Microstructural study of thin films of 5 mol% gadolinia-doped ceria prepared by pulsed laser ablation

Microstructural characterization of thin films of 5 mol% gadolinia-doped ceria films deposited by pulsed laser ablation in the energy range 100–600 mJ/pulse has been investigated. As-deposited films were found to be nanocrystalline with preferred orientation. X-ray diffraction (XRD) analysis revealed that the size of the nanocrystals of doped ceria does not vary significantly with increasing laser energy, while transmission electron microscopy (TEM) study showed a uniform distribution of nanocrystals of 8–10 nm for energies ≤200 mJ/pulse and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Though, the laser-ablated films were totally free from secondary phases, lattice imaging of the large grained doped ceria showed growth-induced defects such as dislocations and ledges. This artice was accidentally published twice. This is the second publication, please cite only the authoritative first one which is available at . An additional erratum is available at . An erratum to this article can be found at     

Microstructural study of thin films of 5 mol% gadolinia doped ceria prepared by pulsed laser ablation

Microstructural characterization of thin films of 5 mol% gadolinia doped ceria films deposited by pulsed laser ablation in the energy range 100–600 mJ/pulse has been investigated, as deposited films were found to be nanocrystalline with preferred orientation. X-ray diffraction analysis revealed that the size of the nanocrystals of doped ceria does not vary significantly with increasing laser energy, whereas transmission electron microscopy study showed a uniform distribution of nanocrystal of 8–10 nm for energies ≤200 mJ/pulse and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Although the laser-ablated films were totally free from secondary phases, lattice imaging of the large grained doped ceria showed growth-induced defects, such as dislocations and ledges.     

On the growth of gadolinia-doped ceria by pulsed laser deposition

In order to establish a new platform to manufacture micro-sized solid oxide fuel cells (SOFCs) with low operating temperatures, new design concepts, new preparation methods and new materials are being explored. Our studies in this paper are focused on the electrolyte material, and in particular gadolinia doped ceria (GDC), an electrolyte material, likely to replace the traditional yttria-stabilised zirconia (YSZ) for low temperature applications. GDC films were grown on a single crystal Si by pulsed laser deposition (PLD). The microstructure of the films as a function of growth time has been studied. We have found that the mean grain size increases with film thickness h as h^2/5, in agreement with theoretical results.     

Epitaxial growth of atomically flat gadolinia-doped ceria thin films by pulsed laser deposition

Epitaxial growth of Ce_0.8Gd_0.2O₂(CGO) films on (001) TiO₂-terminated SrTiO₃ substrates by pulsed laser deposition was investigated using in situ reflective high energy electron diffraction. The initial film growth shows a Stransky–Krastanov growth mode. However, this three-dimensional island formation is replaced by a two-dimensional island nucleation during further deposition, which results in atomically smooth CGO films. The obtained high-quality CGO films may be attractive for the electrolyte of solid-oxide fuel cells operating at low temperature.     

Thermal properties of 15-mol% gadolinia doped ceria thin films prepared by pulsed laser ablation

Thermal properties of 15-mol% gadolinia doped ceria thin films (Ce_0.85Gd_0.15 O_1.925) prepared by pulsed laser ablation on silicon substrates in the temperature range 473–973 K are presented. Thermal diffusivities and thermal conductivities were evaluated using photoacoustic spectroscopy. The influence of grain size on thermal properties of the films as a function of deposition temperature is studied. It is observed that the thermal diffusivity and the conductivity of these films decreases up to 873 K and then increases with substrate temperatures. The thermal properties obtained in these films are discussed on the basis of influence of grain size on phonon scattering.     

Epitaxial ZrC thin films grown by pulsed laser deposition

ZrC thin films were grown on (0 0 1)Si, (1 1 1)Si and (0 0 0 1)sapphire substrates by the pulsed laser deposition (PLD) technique. X-ray diffraction, X-ray reflectivity and Auger electron spectroscopy investigations were used to characterize the structure and composition of the deposited films. It has been found that films grown at temperatures higher than 700 °C under very low water vapor pressures were highly textured. Films deposited on (0 0 1)Si grew with the (0 0 1) axis perpendicular to the substrate, while those deposited on (1 1 1)Si and (0 0 0 1)sapphire grew with the (1 1 1) axis perpendicular to the substrate. Pole figures investigations showed that films were epitaxial, with in-plane axis aligned to those of the substrate.     

