2-Dodecyl benzotriazole and 9,9-dioctylfluorene containing alternating copolymers poly((9,9-dioctylfluorene)-2,7-diyl-(2-dodecyl-benzo[1,2,3]triazole)) (P1), poly((9,9-dioc-tylfluorene)-2,7-diyl-(4,7-bis(thien-2-yl) 2-dodecyl benzo[1,2,3]triazole)) (P2), poly((9,9 dioctylfluorene)-2,7-diyl-(4,7-bis(3-hexylthien-5-yl) 2-dodecyl-benzo[1,2,3]triazole)) (P3) were synthesized via Suzuki polycondensation. Synthesized monomers and copolymers were characterized by Nuclear Magnetic Resonance (1H-NMR, 13C-NMR). Optical and electronic properties of resulting alternating copolymers were investigated by means of Cyclic Voltammetry (CV), Ultraviolet&ndash / Visible Spectroscopy and spectroelectrochemistry. All three polymers showed both p and n doping behaviors and multicolored electrochromic states. In order to learn switchingtimes and percent transmittance changes kinetic studies were also performed. Thermal properties of the polymers were investigated via Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). Due to the convenient HOMO and LUMO levels, band gaps, strong absorptions in the visible region and thermal stability, polymers were tested in Organic Solar Cell (OSC) device applications. The preliminary investigation indicated that polymers had promising power conversion efficiencies.

The interest towards organic semi-conductors increased due to their tunable band gaps, redox properties, processability and low cost in the field of conducting polymers. Electrochromic materials have the ability to change color by altering their redox state. In the context of low cost flexible display device technology, requirements can be fulfilled with accessible multi-colored electrochromic polymers. In this study, we report the chemical synthesis and electrochromic properties of two spray processable, ambipolar, fluorescent and multi-color to transmissive electrochromic polymers. The electrochromic properties of these polymers were examined by cyclic voltammetry, spectroelectrochemistry, kinetic studies. Polymers, PTBTPh and PTBTTh, have multi-colored oxidation states and easily accessible ndoped states, which allowed us to achieve transmissive films in a low working potential. Electrochemical and spectral results showed that both polymers are potential materials for electrochromic display devices.

O comportamento eletroquímico do aço-carbono 1005, do aço galvanizado e do zinco foi estudado em meios aerados de ácido sulfúrico 0,5 mol.L-1 (aço-carbono) e cloreto de sódio 0,01 mol.L-1 na ausência e presença do inibidor de corrosão benzotriazol (BTAH), a 25 ºC. Foram empregadas como técnicas ensaios gravimétricos, medidas de transitórios de potencial de circuito aberto, voltametria linear, espectroscopia de impedância eletroquímica (EIE), varredura com eletrodo vibratório (SVET), microscopia eletrônica de varredura (MEV), espectroscopia por dispersão de energia (EDS), espectroscopia eletrônica de raio X (XPS), espectroscopia Raman. O BTAH se mostrou inibidor para os três materiais metálicos nos meios estudados, comportando-se como inibidor misto. A sua ação inibidora decresce na ordem Zn>aço carbono>aço galvanizado em meio de cloreto de sódio. Para o aço-carbono em meio de ácido sulfúrico a adição de íons Cu(II) eleva a eficiência do BTAH, mas em tempos mais elevados de imersão há formação de cobre metálico que promove corrosão galvânica. Em meio de cloreto de sódio os filmes formados sobre aço e sobre zinco correspondem aos respectivos complexos Fe(III) e Fe(II) e de Zn(II) com BTAH. A ação sobre o zinco do BTAH, no caso do aço galvanizado reduz a eficiência na proteção catódica conferida pelo zinco ao aço. A eficiência inibidora sobre aço-carbono depende da composição da liga e da natureza das inclusões presentes no material. Estudos sobre a secção transversal do aço galvanizado em meio de cloreto de sódio mostraram que o BTAH inibe a oxidação do zinco, com formação do complexo, e a redução do oxigênio sobre o aço, com adsorção da molécula de BTAH. O filme formado sobre zinco, ensaiado separadamente, obedece à isoterma de Langmuir, com valores de energia livre padrão de adsorção que evidenciam a natureza química da adsorção, apontando para um complexo com BTAH. / The electrochemical behavior of carbon steel, galvanized steel and zinc has been studied in aerated 0.5 mol.L-1 sulfuric acid and 0.01 mol.L-1 sodium chloride solutions in the absence and presence of benzotriazole (BTAH) at 25ºC. Weight loss experiments, open circuit potential, transient measurements, linear voltammetry, electrochemical impedance spectroscopy (EIS), scanning electronic microscopy (SEM), energy dispersive spectroscopy (EDS), canning vibrating electrode technique (SVET), X-ray photoelectron spectroscopy and Raman spectroscopy used as techniques. BTAH has shown inhibition for the three materials in the media studied and acted as a mixed inhibitor. Its inhibitive effect decreases in the sequence Zn>carbon steel>galvanized steel in chloride medium. In sulfuric medium the BTAH efficiency is improved with the presence of Cu(II) ions but this effect is suppressed at long times immersion when metallic copper is formed promoting galvanic corrosion. The films formed on zinc and carbon steel in chloride medium correspond, respectively to a Fe(II), Fe(III) mixed complex and to Zn(II) complex with BTAH. Studies on the cross section of galvanized steel (cut edge) have shown that the high effect of BTAH as inhibitor for zinc tends to decrease the efficiency of cathodic protection of this metal on carbon steel. For carbon steel in sulfuric medium the composition and the nature of inclusions have an important role on the inhibitor efficiency. On the cut edge the inhibitor promotes the formation of a zinc complex on this metal and it is adsorbed on carbon steel as a molecule inhibiting the oxygen reduction. The film formed on zinc when separately studied obeys to a Langmuir isotherm with standard adsorption free energy values denoting the presence of chemical adsorption as an indicative of the presence of a complex

