Dynamique de croissance par plasma RF magnétron des couches minces à base d’oxyde de zinc

Le but de cette thèse était d’étudier la dynamique de croissance par pulvérisation par plasma RF magnétron des couches minces à base d’oxyde de zinc destinées à des applications électroniques, optoélectroniques et photoniques de pointe. Dans ce contexte, nous avons mis au point plusieurs diagnostics permettant de caractériser les espèces neutres et chargées dans ce type de plasmas, notamment la sonde électrostatique, la spectroscopie optique d’émission et d’absorption, ainsi que la spectrométrie de masse. Par la suite, nous avons tenté de corréler certaines caractéristiques physiques de croissance des couches de ZnO, en particulier la vitesse de dépôt, aux propriétés fondamentales du plasma. Nos résultats ont montré que l’éjection d’atomes de Zn, In et O au cours de la pulvérisation RF magnétron de cibles de Zn, ZnO et In2O3 n’influence que très peu la densité d’ions positifs (et donc la densité d’électrons en supposant la quasi-neutralité) ainsi que la fonction de distribution en énergie des électrons (populations de basse et haute énergie). Cependant, le rapport entre la densité d’atomes d’argon métastables (3P2) sur la densité électronique décroît lorsque la densité d’atomes de Zn augmente, un effet pouvant être attribué à l’ionisation des atomes de Zn par effet Penning. De plus, dans les conditions opératoires étudiées (plasmas de basse pression, < 100 mTorr), la thermalisation des atomes pulvérisés par collisions avec les atomes en phase gazeuse demeure incomplète. Nous avons montré que l’une des conséquences de ce résultat est la présence d’ions Zn+ suprathermiques près du substrat. Finalement, nous avons corrélé la quantité d’atomes de Zn pulvérisés déterminée par spectroscopie d’émission avec la vitesse de dépôt d’une couche mince de ZnO mesurée par ellipsométrie spectroscopique. Ces travaux ont permis de mettre en évidence que ce sont majoritairement les atomes de Zn (et non les espèces excitées et/ou ioniques) qui gouvernent la dynamique de croissance par pulvérisation RF magnétron des couches minces de ZnO.

Growth and Characterisation of Radio Frequency Magnetron Sputttered Indium Tin Oxide Thin Films

The increasing interest in the interaction of light with electricity and electronically active materials made the materials and techniques for producing semitransparent electrically conducting films particularly attractive. Transparent conductors have found major applications in a number of electronic and optoelectronic devices including resistors, transparent heating elements, antistatic and electromagnetic shield coatings, transparent electrode for solar cells, antireflection coatings, heat reflecting mirrors in glass windows and many other. Tin doped indium oxide (indium tin oxide or ITO) is one of the most commonly used transparent conducting oxides. At present and likely well into the future this material offers best available performance in terms of conductivity and transmittivity combined with excellent environmental stability, reproducibility and good surface morphology. Although partial transparency, with a reduction in conductivity, can be obtained for very thin metallic films, high transparency and simultaneously high conductivity cannot be attained in intrinsic stoichiometric materials. The only way this can be achieved is by creating electron degeneracy in a wide bandgap (Eg > 3eV or more for visible radiation) material by controllably introducing non-stoichiometry and/or appropriate dopants. These conditions can be conveniently met for ITO as well as a number of other materials like Zinc oxide, Cadmium oxide etc. ITO shows interesting and technologically important combination of properties viz high luminous transmittance, high IR reflectance, good electrical conductivity, excellent substrate adherence and chemical inertness. ITO is a key part of solar cells, window coatings, energy efficient buildings, and flat panel displays. In solar cells, ITO can be the transparent, conducting top layer that lets light into the cell to shine the junction and lets electricity flow out. Improving the ITO layer can help improve the solar cell efficiency. A transparent ii conducting oxide is a material with high transparency in a derived part of the spectrum and high electrical conductivity. Beyond these key properties of transparent conducting oxides (TCOs), ITO has a number of other key characteristics. The structure of ITO can be amorphous, crystalline, or mixed, depending on the deposition temperature and atmosphere. The electro-optical properties are a function of the crystallinity of the material. In general, ITO deposited at room temperature is amorphous, and ITO deposited at higher temperatures is crystalline. Depositing at high temperatures is more expensive than at room temperature, and this method may not be compatible with the underlying devices. The main objective of this thesis work is to optimise the growth conditions of Indium tin oxide thin films at low processing temperatures. The films are prepared by radio frequency magnetron sputtering under various deposition conditions. The films are also deposited on to flexible substrates by employing bias sputtering technique. The films thus grown were characterised using different tools. A powder x-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive x-ray analysis (EDX) and scanning electron microscopy (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UVVIS- NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using vander Pauw four probe technique. The plasma generated during the sputtering of the ITO target was analysed using Langmuir probe and optical emission spectral studies.

