Kesterite Cu2ZnSnS4 (CZTS) is interesting as a sustainable photovoltaic technology due to its earth-abundant elements and suitable semiconducting properties. To date, a record efficiency of 12.6% has been achieved but further improvements are required to reach high efficiency for industrial implementation. Among the limiting issues is the understanding of the annealing process, which is crucial in promoting high material quality. In particular, the knowledge of the effects of segregated secondary compounds on solar cell performance is lacking. In contrast to formation of ZnS particles throughout CZTS film, it is notable that SnS forms and usually segregates on the CZTS top and rear surfaces. The influence of SnS on CZTS solar cells was studied by electron beam induced current measurements. It is found that SnS presence on the CZTS surfacecan introduce “dead area”, whereas it seems beneficial for solar cell current when accumulates on the CZTS rear. For SnS passivation and from investigation of the passivation effect from an Al2O3 thin layer at the CZTS rear, improvement in overall device performance could not be demonstrated, due to either poor CZTS bulk or non-optimal device structure. The limitation in CZTS bulk quality was shown from a thickness study where carrier collection saturated already about 700-1000 nm CZTS thickness. Formation of SnS alongside CZTS implies the anneal is limited by a deficient sulfur partial pressure (PS2). By looking into Sn-S phase transformations in SnS2 films after annealing, we find that PS2 drops rapidly over the annealing time, which could be well-correlated to a series of changes in CZTS material quality including secondary phase formations and defect modifications. It is shown that annealing CZTS under sufficiently high PS2 is critical for CZTS solar cells with high open circuit voltage (upto 783mV was reached), possibly due to the defect modification. Besides SnS, it is observed that NaxS compounds are also readily formed on CZTS surfaces, due to Na diffusion from the glass substrate during annealing. NaxS negatively affects the formation of the CdS/CZTS interface during chemical bath deposition. It can be removed by an oxidation process or wet chemical etching.

Ferroelectric materials have been extensively studied theoretically and experimentally for many decades. Their ferroelectric, piezoelectric, pyroelectric, dielectric and electro-optical properties offer great promise in various applications such as non-volatile random access memory devices, non linear optics, motion and thermal sensors, and tunable microwave devices. Advanced applications for high dielectric constant insulators and nonvolatile memories in semiconductor industry have led to a meteoric rise of interest in the ferroelectrics recently. As most studied and technically important ferroelectric materials, lead zirconate titanate (PZT) and barium strontium titanate (BST) are widely investigated to understand their properties for potential device applications. Using radio frequency magnetron sputtering, single crystalline PZT and BST thin films have been achieved on SrTiO3 substrates, and been characterized for their structural and electrical properties. Eyeing their different potential applications, ferroelectric, pyroelectric and dielectric properties of PZT and BST thin films were studied. In addition, the introduction of bridge layers (nucleation or buffer layers) grown by molecular beam epitaxy (MBE) has been employed to facilitate the heterostructure growth of PZT thin films on GaN and BST thin films on sapphire substrates. Highly (111)-oriented perovskite PZT thin films were achieved on silicon-doped GaN (0001)/c-sapphire with a PbTiO3/PbO oxide bridge layer. And (001)-oriented BST thin films were grown on a-plane sapphire with an MgO/ZnO bridge layer. This dissertation also discusses the realization of PZT ferroelectric field effect transistors (FeFET). Two different 1T FeFET structures were successfully fabricated and their electrical properties were examined. Ferroelectric behavior was observed in the plot of source-drain current versus gate voltage where it exhibited a large counterclockwise hysteresis with 50% current modulation.

