Optical properties of zirconium oxynitride films: the effect of composition, electronic and crystalline structures

tThis work is devoted to the investigation of zirconium oxynitride (ZrOxNy) films with varied opticalresponses prompted by the variations in their compositional and structural properties. The films wereprepared by dc reactive magnetron sputtering of Zr, using Ar and a reactive gas mixture of N2+ O2(17:3).The colour of the films changed from metallic-like, very bright yellow-pale and golden yellow, for low gasflows to red-brownish for intermediate gas flows. Associated to this colour change there was a significantdecrease of brightness. With further increase of the reactive gas flow, the colour of the samples changedfrom red-brownish to dark blue or even to interference colourations. The variations in composition dis-closed the existence of four different zones, which were found to be closely related with the variationsin the crystalline structure. XRD analysis revealed the change from a B1 NaCl face-centred cubic zirco-nium nitride-type phase for films prepared with low reactive gas flows, towards a poorly crystallizedover-stoichiometric nitride phase, which may be similar to that of Zr3N4with some probable oxygeninclusions within nitrogen positions, for films prepared with intermediate reactive gas flows. For highreactive gas flows, the films developed an oxynitride-type phase, similar to that of -Zr2ON2with someoxygen atoms occupying some of the nitrogen positions, evolving to a ZrO2monoclinic type structurewithin the zone where films were prepared with relatively high reactive gas flows. The analysis carriedout by reflected electron energy loss spectroscopy (REELS) revealed a continuous depopulation of thed-band and an opening of an energy gap between the valence band (2p) and the Fermi level close to 5 eV.The ZrN-based coatings (zone I and II) presented intrinsic colourations, with a decrease in brightness anda colour change from bright yellow to golden yellow, red brownish and dark blue. Associated to thesechanges, there was also a shift of the reflectivity minimum to lower energies, with the increase of thenon-metallic content. The samples lying in the two last zones (zone III, oxynitride and zone IV, oxide films)revealed a typical semi-transparent-optical behaviour showing interference-like colourations only dueto the complete depopulation of the d band at the Fermi level. The samples lying in these zones presentedalso an increase of the optical bandgap from 2 to 3.6 eV.

Microstructural evolution of Au/TiO2 nanocomposite films: The influence of Au concentration and thermal annealing

Nanocomposite thin films consisting of a dielectric matrix, such as titanium oxide (TiO2), with embedded gold (Au) nanoparticles were prepared and will be analysed and discussed in detail in the present work. The evolution of morphological and structural features was studied for a wide range of Au concentrations and for annealing treatments in air, for temperatures ranging from 200 to 800 °C. Major findings revealed that for low Au atomic concentrations (at.%), there are only traces of clustering, and just for relatively high annealing temperatures, T ≥ 500 °C. Furthermore, the number of Au nanoparticles is extremely low, even for the highest annealing temperature, T = 800 °C. It is noteworthy that the TiO2 matrix also crystallizes in the anatase phase for annealing temperatures above 300 °C. For intermediate Au contents (5 at.% ≤ CAu ≤ 15 at.%), the formation of gold nanoclusters was much more evident, beginning at lower annealing temperatures (T ≥ 200 °C) with sizes ranging from 2 to 25 nm as the temperature increased. A change in the matrix crystallization from anatase to rutile was also observed in this intermediate range of compositions. For the highest Au concentrations (> 20 at.%), the films tended to form relatively larger clusters, with sizes above 20 nm (for T ≥ 400 °C). It is demonstrated that the structural and morphological characteristics of the films are strongly affected by the annealing temperature, as well as by the particular amounts, size and distribution of the Au nanoparticles dispersed in the TiO2 matrix.

