LiMn2O4 films grown by pulsed-laser deposition

LiMn₂O₄ films have been deposited onto silicon wafer by pulsed-laser deposition (PLD) technique in order to test their reliability as cathode materials in rechargeable lithium microbatteries. The film formation has been studied as a function of the preparation conditions, i.e., composition of the target, substrate temperature, and oxygen partial pressure in the deposition chamber. Depending on the conditions of deposition, Mn₂O₃ was present as an impurity phase. When deposited onto silicon substrate maintained at 300 °C in an oxygen pressure of 100 mTorr from the target LiMn₂O₄+15 % Li₂O, the PLD films are well-textured with crystallite size of 300 nm. It is found that such a film crystallizes in the spinel structure (Fd3m symmetry) as evidenced by x-ray diffraction and Raman scattering measurements. Surface morphologies of layers were investigated by SEM. The cells Li//LiMn₂O₄ have been tested by cyclic voltammetry and galvanostatic charge-discharge techniques in the range 3.0–4.2 V. The voltage profiles show the two expected steps for Li_xMn₂O₄ with a specific capacity as high as 120 mC/cm² μm. The chemical diffusion coefficients for the Li_xMn₂O₄ thin films appear to be in the range of 10⁻¹¹-10⁻¹² cm²/s. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Laser photolytic deposition of molybdenum and tungsten thin film microstructures

We have deposited thin metal films of Mo and W with sub-m lateral resolution using the photodissociation of the carbonyls by the frequency doubled radiation of an Arion laser at cw and ps-pulse operation, respectively. In both regimes similar curves are obtained for the intensity dependence of the deposition rate. No difference was observed for the lateral resolution using cw or ps-pulse irradiation. Measurements of the deposition rate as a function of the spot size indicate that the decomposition occurs in the adsorbed phase.     

Pressure effects during pulsed-laser deposition of barium titanate thin films

2 , Ar) in a broad pressure range (10^-7–1 mbar) are correlated to the plasma expansion dynamics. It is found that the deposited films present an excess of Ba in the intermediate pressure range (10^-2<P<10^-1 mbar) and a peaked distribution of Ba to Ti atoms ratio, that is not related to either the substrate temperature or the nature of the gas environment. The results are discussed in terms of the dependence of the plume length (L_P) on the gas pressure and the existence of scattering processes for distances (d) from the target lower than L_P and the diffusion of the ejected species for L_P<d. Received: 7 November 1997/Accepted: 8 November 1997     

TbMnO3 epitaxial thin films by pulsed-laser deposition

Epitaxial TbMnO₃ films have been fabricated on SrTiO₃(001) and LaAlO₃(001) substrates by pulsed laser deposition (PLD), the structure and surface morphology of the films were characterized by X-ray diffraction with Cu K_α radiation and atomic force microscopy. The electrical transport and magnetic properties of the TbMnO₃ films and bulk were examined, the resistivity and the forbidden band width E_g change with epitaxial orientation, semiconductor transport properties are found in the films and bulk, the average of the E_g of the films on SrTiO₃ and on LaAlO₃ is equal to the E_g of the bulk. The two TMO films have different magnetization mode, the magnetization of the film on SrTiO₃ have an analogy to that of TbMnO₃ single crystal.     

Cadmium deposition on transparent substrates by laser induced dissociation of Cd(CH3)2 at visible wavelengths

The laser initiated formation of Cd-deposits from dimethylcadmium (DMCd) on quartz substrates has been investigated at various wavelengths between 337 and 676 nm. In this range substrate and DMCd are both transparent. The deposition mechanism is initiated by multiphoton dissociation of DMCd molecules adsorbed at the glass substrate and continues by pyrolysis of DMCd molecules at the laser-heated metallic deposit. Metal structures with a resolution below 1 m have been obtained.     

Thick gold-film deposition by high-repetition visible pulsed-laser chemical vapor deposition

A highly conductive gold film, over 10 m-thick with well-controlled linewidth, has been successfully deposited from dimethyl-gold-acetylacetonate and its fluorinated derivative by pyrolytic CVD (Chemical Vapor Deposition) with a high-repetition, visible, pulsed laser. The thermal damage to the polyimide substrate has been substantially suppressed by reducing the thermal diffusion length within 0.2 m in pulsed-laser-induced transient heating, in contrast to the cw laser-CVD scheme. Reproducible and low contact resistance as low as 0.5 between the written line and the existing gold line has been obtained. Sufficiently tough adhesion to polyimide has been observed for the deposit from dimethyl-gold-acetylacetonate. Reasonable agreement has been obtained between the observed deposition characteristics and analytical results for precursor supply rate and temperature increase during short-pulse irradiation.     

