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.     

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.     

High fluence deposition of polyethylene glycol films at 1064 nm by matrix assisted pulsed laser evaporation (MAPLE)

Matrix assisted pulsed laser evaporation (MAPLE) has been applied for deposition of thin polyethylene glycol (PEG) films with infrared laser light at 1064 nm. We have irradiated frozen targets (of 1 wt.% PEG dissolved in water) and measured the deposition rate in situ with a quartz crystal microbalance. The laser fluence needed to produce PEG films turned out to be unexpectedly high with a threshold of 9 J/cm², and the deposition rate was much lower than that with laser light at 355 nm. Results from matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis demonstrate that the chemistry, molecular weight and polydispersity of the PEG films were identical to the starting material. Studies of the film surface with scanning electron microscopy (SEM) indicate that the Si-substrate is covered by a relatively homogenous PEG film with few bare spots.     

Growth of oxide thin films for optical gas sensor applications

Tungsten trioxide and titanium dioxide thin films were synthesised by pulsed laser deposition. We used for irradiations of oxide targets an UV KrF* (λ = 248 nm, τ_FWHM ≅ 20 ns, ν = 2 Hz) excimer laser source, at 2 J/cm² incident fluence value. The experiments were performed in low oxygen pressure. The (0 0 1) SiO₂ substrates were heated during the thin film deposition process at temperature values within the 300-500 °C range. The structure and crystalline status of the obtained oxide thin films were investigated by high resolution transmission electron microscopy. Our analyses show that the films are composed by nanoparticles with average diameters from a few to a few tens of nm. Moreover, the films deposited at substrate temperatures higher than 300 °C are crystalline. The tungsten trioxide films consist of a mixture of triclinic and monoclinic phases, while the titanium dioxide films structure corresponds to the tetragonal anatase phase. The oxide films average transmittance in the visible-infrared spectral range is higher than 80%, which makes them suitable for sensor applications.     

Computational and experimental study of the cluster size distribution in MAPLE

A combined experimental and computational study is performed to investigate the origin and characteristics of the surface features observed in SEM images of thin polymer films deposited in matrix-assisted pulsed laser evaporation (MAPLE). Analysis of high-resolution SEM images of surface morphologies of the films deposited at different fluences reveals that the mass distributions of the surface features can be well described by a power-law, Y(N) ∝ N^−t, with exponent −t ≈ −1.6. Molecular dynamic simulations of the MAPLE process predict a similar size distribution for large clusters observed in the ablation plume. A weak dependence of the cluster size distributions on fluence and target composition suggests that the power-law cluster size distribution may be a general characteristic of the ablation plume generated as a result of an explosive decomposition of a target region overheated above the limit of its thermodynamic stability. Based on the simulation results, we suggest that the ejection of large matrix-polymer clusters, followed by evaporation of the volatile matrix, is responsible for the formation of the surface features observed in the polymer films deposited in MAPLE experiments.     

Matrix assisted pulsed laser evaporation of cinnamate-pullulan and tosylate-pullulan polysaccharide derivative thin films for pharmaceutical applications

We have demonstrated the successful thin film growth of two pullulan derivatives (cinnamate-pullulan and tosylate-pullulan) using matrix assisted pulsed laser evaporation (MAPLE). Our MAPLE system consisted of a KrF* laser, a vacuum chamber, and a rotating target holder cooled with liquid nitrogen. Fused silica and silicon (1 1 1) wafers were used as substrates. The MAPLE-deposited thin films were characterized by transmission spectrometry, profilometry, atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. The deposited layers ranged from 250 nm to 16.5 μm in thickness, depending on the laser fluence (0.065-0.5 J cm⁻²) and number of pulses applied for the deposition of one structure (1500-13,300). Our results confirmed that MAPLE was well-suited for the transfer of cinnamate-pullulan and tosylate-pullulan.     