Owing to the large electric-field-dependent permittivity, ferroelectric thin films have attracted a great deal of attention on applications in miniature tunable microwave components with high performance and cost reduction, such as phase shifters, tunable oscillators, delay lines, and antennas. These tunable devices require large change in the dielectric constant with applied field and a low loss at microwave frequencies. As one of the promising ferroelectric materials, barium strontium titanate thin film, especially Ba0.5Sr0.5TiO3 (BST) films, have raises great research interests due to its high dielectric constant, which is tunable in an external electric field, combined with relative low loss at microwave frequencies. Tunable microwave components, such as phase shifter, based on the BST films have been widely investigated. Since the polarization, the significant characterization of ferroelectrics, is very sensitive to distortion in crystal structure of ferroelectrics, strain can be effectively utilized to tailor the dielectric properties of BST films. Due to the lattice-mismatch from the substrate and various deposition conditions, epitaxial BST thin film usually contains residual strain generated during film growth. Strain control by improved deposition technique and implementing thermal treatment as well as choosing suitable substrate has attracted intensive attentions in ferroelectric film fabrication. Theory predicts that high dielectric properties can be achieved when free strain or slightly tensile strain left in the BST thin film at room temperature. Microwave application, such as phase shifter, also expects the enhanced tunability by an applied electric field. In this dissertation, single crystalline BST thin films deposited by radio frequency magnetron sputtering on SrTiO3 and DyScO3 substrates were studied. The crystal structure characteristics, including lattice parameters and film strain, were determined using X-ray diffraction. A new growth technique, three-step technique, was introduced and implemented into BST thin film deposition. The application of this new technique in deposition dramatically reduced the compressive strain in the films. We use microwave measurements on coplanar waveguides to evidence the improvement on dielectric properties achieved by tailoring the film strain. Additionally, we studied the BST film deposited by pulsed laser deposition (PLD) with introducing a sputtered seed layer of BST thin film. Compared with the BST film directly deposited on the substrate by PLD deposition, the films with a seed layer showed a large enhancement on the dielectric constant and tunability. The discussion on the change in film strain and dielectric performance of the PLD deposited films further proved the influence of film strain on dielectric properties. We discussed the design, fabrication, and measurement of coplanar waveguide transmission lines as phase shifters fabricated BST films. The thin BST films (~700 nm) on DyScO3 substrates deposited by sputtering demonstrated that the three-step deposition technique improved differential phase shift and microwave figure of merit to a great extent. The introduction of the sputtered seed layer into the PLD deposition of a thicker BST film (~2.15 μm) showed a dramatically enhancement on differential phase shift and microwave figure of merit. The enhanced performance on different series of BST films in microwave frequencies is consistent with the improvement on crystal structure, especially with the change in film strain.

The theoretical part deals with basic characteristics of low-temperature, low-pressure plasma. It also describes the principles of preparation of polymer and nanocomposite films using this type of plasma. It further explains the basic principles of methods used to characterize our samples. The experimental section shows a technology to produce hard polymeric coatings with metal (Cu) nanoparticles (NPs) fabricated by gas aggregation source (GAS). This approach has an important advantage that Cu concentration and matrix properties can be controlled independently. Characterization of the films in terms of chemical composition, morphology, optical and mechanical properties is described here alongside with description of Cu NPs production using GAS with variable aggregation length. The a- C:H matrix was deposited in a mixture of Ar and n-hexane on the substrates placed on a RF electrode. The beam of the NPs was normal to the substrate plane. In this arrangement it was possible to control hardness of the films and by operational parameters of the GAS also the amount of the NPs in the film. In the last section fabrication of nanocomposite films of titanium and nylon NPs is shown. Powered by TCPDF (www.tcpdf.org)