Enhanced hardness in B-doped ZnO thin films on fused quartz substrates by pulsed-laser deposition

B-doped ZnO thin films have been fabricated on fused quartz substrates using boron-ZnO mosaic target by pulsed-laser deposition technique, and the mechanical properties have been studied by nanoindentation continuous stiffness measurement technique and transmission electron microscope (TEM). Nanoindentation measurement revealed that the hardness of B-doped ZnO films, 9.32 ± 0.90 to 12.10 ± 1.00 GPa, is much greater than that of undoped ZnO films and very close to that of traditional semiconductor Si. The mean transmittance (%) is larger than 81% in the visible range (380-780 nm) for all the films, and the Hall effect measurement showed that the carrier density is around 2 × 10²⁰ cm⁻³ and the resistivity lower than 3 × 10⁻³ Ω cm. TEM characteristics show undoped thin films have more amorphous area between grains while the B-doped ZnO films have thin grain boundaries. We suggest that the grain boundaries act as the strain compensation sites and the decrease in thickness of grain boundaries enhances the hardness of the B-doped ZnO films.     

On the spray-drying deposition of TiO2 photocatalytic films

The photocatalytic activity of TiO₂ films deposited on different substrates by the spray-drying method using suspensions of commercially available TiO₂ (Degussa P25 or Tronox) as starting material was studied. The influence of the type of the initial TiO₂, preparation conditions (temperature of the substrate during the film deposition, temperature of the post-deposition annealing), substrate material (glass, fused silica, stainless steel and graphite), the presence of additives in the spraying suspension (polyethylene glycol, ethylene glycol and acetylacetone) and its sonication before spraying on the morphology, size of crystallites and phase composition (rutile/anatase ratio) was studied. Optimal conditions for spray deposition of the films are suggested.     

Lead films produced by laser vapor deposition

The deposition of lead film on quartz substrates by photolysing tetraethyl lead vapor with a laser is reported. The dependence of the deposition rate on the pressure of tetraethyl lead, on the light intensity and on the pressure of the buffer gas is measured. Deposition phenomena at low light intensity are discussed.     

Femtosecond-excimer-laser patterning of YBa2Cu3O7 films

Projection patterning of Y-Ba-Cu-O films on (100) SrTiO₃ and (100) MgO substrates using femtosecond KrF-excimer-laser pulses is reported     

Effects of temperature and oxygen pressure on binary oxide growth using aperture-controlled combinatorial pulsed-laser deposition

In pulsed-laser deposition (PLD), there are many processing parameters that influence film properties such as substrate-target distance, background reactive gas pressure, laser energy, substrate temperature and composition in multi-component systems. By introducing a 12.7-mm diameter circular aperture in front of a 76.2-mm silicon wafer and rotating the substrate while changing conditions during the PLD process, these parameters may be studied in a combinatorial fashion, discretely as a function of processing conditions. We demonstrate the use of the aperture technique to systematically study the effects of oxygen partial pressure on the film stoichiometry and growth rate of VO_x, using Rutherford backscattering spectrometry (RBS). In another example, we discuss the effect of growth temperature on TiO₂ films characterized by X-ray diffraction and Fourier transform far-infrared (Terahertz) absorption spectroscopy. We demonstrate that we have considerable combinatorial control of other processing variables besides composition in our combi-PLD system. These may be used to systematically study film growth and properties.     

The mechanism of copper oxide segregations in Y-Ba-Cu-O/YSZ thin films

Experimental results show that copper-oxide segregation occurs by chemical reaction at the interface between Y-Ba-Cu-O thin films and ZrO₂ substrates, which results in a layer of BaZrO₃ (thickness 0.8 m). A buffer layer of silver inbetween the film and substrate as a barrier for the diffusion of Ba atoms into YSZ or the formation of silver-copper alloys during a high temperature annealing process prevents the copper oxide segregation. It is concluded that BaZrO₃ is a prospective candidate substrate for the fabrication of high-T _cthin films.This work was supported by the National Center for Research and Development on Superconductivity     

Dielectric and ferroelectric properties of pulsed-laser deposited BaTiO3 films

3 films were produced by KrF excimer-laser ablation. Films deposited on fused silica substrates were polycrystalline without preferential orientation and had cubic rather than tetragonal structure. BaTiO₃/Au/Ti/fused silica films showed a large dielectric constant, which increased with the thickness of the film, but poor ferroelectric properties. This behavior seems to be related to the small size of grains. On (100)MgO substrates oriented films were obtained. BaTiO₃/YBa₂Cu₃O_7-δ/(100)MgO films showed a large dielectric constant also and improved ferroelectric properties. Although this indicates a larger degree of tetragonality, the tetragonal structure of single crystal BaTiO₃ has not yet developed. Localized reduction and metallization of BaTiO₃/(100)MgO films by means of Ar⁺-laser radiation was demonstrated. This technique allows to produce conducting patterns in a single-s tep process. Received: 6 January 1997/Accepted: 21 April 1997     

Artificially nanostructured Cu:Al2O3 films produced by pulsed laser deposition

The processes leading to the formation of Cu:Al₂O₃ composite films on Si (001) with a well defined nanostructure by alternate pulsed laser deposition (a-PLD) in vacuum are investigated. Alternately amorphous Al₂O₃ layers and Cu nanocrystals nucleated on the Al₂O₃ surface are formed, according to the PLD sequence. The Al₂O₃ deposited on the Cu nanocrystals fills in the space between them until they are completely buried, and subsequently, a continuous dense layer with a very flat surface (within 1 nm) is developed. The nucleation process of the nanocrystals and their resulting oblate ellipsoidal shape are discussed in terms of the role of the energetic species involved in the PLD process and the metal–oxide interface energy. Received: 4 July 2000 / Accepted: 5 July 2000 / Published online: 13 September 2000     