Study of the structure and electrical properties of the copper nitride thin films deposited by pulsed laser deposition

Copper nitride thin films were prepared on glass and silicon substrates by ablating a copper target at different pressure of nitrogen. The films were characterized in situ by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and ex situ by X-ray diffraction (XRD). The nitrogen content in the samples, x = [N]/[Cu], changed between 0 and 0.33 for a corresponding variation in nitrogen pressure of 9 × 10⁻² to 1.3 × 10⁻¹ Torr. Using this methodology, it is possible to achieve sub-, over- and stoichiometric films by controlling the nitrogen pressure. The XPS results show that is possible to obtain copper nitride with x = 0.33 (Cu₃N) and x = 0.25 (Cu₄N) when the nitrogen pressure is 1.3 × 10⁻¹ and 5 × 10⁻² Torr, respectively. The lattice constants obtained from XRD results for copper nitride with x = 0.25 is of 3.850 Å and with x = 0.33 have values between 3.810 and 3.830 Å. The electrical properties of the films were studied as a function of the lattice constant. These results show that the electrical resistivity increases when the lattice parameter is decreasing. The electrical resistivity of copper nitride with x = 0.25 was smaller than samples with x = 0.33.     

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.     

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.     

Processing of poly(1,3-bis-(p-carboxyphenoxy propane)-co-(sebacic anhydride)) 20:80 (P(CPP:SA)20:80) by matrix-assisted pulsed laser evaporation for drug delivery systems

We have demonstrated successful thin film growth of poly(1,3-bis-(p-carboxyphenoxy, propane)-co-(sebacic anhydride)) (20:80) by matrix-assisted pulsed laser evaporation using a KrF* excimer laser (λ = 248 nm, τ = 25 ns, ν = 10 Hz). The deposited thin films have been investigated by Fourier transform infrared spectroscopy, and atomic force microscopy. We have demonstrated that the main functional groups of poly(1,3-bis-(p-carboxyphenoxy, propane)-co-(sebacic anhydride)) (20:80) are present in the deposited film. The effect of matrix on both thin film structure and surface morphology was also examined. The goal of this work is to explore laser processing of this material to create suitable constructs for drug delivery applications.     

Biocompatible and bioactive nanostructured glass coatings synthesized by pulsed laser deposition: In vitro biological tests

We report on the synthesis by pulsed laser deposition with a KrF* excimer laser source (λ = 248 nm, τ = 25 ns) of bioglass thin films of 6P57 and 6P61 types. Physiology, viability, and proliferation of human osteoblast cells were determined by quantitative in vitro tests performed by flow cytometry on primary osteoblasts cultured on pulsed laser deposited bioglasses. Both types of glass films proved to be appropriate mediums for cell survival and proliferation. In a parallel investigation, cell morphology and adhesion to the surface was studied by fluorescence microscopy and scanning electron microscopy. Strong bonds between the materials and cells were found in both cases, as osteoblast pseudopodes penetrated deep into the material. According to our observations, the 6P57 glass films were superior with respect to viability and proliferation performances.     

Doped thin metal oxide films for catalytic gas sensors

TiO₂ and Pt doped TiO₂ thin films were grown by pulsed laser deposition on 〈0 0 1〉 SiO₂ substrates. The doped films were compared with undoped ones deposited in similar experimental conditions. An UV KrF* (λ = 248 nm, τ_FWHM ≅ 20 ns, ν = 2 Hz) excimer laser was used for the irradiation of the TiO₂ or Pt doped TiO₂ targets. The substrate temperatures were fixed during the growth of the thin films at values within the 300-500 °C range. The films’ surface morphology was investigated by atomic force microscopy and their crystalline quality by X-ray diffractometry. The corresponding transmission spectra were recorded with the aid of a double beam spectrophotometer in the spectral range of 400-1100 nm. No contaminants or Pt segregation were detected in the synthesized anatase phase TiO₂ thin films composition. Titania crystallites growth inhibition was observed with the increase of the dopant concentration. The average optical transmittance in the visible-infrared spectral range of the films is higher than 85%, which makes them suitable for sensor applications.     