Les procédés de dépôt en phase vapeur sont particulièrement performants pour la synthèse de revêtements à propriétés contrôlées. Plus spécifiquement, ce travail de recherche porte sur l'élaboration de revêtements biocompatibles, sur alliage titane TiAl6V4, obtenus par pulvérisation magnétron en conditions réactives. Dans un premier temps, nous avons décrit les procédés de mise en forme des implants commerciaux pour pouvoir les reproduire au niveau du laboratoire. Dans un second, nous avons focalisé notre étude sur l'effet de la structure cristallographique de films de zircone sur leur caractère biocompatible à partir de cultures cellulaires de fibroblastes. Les résultats ainsi obtenus démontrent très nettement des différences de comportement entre des films de zircone monoclinique, quadratique ou cubique. Dans l'objectif d'apporter des éléments d'information permettant de discuter de ces effets, d'autres séries de revêtements céramiques ont été élaborées comme par exemple des oxydes de titane ou de zirconium amorphes, de l'oxyde d'yttrium, de l'oxyde d'aluminium ou encore du carbone amorphe. Les cultures cellulaires pratiquées sur ces échantillons ont permis de démontrer le caractère biocompatible de l'oxyde d'yttrium excluant ainsi tout effet nocif de cet élément dans les zircones dopées / The vapor deposition processes are particularly successful for the synthesis of coatings with tuneable properties. More specifically, this research deals with the development of biocompatible coatings on titanium alloys TA6V obtained by magnetron sputtering in reactive conditions. At first, we described the processes to design the commercial medical implants to be able to reproduce them within the laboratory. In the second, we focused our study on the effect of the crystallographic structure of zirconia-based coatings on their biocompatible character from cell cultures of fibroblasts. The results obtained demonstrate a significant variation of cell behavior for the three the zirconia structures: monoclinic, tetragonal or cubic. In the purpose to bring relevant information that allow discussing these effects, another series of ceramic coatings were developed as for instance amorphous oxides of titanium or zirconium, yttrium oxide,, aluminum oxide or amorphous carbon. The cell response on these samples demonstrates to the biocompatible properties of the yttrium oxide, excluding any harmful effect of this element in the doped zirconia

Le La2CuO4 est un isolant antiferromagnétique qui devient supraconducteur lorsqu'il est suffisamment oxydé. Cette étude qui porte sur la faisabilité de la synthèse de films de La2CuO4 par pulvérisation magnétron sur des substrats à moindre coût a été développée selon trois axes : l'élaboration des films, l'étude de leur cristallisation et l'influence de la nature du substrat sur leur tenue mécanique. Sous l'aspect élaboration ont été regroupés la présentation et la comparaison de quatre procédés d'élaboration. Nous avons ainsi déterminé que le procédé utilisant une cible céramique est le procédé permettant d'obtenir la zone homogène la plus étendue. La structure des films après recuit dans l'air a été déterminée par diffraction des rayons X et par microscopie électronique en transmission. Ces techniques ont permis de démontrer que les films cristallisent majoritairement dans une structure quadratique métastable et dans une moindre mesure dans une structure orthorhombique. L'effet de la composition chimique des films, de la nature du substrat et sur la cristallisation des films ont été étudiés. Il apparaît que l'utilisation de substrats en acier constitue une voie prometteuse pour la synthèse de films de La2CuO4. En utilisant des techniques de microscopie in situ, nous avons démontré que le recuit induit la formation de défauts en surface des films. La nature de ces défauts dépend des propriétés thermiques des substrats. Pour expliquer ces résultats, nous avons estimé les coefficients de dilatation thermique apparents de nos films à partir d'analyses par diffraction des rayons X. Ceci nous a permis de proposer un modèle d'initiation de la délamination des films / Lanthanum cuprate is an antiferromagnetique insulator that becomes superconducting when sufficiently oxidized. The aim of this study is to show the feasibility of the lanthanum cuprate thin film deposition by magnetron sputtering on low cost substrates. This work is developed around three points: the synthesis of the films, a study of their crystallization and the influence of the substrate nature on the films delamination. The synthesis aspect includes the presentation of the four different synthesis processes and a comparison of these processes in terms of reproducibility, chemical composition and thickness homogeneous zones. The process using a ceramic target was determined to have the larger homogeneous zone but does not allow obtaining stoichiometric films. The films structure after annealing in air has been determined by X-ray diffraction and Transmission Electronic Microscopy. This technique allowed us to demonstrate that the films mostly crystallize in a metastable tetragonal structure and in a lesser extend in orthorhombic structure. The effects of the chemical composition of the film, the substrate nature, and the annealing atmosphere on the films crystallization were studied. The use of steel as a substrate is promising way to the elaboration of La2CuO4 thin films. By using in situ microscope techniques, we showed that the thermal treatment induces defaults formation on the film surface. The natures of these defaults strongly depend on the substrate nature. To explain these results, the apparent thermal expansion coefficients of the films were calculated from x-ray diffraction analyses. These results allowed us to suggest a film delamination initiation model