Les amines homoallyliques sont des synthons clés pour la construction de nombreuses molécules d’intérêt biologique. Du fait de la double liaison carbone-carbone du fragment allylique, facilement fonctionnalisable, elles sont également très utilisées en synthèse organique. Ce travail de recherche s’oriente sur la synthèse d’amines homoallyliques grâce à des complexes de titane. En effet, le couplage réducteur d’imines et de diènes promu par du titane permet la formation d’amines homoallyliques diastéréoisomères syn et anti. La diastéréosélectivité de la réaction est directement affectée par le substituant porté par l’atome d’azote. Selon qu’il s’agit d’un groupement benzyle ou phényle, la sélectivité sera marquée en faveur de l’amine syn ou anti respectivement. De plus, l’ajout de l’acide de Lewis BF3.OEt2 permet de diminuer considérablement le temps de réaction mais également d’inverser la diastéréosélectivité obtenue avec la réaction sans acide de Lewis.L’instabilité des amines homoallyliques durant le processus de purification a permis d’autre part de mettre en lumière un réarrangement cationique 2-Aza-Cope. Ce réarrangement a été appliqué à la synthèse catalytique d’homocrotylamines et d’un acide aminé , insaturé. Ce manuscrit rapporte également la synthèse d’amines homoallyliques par couplage entre des diènes et des dérivés benzotriazole. Ces dérivés génèrent des iminiums qui réagissent plus efficacement que les imines pour former les amines souhaitées. De plus, la réaction effectuée avec des dérivés de type bis(benzotriazole) conduit sélectivement à des homoallyl-(E)- homocrotylamines. Cette réactivité est expliquée par une triple réaction en cascade à savoir : allyltitanation – réarrangement cationique 2-Aza-Cope – allyltitanation.D’autre part, une partie de ce manuscrit s’intéresse à la réaction entre le complexe Ti(NMe2)4 et des dioxocyclames qui forment de nouvelles diamidines macrocyliques. Les propriétés chimiques de ces amidines présentent de nombreux intérêts pour la formation de complexes avec des métaux tels que le Cu, le Ni et le Pd. Les analyses des complexes méritent d’être approfondies afin de déterminer sans ambigüité leur structure et de mieux comprendre le mode de coordination de ces nouveaux macrocycles azotés. / Homoallylic amines are key reagents for the formation of a large number of biologically interesting products. Due to the double bond of their allylic moiety, easily functionalisable, they are commonly used in organic synthesis. This research work deals with the synthesis of homoallylic amines thanks to titanium complexes. In fact, the reductive coupling between of imines and dienes promoted by titanium allows the formation of diastereoisomeric homoallylamines syn and anti. The diastereoselectivity of the reaction is directly affected by the nitrogen substituent. Whether it is benzyl or phenyl, the selectivity will be in favour of syn or anti respectively. Moreover, the addition of a the Lewis acid BF3.OEt2 not only considerably decreases the reaction time but also inverts the diastereoselectivity obtained with the reaction without a Lewis acid.The decomposition of homoallylamines during the purification process allowed to highlights a cationic 2-Aza-Cope rearrangement. This rearrangement was applied to the catalytic synthesis of homocrotylamines and of a _,_ unsaturated amino acid. This manuscript also reports the synthesis of homoallylamines by coupling between dienes and benzotriazole derivatives. These derivatives generate iminiums which react efficiently than imines to form the desired amines. Moreover, the reaction ran with bis(benzotriazole) derivatives lead selectively to homoallyl-(E)-homocrotylamines. This reactivity is explained by a triple cascade reaction meaning an allyltitanation - cationic 2-Aza-Cope rearrangement – allyltitanation.Secondly, part of this thesis focuses on the reaction between Ti(NMe2)4 complex and dioxocyclams to produce new macrocyclic diamidines. The chemical properties of this amidines present several interests for the formation of complexes with metals such as Cu, Ni and Pd. The analyses of the complexes deserve further investigation to determine unambiguously their structure in order to understand much better the coordination of these new nitrogen macrocycles.

