This work describes the synthesis of dendrimer-encapsulated nanoparticles (DENs) and the expansion of the characterization ability for these materials. The dendrimer-template method for the synthesis of nanoparticles allows precise control over the size, composition and structure of nanoparticles in the 40-250 atom range. In this size regime, the surface structure of the nanoparticles dominates their catalytic properties. The long term goal of this research is to correlate the structure of these nanoparticles to their catalytic activity, improving the ability to predict superior catalysts a priori. As a prerequisite for this analysis, the precise structure of the catalytically active nanoparticle must be determined. Characterization of nanoparticles in the 1-2 nm region is significantly more difficult than more commonly used nanoparticles of 3-5 nm diameter or larger. Typical characterization of these nanoparticles involves UV-vis spectroscopy for Mie absorbance and transmission electron microscopy for size analysis. This work involves the use of extended X-ray absorption-fine structure (EXAFS) to determine the local structure of the nanoparticles. For monometallic Pt DENs, EXAFS was combined with UV-vis, TEM, X-ray photoelectron spectroscopy (XPS) and electrochemistry to determine that the Pt system is not simply nanoparticles but a more complex, bimodal state. EXAFS has also been used to differentiate between different bimetallic structures. For PdAu DENs, there are two synthetic methods used. When both metals are reduced simultaneously, the resulting nanoparticles have a quasi-random alloy structure. These nanoparticles were then extracted from the dendrimer into an organic solvent by use of alkanethiols. The extraction process changed the alloy structure into Au-core/Pd-shell. When Pd and Au were reduced in sequence, the DENs were formed as a Au-core/Pd-shell material, regardless of the order of the reduction of the metals. The Au-core/Pd-shell structure was also present after extraction. In addition to structural analysis to determine the result of different synthetic methods, EXAFS was also used in situ to measure the structure of Pt DENs during the oxidation of absorbed CO. These in situ measurements are important for determining the structure of the actual catalyst rather than the precursor nanoparticle. In this case, the Pt DENs changed from a bimodal distribution into fully reduced nanoparticles by the application of a reducing potential. The binding of CO to the Pt DENs and subsequent oxidation did not cause measurable agglomeration of the nanoparticles. This reduction of the Pt system by electrochemical means was also explored as a synthetic method. The Pt-dendrimer complex was placed on a TEM grid for electrochemical treatment. A potential step was shown to reduce some of the Pt-dendrimer complexes into Pt nanoparticles of the expected size. However, most of the complexes were not reduced. Therefore, only the standard chemical reduction followed by electrochemical treatment is sufficient to fully reduce the nanoparticle samples. This work has explored additional synthetic methods for the synthesis of monometallic and bimetallic DENs. The use of EXAFS, as well as other advanced characterization techniques, has advanced knowledge of the structure of various DENs. Both the characterization toolset and the synthetic methods will provide a basis for investigations of catalytically active materials. / text

Στην παρούσα διπλωματική εργασία αναλύονται λεπτά υμένια (thin films) διαφόρων πολυμερικών ή ολιγομερών οργανικών ενώσεων, με την επεξεργασία μετρήσεων που είχαν ληφθεί με την επιφανειακά ευαίσθητη τεχνική της φασματοσκοπίας φωτοηλεκτρονίων από ακτίνες Χ (XPS). Από την ανάλυση των φασμάτων XPS προκύπτουν συμπεράσματα τόσο για την παρουσία συγκεκριμένων χημικών στοιχείων στα δείγματα (ποιοτική ανάλυση) όσο και για την συγκέντρωση των στοιχείων αυτών στην περιοχή ανάλυσης (ποσοτική ανάλυση). / This thesis analyzed thin films (thin films) various polymeric or oligomeric organic compounds, the processing of measurements taken with the surface sensitive technique of spectroscopy X-ray photoelectron (XPS). From the analysis of XPS spectra resulting conclusions as to the presence of certain chemical elements in samples (qualitative analysis) and for the concentration of these elements in the analysis (quantitative analysis).