Pulsed laser deposition of fluoride glass thin films

The development of integrated waveguide lasers for different applications such as marking, illumination or medical technology has become highly desirable. Diode pumped planar waveguide lasers emitting in the green visible spectral range, e.g. thin films from praseodymium doped fluorozirconate glass matrix (called ZBLAN, owing to the main components ZrF₄, BaF₂, LaF₃, AlF₃ and NaF) as the active material pumped by a blue laser diode, have aroused great interest. In this work we have investigated the deposition of Pr:ZBLAN thin films using pulsed laser radiation of λ = 193 and λ = 248 nm. The deposition has been carried out on MgF₂ single crystal substrates in a vacuum chamber by varying both processing gas pressure and energy fluence. The existence of an absorption line at 210 nm in Pr:ZBLAN leads to absorption and radiative relaxation of the absorbed laser energy of λ = 193 nm preventing the evaporation of target material. The deposited thin films consist of solidified and molten droplets and irregular particulates only. Furthermore, X-ray radiation has been applied to fluoride glass targets to enhance the absorption in the UV spectral region and to investigate the deposition of X-ray treated targets applying laser radiation of λ = 248 nm. It has been shown that induced F-centres near the target surface are not thermally stable and can be easily ablated. Therefore, λ = 248 nm is not suitable for evaporation of Pr:ZBLAN.     

Characterization of pulsed laser deposited chalcogenide thin layers

In this work we report on pulsed laser deposition (PLD) of chalcogenide thin films from the systems (AsSe)_100−xAgI_x and (AsSe)_100−xAg_x for sensing applications. A KrF* excimer laser (λ = 248 nm; τ_FWHM = 25 ns) was used to ablate the targets that had been prepared from the synthesised chalcogenide materials. The films were deposited in either vacuum (4 × 10⁻⁴ Pa) or argon (5 Pa) on silicon and glass substrates kept at room temperature. The basic properties of the films, including their morphology, topography, structure, and composition were characterised by complementary techniques. Investigations by X-ray diffraction (XRD) confirmed the amorphous nature of the films, as no strong diffraction reflections were found. The film composition was studied by energy dispersive X-ray (EDX) spectroscopy. The morphology of the films investigated by scanning electron microscopy (SEM), revealed a particulate-covered homogeneous surface, typical of PLD. Topographical analyses by atomic force microscopy (AFM) showed that the particulate size was slightly larger in Ar than in vacuum. The uniform surface areas were rather smooth, with root mean square (rms) roughness increasing up to several nanometers with the AgI or Ag doping. Based upon the results from the comprehensive investigation of the basic properties of the chalcogenide films prepared by PLD and their dependence on the process parameters, samples with appropriate sorption properties can be selected for possible applications in cantilever gas sensors.     

Bioactive glass and hydroxyapatite thin films obtained by pulsed laser deposition

Bioactive glass (BG), calcium hydroxyapatite (HA), and ZrO₂ doped HA thin films were grown by pulsed laser deposition on Ti substrates. An UV KrF^* (λ = 248 nm, τ ≥ 7 ns) excimer laser was used for the multi-pulse irradiation of the targets. The substrates were kept at room temperature or heated during the film deposition at values within the (400-550 °C) range. The depositions were performed in oxygen and water vapor atmospheres, at pressure values in the range (5-40 Pa). The HA coatings were heat post-treated for 6 h in a flux of hot water vapors at the same temperature as applied during deposition. The surface morphology, chemical composition, and crystalline quality of the obtained thin films were studied by scanning electron microscopy, atomic force microscopy, and X-ray diffractometry. The films were seeded for in vitro tests with Hek293 (human embryonic kidney) cells that revealed a good adherence on the deposited layers. Biocompatibility tests showed that cell growth was better on HA than on BG thin films.     