Le but de ce travail est de développer et de caractériser une nouvelle génération de revêtements multicouches anti-usure et anticorrosif à base de nitrure de chrome. A cause des conditions de sollicitations sévères auxquelles les outils de coupe sont soumis en plus des enjeux environnementaux liés à l’utilisation des fluides de coupe lors de l’usinage du bois, les monocouches qui constituent notre système multicouches doivent présenter des caractéristiques spécifiques. De ce fait, des couches minces de Cr, CrN et CrAlN ont été déposées sur un acier à outils de coupe du bois et sur des substrats de siliciums par pulvérisation magnétron réactive DC. Nous nous sommes intéressés dans un premier temps à optimiser les monocouches. Ensuite, ces revêtements ont été associés pour élaborer des multicouches Cr/CrN/CrAlN qui ont alors été caractérisées. Nous avons étudié les propriétés physico-chimiques, mécaniques, tribologiques et le comportement à la corrosion de différents revêtements multicouches. Les résultats obtenus indiquent que l’application d’un revêtement multicouches pouvait apporter des améliorations considérables à la résistance à l’usure et à la corrosion des outils de coupe du bois. / The aim of this study was to develop and characterize a new generation of wear and corrosion resistant multilayers Cr-N based coatings. Due to the severe conditions that wood cutting tools are subjected in addition to the environmental issue associated with the use of cutting fluids during wood machining, the monolayers that constitute our multilayers system must have specific characteristics. As a result, thin layers of Cr, CrN and CrAlN have been deposited on wood cutting tools steel and silicon substrates by DC reactive magnetron sputtering to be optimized. Then, the optimal monolayerscoatings were combined to develop the Cr/CrN/CrAlN multilayers. that were characterized to determine their physicochemical, mechanical, tribological properties and their corrosion behavior. The results obtained indicated that the application of a multilayer coating can greatly improve the wear and corrosion resistance of a wood cutting tools steel.

Orientador: José Humberto Dias da Silva / Coorientador: Paulo Noronha Lisboa Filho / Banca: Valmor Roberto Mastelaro / Banca: Wido Herwig Schreiner / Banca: Francisco Eduardo Contijo Guimarães / Banca: Antonio Ricardo Zanata / Resumo: A busca por um melhor entendimento da inter-relação entre os parâmetros envolvidos no processo de crescimento de filmes de dióxido de titânio (Tio2) e as propriedades estruturais, eletrônicas e magnéticas resultantes foi a principal motivação deste trabalho. Para isso, filmes Ti)2 foram crescidos usando a técnica de RF magnetron sputtering em diferentes condições. Um primeiro conjunto de filmes de Ti)2 não dopados foi depositado com fluxo contínuo de O2. Em outro conjunto, utilizou-se sistemáticas interrupções no fluxo de O2 durante a deposição. O último grupo de amostras foi depositado usando fluxo contínuo O2 e dopagem com Mn. Os filmes do primeiro grupo apresentaram morfologia colunar com estrutura majoritariamente anatase e com gap óptico de ~3,3 eV, independente da temperatura dos substratos (450ºC e 600ºC) e da razão Ar/O2 utilizada. A diminuição do fluxo de O2 provocou um aumento da absorção sub-gap que foi associada a um aumento dos defeitos eletrônicos no material. Um tratamento térmico em vácuo a 800ºC, realizado sobre filmes de TiO2 puros, revelou um aumento da fração rutila e da absorção óptica, o que também foi associado a um aumento da concentração de defeitos eletrônicos. A análise dos filmes onde o fluxo de oxigênio foi sistematicamente interrompido durante a deposição mostrou que o aumento no número de interrupções não interferiu significativamente na morfologia colunar dos filmes, mas produziu um considerável aumento na fração rutila dos filmes, bem como um aumento na absorção óptica sub-gap. O aumento na absorção na região do visível e infravermelho próximo foi atribuído a um aumento na concentração de defeitos que, de acordo com cálculos baseados na teoria do funcional da densidade, estão relacionados a estados de energia provenientes de vacâncias de oxigênio. Os filmes de TiO2 dopados com diferentes concentrações de Mn pertencentes ao terceiro grupo também / Abstract: The search for a better understanding of the interrelation between the parameters involved in the process of film growth and the resulting structural, electronic and magnetic properties was the main motivation of this work. To the purpose, TiO2 films were grown by RF magnetron sputtering technique in different conditions. In a first set, TiO2 films were deposited with continuous O2 flow. In another set, systematic interruptions in the O2 flow were performed during the deposition. The last group of samples was deposited using a continuous O2 flow and Mn doping. A detailed analysis of the first group showed that these films exhibit columnar morphology with mainly anatase structure and optical gap of ~3.3eV, independent of the substrate temperature (450ºC and 600ºC) and the ratio used. THe decrease in O2 flux caused an increase in the sug gap absorption which associated with the increase in electronic defects of the material. Anneling in vacuum at 800ºC performed on pure TiO2 films showed an increase in the rutilo fraction, a red shift of the optical absorption edge, and an increase of the