The mechanism by which chiral selectivity takes place is complicated by the surface morphology, the possible involvement of the solvent, and the characteristics of the chiral molecules at the surface. My goal is to model and understand the factors which lead to significant discrimination in the case of three closely related chiral stationary phases: N-(1-phenylethyl)-N’-[3-(triethoxysilyl)propyl]-urea (PEPU), [(3,5-dinitrobenzoyl)-amino]-N-[3-(triethoxysilyl)propyl]-2-phenylacetamide (DNB-phenyglycine), and [(3,5-dinitrobenzoyl)amino]-N-[3-(triethoxysilyl)propyl]-4-methylpentanamide (DNB-leucine). Ab initio calculations are used to develop molecular models of these chiral selectors. These models are employed in molecular dynamics (MD) simulations, which provide the theoretical framework for modelling chiral interfaces in different solvent mixtures. The MD simulations of PEPU interfaces show that, in alcohol/water mixtures, the alcohols form domains at the interface with the hydrophobic portions of the molecule tending to orient towards the surface. This disrupts the water hydrogen bonding networks at the interface and leads to the exclusion of water from the surface region relative to the bulk. The MD simulations of DNB-phenylglycine and DNB-leucine selectors in hexane/2-propanol mixtures demonstrate that the interfaces are distinct both in terms of the selector orientations at the surface and in the number of hydrogen bonds formed with 2-propanol. This occurs despite the structural similarity between these two selectors. The interfaces are also prepared experimentally by attaching the chiral selectors onto oxidized Si(111) samples and AFM tips. In particular, for DNB-phenylglycine and DNB-leucine samples, two synthetic routes have been explored. Using AFM, the morphologies of the resulting chiral interfaces are obtained. X-ray photoelectron spectroscopy and refraction-absorption infrared spectroscopy provide information regarding the relative distribution of the compounds on the surface. Using chemical force microscopy (CFM) measurements, chiral self-selectivity is examined in various solvent mixtures. For PEPU interfaces, the extent of hydrogen bonding at the surface is the dominant contributor to the measured forces. In the case of DNB-phenylglycine and DNB-leucine, CFM measurements of the chiral self-selectivity in 2-propanol demonstrate that chiral discrimination is present in both systems, but larger forces are observed for DNB-phenylglycine, consistent with the molecular dynamics study that shows much weaker solvent interactions with this species. / Thesis (Ph.D, Chemistry) -- Queen's University, 2008-08-14 11:26:37.436

Darbo tikslas yra ištirti etaloninių vanadžio pentoksido ir dioksido Rentgeno fotoelektronų spektrus siekiant nustatyti cheminį poslinkį tarp oksidų V 2p spektrų smailių. Darbe išsamiai aprašytos vanadžio dioksido ir prntoksido struktūros, oksidų savybės, Rentgeno fotoelektronų spektroskopijos metodo pagrindai bei V2O5 ir VO2 Rentgeno fotoelektronų spektrų ypatumai. Aprašyti atliktų eksperimentų metodai. Pateikti eksperimentų ir literatūrinės duomenų bazės analizės rezultatai. Atliktas darbas leido nustatyti sekančius faktus: cheminis poslinkis tarp vanadžio dioksido ir pentoksido etaloninių bandinių Rentgeno fotoelektronų spektrų V 2p3/2 smailių lygus 0.7 eV matuojant spektrus spektrometru XSAM 800 (Kratos Analytical, Anglija); literatūrinių duomenų analizę parodė, kad tikimiausia cheminio poslinkio vertė tarp V 2p3/2 smailių įvairiuose vanadžio junginiuose lygi 1.1 eV; skirtumas tarp eksperimentiškai gautos cheminio poslinkio vertės ir analogiško dydžio gauto iš literatūrinių duomenų analizės sąlygotas tuo, kad buvo matuojami gryni VO2 ir V2O5 bandiniai, o analizei buvo naudojama duomenų visumą apie įvairius vanadžio junginius. / The main aim of the presented work was to investigate the chemical shift between XPS V 2p peaks of standard V2O5 and VO2 samples. The structure and physical properties of vanadium dioxide and pentoxide, X-ray photoelectron spectroscopy basis and some singularities of these oxides XPS spectra are presented. The experimental methods, the results of experiments and the literature analysis results are described. The executed work has allowed establishing following facts: the chemical shift between vanadium dioxide and pentoxide standard samples XPS V 2p peaks is equal to 0.7 eV; the analysis of the literature base shows that this shift for various vanadium compounds is 1.1 eV; the difference between measured chemical shift and chemical shift value established from literature analysis is caused because XPS spectra of pure oxides samples was measured in present work and the analysis of the literature base was performed for various vanadium compounds.