Multifunctional Ti–Me (Me=Al, Cu) thin film systems for biomedical sensing devices

Ti-Me binary intermetallic thin films based on a titanium matrix doped with increasing amounts of Me (Me = Al, Cu) were prepared by magnetron sputtering (under similar conditions), aiming their application in biomedical sensing devices. The differences observed on the composition and on the micro(structural) features of the films, attributed to changes in the discharge characteristics, were correlated with the electrical properties of the intermetallic systems (Ti-Al and Ti-Cu). For the same Me exposed areas placed on the Ti target (ranging from 0.25 cm2 to 20 cm2) the Cu content increased from 3.5 at.% to 71.7 at.% in the Ti-Cu system and the Al content, in Ti-Al films, ranged from 11 to 45 at.%. The structural characterization evidenced the formation of metastable Ti-Me intermetallic phases for Al/Ti atomic ratios above 0.20 and for Cu/Ti ratios above 0.25. For lower Me concentrations, the effect of the α-Ti(Me) structure domains the overall structure. With the increase amount of the Me into Ti structure a clear trend for amorphization was observed. For both systems it was observed a significant decrease of the electrical resistivity with increasing Me/Ti atomic ratios (higher than 0.5 for Al/Ti atomic ratio and higher than 1.3 for Cu/Ti atomic ratio). Although similar trends were observed in the resistivity evolution for both systems, the Ti-Cu films presented lower resistivity values in comparison to Ti-Al system.

Flexible thin-film lithium battery

Tese de Doutoramento Programa Doutoral em Engenharia Electrónica e Computadores.

Microstructure and secondary phases in coevaporated CuInS2 films: Dependence on growth temperature and chemical composition

The microstructure of CuInS2-(CIS2) polycrystalline films deposited onto Mo-coated glass has been analyzed by Raman scattering, Auger electron spectroscopy (AES), transmission electron microscopy, and x-ray diffraction techniques. Samples were obtained by a coevaporation procedure that allows different Cu-to-In composition ratios (from Cu-rich to Cu-poor films). Films were grown at different temperatures between 370 and 520-°C. The combination of micro-Raman and AES techniques onto Ar+-sputtered samples has allowed us to identify the main secondary phases from Cu-poor films such as CuIn5S8 (at the central region of the layer) and MoS2 (at the CIS2/Mo interface). For Cu-rich films, secondary phases are CuS at the surface of as-grown layers and MoS2 at the CIS2/Mo interface. The lower intensity of the MoS2 modes from the Raman spectra measured at these samples suggests excess Cu to inhibit MoS2 interface formation. Decreasing the temperature of deposition to 420-°C leads to an inhibition in observing these secondary phases. This inhibition is also accompanied by a significant broadening and blueshift of the main A1 Raman mode from CIS2, as well as by an increase in the contribution of an additional mode at about 305 cm-1. The experimental data suggest that these effects are related to a decrease in structural quality of the CIS2 films obtained under low-temperature deposition conditions, which are likely connected to the inhibition in the measured spectra of secondary-phase vibrational modes.

Properties of nitrogen doped silicon films deposited by low-pressure chemical vapor deposition from silane and ammonia

Nitrogen doped silicon (NIDOS) films have been deposited by low-pressure chemical vapor deposition from silane SiH4 and ammonia NH3 at high temperature (750°C) and the influences of the NH3/SiH4 gas ratio on the films deposition rate, refractive index, stoichiometry, microstructure, electrical conductivity, and thermomechanical stress are studied. The chemical species derived from silylene SiH2 into the gaseous phase are shown to be responsible for the deposition of NIDOS and/or (silicon rich) silicon nitride. The competition between these two deposition phenomena leads finally to very high deposition rates (100 nm/min) for low NH3/SiH4 gas ratio (R¿0.1). Moreover, complex variations of NIDOS film properties are evidenced and related to the dual behavior of the nitrogen atom into silicon, either n-type substitutional impurity or insulative intersticial impurity, according to the Si¿N atomic bound. Finally, the use of NIDOS deposition for the realization of microelectromechanical systems is investigated.

