Dielectric response of K(Ta,Nb)O3 thin films

The dielectric response of K(Nb,Ta)O₃ films grown on (001) MgAl₂O₄ (100) by pulsed laser deposition from a mosaic target of KTa_0.63Nb_0.37O₃ and KNO₃ has been examined. In particular, the effects of growth temperature (650–800 °C), growth pressure (1–100 mTorr O₂), and annealing conditions on the tunability, dielectric constant, and dielectric losses in interdigitated capacitor device structures fabricated with these films are described. Annealing treatments lead to a reduction in the loss tangents for most of the films considered. Figure of merit calculations indicate that the best dielectric response (tunability=37%, tan =0.022) is achieved for films grown at 750 °C in an oxygen pressure of 100 mTorr and then annealing at 1000 °C for 2 h in air.     

Influence of ambient oxygen pressure on the preferred orientation, microstructures, and dielectric properties of (Ba1-xSrx)TiO3 thin films with compositionally graded structures

Compositionally graded (Ba_1-xSr_x)TiO₃ (BST) thin films, with x decreasing from 0.25 to 0.0, were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by pulsed-laser ablation at 600 °C and under ambient oxygen pressures ranging from 50 to 400 mTorr. The influence of the ambient gas pressure on the preferred orientation, microstructures, and dielectric properties of compositionally graded BST films was investigated by X-ray diffraction, scanning electron microscopy, and dielectric frequency spectra, respectively. As the ambient oxygen pressure was increased, the preferred orientation evolved in the order: (100)+(110)(110)+(111) random orientation, and the surface roughness of the graded BST films also increased. The graded BST films deposited at high ambient oxygen pressures (300400 mTorr) exhibited a grainy structure with polycrystalline grains throughout the film thickness, whereas the graded films deposited at low ambient oxygen pressures (50200 mTorr) possessed a columnar structure. The evolution of the microstructure was ascribed to the different physical and chemical properties of the species that were incident onto the substrates at the various oxygen pressures. The dielectric properties of the graded BST films were dependent upon the ambient oxygen pressures. The graded BST films deposited at 200 mTorr exhibited the highest dielectric constant. PACS 77.55.+f; 77.22.Ch; 81.15.Fg     

Size and Interface Control of Novel Nanocrystalline Materials Using Pulsed Laser Deposition

We have developed a novel method based upon pulsed laser deposition to produce nanocrystalline materials with an accurate grain size and interface control. Using this method, the grain size in the case of Cu thin films was controlled by introducing a few monolayers of insoluble elements having high surface energy such as W, which increases interfacial energy and provides more nucleation sites. The grain size is determined by the thickness of Cu layer and the substrate temperature at which it transforms into islands (nanocrystalline grains) of fairly uniform size which we desgnate as self-assembling approach. Using this approach, the grain size was reduced from 160nm (Cu or Si (100) substrate) to 70–80nm for a simple W layer (Cu/W/Si (100)) to 4nm for a multilayer (Cu/W/Cu/W/Si (100)) thin film. The hardness of these films was evaluated using a nanoindentation technique, a significant increase in hardness from 2.0GPa for coarse-grained 180nm to 12.5GPa for 7nm films was observed. However, there is decrease in hardness below 7nm for copper nanocrystals. The increase in hardness with the decrease in grain size can be rationalized by Hall–Petch model. However, the decrease in slope and eventually the decrease in hardness below a certain grain size can be explained by a new model based upon grain-boundary deformation (sliding). We also used a similar materials processing approach to produce quantum dots in semiconductor heterostructures consisting of Ge and ZnO dots or nanocrystals in AlN or Al₂O₃ matrix. The latter composites exhibit novel optoelectronic properties with quantum confinement of phonons, electrons, holes and excitons. Similarly, we incorporated metal nanocrystals in ceramics to produce improved mechanical and optical properties.     

