C. Ghica

Pulsed laser deposition of hydroxyapatite thin films on Ti-5Al-2.5Fe substrates with and without buffer layers

We present a method for processing hydroxyapatite (HA) thin films on Ti-5Al-2.5Fe substrates. The films were grown by pulsed laser deposition (PLD) in vacuum at room temperature, using a KrF∗ excimer laser. The amorphous as-deposited HA films were recrystallized in ambient air by a thermal treatment at 550°C. The best results have been obtained when inserting a buffer layer of ceramic materials (TiN, ZrO2 or Al2O3). The films were characterized by complementary techniques: grazing incidence X-ray diffraction (GIXRD), scanning electron microscopy (SEM), cross-section transmission electron microscopy (XTEM), SAED, energy dispersive X-ray spectroscopy (EDS) and nanoindentation. The samples with buffer interlayer preserve the stoichiometry are completely recrystallized and present better mechanical characteristics as compared with that without buffer interlayer.

Polarization-control of the potential barrier at the electrode interfaces in epitaxial ferroelectric thin films.

Electrode interface is a key element in controlling the macroscopic electrical properties of the ferroelectric capacitors based on thin films. In the case of epitaxial ferroelectrics, the electrode interface is essential in controlling the leakage current and the polarization switching, two important elements in the read/write processes of nonvolatile memories. However, the relation between the polarization bound charges and the electronic properties of the electrode interfaces is not yet well understood. Here we show that polarization charges are controlling the height of the potential barriers at the electrode interfaces in the case of Pb(Zr,Ti)O3 and BaTiO3 epitaxial films. The results suggest that the height is set to a value allowing rapid compensation of the depolarization field during the polarization switching, being almost independent of the metals used for electrodes. This general behavior open a new perspective in engineering interface properties and designing new devices based on epitaxial ferroelectrics.

Functionalized magnetite silica thin films fabricated by MAPLE with antibiofilm properties

We report on the fabrication of magnetite/salicylic acid/silica shell/antibiotics (Fe(3)O(4)/SA/SiO(2)/ATB) thin films by matrix-assisted pulsed laser evaporation (MAPLE) to inert substrates. Fe(3)O(4)-based powder have been synthesized and investigated by XRD and TEM. All thin films were studied by FTIR, SEM and in vitro biological assays using Staphylococcus aureus and Pseudomonas aeruginosa reference strains, as well as eukaryotic HEp-2 cells. The influence of the obtained nanosystems on the microbial biofilm development as well as their biocompatibility has been assessed. For optimum deposition conditions, we obtained uniform adherent films with the composition identical with the raw materials. Fe(3)O(4)/SA/SiO(2)/ATB thin films had an inhibitory activity on the ability of microbial strains to initiate and develop mature biofilms, in a strain- and antibiotic-dependent manner. These magnetite silica thin films are promising candidates for the development of novel materials designed for the inhibition of medical biofilms formed by different pathogenic agents on common substrates, frequently implicated in the etiology of chronic and hard to treat infections.

Calcium phosphate thin film processing by pulsed laser deposition and in situ assisted ultraviolet pulsed laser deposition

Calcium orthophosphates (CaP) and hydroxyapatite (HA) were intensively studied in order to design and develop a new generation of bioactive and osteoconductive bone prostheses. The main drawback now in the CaP and HA thin films processing persists in their poor mechanical characteristics, namely hardness, tensile and cohesive strength, and adherence to the metallic substrate. We report here a critical comparison between the microstructure and mechanical properties of HA and CaP thin films grown by two methods. The films were grown by KrF* pulsed laser deposition (PLD) or KrF* pulsed laser deposition assisted by in situ ultraviolet radiation emitted by a low pressure Hg lamp (UV-assisted PLD). The PLD films were deposited at room temperature, in vacuum on Ti–5Al–2.5Fe alloy substrate previously coated with a TiN buffer layer. After deposition the films were annealed in ambient air at 500–600 °C. The UV-assisted PLD films were grown in (10−2–10−1 Pa) oxygen directly on Ti–5Al–2.5Fe substrates heated at 500–600 °C. The films grown by classical PLD are crystalline and stoichiometric. The films grown by UV-assisted PLD were crystalline and exhibit the best mechanical characteristics with values of hardness and Young modulus of 6–7 and 150–170 GPa, respectively, which are unusually high for the calcium phosphate ceramics. To the difference of PLD films, in the case of UV-assisted PLD, the GIXRD spectra show the decomposition of HA in Ca2P2O7, Ca2P2O9 and CaO. The UV lamp radiation enhanced the gas reactivity and atoms mobility during processing, increasing the tensile strength of the film, while the HA structure was destroyed.

Role of laser pulse duration and gas pressure in deposition of AlN thin films

We investigated the relative merits and limits of pulsed laser deposition from AlN targets in vacuum and low-pressure nitrogen in obtaining stoichiometric and crystalline aluminum nitride thin films. We used two UV excimer laser sources (λ=248 nm): a nanosecond system (τFWHM=30 ns) and, a subpicosecond (τFWHM=450 fs) system. The obtained structures were characterized by x-ray diffraction, electron microscopy in cross section, selected area electron diffraction, and profilometry. We demonstrated that the best results are obtained with the sub-ps laser source in vacuum and in low pressure nitrogen when the AlN thin films are very pure, crystalline, clearly exhibiting a tendency to epitaxy. Metallic Al is present in the films deposited with the ns laser source. We believe this is an effect of the gradual decomposition of AlN inside the crater on the target surface under multipulse laser irradiation.