Carbon nanocrystals produced by pulsed laser ablation of carbon

Plasma laser ablation experiments were performed irradiating glassy-carbon targets placed in vacuum through a pulsed Nd:YAG laser operating at the second harmonic (532 nm), 9 ns pulse width and 10⁹ W/cm² density power.

Thin films of ablated carbon were deposited on silicon oxide substrates placed at different distances and angles with respect to the target.

The analysis of the deposited material was carried out by using surface profiler, scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) and Raman spectroscopy.

Results show the evidence of carbon nanocrystals and nanostructures with dimension of the order of 100 nm deposited on the substrates together with a large amount of amorphous phase. The spectroscopic investigations and the SEM images indicate the formation of nanodiamond seeds as a nucleation process induced on the substrate surface. Nanostructures were investigated as a function of the laser intensity and angle distribution. Experimental results were compared with the literature data coming from nanodiamonds growth with different techniques.

Experiments performed at Instituto Nazionale di Fisica Nucleare-Laboratori Nazionali del Sud (INFN-LNS) of Catania (Italy) and data analysis conducted at Dipartimento di Fisica and DFMTA of the Università of Messina (Italy), CNR-ITIS of Messina and ST-Microelectronics of Catania will be presented and discussed.     

Femtosecond pulsed laser ablation of thin gold film

Laser micromachining on 1000 nm-thick gold film using femtosecond laser has been studied. The laser pulses that are used for this study are 400 nm in central wavelength, 150 fs in pulse duration, and the repetition rate is 1 kHz. Plano-concave lens with a focal length of 19 mm focuses the laser beam into a spot of 3 μm (1/e² diameter). The sample was translated at a linear speed of 400 μm/s during machining. Grooves were cut on gold thin film with laser pulses of various energies. The ablation depths were measured and plotted. There are two ablation regimes. In the first regime, the cutting is very shallow and the edges are free of molten material. While in the second regime, molten material appears and the cutting edges are contaminated. The results suggest that clean and precise microstructuring can be achieved with femtosecond pulsed laser by controlling the pulse energy in the first ablation regime.     

Electrical characterization of gadolinia-doped ceria films grown by pulsed laser deposition

Electrical characterization of 10 mol% gadolinia doped ceria (CGO10) films of different thicknesses prepared on MgO(100) substrates by pulsed laser deposition is presented. Dense, polycrystalline and textured films characterized by fine grains (grain sizes < 18 nm and < 64 nm for a 20-nm and a 435-nm film, respectively) are obtained in the deposition process. Grain growth is observed under thermal cycling between 300 and 800°C, as indicated by X-ray-based grain-size analysis. However, the conductivity is insensitive to this microstructural evolution but is found to be dependent on the sample thickness. The conductivity of the nanocrystalline films is lower (7.0×10^?4  S/cm for the 20-nm film and 3.6×10^?3  S/cm for the 435-nm film, both at 500°C) than that of microcrystalline, bulk samples ( $6\times 10^{-3}$  S/cm at 500°C). The activation energy for the conduction is found to be 0.83 eV for the bulk material, while values of 1.06 and 0.80 eV are obtained for the 20-nm film and the 435-nm film, respectively. The study shows that the ionic conductivity prevails in a broad range of oxygen partial pressures, for example down to about 10 ^?26  atm at 500°C.     

Metal thin film ablation with femtosecond pulsed laser

Micromachining thin metal films coated on glass are widely used to repair semiconductor masks and to fabricate optoelectrical and MEMS devices. The interaction of lasers and materials must be understood in order to achieve efficient micromachining. This work investigates the morphology of thin metal films after machining with femtosecond laser ablation using about 1 μm diameter laser beam. The effect of the film thickness on the results is analyzed by comparing experimental images with data obtained using a two-temperature heat transfer model. The experiment was conducted using a high numerical aperture objective lens and a temporal pulse width of 220 fs on 200- and 500-nm-thick chromium films. The resulting surface morphology after machining was due to the thermal incubation effect, low thermal diffusivity of the glass substrate, and thermodynamic flow of the metal induced by volumetric evaporation. A Fraunhofer diffraction pattern was found in the 500-nm-thick film, and a ripple parallel to the direction of the laser light was observed after a few multiple laser shots. These results are useful for applications requiring micro- or nano-sized machining.     