sub gap absorption associated with the increase of the electronic defects. The analysis of the films were the O2 flow was systematically interrupted during the deposition showed that the increase in the number of interruptions did not interfere significantly in the columnar morphology, but produced a significant increase in the fraction of rutile and brookite as well as an increase in sub-gap absorption. The increase in absorption in the visible and near infrared was attributable to an increase in the concentration of defects that, according to calculations based on the density functional theory, should be related to energy states provides by O vacancies. The Mn doped films also present a compact columnar morphology and a strong and systematic favoring of the rutile... (Complete abstract click electronic access below) / Doutor

Esse trabalho teve como objetivo a produção e a caracterização elétrica de filmes finos de telureto com nanopartículas de ouro, depositados pela técnica sputtering, para aplicação em dispositivos de memória. Os filmes finos foram produzidos a partir de alvos cerâmicos de telureto (TeO2-ZnO) e foram nucleadas nanopartículas de ouro para observar sua influência no comportamento de memória. Foi desenvolvida metodologia adequada para a nucleação das nanopartículas por meio de tratamento térmico. Foram produzidos filmes com diferentes concentrações e tamanhos de nanopartículas e diferentes fluxos de oxigênio durante a deposição. Os filmes foram caracterizados por técnicas como Microscopia Eletrônica de Transmissão (TEM), Perfilometria, Espectrometria por Retroespalhamento de Rutherford (RBS) e extração de curvas de Corrente x Tensão (I-V). Por meio das medidas I-V foi possível identificar as melhores condições para aplicações em memória e correlacioná-las com as variáveis de processo estudadas. Resultados obtidos mostraram que a melhor condição para aplicações em memória não volátil foi encontrada em filmes com 100 nm de espessura e depositados com fluxo de oxigênio de 1 sccm, abertura do shutter em 50 e tratados termicamente por 10 ou 20 horas à 325 ºC. Nesses casos, foi observado um abrupto aumento na corrente (4 ordens de grandeza) em aproximadamente 6,5 V para 10 horas de tratamento térmico e 3,5 V para 20 horas de tratamento térmico, indicando a transição do estado inicial de baixa condutividade para outro de alta condutividade. As nanopartículas de ouro proporcionam maior capacidade de armazenamento de elétrons e não favorecem o transporte de corrente através do isolante; elas atuam como armadilhas para as cargas elétricas, o que reduz a corrente de fuga para níveis mais baixos. Foi estudada a influência do diâmetro e da concentração volumétrica das nanopartículas de ouro no valor da tensão elétrica associada à transição abrupta da corrente. Este parâmetro desempenha um papel importante no efeito de memória, pois determina a facilidade/dificuldade em se preencher e saturar as armadilhas (nanopartículas de ouro) com elétrons. Os materiais estudados neste trabalho mostraram-se promissores para aplicações em dispositivos de memória não volátil e possuem características semelhantes aos materiais orgânicos usados para o referido fim. / This work has the objective to fabricate and characterize electrically tellurite thin films containing gold nanoparticles, deposited by the sputtering technique, for application in memory devices. Thin films were produced from ceramic tellurite targets and gold nanoparticles were nucleated in order to observe their influence on memory behavior. An appropriate method was developed for the nucleation of the nanoparticles by means of heat treatment. Films with different nanoparticles sizes and concentration and different oxygen fluxes during the deposition, were produced. The films were characterized by techniques such as Transmission Electron Microscopy (TEM), Profilometry, Rutherford Backscatter Spectrometry (RBS) and current x voltage (I-V) curves. Using I-V measurements, it was possible to identify the best conditions for memory applications and correlate them with the process variables studied. The results showed that the best condition for memory applications was found in films with 100 nm thickness and deposited with oxygen flow of 1 sccm, opening shutter in 50 and heat treated for 10 or 20 hours at 325 ºC. In these cases, current abrupt increase (4 orders of magnitude) was observed at about 6.5 V for 10 hours of heat treatment and 3.5 V for 20 hours of heat treatment, indicating the transition from high impedance state to low impedance state. Gold nanoparticles provide a larger electron storage capability, and do not favor the electric transport through the insulator; they act as traps for electrical charges, which reduces the leak current to lower levels. It was studied the influence of the gold nanoparticles diameter and volumetric concentration on the voltage associated to the abrupt current. These parameters played an important role in the memory effect, as they determined the facility/difficulty to fill and saturate the traps (Au nanoparticles) with electrons. The materials studied in the present work, based on TeO2-ZnO thin films with Au nanoparticles, are promising for applications in nonvolatile memory device with similar characteristics to organic materials used for the same purpose.