No description available.

This thesis describes studies of materials which can be exploited for hydrogen production from water and sunlight. The materials investigated are maghemite (γ-Fe2O3), magnetite (Fe3O4) and especially hematite (α-Fe2O3), which is an iron oxide with most promising properties in this field. Hematite has been deposited using Atomic Layer Deposition (ALD) - a thin-film technique facilitating layer-by-layer growth with excellent thickness control and step coverage. The iron oxides were deposited using bis-cyclopentadienyl iron (Fe(Cp)2) or iron pentacarbonyl (Fe(CO)5) in combination with an O2 precursor. Since it is crucial to have good control of the deposition process, the influence of substrate, process temperature, precursor and carrier gas have been investigated systematically. By careful control of these deposition parameters, three polymorphs of iron oxide could be deposited: hematite (α-Fe2O3), maghemite (γ-Fe2O3) and magnetite (Fe3O4). The deposited materials were characterized using X-ray Diffraction, Raman and UV-VIS Spectroscopy, and Scanning Electron Microscopy. Hard X-ray Photoelectron Spectroscopy (HAXPES) was also used, since it is a non-destructive, chemically specific, surface sensitive technique – the surface sensitivity resulting from the short mean escape depth of the photoelectrons. The depth probed can be controlled by varying the excitation energy; higher photoelectron energies increasing the inelastic mean-free-path in the material. HAXPES studies of atomic diffusion from F-doped SnO2 substrates showed increased doping levels of Sn, Si and F in the deposited films. Diffusion from the substrate was detected at annealing temperatures between 550 °C and 800 °C. Films annealed in air exhibited improved photocatalytic behavior; a photocurrent of 0.23 mA/cm2 was observed for those films, while the as-deposited hematite films showed no photo-activity whatsoever. The optical properties of low-dimensional hematite were studied in a series of ultra-thin films (thicknesses in the 2-70 nm range). The absorption maxima were shifted to higher energies for films thinner than 20 nm, revealing a different electronic structure in thin films.

The present research focuses on the coupling of mechanical and electrical properties of materials and culminates in a direct connection between applied strain to thin-films, thin-film electron binding energy, the energy loss via plastic deformation provided by an indentation, and the substrate resistance. The methods used in this research include X-ray photoelectron spectroscopy (XPS), nanoindentation, digital optical microscopy, and sputter coat deposition. It is discovered that there is a shift in electron binding energy on the scale of 0.2 eV to 1.4 eV in gold and palladium thin-films sputtered on polyvinylidene fluoride (PVDF) through the application of strain induced by a convex shape. There is a change in the area beneath the load-displacement curve measured via indentation from 5.55 x 10^-10 J to 4.78 x 10^-10 J when the gold-palladium thin-film sputtered on PVDF is changed from the flat arrangement to the convex arrangement. Furthermore, the strain also changed the electrical resistance of aluminum foil, which indicates that the substrate electrical resistance is affected by the induced strain. The internal resistance of a circuit developed for this research changed from 7.76 ohms for flat samples to 8.03 ohms and 8.33 ohms for flat and convex samples, respectively. It is expected that the research can be used to estimate the strain in nanogears and other devices at small length scales.

Corrosion is a common issue which must be accounted for when designing all metal products in our society. Many factors need to be considered when new alloys are created, and further knowledge of the corrosion process would be of great use for companies worldwide. The purpose of this thesis was to investigate if X-ray Photoelectron Spectroscopy, XPS, can be used to characterise and quantify corrosion products. With the goal to develop a method that can be used for further studies to increase our understanding of the corrosion process. Aluminium alloy AA3003 was subjected to an immersion corrosion test in an acidified salt solution for different periods of time and the produced chemical compounds were characterised using XPS. The results revealed a direct connection between corrosion time and formed product, which after characterisation proved to be aluminium hydroxide, Al(OH)3. It was concluded that XPS can be used for corrosion studies and is a method that shows great potential and should be further developed. / I metallindustrin är korrosion ett ständigt förekommande problem som måste tas i beaktande vid design av metallprodukter. Många faktorer är avgörande när nya legeringar utvecklas och en djupare kunskap om korrosionsprocessen och dess mekanismer är av stort värde för företag världen över. Syftet med detta examensarbete var att undersöka huruvida röntgen-fotoelektron-spektroskopi, XPS, kan användas för att kvalitativt och kvantitativt karakterisera de korrosionsprodukter som bildas vid korrosion. Med målet att presentera en metod som kan användas för att vidare undersöka och öka vår förståelse för korrosionsprocessen. Aluminiumlegering AA3003 utsattes för accelererad korrosion i en surgjord saltlösning under varierande tid och korrosionsprodukter karakteriserades med XPS. Resultatet påvisade direkt korrelation mellan korrosionstid och mängd produkt. Korrosionsprodukten visade sig vara aluminiumhydroxid, Al(OH)3, och med det i åtanke kunde slutsatsen dras att XPS kan användas vid studier av korrosion. Den utvärderade metoden visar stor potential och detta examensarbete öppnar upp för vidare forskning som kan komma att öka förståelsen för korrosionsprocessen och hur den kan kontrolleras.