Magnetic properties of strontium hexaferrite films prepared by pulsed laser deposition

The magnetic properties of strontium hexaferrite (SrFe₁₂O₁₉) films fabricated by pulsed laser deposition on the Si(100) substrate with Pt(111) underlayer have been studied as a function of film thickness (50–700 nm). X-ray diffraction patterns confirm that the films have c-axis perpendicular orientation. The coercivities in perpendicular direction are higher than those for in-plane direction which indicates the films have perpendicular magnetic anisotropy. The coercivity was found to decrease with increasing of thickness, due to the increasing of the grain size and relaxation in lattice strain. The 200 nm thick film exhibits hexagonal shape grains of 150 nm and optimum magnetic properties of M_s=298 emu/cm³ and H_c=2540 Oe.     

Potential of Nd:YAG pulsed laser deposition method for coated conductor production

A Nd:YAG laser is environmentally safe and economical with no poisonous or hazardous gases and no expensive gases. We prepared Y123 films by using the fourth harmonic Nd:YAG pulsed laser deposition (PLD) method and optimized the deposition conditions on MgO single crystalline substrates and IBAD-MgO substrates for Y123 coated conductor. We found that the optimal deposition conditions acquired bi-axially aligned Y123 films on both substrates with T_c ∼ 90 K and J_c > 1 MA/cm² at 77 K in self-field. For obtaining high I_c, we fabricated thick Y123 films on both substrates and the maximum I_c per 1 cm in width reached 186 A/cm-width on the IBAD-MgO substrate. Interestingly, there were no a-axis oriented grains within the films up to 1.8 μm thick. This might be an especial feature of the Nd:YAG-PLD method. We believe that the Nd:YAG-PLD method is promising method for RE123 coated conductor production.     

Modeling of CW laser diode irradiation of amorphous silicon films

The purpose of this work is to determine the optimal parameters required to crystallize thin amorphous silicon films on glass substrate with a continuous wave (CW) laser diode (λ = 808 nm), using a numerical model developed in COMSOL Multiphysics. The numerical simulation of the laser crystallization process takes into account the solid-liquid phase change and the difference between the melting temperature of amorphous (Tm_a-Si = 1420 K) and that of crystalline silicon (Tm_c-Si = 1690 K). We have varied the main parameters controlling the crystallization process, namely the power and the scan speed of the laser beam. Furthermore the initial temperature as well as the thickness of the a-Si:H layer were also taken as a parameter to optimize the process. We have determined the melting, crystallization and ablation energy threshold versus the different operational parameters.     

Amorphous Ni-Al underlayer-accelerated L10 ordering transition of FePt thin films

In the present study, we succeeded in accelerating the L1₀ ordering transition of FePt thin films by employing amorphous Ni-Al as underlayers. The coercivity H_c = 5 kOe and ordering parameter S = 0.67 of FePt thin films deposited on a Ni-Al underlayer with a thickness of ∼5 nm after 380 °C annealing for 30 min are significantly higher than those H_c = 0.4 kOe and S = 0.35 of the films without the Ni-Al underlayer. The L1₀ ordering process of and the coercivity of FePt thin films can be significantly tuned by varying the thickness of the Ni-Al underlayer.     

Structural modification of laser annealed a-Si1−xCx:H films

Hydrogenated amorphous silicon carbon films, with relatively low hydrogen content and carbon fraction x, C/(C + Si), ranging from 0.20 to 0.57 have been deposited by RF-plasma enhanced chemical vapor deposition (PECVD) for excimer laser annealing experiments. After the laser treatments all the films show structural modifications. It has been obtained that with increasing x the crystallinity degree of the Si phase decreases, while that of the SiC phase increases and becomes predominant for x = 0.39. In the overstoichiometric samples only the c-SiC phase has been observed. In all the treated samples 3C-SiC crystallites have been detected.