Sr-ferrite thin films grown on sapphire by pulsed laser deposition

High-quality epitaxial strontium-hexaferrite (SrFe12O19) thin films were grown by pulsed laser deposition (PLD) on c-cut sapphire using KrF∗ excimer laser at a fluency of 2 J/cm2 and substrate temperature of 800°C in 100 mTorr oxygen environment. The X-ray diffraction (XRD) and morphology analyzes showed films with excellent crystalline structure and flat surface. The thickness was found to influence considerably the surface morphology and magnetic properties of the as-deposited films. The highest orientation and the best morphology with smooth surface and fine grain structure was obtained for the film having a thickness of 750 nm. The highest coercive force of 1453 Oe was measured for this film in perpendicular to the plane direction.

Polarization induced self-doping in epitaxial Pb(Zr0.20Ti0.80)O3 thin films

The compensation of the depolarization field in ferroelectric layers requires the presence of a suitable amount of charges able to follow any variation of the ferroelectric polarization. These can be free carriers or charged defects located in the ferroelectric material or free carriers coming from the electrodes. Here we show that a self-doping phenomenon occurs in epitaxial, tetragonal ferroelectric films of Pb(Zr0.2Ti0.8)O3, consisting in generation of point defects (vacancies) acting as donors/acceptors. These are introducing free carriers that partly compensate the depolarization field occurring in the film. It is found that the concentration of the free carriers introduced by self-doping increases with decreasing the thickness of the ferroelectric layer, reaching values of the order of 1026 m−3 for 10 nm thick films. One the other hand, microscopic investigations show that, for thicknesses higher than 50 nm, the 2O/(Ti+Zr+Pb) atomic ratio increases with the thickness of the layers. These results suggest that the ratio between the oxygen and cation vacancies varies with the thickness of the layer in such a way that the net free carrier density is sufficient to efficiently compensate the depolarization field and to preserve the outward direction of the polarization.

Pulsed laser deposition of lithium niobate: a parametric study

We report the deposition of high optical quality LiNbO 3 thin films on Si(111) substrates by pulsed laser ablation using a KrF * excimer laser (λ = 248 nm, τ = 20 ns) source. Experiments have been conducted in oxygen at 5-20 Pa. Si(111) collectors were uniformly heated at 500-700°C. Some of the as-deposited collectors were submitted to an in-situ thermal treatment in oxygen (10 3 -10 4 Pa) at the same temperature. The deposited thin films were characterised by grazing incidence X-ray diffraction (GIXRD), transmission electron microscopy (TEM) and spectroscopic ellipsometry (SE). Our LiNbO 3 thin films, achieved at relatively low temperature (550°C), are the first textured and high optical quality pulsed laser deposited films on Si.

High Permittivity (1 - x)Ba(Zr(0.2)Ti(0.8))O3 - x(Ba(0.7)Ca(0.3))TiO3 (x = 0.45) Epitaxial Thin Films with Nanoscale Phase Fluctuations.

Epitaxial (1 - x)Ba(Ti0.8Zr0.2)TiO3 - x(Ba0.7Ca0.3)TiO3, x = 0.45 (BCZT 45), thin films have been deposited on (001) SrTiO3 (STO) and (001/100) SrLaAlO4 (SLAO) substrates by pulsed laser deposition. X-ray diffraction and high-resolution transmission electron microscopy (HRTEM) confirmed the epitaxial growth of the films. A high structural quality has been evidenced for the BCZT/STO films. Geometric phase analysis (GPA) associated with the HRTEM enabled us to obtain microstrain analysis and the in-plane and out-of-plane lattice parameter variation on different areas. Tetragonality ratio fluctuations at nanoscale level which are relevant for the existence of nanodomains have been evidenced on the BCZT/STO films. The in-plane dielectric constant has been measured on interdigital electrodes deposited by lift-off technique on the top of the films. High values of dielectric permittivity (>3000) combined with low dielectric loss (<0.01) are obtained for BCZT 45 film deposited on STO substrate, showing nearly constant values between 1 kHz and 10 MHz. The high dielectric permittivity of BCZT thin films was attributed to their high structural quality and to the loss of rotation stability of the polarization associated with the presence of nanodomains. This results into a divergence of fluctuations of polarization direction and a peak of dielectric susceptibility. The enhanced switching of such nanodomain configuration was probed by piezoforce microscopy, by writing and reading domains during topography scanning.

General equivalent circuit derived from capacitance and impedance measurements performed on epitaxial ferroelectric thin films

Voltage and frequency dependent capacitance measurements were performed on epitaxial BaTiO3 and Pb(Zr0.2Ti0.8)O3 thin films deposited on single crystal SrTiO3 substrates with (001) and (111) orientations. The measured capacitors have common bottom SrRuO3 contact and different metals as top electrodes: SrRuO3, Pt, Cu, Al, and Au. The capacitance-voltage characteristics were used to extract information regarding the density of the free carriers and the linear contribution to the static dielectric constant. The frequency dependent impedance was used to develop a suitable equivalent circuit for the epitaxial ferroelectric capacitors. It was found that the frequency dependence of the imaginary part of the impedance can be well simulated, in all cases, using a circuit composed of Schottky-type capacitance related to electrode interfaces, contact resistance, and the R-C parallel connection related to the ferroelectric volume of the film. Values for the components of the equivalent circuit were obtained by fittin...