Growth of polycrystalline LaNi<Subscript>1-x</Subscript>Co<Subscript>x</Subscript>O<Subscript>3</Subscript> (<Emphasis Type="BoldItalic">x</Emphasis> =0.3,0.5) thin films on Si(100) by pulsed laser deposition

Polycrystalline LaNi_1-xCo_xO₃ (x=0.5,0.3) thin films have been deposited on polished Si(100) substrates by pulsed laser deposition. The films are grown at 650 °C in ambient oxygen pressure of 0.4 mbar with an incident laser fluence of 1.5 J/cm² delivered by a KrF excimer laser. The lattice parameters of the as-grown films are slightly larger (0.05–0.4%) than those of the powders used to prepare the targets. The films exhibit weak texturing along the (012) direction. The low-temperature magnetic properties of the films, i.e. the coercive force, the remanence and the saturation magnetization, are enhanced compared to the powders. Furthermore, the x=0.3 film exhibits a low, almost temperature-independent resistivity above 200 K [(300 K)30 cm] and thus we propose it as a potential candidate material for electrode applications, e.g. in ferroelectric devices. PACS 68.55.-a; 73.61.-r; 81.15.Fg     

Chemistry and microstructure of PLD (Ti,Al)CxN1-x coatings deposited at room temperature

The aim of the present work was the improvement of titanium-aluminium nitride (TiAlN) coatings by the solid-solution hardening with carbon atoms leading to titanium-aluminium carbon-nitride (Ti,Al)C_xN_1-x coatings with varying carbon (x) and nitrogen contents. The request of low deposition temperatures necessary for the coating of heat sensitive materials like tool steels of high hardness and polymers was reached by the application of the room temperature pulsed laser deposition (PLD) technique. A Nd:YAG laser of 1064 nm wavelength operated at two different laser pulse energies was used in the ablation experiments of pure TiAl targets (50 at.% Al) in various C₂H₂-Ar gas mixtures. Different pulse energies of the laser resulted in changes of the ratio of Ti/Al atoms in the grown coatings. Furthermore, the results reveal a strong proportionality of the gas mixture to the C and N content of the coatings. In the coatings deposited at low C₂H₂ gas flows the XRD investigations showed crystalline phases with fcc TiN type lattices, whereas high acetylene flows during deposition resulted in the formation of fully amorphous coatings and carbon precipitation or cluster boundaries found in Raman investigations. PACS 81.15.Fg; 46.55.+d     

Pulsed laser deposition of non-stoichiometric silicon nitride (SiNx) thin films

Silicon nitride (SiN_x) thin films of various stoichiometries (x) were prepared on Si (100) substrates applying the Nd:YAG (=1064 nm) pulsed laser deposition (PLD) process in the shaded off-axis technique at room temperature. The specific arrangement of this technique with perpendicular target (Si) and substrate surfaces and a metallic screen in between guarantees very low particulate (droplet) deposition and, thus, excellent surface qualities. Compared to the usually used on-axis deposition technique consisting of a parallel arrangement of the target and substrate surface, the coating surface covered with particulates is about 100 times lower reaching a maximum of 0.2% on 400 nm thick films. The variation the N₂ partial pressure affects the nitrogen content and the silicon bonding structure of the films analysed by means of SIMS and XPS, respectively. As a consequence the optical properties (e.g.m refractive index) are tailorable in a wide spectral range between 250 and 1200 nm. PACS 81.15.Fg; 78.20.Ci     

Crystalline growth of cubic (Eu, Nd):Y2O3 thin films on α -Al2O3 by pulsed laser deposition

In this paper we report on the growth of crystalline, europium- and neodymium-doped cubic yttria ((Eu,Nd):Y₂O₃) thin films on hexagonal corundum (-Al₂O₃ ) substrates using the pulsed laser deposition (PLD) technique. A KrF excimer laser was used to ablate material from ceramic (Eu, Nd):Y₂O₃ targets. The yttria films were deposited on the -Al₂O₃ (0001) substrates. X-ray diffractometry (XRD) revealed that the films grew in the Y₂O₃[111]-direction. The surface topography of the films was investigated using atomic force microscopy (AFM). PACS 81.15.Fg; 42.70.hj; 68.55.Jk     