Growth of zinc oxide thin films for optoelectronic application by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on quartz, silicon, and polymer substrates by pulsed laser deposition (PLD) technique at different oxygen partial pressures (0.007 mbar to 0.003 mbar). Polycrystalline ZnO films were obtained at room temperature when the oxygen pressure was between 0.003 mbar and .007 mbar, above and below this pressure the films were amorphous as indicated by the X-ray diffraction (XRD). ZnO films were deposited on Al2O3 (0001) at different substrate temperatures varying from 400oC to 600oC and full width half maximum (FWHM) of XRD peak is observed to decrease as substrate temperature increases. The optical band gaps of these films were nearly 3.3 eV. A cylindrical Langmuir probe is used for the investigation of plasma plume arising from the ZnO target. The spatial and temporal variations in electron density and electron temperature are studied. Optical emission spectroscopy is used to identify the different ionic species in the plume. Strong emission lines of neutral Zn, Zn+ and neutral oxygen are observed. No electronically excited O+ cations are identified, which is in agreement with previous studies of ZnO plasma plume.

Spectral Characterization of Laser Induced Plasma from Titanium Dioxide

Optical emission from TiO2 plasma, generated by a nanosecond laser is spectroscopically analysed. The main chemical species are identified and the spatio-temporal distribution of the plasma parameters such as electron temperature and density are characterized based on the study of spectral distribution of the line intensities and their broadening characteristics. The parameters of laser induced plasma vary quickly owing to its expansion at low background pressure and the possible deviations from local thermodynamic equilibrium conditions are tested to show its validity.

Spectral Characterization of Laser Induced Plasma from Titanium Dioxide

Optical emission from TiO2 plasma, generated by a nanosecond laser is spectroscopically analysed. The main chemical species are identified and the spatio-temporal distribution of the plasma parameters such as electron temperature and density are characterized based on the study of spectral distribution of the line intensities and their broadening characteristics. The parameters of laser induced plasma vary quickly owing to its expansion at low background pressure and the possible deviations from local thermodynamic equilibrium conditions are tested to show its validity.

Spectral Characterization of Laser Induced Plasma from Titanium Dioxide

Optical emission from TiO2 plasma, generated by a nanosecond laser is spectroscopically analysed. The main chemical species are identified and the spatio-temporal distribution of the plasma parameters such as electron temperature and density are characterized based on the study of spectral distribution of the line intensities and their broadening characteristics. The parameters of laser induced plasma vary quickly owing to its expansion at low background pressure and the possible deviations from local thermodynamic equilibrium conditions are tested to show its validity

Spectral Characterization of Laser Induced Plasma from Titanium Dioxide

Optical emission from TiO2 plasma, generated by a nanosecond laser is spectroscopically analysed. The main chemical species are identified and the spatio-temporal distribution of the plasma parameters such as electron temperature and density are characterized based on the study of spectral distribution of the line intensities and their broadening characteristics. The parameters of laser induced plasma vary quickly owing to its expansion at low background pressure and the possible deviations from local thermodynamic equilibrium conditions are tested to show its validity.

Fine structure in the time of flight distribution of C2 in laser produced plasma from graphite

Time resolved optical emission spectroscopy is employed to study the expansion dynamics of C2 species in a graphite plasma produced during the Nd : YAG ablation. At low laser fluences a single peak distribution with low kinetic energy is observed. At higher fluences a twin peak distribution is found. It has been noted that these double peak time of flight distribution splits into a triple peak structure at distances >_ 17mm from the target surface. The reason for the occurrence of multiple peak is due to different formation mechanisms of C2 species

The ecological impact of conquest and colonization on a medieval frontier landscape: combined palynological and geochemical analysis of lake sediments from Radzyń Chełminski, northern Poland