Plasma polymerization techniques were used to synthesize and deposit hydrogel on silicon (Si) substrate. Hydrogel is a network of polymer chains that are water-insoluble and has a high degree of flexibility. The various fields of applications of hydrogel include drug release, biosensors and tissue engineering etc. Hydrogel synthesized from different monomers possess a common property of moisture absorption. In this work two monomers were used namely 1-amino-2-propanol (1A2P) and 2(ethylamino)ethanol (2EAE) to produce polymer films deposited on Si ATR crystal. Their moisture uptake property was tested using FTIR-ATR technique. This was evident by the decrease in -OH band in increasing N2 purging time of the films. Secondly, two monomer compounds namely vinyl acetic acid and glycidyl methacrylate which have both amine and carboxylic groups are used as solid surface for the immobilization of bovine serum albumin (BSA). Pulsed plasma polymerization was used to polymerize these monomers with different duty cycles. Initial works in this field were all about protein surface adsorption. But more recently, the emphasis is on covalent bonding of protein on to the surface. This immobilization of protein on solid surface has a lot of applications in the field of biochemical studies. The polymerization of vinyl acetic acid and glycidyl methacrylate were shown as successful method to attach protein on them. Chemical mechanical polishing (CMP) of Cu is one of the processes in the integrated chips manufacturing industry. Benzotriazole is one of the constituents of this CMP slurry used as corrosion inhibitor for Cu. Benzotriazole (C6H5N3) is a nitrogen heterocyclic derivative having three nitrogen atoms, each with an unshared pair of electrons, forming five-membered ring structure. This molecule coordinates with Cu atoms by loosing a proton from one of its nitrogen atom and thereby forming a film which is polymeric in nature that prevents further oxidation of Cu. In this work, aqueous solution of BTA was used to study the adsorption characteristics on Cu when a Cu electrodeposited Si was immersed in to it. This study was performed using ATR-FTIR technique. The adsorption of BTA on Cu surface was evident by the presence of aryl C-H stretching band at 3061 cm-1.

Benzotriazoles (BTs) such as 1H-benzotriazole (1H-BT), 5-methyl-1H-benzotriazole (5Me-BT) and 4-methyl-1H-benzotriazole (4Me-BT) have a wide range of industrial applications. BTs are present for example in dishwasher detergents, in automotive antifreeze formulations and aircraft de-icing/anti-icing fluids (ADAF) as corrosion inhibitors. BTs belong to the group of “emerging contaminants” that have got in recent years more and more in the focus of environmental scientists, policy makers and the general public. These compounds are ubiquitous and highly mobile in the aquatic environment. It has been already shown that BTs have negative effects on aquatic organisms. The objective of the present study was among others to monitor 1H-BT, 4Me-BT and 5Me-BT in river- and wastewater. River water samples were taken from five rivers in the Hengstbach/Schwarzbach catchment area, a medium-sized catchment area of about 400 km². River water grab samples were taken during six different sampling. The aim of this monitoring study was to get a seasonal catchment-wide overview on measured concentrations and mass loads of BTs. BTs concentrations were determined in 24-hours influent composite samples taken on different month from three wastewater influents in Germany. In addition, 2-hours composite influent samples collected during one day in April were analyzed to determine the daily periodic emissions of BTs mass flows. Moreover, ADAF used at German airports and three dishwasher detergent tablets commonly used in Germany were analyzed for the presence of BTs to study the distribution pattern of those compounds in different products. An analytical method based on SPE and GC-MS has been developed and optimized for the determination of the presence of the corrosion inhibitors 1H-BT, 4Me-BT and 5Me-BT in environmental samples.

No description available.