Features of the film-growth conditions by cross-beam pulsed-laser deposition

Spatial and energetic characteristics of the plasma plume by cross-beam pulsed-laser deposition (CBPLD) were investigated. Effective droplets filtering together with high efficiency of material usage are observed by this approach. Time-of-flight (TOF) technique with electrostatic ion collectors (Langmuir probes operating in the ion-collecting mode) were applied to obtain kinetic energy distribution functions of ionized particles and to compare the ionization degrees of the plasma by the CBPLD and by the conventional PLD. The average and maximum kinetic energies of the ions by the CBPLD are found to be 2–3 times lower as compared to the conventional PLD. At the same time, the fraction of ionized species and highly exited neutrals (Rydberg atoms) in the CBPLD plasma is 1.5–2 times larger in comparison to the conventional approach. Re-sputtering of the material of the growing film by fast ions is a considerable effect in both the PLD methods by the chosen experimental conditions. The angular width of the directional pattern of the plasma plume by CBPLD is comparable to that typical for the conventional PLD. Received: 21 December 1998 / Accepted: 28 March 1999 / Published online: 7 July 1999     

C-axis oriented growth of magnetron sputtered YBaCuO thin films on MgO substrates

Highly textured YBaCuO thin films were sputtered on MgO (100)-oriented single crystal substrates at ambient temperature followed by an anneal in oxygen for 1 h at temperatures up to 920 °C. X-ray diffractograms of the highly textured films indicate an orientation of the c-axis of the YBaCuO lattice perpendicular to the substrate surface. There are strong indications that the oriented c-axis growth is due to a CuO self-flux effect. Auger measurements reveal a copper diffusion profile into the substrate down to a depth of more than 400 nm.     

Excimer laser photolysis of molybdenum hexacarbonyl with buffer gas

We have studied the photolysis of molybdenum hexacarbonyl by focused excimer laser radiation. It was found that electronically excited Mo atoms detected in the focus region of a KrF laser are due to a direct two photon absorption transition. The upper limit of the energy for complete dissociation of Mo(CO)₆ has been derived from these results. Two photon dissociation in the gas phase should be the dominant process at metal film deposition on substrates positioned perpendicularly and near to the focus. Adding buffer gases to the organometallic vapor particle formation was observed in the whole irradiated gas volume. The analysis of scattered He-Ne laser light yields information about the density and size of these particles. Some conclusions are drawn with respect to structured metal film deposition with high spatial selectivity.Dedicated to Prof. Dr. Herbert Welling on the occasion of his 60th birthday     

Preparation and characterization of Cu-Cu2O cermet films

Metal-insulator composites (cermets) find use in a wide range of applications. In this paper the preparation of cermet films by dc reactive magnetron sputtering is presented. These cermets have been characterised by measuring their electrical resistance and the properties have been correlated to the microstructure and composition. Magnetron sputtering is found to be very effective in controlling the composition of the deposited films, enabling the preparation of films with tailored properties.     

Structural, electrical, and surface characteristics of La0.5Sr0.5CoO3 thin films prepared by pulsed-laser deposition

A parametric study of the growth of La_0.5Sr_0.5CoO₃ (LSCO) thin films on (100) MgO substrates by pulsed-laser deposition (PLD) is reported. Films are grown under a wide range of substrate temperature (450–800 °C), oxygen pressure (0.1–0.9 mbar), and incident laser fluence (0.8–2.6 J/cm²). The optimum ranges of temperature, oxygen pressure, and laser fluence to produce c-axis oriented films with smooth surface morphology and high metallic conductivity are identified. Films deposited at low temperature (500 °C) and post-annealed in situ at higher temperatures (600–800 °C) are also investigated with respect to their structure, surface morphology, and electrical conductivity. Received: 20 November 1998 / Accepted: 6 July 1999 / Published online: 21 October 1999     

Al2O3 thin films by plasma-enhanced chemical vapour deposition using trimethyl-amine alane (TMAA) as the Al precursor

2 O₃ thin films by plasma-enhanced chemical vapour deposition (PECVD) using trimethyl-amine alane (TMAA) as the Al precursor. The thin films were deposited on both Si and quartz silica (SiO₂) substrates. Deposition rates were typically 60 Å min^-1 keeping the TMAA temperature constant at 45 °C. The deposited Al₂O₃ thin films were stoichiometric alumina with low carbon contamination (0.7–1.3 At%). The refractive index ranged from 1.54 to 1.62 depending on the deposition conditions. The deposition rate was studied as a function of both the RF power and the substrate temperature. The structure and the surface of the deposited Al₂O₃ thin films were studied using X-ray diffraction, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Received: 20 May 1997/Accepted: 12 June 1997