Slavic and German colonization of the southern Baltic between the 8th and 15th centuries A.D. is well-documented archaeologically and historically. Despite the large number of pollen profiles from Poland, few palaeoecological studies have examined the ecological impact of a process that was central to the expansion of European, Christian, societies. This study aims to redress this balance through multiproxy analysis of lake sediments from Radzyń Chełminski, Northern Poland, using pollen, element geochemistry (Inductively Coupled-Optical Emission Spectroscopy [ICP-OES]), organic content, and magnetic susceptibility. The close association between lake and medieval settlements presents the ideal opportunity to reconstruct past vegetation and land-use dynamics within a well-documented archaeological, historical, and cultural context. Three broad phases of increasing landscape impact are visible in the pollen and geochemical data dating from the 8th/9th, 10th/11th, and 13th centuries, reflecting successive phases of Slavic and German colonization. This involved the progressive clearance of oak-hornbeam dominated woodland and the development of an increasingly open agricultural landscape. Although the castles and towns of the Teutonic Order remain the most visible signs of medieval colonization, the palynological and geochemical data demonstrate that the major phase of woodland impact occurred during the preceding phase of Slavic expansion; Germans colonists were entering a landscape already significantly altered.

Biomineralisation by earthworms: an investigation into the stability and distribution of amorphous calcium carbonate

Background Many biominerals form from amorphous calcium carbonate (ACC), but this phase is highly unstable when synthesised in its pure form inorganically. Several species of earthworm secrete calcium carbonate granules which contain highly stable ACC. We analysed the milky fluid from which granules form and solid granules for amino acid (by liquid chromatography) and functional group (by Fourier transform infrared (FTIR) spectroscopy) compositions. Granule elemental composition was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES) and electron microprobe analysis (EMPA). Mass of ACC present in solid granules was quantified using FTIR and compared to granule elemental and amino acid compositions. Bulk analysis of granules was of powdered bulk material. Spatially resolved analysis was of thin sections of granules using synchrotron-based μ-FTIR and EMPA electron microprobe analysis. Results The milky fluid from which granules form is amino acid-rich (≤ 136 ± 3 nmol mg−1 (n = 3; ± std dev) per individual amino acid); the CaCO3 phase present is ACC. Even four years after production, granules contain ACC. No correlation exists between mass of ACC present and granule elemental composition. Granule amino acid concentrations correlate well with ACC content (r ≥ 0.7, p ≤ 0.05) consistent with a role for amino acids (or the proteins they make up) in ACC stabilisation. Intra-granule variation in ACC (RSD = 16%) and amino acid concentration (RSD = 22–35%) was high for granules produced by the same earthworm. Maps of ACC distribution produced using synchrotron-based μ-FTIR mapping of granule thin sections and the relative intensity of the ν2: ν4 peak ratio, cluster analysis and component regression using ACC and calcite standards showed similar spatial distributions of likely ACC-rich and calcite-rich areas. We could not identify organic peaks in the μ-FTIR spectra and thus could not determine whether ACC-rich domains also had relatively high amino acid concentrations. No correlation exists between ACC distribution and elemental concentrations determined by EMPA. Conclusions ACC present in earthworm CaCO3 granules is highly stable. Our results suggest a role for amino acids (or proteins) in this stability. We see no evidence for stabilisation of ACC by incorporation of inorganic components.

The influence of albumin on the anodic dissolution of chromium present in UNSS31254 stainless steel in chloride environment

The influence of bovine serum albumin (BSA) on the anodic dissolution of chromium present in UNS S31254 stainless steel (SS) in 0.15 mol L-1 NaCl at 37.0 +/- 0.5 degrees C has been studied, using anodic potentiostatic polarization curves and optical emission spectroscopy. Electrochemical results have shown that BSA has little effect on the transpassivation potential (E-T) and on the passivation current density values. However on the passivation range, BSA diminishes the intensity of the anodic wave seen at about E=750mV versus SCE attributed to Cr(III)/Cr(VI) oxidation. Optical emission spectroscopy results have shown that BSA prevents the anodic dissolution of chromium to occur and minimizes iron dissolution above the transpassivation potential (E=1160 mV versus SCE). (C) 2007 Elsevier B.V. All rights reserved.

