in optimizing our depositions of the polymer. We demonstrated MAPLE was able to improve current approaches to grow high quality thin films of poly(d,l-lactide), including a porosity control highly required in targeted drug delivery.     

On the stoichiometry of mass transfer from solid to plasma during pulsed laser ablation of brass

We have performed spectroscopic analysis of the plasma produced by pulsed laser ablation of brass in a low pressure argon atmosphere. The intensities of several spectral lines of copper, zinc and lead were measured for succeeding laser pulses applied to the same irradiation site. The intensities and spectral shapes of the observed transitions were compared to the spectral radiance computed for plasma in local thermal equilibrium. At a delay of 600 ns after the laser pulse, the plasma is characterized by typical values of temperature and electron density of 1.1 × 10⁴ K and 1.2 × 10¹⁷ cm^− 3, respectively, and an elemental composition equal to that of the sample. Small changes of spectral line intensities were observed with increasing number of applied laser pulses. They were attributed to the alteration of the plume expansion dynamics as a consequence of crater formation on the sample surface. The results indicate that the mass transfer from the solid to the plasma is stoichiometric.     

Structural characterization of AlN films synthesized by pulsed laser deposition

We obtained AlN thin films by pulsed laser deposition (PLD) from a polycrystalline AlN target using a pulsed KrF* excimer laser source (248 nm, 25 ns, intensity of ∼4 × 10⁸ W/cm², repetition rate 3 Hz, 10 J/cm² laser fluence). The target-Si substrate distance was 5 cm. Films were grown either in vacuum (10⁻⁴ Pa residual pressure) or in nitrogen at a dynamic pressure of 0.1 and 10 Pa, using a total of 20,000 subsequent pulses. The films structure was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectral ellipsometry (SE). Our TEM and XRD studies showed a strong dependence of the film structure on the nitrogen content in the ambient gas. The films deposited in vacuum exhibited a high quality polycrystalline structure with a hexagonal phase. The crystallite growth proceeds along the c-axis, perpendicular to the substrate surface, resulting in a columnar and strongly textured structure. The films grown at low nitrogen pressure (0.1 Pa) were amorphous as seen by TEM and XRD, but SE data analysis revealed ∼1.7 vol.% crystallites embedded in the amorphous AlN matrix. Increasing the nitrogen pressure to 10 Pa promotes the formation of cubic (≤10 nm) crystallites as seen by TEM but their density was still low to be detected by XRD. SE data analysis confirmed the results obtained from the TEM and XRD observations.     

Maple prepared organic heterostructures for photovoltaic applications

In this study, we present the deposition of ZnPc, Alq3, and PTCDA thin films using Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. We also report the realisation of multilayer structures, made by the successive application of MAPLE. The films have been characterized by spectroscopic (UV–VIS and Photoluminescence) and microscopic (SEM and AFM) methods, and the effect of different deposition conditions such as fluence, number of pulses, and target concentration on the properties has been analysed. This paper also presents some investigations on the electrical conduction in sandwich type structures ITO or Si/organic layer/Au or Cu and ITO/double organic layer/Cu, emphasising the dominant effect of the height of the energetic barriers at the inorganic/organic and organic/organic interfaces.     

Bioglass thin films for biomimetic implants

Pulsed laser deposition (PLD) method was used to obtain bioglass (BG) thin film coatings on titanium substrates. An UV excimer laser KrF* (λ = 248 nm, τ = 25 ns) was used for the multi-pulse irradiation of the BG targets with 57 or 61 wt.% SiO₂ content (and Na₂O-K₂O-CaO-MgO-P₂O₅ oxides). The depositions were performed in oxygen atmosphere at 13 Pa and for substrates temperature of 400 °C. The PLD films displayed typical BG of 2-5 μm particulates nucleated on the film surface or embedded in. The PLD films stoichiometry was found to be the same as the targets. XRD spectra have shown, the glass coatings obtained, had an amorphous structure. One set of samples, deposited in the same conditions, were dipped in simulated body fluids (SBFs) and subsequently extracted one by one after several time intervals 1, 3, 7, 14 and 21 days. After washing in deionized water and drying, the surface morphology of the samples and theirs composition were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), IR spectroscopy (FTIR) and energy dispersive X-ray analysis (EDX). After 3-7 days the Si content substantially decreases in the coatings and PO₄³⁻ maxima start to increase in FTIR spectra. The XRD spectra also confirm this evolution. After 14-21 days the XRD peaks show a crystallized fraction of the carbonated hydroxyapatite (HAP). The SEM micrographs show also significant changes of the films surface morphology. The coalescence of the BG droplets can be seen. The dissolution and growth processes could be assigned to the ionic exchange between BG and SBFs.     

Laser prepared organic heterostructures based on star-shaped arylenevinylene compounds

This paper presents some studies about the preparation by matrix-assisted pulsed laser evaporation (MAPLE) technique of organic bulk heterojunctions made from the mixture of a star-shaped arylenevinylene compound, 4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine as donor and fullerene derivative, [6, 6]-phenyl C61 butyric acid butyl ester, as acceptor, in the weight ratio 1:2. The mixed layer has been characterized by spectroscopic (UV–Vis, Fourier transform infrared) and microscopic (AFM) methods, and the effects of the deposition conditions (number of pulses) and of a buffer layer of poly(aniline-co-aniline propane sulfonic acid) or poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) have been analyzed. The study of the electrical properties has revealed a typical solar cell behavior for the heterostructure glass/ITO/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine: [6, 6]-phenyl C61 butyric acid butyl ester/Al, confirming that MAPLE could be an adequate method for the preparation of active layer based on bulk heterojunction for solar cells.     

Charge density waves in nanocrystalline thin films of blue bronze K0.3MoO3

Thin granular films of charge density wave (CDW) system K_0.3MoO₃ were prepared by pulsed laser deposition and investigated by various standard characterization methods such as GI-XRD, electric transport, TOF-ERDA, AFM and UV–visible spectroscopy. While all these methods indicate that the thin films consist of nanometer grains of K_0.3MoO₃, it is only the non-destructive femtosecond time-resolved spectroscopy (fsTRS) that demonstrates the charge density wave nature of the ground state and therefore proves directly the presence of K_0.3MoO₃. Furthermore, the comparison of the fsTRS data obtained in thin films and in single crystals shows the reduction of the charge density wave transition temperature and of the photoinduced signal strength in granular thin films with respect to single crystals, which is attributed to the granularity and crystal growth morphology. Our results establish fsTRS technique as the essential tool for the detection and characterization of complex ground states in nano-sized systems.