Advances in the interconnection technology have played a key role in the continued improvement of the integrated circuit (IC) density, performance and cost. Copper (Cu) metallization, dual damascenes processing and integration of copper with low dielectric constant material are key issues in the IC industries. Chemical mechanical planarization of copper (CuCMP) has emerged as an important process for the manufacturing of ICs. Usually, Cu-CMP process consists of several steps such as the removal of surface layer by mechanical action of the pad and the abrasive particles, the dissolution of the abraded particles in the CMP solution, and the protection of the recess areas. The CMP process occurs at the atomic level at the pad/slurry/wafer interface, and hence, slurries and polishing pads play critical role in its successful implementation. The slurry for the Cu-CMP contains chemical components to facilitate the oxidation and removal of excess Cu as well as passivation of the polished surface. During the process, these slurry chemicals also react with the pad. In the present study, investigations were carried out to understand the effect of hydrogen peroxide (H2O2) as an oxidant and benzotriazole (BTA) as an inhibitor on the CMP of Cu. Interaction of these slurry components on copper has been investigated using electrochemical studies, x-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). In the presence of 0.1M glycine, Cu removal rate was found to be high in the solution containing 5% H2O2 at pH 2 because of the Cu-glycine complexation reaction. The dissolution rate of the Cu was found to increase due to the formation of highly soluble Cu-glycine complex in the presence of H2O2. Addition of 0.01M BTA in the solution containing 0.1M glycine and 5% H2O2 at pH 2 exhibited a reduction in the Cu removal rate due to the formation of Cu-BTA complex on the surface of the Cu further inhibiting the dissolution. XPS and SIMS investigations revealed the formation of such Cu-glycine complex, which help understand the mechanism of the Cu-oxidant-inhibitor interaction during polishing. Along with the slurry, pads used in the Cu-CMP process have direct influence an overall process. To overcome problems associated with the current pads, new application specific pad (ASP) have been developed in collaboration with PsiloQuest Inc. Using plasma enhanced chemical vapor deposition (PECVD) process; surface of such ASP pads were modified. Plasma treatment of a polymer surface results in the formation of various functional groups and radicals. Post plasma treatment such as chemical reduction or oxidation imparts a more uniform distribution of such functional groups on the surface of the polymer resulting in unique surface properties. The mechanical properties of such coated pad have been investigated using nanoindentation technique in collaboration with Dr. Vaidyanathan’s research group. The surface morphology and the chemistry of the ASP are studied using scanning electron microcopy (SEM), x-ray photoelectron spectroscopy (XPS), and fourier transform infrared spectroscopy (FTIR) to understand the formation of different chemical species on the surface. It is observed that the mechanical and the chemical properties of the pad top surface are a function of the PECVD coating time. Such PECVD treated pads are found to be hydrophilic and do not require being stored in aqueous medium during the not-in-use period. The metal removal rate using such surface modified polishing pad is found to increase linearly with the PECVD coating time. Overall, this thesis is an attempt to optimize the two most important parameters of the Cu-CMP process viz. slurry and pads for enhanced performance and ultimately reduce the cost of ownership (CoO).

Foi estudado o comportamento eletroquímico de interfases Cu/H2SO4 0,5 mol L-1 na ausência e presença de compostos triazólicos - benzotriazol (BTAH) e tolitriazol (TTAH) e de surfactantes: dodecilsulfato de sódio (SDS aniônico) e cloreto de dodecilamônio (DAC catiônico) a 25ºC, empregando eletrodo parado e de disco rotativo (EDR). Foram empregadas como técnicas medidas de potencial de circuito aberto, polarização potenciostática e potenciodinâmica, cronoamperometria, espectroscopia de impedância eletroquímica e microscopia óptica. As características inibidoras do filme formado dependem da natureza dos aditivos e das condições hidrodinâmicas. As interfases contendo BTAH, TTAH, BTAH + TTAH, BTAH + SDS e TTAH + SDS apresentaram uma faixa ampla de potencial em que o cobre se mostrou passivado, chegando a 200 mV para a mistura BTAH + SDS empregando EDR. Densidades de corrente de passivação tão baixas quanto 2µA cm-2 foram observadas com EDR na presença de BTAH + TTAH. As misturas composto triazólico - surfactante mostraram filmes menos resistentes. Os surfactantes isolados não produzem faixa passiva e antecipam o potencial de oxidação do cobre com eletrodo parado. As misturas triazol - DAC só produzem faixa passiva com EDR. Todos os aditivos se mostraram inibidores para a reação H+/H2, destacando-se, com eletrodo parado, BTAH, TTAH e BTAH + TTAH. / The electrochemical behavior of 0.5 mol.L-1 Cu/H2SO4 interphases has been studied in the presence and in the absence of triazolic compounds-benzotriazole (BTAH) and tolitriazole (TTAH) and of surfactants - sodium dodecylsulphate (anionic, SDS) and dodecylammonium chloride (cationic, DAC) at 25ºC, using non-stirred electrode and rotating disc electrode (RDE). Open circuit potential, potentiostatic and potenctiodinamic polarization, chronoamperometry, electrochemical impedance spectroscopy, and optical microscopy were used as techniques. The inhibitive features of the formed film depend on both the nature of the additives and on the hydrodynamic conditions. The interphases containing BTAH, TTAH, BTAH + TTAH, BTAH + SDS e TTAH + SDS presented a wide potential range where the copper is passivated, reaching to 200 mV for BTAH + SDS mixture using RDE. Low passivating current densities (2µA cm-2) were observed with RDE in the presence of BTAH + TTAH. Triazolic compound?surfactant mixtures have originated less resistant films. Isolated surfactants do not originate passive ranges and anticipate the oxidation potential of copper under non stationary conditions. The mixtures triazole-DAC only produce passive range at stationary conditions. All the additives have shown to be inhibitors for the H+/H2 reaction, specially BTAH, TTAH e BTAH + TTAH using non stirred conditions.