The role of HBF(4) in electro-catalysis: Arsenic contamination and anion adsorption

We present in this work a comprehensive investigation of the role played by dissolved tetrafluoroboric acid on the electrochemical response of a polycrystalline platinum electrode in acidic media. HBF(4) from two different suppliers was employed and characterized in terms of the amount of arsenic contamination by Inductively Coupled Plasma-Optical Emission Spectroscopy. The effect of different amounts of HBF(4) on the voltammetric profile of the Pt vertical bar HClO(4)(aq) interface was investigated by means of electrochemical quartz crystal nanobalance (EQCN). Despite the comparable cyclic voltammograms, the presence of arsenic in one of the two HBF(4) used resulted in dramatic variations in the mass change profile, which evidences the deposition/dissolution of arsenic prior to the surface oxidation. For the arsenic-free HBF(4), its effect on the mass change profile was mainly associated to anion adsorption. The impact of dissolved HBF(4) on the electro-oxidation of formic acid was rationalized in terms of two contributions: current enhancement at low potentials due to the arsenic-assisted formic acid electro-oxidation and inhibition at high potentials due to anion adsorption. (C) 2011 Elsevier B.V. All rights reserved.

Análise por meio de espectroscopia de emissão óptica das espécies ativas em nitretação iônica e gaiola catódica

Plasma process like ionic nitriding and cathodic cage plasma nitriding are utilized in order to become hard surface of steels. The ionic nitriding is already accepted in the industry while cathodic cage plasma nitriding process is in industrial implementation stage. Those process depend of plasma parameters like electronic and ionic temperature (Te, Ti), species density (ne, ni) and of distribution function of these species. In the present work, the plasma used to those two processes has been observed through Optical Emission Spectroscopy OES technique in order to identify presents species in the treatment ambient and relatively quantify them. So plasma of typical mixtures like N2 H2 has been monitored through in order to study evolution of those species during the process. Moreover, it has been realized a systematic study about leaks, also thought OES, that accomplish the evolution of contaminant species arising because there is flux of atmosphere to inside nitriding chamber and in what conditions the species are sufficiently reduced. Finally, to describe the physic mechanism that acts on both coating techniques ionic nitriding and cathodic cage plasma nitriding

Modificação de membranas de quitosana por plasma para uso biológico

Chitosan membranes have been modified by plasma, utilizing the following gases: nitrogen (N2), methane (CH4), argon (Ar), oxygen (O2) and hydrogen. The modified membranes by plasma were compared to the unmodified ones. The membranes were characterized by absorption assay, contact angle, atomic force microscopy (AFM). Also, permeability assay of sodium sulfamerazine from such membranes were carried out. Through the absorption assay and contact angle it was possible to obtain information of the wettability of the membranes and what changes the plasma treatment can promote in relation to it. The plasma treatment using oxygen promoted increase of the wetability and swelling while the samples treated with methane decrease of the wetability and swelling. Through the Optical Emission Spectroscopy (OES) it was possible to identify which species were present in the plasma during the treatment. And through the AFM analysis it was possible to observe the changes nanotopography occurred on the surface of the samples. Permeability assay were archived for all treated membranes and compared to no treated ones. Due to that assay it was possible verify which the plasma treatment increased the permeability spectrum of the membranes which has varied from 1,4548 *10-5cm2.min-1 to 2,7713*10-5cm2.min-1. Chitosan membranes with permeability varied are importance in systems drug delivery, to liberate a wide variety of drugs

Tratamento termoquímico do titânio auxiliado por plasma de ar - N2 - O2

Discs were grade II cp Ti oxynitride by plasma of Ar - N2 - O2 using different proportions of individual gases. These ratios were established from analysis of optical emission spectroscopy (OES) of plasma species. The proportions that resulted in species whose spectra showed an abrupt change of light intensity were chosen for this study. Nanohardness tests revealed that there was a correlation between the intensity of N2 + species with the hardness, because the treatments where they had a higher intensity, obtained a higher value nanohardness, although the crystalline phases have remained unchanged. With respect to topography, it was observed that in general, the surface roughness is related to the intensities of plasma species, because they may have different values depending on the behavior of the species. Images obtained by optical microscopy revealed a surface with grains of different colors to optical reflectance showed a peak of reflection in the red area. Measures the contact angle and surface tension showed hydrophilic properties and hydrophilic with little variation of polar and dispersive components of surface tension