Gas-sensing properties of sprayed films of (CdO)x(ZnO)1-x mixed oxide

A novel NO2 sensor based on (CdO)x(ZnO)1-x mixed-oxide thin films deposited by the spray pyrolysis technique is developed. The sensor response to 3-ppm NO2 is studied in the range 50°C-350°C for three different film compositions. The device is also tested for other harmful gases, such as CO (300 ppm) and CH4 (3000 ppm). The sensor response to these reducing gases is different at different temperatures varying from the response typical for the p-type semiconductor to that typical for the n-type semiconductor. Satisfactory response to NO2 and dynamic behavior at 230°C, as well as low resistivity, are observed for the mixed-oxide film with 30% Cd. The response to interfering gas is poor at working temperature (230°C). On the basis of this study, a possible sensing mechanism is proposed.

Coverage effects on the magnetism of Fe/MgO(001) ultrathin films

Different aspects of the structure-magnetism and morphology-magnetism correlation in the ultrathin limit are studied in epitaxial Fe films grown on MgO(001). In the initial stages of growth the presence of substrate steps, intrinsically higher than an Fe atomic layer, prevent the connection between Fe islands and hence the formation of large volume magnetic regions. This is proposed as an explanation to the superparamagnetic nature of ultrathin Fe films grown on MgO in addition to the usually considered islanded, or Vollmer-Weber, growth. Using this model, we explain the observed transition from superparamagnetism to ferromagnetism for Fe coverages above 3 monolayers (ML). However, even though ferromagnetism and magnetocrystalline anisotropy are observed for 4 ML, complete coverage of the MgO substrate by the Fe ultrathin films only occurs around 6 ML as determined by polar Kerr spectra and simulations that consider different coverage situations. In annealed 3.5 ML Fe films, shape or configurational anisotropy dominates the intrinsic magnetocrystalline anisotropy, due to an annealing induced continuous to islanded morphological transition. A small interface anisotropy in thicker films is observed, probably due to dislocations observed at the Fe¿MgO(001) interface.

Composition and growth mode of MoSx sputtered films

MoS(x) lubricating thin films were deposited by nonreactive, reactive, and low energy ion-assisted radio-frequency (rf) magnetron sputtering from a MoS2 target. Depending on the total and reactive gas pressures, the film composition ranges between MoS0.7 and MoS2.8. A low working pressure was found to have effects similar to those of low-energy ion irradiation. Films deposited at high pressure have (002) planes preferentially perpendicular to the substrate, whereas films deposited at low pressure or under low-energy ion irradiation have (002) mainly parallel to it. Parallel films are sulfur deficient (MoS1.2-1.4). Their growth is explained in terms of an increased reactivity of the basal surfaces, itself a consequence of the creation of surface defects due to ion irradiation. The films exhibit a lubricating character for all compositions above MoS1.2. The longest lifetime in ball-on-disk wear test was found for MoS1.5.

Three-dimensional aspects of fluid flows in channels. II. Effects of meniscus and thin film regimes on viscous fingers

We perform a three-dimensional study of steady state viscous fingers that develop in linear channels. By means of a three-dimensional lattice-Boltzmann scheme that mimics the full macroscopic equations of motion of the fluid momentum and order parameter, we study the effect of the thickness of the channel in two cases. First, for total displacement of the fluids in the channel thickness direction, we find that the steady state finger is effectively two-dimensional and that previous two-dimensional results can be recovered by taking into account the effect of a curved meniscus across the channel thickness as a contribution to surface stresses. Second, when a thin film develops in the channel thickness direction, the finger narrows with increasing channel aspect ratio in agreement with experimental results. The effect of the thin film renders the problem three-dimensional and results deviate from the two-dimensional prediction.