O presente trabalho tem como objetivo principal a produção e estudo de filmes de nitreto de alumínio (AlN) depositados por pulverização catódica (sputtering) reativa e a fabricação e caracterização de guias de onda tipo pedestal utilizando o AlN como núcleo. Inicialmente, filmes de AlN foram fabricados por pulverização catódica reativa (sputtering) de rádio frequência (RF) utilizando um alvo de alumínio (Al) com 99,999% de pureza, e nitrogênio (N2) como gás reativo. Subsequentemente, os filmes foram caracterizados mediante as técnicas de elipsometria, difração de raios X (DRX), espectroscopia de absorção por transformada de fourier na região do infravermelho (FTIR) e espectroscopia de absorção na região do ultravioleta e do visível (UV-VIS). Tendo as melhores condições ópticas e físicas para a deposição de filmes de AlN, foram fabricados neste trabalho guias de onda tipo pedestal utilizando estes filmes como núcleo. O guia de onda pedestal traz um processo de fabricação alternativo, em que a geometria do guia de onda determina-se na camada anterior ao do núcleo, assim já não é necessário delinear as paredes laterais da camada de núcleo facilitando desta forma, o processo de fabricação do dispositivo. Os guias de tipo pedestal fabricados neste trabalho foram definidos através da corrosão parcial do óxido de silício (SiO2) mediante a técnica de RIE (Reactive Ion Etching) usando gases trifluorometano (CHF3) e oxigênio (O2) como gases reativos. Uma vez definido o pedestal, um filme de nitreto de alumínio é depositado sobre o SiO2 com a finalidade de constituir o núcleo do guia de onda. O ar foi utilizado como revestimento superior, cujo índice de refração (n = 1) aumenta o confinamento da luz no núcleo e também para poder possibilitar a caracterização das perdas ópticas do dispositivo. Para esta caracterização usamos a técnica de vista superior que permitiu a análises das perdas ópticas de propagação para diferentes alturas de pedestal e diferentes espessuras de núcleo tanto para filmes de AlN orientado no plano cristalino (002) quanto para filmes de AlN amorfos. / The main objective of this work is the production and study of Aluminum Nitride (AlN) films deposited by reactive sputtering and the fabrication and characterization of pedestal optical waveguides using AlN as core. Initially, aluminum nitride films were produced by reactive sputtering using a 99.999% aluminum (Al) purity target, and nitrogen (N2) as the reactive gas. Subsequently, the films were characterized by ellipsometry, X-ray Diffraction, Fourier Transform Infrared Spectroscopy (FTIR) and Ultraviolet-visible spectroscopy (UV-VIS). Once the best optical and physical conditions for the deposition of AlN films were obtained, pedestal waveguides using these films as a nucleus were fabricated in this work. The pedestal waveguide provides an alternative manufacturing process where the geometry of the waveguide is determined in the pre-core layer, so it is no longer necessary to delineate the side walls of the core layer thereby facilitating the device fabrication process. The pedestal waveguides fabricated in this work were defined by the partial corrosion of SiO2 by the RIE (Reactive Ion Etching) technique using CHF3 and O2 gases as reactive gases. Once the pedestal is completed, an aluminum nitride film is deposited onto the SiO2 layer as the waveguide core. The air was used as an upper cladding, whose refractive index (n ? 1) increases the confinement of the light in the core and also allows the optical loss characterization. For this characterization, we used the superior view technique that allowed the analysis of optical propagation losses for different pedestal heights and different core thicknesses for both highly (002) oriented and amorphous AlN films.