Electroless deposition of Ag on Pd-activated TiN/p-Si(100) substrate

Nano-thick Ag films were electrolessly deposited on TiN/p-Si(100) substrates. The substrates were prepared by sputtering TiN on p-Si(100) wafers. An activation process of the substrates was performed by immersing the substrates in a solution of 0.0019 moLL^-1PdCl₂+0.45 moLL^-1HF+8.7 moLL^-1aceticacid+0.036 moLL^-1 HCl so as to obtain the Pd seed layer. The general composition of the electroless Ag bath was 0.0032 moLL^-1AgNO₃+2.24 moLL^-1NH₃+0.56 moLL^-1aceticacid+0.1 moLL^-1 NH₂NH₂ at pH 10.2. The morphologies of the Pd seed layer and the Ag films were characterized by atomic force microscopy (AFM). The effect of the Pd activation on electroless Ag deposition was tested by open circuit potential with time technology (OCP-t). For comparison, the morphology of the films deposited by electrochemical deposition on the substrates was also studied by AFM. PACS 82.45.Mp; 81.15.Pq; 81.10.Dn     

Growth of polycrystalline La0.5Sr0.5CoO3 films by femtosecond pulsed laser deposition

In this paper we present the growth of La_0.5Sr_0.5CoO₃ (LSCO) films on MgO, quartz, and silicon substrates by pulsed laser deposition (PLD) using a Ti:sapphire laser (50 fs, 800 nm wavelength). The morphology and the structure of the films were studied by X-ray diffraction, atomic force microscopy, and scanning electron microscopy. The films were polycrystalline and exhibit a good adherence to the Si substrate. Different deposition parameters such as substrate temperature, oxygen pressure, and laser fluence were varied to achieve good surface quality and low resistivity crystalline films. We also defined the optimum conditions in which the deposited film surface is particulate free. The best films (droplets free) were grown at 625 °C, in an ambient oxygen pressure of 6 mbar, with an incident laser fluence of 0.19 J/cm². This is a mandatory step in the complex work of fabricating La_0.5Sr_0.5CoO₃/BaTiO₃/La_0.5Sr_0.5CoO₃ heterostructures for the development of thin film capacitors for non-volatile ferroelectric access memory devices. PACS 81.15 Fg; 42.62-b; 68.65.Ac     

Reactive pulsed laser deposition and laser induced crystallization of SnO2 transparent conducting thin films

Transparent conducting SnO₂ thin films with a thickness between 1000–2000 Å were deposited on glass, quartz and silicon substrates using standard pulsed laser deposition techniques with two different targets (Sri and SnO₂) and with three different laser wavelengths (1.06, 0.532 and 0.266 ) from a Q-switched Nd: YAG laser. Tin dioxide films with optical transmission over most of the visible spectrum exceeding 80% were obtained using a Sn target and a background oxygen pressure of 20 Pa. The electrical resistivity () depended strongly on the substrate temperature during deposition, with the lowest values of of about 10^–2 -cm obtained when the substrate was maintained at 400°C during deposition. Using SnO₂ targets, predominantly amorphous phase SnO₂ films were deposited on Si substrates and then transformed into polycrystalline Sn₃O₄ by laser induced crystallization ( = 1.06 m). Whereas these later films were essentially non-conducting as deposited ( > 400 -cm), the electrical resistivity was permanently reduced after laser induced crystallization by a factor greater than 1000 to a value of approximately 4 × 10^–1 -cm.     

Preparation of single-crystal-like MgO films on Si and orientation control of platinum films on MgO/Si

Growth of a Pt/MgO bilayer on Si(100) was investigated by pulsed-laser deposition. The growth modes of both MgO and platinum films are layer-by-layer growth, which were revealed by in situ reflection high energy electron diffraction observations. Two kinds of orientations of platinum films, viz. epitaxially (100) and (111)-oriented platinum films, were obtained on the same MgO(100)/Si(100) substrate only by varying the laser fluence. The effect of laser fluence on the orientation of platinum films is briefly discussed. The platinum films prepared in our experiments are epitaxially grown and exhibit atomic-scale surface flatness. It is believed that the improvement in the quality of platinum films can be attributed to the perfectly single-crystalline quality of the MgO buffer layer, which was further confirmed by the excellent dielectric properties. For a 150 nm thick MgO film, the leakage current density was found to be 10^-7 Acm^-2 with an electric field of 8×10⁵ Vcm^-1 and the relative dielectric constant (_r) was 10.6. PACS 68.55.Jk; 81.15.Fg; 85.50.Gk     