Properties of Dy-doped ZnO nanocrystalline thin films prepared by pulsed laser deposition

Highly transparent conductive Dy₂O₃ doped zinc oxide (ZnO)_1-x(Dy₂O₃)_x nanocrystalline thin films with x from 0.5% to 5% have been deposited on glass substrate by pulsed laser deposition technique. The structural, electrical and optical properties of Dy₂O₃ doped thin films were investigated as a function of the x value. The experimental results show that the Dy concentration in Dy-doped ZnO thin films has a strong influence on the material properties especially electrical properties. The resistivity decreased to a minimum value of 5.02 × 10⁻⁴ Ω cm with x increasing from 0.5% to 1.0%, then significantly increased with the further increasing of x value. On the contrary, the optical direct band gap of the (ZnO)_1-x(Dy₂O₃)_x films first increased, then decreased with x increasing. The average transmission of Dy₂O₃ doped zinc oxide films in the visible range is above 90%.     

Chemical composition of ZrC thin films grown by pulsed laser deposition

ZrC films were grown on (1 0 0) Si substrates by the pulsed laser deposition (PLD) technique using a KrF excimer laser working at 40 Hz. The nominal substrate temperature during depositions was set at 300 °C and the cooling rate was 5 °C/min. X-ray diffraction investigations showed that films deposited under residual vacuum or under 2 × 10⁻³ Pa of CH₄ atmosphere were crystalline, exhibiting a (2 0 0)-axis texture, while those deposited under 2 × 10⁻² Pa of CH₄ atmosphere were found to be equiaxed and with smaller grain size. The surface elemental composition of as-deposited films, analyzed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS), showed the usual high oxygen contamination of carbides. Once the topmost 2-4 nm region was removed, the oxygen concentration rapidly decreased, down to around 3-8% only in bulk. Simulations of the X-ray reflectivity (XRR) curves indicated a smooth surface morphology, with roughness values below 1 nm (rms) and films density values of around 6.30-6.45 g/cm³, very close to the bulk density. The growth rate, estimated from thickness measurements by XRR was around 8.25 nm/min. Nanoindentation results showed for the best quality ZrC films a hardness of 27.6 GPa and a reduced modulus of 228 GPa.     

Target-plane deposition of diamond-like carbon in pulsed laser ablation of graphite

In pulsed Nd:YAG laser ablation of highly oriented pyrolytic graphite (HOPG) at 10⁻⁶ Torr, diamond-like carbon (DLC) are deposited at laser wavelengths of 1064, 532, and 355 nm on substrates placed in the target-plane. These target-plane samples are found to contain varying sp³ content and composed of nanostructures of 40-200 nm in size depending on the laser wavelength and laser fluence. The material and origin of sp³ in the target-plane samples is closely correlated to that in the laser-modified HOPG surface layer, and hardly from the backward deposition of ablated carbon plume. The surface morphology of the target-plane samples shows the columnar growth and with a tendency for agglomeration between nanograins, in particular for long laser wavelength at 1064 nm. It is also proposed that DLC formation mechanism at the laser-ablated HOPG is possibly via the laser-induced subsurface melting and resolidification.     

Metal nanoparticle production by pulsed laser nanostructuring of thin metal films

The controllable nanostructuring of thin metal films by nanosecond UV laser pulses is introduced as a novel technique for the production of metal nanoparticles supported on a range of different oxide substrates, including indium tin oxide. This processing is performed at low macroscopic temperatures. The physical mechanisms underlying the nanostructuring are discussed and applications for these nanoparticle films, including as catalysts for nanotube/nanowire growth and in surface enhanced Raman spectroscopy measurements, are introduced.     

Mn doped ZnO nanostructured thin films prepared by ultrasonic spray pyrolysis method

Mn-doped ZnO thin films with different percentage of Mn content (0, 1, 3 and 5 at.%) and substrate temperature of 350 °C, were deposited by a simple ultrasonic spray pyrolysis method under atmospheric pressure. We have studied the structural and optical properties by using X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and ultra-violet visible near infrared (UV–Vis-NIR) spectroscopy. The lattice parameters calculated for the Mn-doped ZnO from XRD pattern were found to be slightly larger than those of the undoped ZnO, which indicate substitution of Mn in ZnO lattice. Compared with the Raman spectra for ZnO pure films, the Mn-doping effect on the spectra is revealed by the presence of additional peak around 524 cm⁻¹ due to Mn incorporation. With increasing Mn doping the optical band gap increases indicating the Burstein–Moss effect.     