Three-dimensional aspects of fluid flows in channels. I. Meniscus and thin film regimes

We study the forced displacement of a fluid-fluid interface in a three-dimensional channel formed by two parallel solid plates. Using a lattice-Boltzmann method, we study situations in which a slip velocity arises from diffusion effects near the contact line. The difference between the slip and channel velocities determines whether the interface advances as a meniscus or a thin film of fluid is left adhered to the plates. We find that this effect is controlled by the capillary and Péclet numbers. We estimate the crossover from a meniscus to a thin film and find good agreement with numerical results. The penetration regime is examined in the steady state. We find that the occupation fraction of the advancing finger relative to the channel thickness is controlled by the capillary number and the viscosity contrast between the fluids. For high viscosity contrast, lattice-Boltzmann results agree with previous results. For zero viscosity contrast, we observe remarkably narrow fingers. The shape of the finger is found to be universal.

Enhanced electron-electron correlations in nanometric epitaxial SrRuO3 epitaxial films

Epitaxial and fully strained SrRuO3 thin films have been grown on SrTiO3(100). At initial stages the growth mode is three-dimensional- (3D-)like, leading to a finger-shaped structure aligned with the substrate steps and that eventually evolves into a 2D step-flow growth. We study the impact that the defect structure associated with this unique growth mode transition has on the electronic properties of the films. Detailed analysis of the transport properties of nanometric films reveals that microstructural disorder promotes a shortening of the carrier mean free path. Remarkably enough, at low temperatures, this results in a reinforcement of quantum corrections to the conductivity as predicted by recent models of disordered, strongly correlated electronic systems. This finding may provide a simple explanation for the commonly observed¿in conducting oxides-resistivity minima at low temperature. Simultaneously, the ferromagnetic transition occurring at about 140 K, becomes broader as film thickness decreases down to nanometric range. The relevance of these results for the understanding of the electronic properties of disordered electronic systems and for the technological applications of SrRuO3¿and other ferromagnetic and metallic oxides¿is stressed.

Low temperature amorphous and nanocrystalline silicon thin film transistors deposited by Hot-Wire CVD on glass substrate

Amorphous and nanocrystalline silicon films obtained by Hot-Wire Chemical Vapor Deposition have been incorporated as active layers in n-type coplanar top gate thin film transistors deposited on glass substrates covered with SiO 2. Amorphous silicon devices exhibited mobility values of 1.3 cm 2 V - 1 s - 1, which are very high taking into account the amorphous nature of the material. Nanocrystalline transistors presented mobility values as high as 11.5 cm 2 V - 1 s - 1 and resulted in low threshold voltage shift (∼ 0.5 V).

Substrate influence on the properties of doped thin silicon layers grown by Cat-CVD

We present structural and electrical properties for p- and n-type layers grown close to the transition between a-Si:H and nc-Si:H onto different substrates: Corning 1737 glass, ZnO:Al-coated glass and stainless steel. Structural properties were observed to depend on the substrate properties for samples grown under the same deposition conditions. Different behaviour was observed for n- and p-type material. Stainless steel seemed to enhance crystallinity when dealing with n-type layers, whereas an increased crystalline fraction was obtained on glass for p-type samples. Electrical conduction in the direction perpendicular to the substrate seemed to be mainly determined by the interfaces or by the existence of an amorphous incubation layer that might determine the electrical behaviour. In the direction perpendicular to the substrate, n-type layers exhibited a lower resistance value than p-type ones, showing better contact properties between the layer and the substrate.

Optimisation of doped microcrystalline silicon films deposited at very low temperatures by Hot-Wire CVD

In this paper we present new results on doped μc-Si:H thin films deposited by hot-wire chemical vapour deposition (HWCVD) in the very low temperature range (125-275°C). The doped layers were obtained by the addition of diborane or phosphine in the gas phase during deposition. The incorporation of boron and phosphorus in the films and their influence on the crystalline fraction are studied by secondary ion mass spectrometry and Raman spectroscopy, respectively. Good electrical transport properties were obtained in this deposition regime, with best dark conductivities of 2.6 and 9.8 S cm -1 for the p- and n-doped films, respectively. The effect of the hydrogen dilution and the layer thickness on the electrical properties are also studied. Some technological conclusions referred to cross contamination could be deduced from the nominally undoped samples obtained in the same chamber after p- and n-type heavily doped layers.