Degenerate electrical conductive and excitonic photoluminescence properties of epitaxial films of wide gap p-type layered oxychalcogenides, LnCuOCh (Ln=La, Pr and Nd; Ch=S or Se)

Electrical and photoluminescence properties were investigated for epitaxial films of layered oxychalcogenides, LnCuOCh (Ln=La, Pr, and Nd, Ch=S or Se). Epitaxial films of Mg 10 at.% doped LaCuOS_1-xSe_x are the first demonstration of degenerate conduction with high hole concentration >10²⁰ cm^-3 in wide gap p-type semiconductors. Ion substitution varied the excitonic emission energy from 3.21 eV to 2.89 eV while lanthanide and chalcogenide ion substitutions displayed the opposite tendency against cell volume. These unique properties are discussed with respect to the electronic structure originating from the layered crystal structure. PACS 72.20.-i; 73.50.-h; 78.55.Hx; 78.66.-w     

Pulsed laser deposition of c * axis oriented pentacene films

Pulsed laser desorption and film deposition behaviors have been investigated on pentacene as an organic molecule primarily due to its applications in electronics. The laser desorption time-of-flight (LDTOF) mass spectrum exhibited a single parent peak when a pressed pentacene pellet was ablated by an N₂ laser beam of its fluence lower than 100 mJ/cm², indicating that pentacene could be evaporated without an appreciable photodecomposition by the pulsed laser beam. Nd:YAG pulsed laser deposition of pentacene films was performed using such optimization parameters as laser fluences and wavelength (second, third and forth harmonic generations (SHG, THG, FHG)). The analyses with AFM, XRD and UV-Vis spectroscopy revealed the fabrication of c^* axis oriented pentacene films on quartz, silicon, and CaF₂ substrates by the SHG. The SHG films have a surface morphology superior to those of films deposited by THG and FHG. PACS 81.15.Fg; 81.05.Lg; 82.80.Rt     

Nano-structured oriented carbon films grown by PLD and CVD methods

PLD and CVD methods, plasma or bias assisted, have been used to prepare thin films of nano-clustered graphite. The experimental conditions (vz. deposition apparatus, substrate temperature, working pressure, inert sustaining gases, parent species, and applied voltage) have been changed with the final aim of obtaining small graphene particles with the basal planes oriented along the growth vector and perpendicular to the n-Si100 substrate. Pulsed laser ablation (Nd:YAG, 2nd harmonic: =532 nm, h=2.33 eV, =7 ns, =10 Hz, 7 J/cm²), assisted by an RF-plasma, of a pyrolytic graphite target gave good results for nano-structure formation, provided high substrate temperature and high inert gas pressure are maintained. CVD methods, in the presence of high substrate temperature and a DC bias, showed a good attitude to drive a longitudinal growth of graphene layers and nano-wires from a reactive gas flow of Argon/Hydrogen and Methane. The morphology of the films grown at different conditions have been characterised by scanning electron microscopy (SEM). Film quality and nano-particle dimensions have been estimated by Raman spectroscopy. PACS 81.07.-b; 81.15.-z; 78.30.-j; 68.37.-d     

Tailoring of the functional properties of sol–gel films on Pt/TiO2/SiO2/(100)Si substrates: (Pb,La)TiO3/(Pb,Ca)TiO3 multilayer heterostructures

Preferentially oriented sol–gel (Pb,Ca)TiO₃/(Pb,La)TiO₃/(Pb,Ca)TiO₃ and (Pb,La)TiO₃/(Pb,Ca)TiO₃/(Pb,La)TiO₃ multilayer heterostructure thin films deposited on silicon-based substrates have been studied and compared with identically prepared (Pb,La)TiO₃ (PTL) and (Pb,Ca)TiO₃ (PTC) films. The existence in their texture of two components that contribute to the net polarization in the direction normal to the plane of the film, 001 and 111, results in significant ferroelectric and pyroelectric properties. P_r=26 Ccm^-2 and =28.5×10^-9 Ccm^-2K^-1, and P_r=17 Ccm^-2 and =22.8×10^-9 Ccm^-2K^-1, have been achieved, respectively, in the PTL/PTC/PTL and PTC/PTL/PTC heterostructures. The surface roughness of these films provides a high specific surface that can be interesting for infrared detectivity. An increase of the dielectric permittivity in the whole temperature interval up to the transition temperature has been observed for both heterostructures with respect to the PTL and PTC films. This effect is due to a release of stress in the heterostructures that is revealed by the increase of the tetragonal distortion, c/a, of these films. PACS 68.55.Jk; 77.80.-e; 77.84.Dy     