Foi estudado o efeito do dodecilsulfato de sódio (SDS) na ausência e presença do Benzotriazol (BTAH) sobre as interfases Cu/H2SO4 0,5 mol L-1 e Cu/HCl 1 mol L-1. Foram empregadas técnicas eletroquímicas estacionárias, impedância eletroquímica e espectroscopia Raman \"in situ\". Análise da superfície, após ensaios, foi feita por ressonância ciclotrônica de íons empregando transformada de Fourier. Nos dois meios estudados foi observado que o SDS não modifica significativamente o potencial de corrosão (Ecorr) mas favorece a dissolução do óxido de cobre formado ao ar. O SDS, o BTAH e a mistura SDS-BTAH inibem a reação W+/H2, devido à formação de um filme na superfície do cobre. Na presença de SDS, o filme obedece ao modelo de Langmuir modificado, onde cada molécula ocupa mais de um sítio ativo. Foram determinadas constantes de equilíbrio de adsorção para o SDS, iguais a 1,7x103 L mol-1 e 5,0x104 L mol-1 sobre cobre em meios de H2SO4 0,5 mol L-1 e HCl 1 mol L-1 respectivamente. O efeito sinérgico do SDS sobre a ação do BTAH foi melhor evidenciado em meio de H2SO4 0,5 mol L-1, onde se constatou a co-adsorção SDS-BTAH e a modificação dos espectros de um pela presença do outro, em toda a faixa de potenciais estudada, acima e abaixo do Ecorr. O SDS não modifica o mecanismo de dissolução do cobre em meio de H2SO4 0,5 mol L-1, no Ecorr, a baixas e altas sobretensões. Em meio de HCl 1 mol L-1, há evidências da formação do complexo Cu-OSO3-C12H25. Nos dois meios a adsorção do SDS se dá através das partes hidrofóbica e hidrofílica. / The effect of sodium dodecylsulfate (SDS) on the Cu/0.5 mol L-1 H2SO4 and Cu/1.0 mol L-1 HCl interphases in the absence and presence of benzotriazole (BTAH) has been studied. Steadystate electrochemical measurements, electrochemical impedance and \"in situ\" Raman spectroscopy were used as techniques. Surface analysis was made using Fourier transform ion cyclotron resonance (FTICR). It was observed that SDS does not change the corrosion potential value (Ecorr) but it increases the copper oxide dissolution rate in the two media studied. SDS, BTAH and the SDS-BTAH mixtures inhibit the H+/H2 reaction on the copper surface. In the presence of SDS, this film obeys a modified Langmuir model where each molecule uses more than one adsorption site. Adsorption equilibrium constants, of l.7x103 L mol-1 and 5.0x104 L mol-1, for SDS in 0.5 mol L-1 H2SO4 and 1.0 mol L-1 HCl solutions were obtained respectively. A synergetic effect of SDS on BTAH action was better observed in 0.5 mol L-1 H2SO4 medium. The SDS-BTAH co-adsorption and the change of the Raman spectra of each other has been verified on the entire range of potentials studied. SDS neighter changes the mechanism of copper dissolution in 0.5 mol L-1 H2SO4 medium at the Ecorr nor at low and high anodic overvoltages. In 1.0 mol L-1 HCl solutions there is an evidence of the Cu-OSO3C12H25 complex formation. The SDS adsorption occurs from hydrophobic and hydrophilic moieties.