Excimer laser ablation of thin titanium oxide films on glass

Thin titanium dioxide films are deposited on glass substrates by magnetron sputter deposition. They are irradiated in air, by means of a KrF excimer laser. The ablation rate is measured as a function of the laser fluence per pulse, F, and of the number of pulses, N. Above a fluence threshold, the films are partially ablated. The ablated thickness does not vary linearly with N. This is the signature of a negative feedback between the film thickness and the ablation rate. The origin of this negative feedback is shown to be due to either thermal or electronic effects, or both. At high F, the film detachs from the substrate.     

Investigation of the relationship between the ionic conductivity and the local structures of singly and doubly doped ceria compounds using EXAFS measurement

The oxide ionic conductivity measurements of singly and doubly doped ceria compounds were carried out. Singly and doubly doped ceria used in this study were Ce_0.8Ln_0.2O_1.9 (Ln=Y, Sm, Nd, or La) and Ce_0.8La_0.1Y_0.1O_1.9, respectively. Lattice constants of these compounds were in proportion to the ionic radius of the dopant(s). The doubly doped ceria compound showed oxide ionic conductivity comparative to the average of that of each corresponding singly doped sample. This finding indicates that the conductivity is influenced by both dopants in the doubly doped compounds. The extended X-ray absorption fine structure (EXAFS) study showed that the coordination number of oxide ions at the nearest neighbor of cation was related to the ionic conductivity. It was found that the conductivity gave the highest value when oxygen vacancies were randomly distributed in the lattice. This indicates that the local structure seriously affects oxide ionic conduction in singly and doubly doped ceria compounds.     

Microstructural studies of bulk and thin film GDC

Ceria rare earth solid solutions are known as solid electrolyte with potential application in oxygen sensors and solid oxide fuel cells. We report the preparation of gadolinia-doped ceria, Ce_0.90Gd_0.10O_1.95, by the conventional solid-state reaction method and the preparation of thin films from a sintered pellet of gadolinia-doped ceria by the pulsed laser deposition technique. The effect of process conditions, such as substrate temperature, oxygen partial pressure, and laser energy on microstructural properties of these films are examined using powder X-ray diffraction, scanning electron microscopy, atomic force microscopy, and Raman spectroscopy.     

Reactive pulsed laser deposition of gold nitride thin films

We report on the growth and characterization of gold nitride thin films on Si 〈1 0 0〉 substrates at room temperature by reactive pulsed laser ablation. A pure (99.95%) Au target was ablated with KrF excimer laser pulses in nitrogen containing atmosphere (N₂ or NH₃). The gas ambient pressure was varied in the range 0.1-100 Pa. The morphology of the films was studied by using optical, scanning electron and atomic force microscopy, evidencing compact films with RMS roughness in the range 3.6-35.1 nm, depending on the deposition pressure. Rutherford backscattering spectrometry and energy dispersion spectroscopy (EDS) were used to detect the nitrogen concentration into the films. The EDS nitrogen peak does not decrease in intensity after 2 h annealing at 250 °C. Film resistivity was measured using a four-point probe and resulted in the (4-20) × 10⁻⁸ Ω m range, depending on the ambient pressure, to be compared with the value 2.6 × 10⁻⁸ Ω m of a pure gold film. Indentation and scratch measurements gave microhardness values of 2-3 GPa and the Young's modulus close to 100 GPa. X-ray photoemission spectra clearly showed the N 1s peak around 400 eV and displaced with respect to N₂ phase. All these measurements point to the formation of the gold nitride phase.     

Deposition of NbC thin films by pulsed laser ablation

Niobium carbide thin films were prepared by pulsed laser ablation of a stoichiometric NbC target. XeCl (308 nm, 30 ns) and Nd:YAG (266 nm, 5 ns) lasers operating at a repetition rate of 10 Hz were used. Films were deposited on Si (100) substrates at room temperature either in vacuum or in an argon atmosphere (2᎒^-1 mbar). Different laser fluences (2, 4 and 6 J/cm²) and different numbers of pulses (1᎒⁴, 2᎒⁴ and 4᎒⁴) were tested. For the first time, NbC films were prepared through a clean procedure without the addition of a hydrocarbon atmosphere. The phase constitution of the films, unit cell size, mean crystallite dimensions and preferred orientation are determined as a function of deposition conditions by X-ray diffraction. Complementary morphological and structural analysis of the films were performed by scanning electron microscopy, atomic force microscopy and Rutherford backscattering spectroscopy.