Pulsed laser deposition of Er:BaTiO3 for planar waveguides

Laser radiation is used for the deposition of dielectric erbium doped BaTiO₃ thin films for photonic applications. Pulsed laser deposition with KrF excimer laser radiation (wavelength 248 nm, pulse duration 20 ns) is used to grow dense, transparent, amorphous, poly-crystalline and single crystalline erbium doped BaTiO₃ thin films. Visible emission due to up-conversion luminescence (wavelength 528 nm and 548 nm) under excitation with diode laser radiation at a wavelength of 970–985 nm is investigated as a function of the erbium concentration of 1–20 mol% and structural film properties. PACS 81.15.Fg; 42.55.Wd; 68.55; 78.55.Hx     

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     

Destabilization of LiBH4 by mixing with LiNH2

It was revealed that LiBH₄ is destabilized by mixing with LiNH₂ and the mixture desorbs a large amount of hydrogen. First-principles calculations predicted that the enthalpies of dehydrogenation for LiBH₄ alone and the mixture of LiBH₄+2LiNH₂ are 75 kJ/molH₂ and 23 kJ/molH₂, respectively. Motivated by this prediction, we experimentally examined the dehydrogenation properties for LiBH₄ and the mixture under hydrogen pressure. The amounts of desorbed hydrogen from LiBH₄ and the mixture at 703 K and 522 K were 10.6 mass% and 7.8 mass%, respectively. The dehydrogenation pressure of the mixture was much higher than that of LiBH₄ alone, although the mixture was measured at approximately 180 K lower temperature. This result suggests that the mixture is much unstable as compared with LiBH₄ alone.PACS 81.05.Zx; 71.20.Ps; 82.30.-b     

Investigation of laser-induced plasma deposition of boron nitride

Laser ionization mass spectrometry (LIMS) was applied to the investigation of the composition of laser plasmas of three different boron nitride modifications (hexagonal -boron nitride with graphite structure, cubic -boron nitride with diamond structure and hexagonal -boron nitride resembling the wurtzite type). Thin films in the 10 nm range were produced in the ion source of the laser mass spectrograph by laser-induced plasma deposition. So we could carry out the plasma diagnostic and the preparation of thin films under the same condition. The cluster distribution in laser plasma is independent of the structure of the BN target. An explanation of laser-induced plasma deposition of boron nitride from the results of mass spectrometric analysis of laser plasmas and of the analysis of deposited thin films (TEM, EELS) was derived.     

Textured thin films grown at room temperature by laser ablation

Thin films of SrFe₁₂O₁₉, BaFe₁₂O₁₉, Pb_0.76La_{0.16 0.08}Zr_0.53Ti_0.47O₃and Sr_0.3Ba_0.7Nb₂O₆ were grown on monocrystalline silicon substrates by pulsed laser deposition using a 20-ns Nd:YAG laser (1064 nm). The deposited thin films were analyzed by X-ray diffraction in the grazing incidence configuration. The analysis showed evidence of textured growth even though the films were grown at room temperature. Emission spectroscopy was used to establish the time of flight of the species within the plasma plume. Velocities of the order of 10⁶ cm/s were obtained. The high kinetic energy of the species is thought to be responsible for the film texture, as it is released in the substrate–film system, favoring a preferential growth. For all the ablated ceramics, singly ionized species were shown to expand at higher velocities than neutrals. For ions, no consistency in the mass–speed relation was obtained, suggesting both the presence of electric fields during the plasma formation and an evaporation of the target that depends on the vapor pressure of the elements. In this way species that are firstly evaporated will be attracted strongly by fast electrons, allowing heavy ions to acquire higher velocities than lighter ones. PACS 81.15.Fg; 52.38.Mf; 68.55.Jk; 52.38.Kd; 52.70.Kz