Metallophthalocyanines and metal nanoparticles were successfully synthesized and applied for the electrooxidation of amitrole, nitrite and hydrazine individually or when employed together. The synthesized materials were characterized using the following techniques: predominantly scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemistry and scanning electrochemical microscopy (SECM). Different electrode modification methods were used to modify the glassy carbon substrates. The methods include adsorption, electrodeposition, electropolymerization and click chemistry. Modifying the glassy carbon substrate with MPc (electropolymerization) followed by metal nanoparticles (electrodeposition) or vice versa, made a hybrid modified surface that had efficient electron transfer. This was confirmed by electrochemical impedance studies with voltammetry measurements having lower detection potentials for the analytes. This work also describes for the first time the micropatterning of the glassy carbon substrate using the SECM tip. The substrate was electrografted with 4-azidobenzenediazonium salt and then the click reaction was performed using ethynylferrocene facilitated by Cu⁺ produced at the SECM tip. The SECM imaging was then used to show the clicked spot.

III-V semiconductors have higher charge carrier mobilities than silicon and are used in photovoltaic devices, optical sensors, and emitters. The high injection velocities obtained with III-V channels allow for faster transistors with low power consumption. However, the large-scale implementation in electronic devices is currently limited by the defective interface formed between III-Vs and their oxides. Clean III-V surfaces are highly reactive in air and form amorphous oxides that lead to a high density of dangling bonds. Satisfying these dangling bonds has been associated with an improvement in electrical performance, directing the development of strategies that decrease the surface reactivity (chemical passivation) and the density of surface states that cause power dissipation (electrical passivation). Sulfur bonds easily to III-V surfaces and has been used to chemically and electrically passivate GaAs. In this work, we investigated liquid phase sulfur chemistries in the chemical passivation of clean InSb(100) and In0.53Ga0.47As(100) surfaces terminated by their group V elements. Our strategy consisted of maximizing the number of bonds between sulfur and antimony or arsenic. A long alkane chain thiol, 1-eicosanethiol (ET, 20 carbon atoms), was used to produce a hydrophobic surface and deposit a dense organic layer by taking advantage of the van der Waals interactions between thiol molecules. The first part of the study involved the optimization of the thiol deposition process on InSb. Self-assembled alkanethiol monolayers were formed by immersing clean InSb substrates in ET solutions in ethanol for 20 h. The layers prevented the formation of detectable oxides for 20 min based on the O Auger x-ray photoelectron spectroscopy (XPS) peak. The thiol layer was completely removed by heating the surface to 227 C in vacuum. In the second part of the study, a 20 h ET deposition was performed on In0.53Ga0.47As(100), and re-oxidation was prevented for up to 4 min based on the O 1s XPS peak. The alkanethiolate layer was removed by heating the samples to 350 C in vacuum. The sulfur coverage after 20 min and 20 h ET depositions was increased by performing a second immersion in (NH4)2S without modifying the thickness of the layer. The best process studied consisted of a 20 h immersion in ET solution followed by a short (NH4)2S step, preventing the formation of oxides for up to 9 min. This is due to the presence of available surface sites and weakly bonded molecules in the layer after a long 20 h ET process. The chemical passivation effect is not uniquely influenced by surface termination, roughness, or lattice constant, but is rather a result of a combination of these factors. Future work will involve the fabrication and electrical characterization of III-V devices modified with various chemical passivation strategies.