Thesis (Ph.D.)--McMaster University, 2003. / Advisor: N. Werstiuk. Includes bibliographical references (leaves 148-156). Also available via World Wide Web.

A new multi-purpose surface analytical instrument (the Hallam instrument) is described, which combines the surface specific information obtained using x-ray photoelectron spectroscopy (XPS), with bulk information obtained using Energy Dispersive X-ray (EDX) detection. A 15kV electron gun and an ultra high vacuum EDX detector give the instrument an EDX mapping capability. To exploit this to its full potential, spatial alignment of EDX maps acquired at various electron beam energies, E[o], was required. The misalignment of images acquired at various E[o] values was investigated, and a means of describing the misalignment as a function of E[o] was presented. An algorithm was developed which would allow the alignment of offline images acquired at different E[o] values. This was demonstrated on images acquired on both the Hallam instrument and on a Phillips XL40 electron microscope. The small area XPS system developed by Kratos analytical gave a spatial resolution of 30pm at the centre of the field of view, although this deteriorated away from the centre. The reasons for this deterioration in spatial resolution were investigated, and two methods of improving the system were presented. The improvements were implemented on the Hallam instrument and demonstrated using a standard silver grid sample. The small area XPS was applied to a TiAINi coated stainless steel sample to demonstrate its application to real samples, and to display the spatial alignment between the XPS and EDX maps. Finally, the instrument was calibrated for quantitative XPS studies. This involves determining the response of the instrument as a function of the photoelectron kinetic energy. From several methods presented in the literature, the most appropriate was chosen for calibration of the 'Hallam' instrument. The effectiveness of the method used was assessed by recording spectrum intensity from pure elemental standards, and comparing the results with intensity values calculated using the calibration curves.

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.

Doctor of Philosophy / Department of Chemistry / Peter M. Sherwood / This work is a detailed study of the interaction between two phosphorous-containing acids and the metals chromium and 316L stainless steel. The objective of this work is to investigate the formation of unique thin films on the two metals and to probe the surface chemistry of these films through the use of core level and valence band X-ray photoelectron spectroscopy (XPS). Chromium forms a wide array of oxides and can exist at several valencies. Valence band XPS is used in conjunction with band structure and multiple scattered wave X[alpha] calculations to distinguish which states are present in the resultant films. Both 99.99% chromium and 316L stainless steel foils were treated with orthophosphoric acid and 1-hydroxyethylidene-1,1-diphosphonic acid, otherwise known as etidronic acid. Two methods developed in the Sherwood research laboratory for forming oxide-free films on metal surfaces are utilized in this work. Core level XPS results did not provide sufficient information to draw conclusions regarding the products formed in the reactions. The valence band results showed clear evidence of multiple forms of phosphates forming on the metal surfaces as evidenced by the subtle differences in separation between the phosphorous 3p and 3s peaks as well as differences in separation between the O2s and phosphorous 3s peaks. The Valence Band XPS results were interpreted by X-[alpha] cluster and band structure calculations. Films formed on chromium foil from the orthophosphoric acid were found to be condensed phosphates that are stable in air. Etidronic acid formed very thin phosphate films on chromium with both treatment methods as well as on 316L stainless steel when the bench top method was applied. Treatment of etched 316L steel in the anaerobic cell generated an etidronate film. This sample was the only etidronate film formed, all other etidronate-based films were generated from disassembled portions of the etidronate ion to form phosphate films.

>Magister Scientiae - MSc / In the wide search for advanced materials for next generation lithium-ion batteries, lithium manganese orthosilicate, Li₂MnSiO₄ is increasingly gaining attention as a potential cathode material by virtue of its ability to facilitate the extraction of two lithium ions per formula unit, resulting in a two-electron redox process involving Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺ redox couples. This property confers on it, a higher theoretical specific capacity of 333 mAhg⁻¹ which is superior to the conventional layered LiCoO₂ at 274 mAhg⁻¹ and the commercially available olivine LiFePO₄ at 170 mAhg⁻¹. Its iron analogue, Li₂FeSiO₄ has only 166 mAhg⁻¹ capacity as the Fe⁴⁺ oxidation state is difficult to access. However, the capacity of Li₂MnSiO₄ is not fully exploited in practical galvanostatic charge-discharge tests due to the instability of the delithiated material which causes excessive polarization during cycling and its low intrinsic electronic conductivity. By reducing the particle size, the electrochemical performance of this material can be enhanced since it increases the surface contact between the electrode and electrolyte and further reduces the diffusion pathway of lithium ions. In this study, a versatile hydrothermal synthetic pathway was employed to produce nanoparticles of Li₂MnSiO₄, by carefully tuning the reaction temperature and the concentration of the metal precursors. The nanostructured cathode material was further coated with a thin film of aluminium oxide in order to modify its structural and electronic properties. The synthesized materials were characterized by microscopic (HRSEM and HRTEM), spectroscopic (FTIR, XRD, SS-NMR, XPS) and electrochemical techniques (CV, SWV and EIS). Microscopic techniques revealed spherical morphologies with particle sizes in the range of 21-90 nm. Elemental distribution maps obtained from HRSEM for the novel cathode material showed an even distribution of elements which will facilitate the removal/insertion of Li-ions and electrons out/into the cathode material. Spectroscopic results (FTIR) revealed the vibration of the Si-Mn-O linkage, ascertaining the complete insertion of Mn ions into the SiO₄⁴⁻ tetrahedra. XRD and ⁷Li MAS NMR studies confirmed a Pmn21 orthorhombic crystal pattern for the pristine Li₂MnSiO₄ and novel Li₂MnSiO₄/Al₂O₃ which is reported to provide the simplest migratory pathway for Li-ions due to the high symmetrical equivalence of all Li sites in the unit cell, thus leading to high electrochemical reversibility and an enhancement in the overall performance of the cathode materials. The divalent state of manganese present in Li₂Mn²⁺SiO₄ was confirmed by XPS surface analysis. Scan rate studies performed on the novel cathode material showed a quasi-reversible electron transfer process. The novel cathode material demonstrated superior electrochemical performance over the pristine material. Charge/discharge capacity values calculated from the cyclic voltammograms of the novel and pristine cathode materials showed a higher charge and discharge capacity of 209 mAh/g and 107 mAh/g for the novel cathode material compared to 159 mAh/g and 68 mAh/g for the pristine material. The diffusion coefficient was one order of magnitude higher for the novel cathode material (3.06 x10⁻⁶ cm2s⁻¹) than that of the pristine material (6.79 x 10⁻⁷ cm2s⁻¹), with a charge transfer resistance of 1389 Ω and time constant (τ) of 1414.4 s rad⁻¹ for the novel cathode material compared to 1549 Ω and 1584.4 s rad-1 for the pristine material. The higher electrochemical performance of the novel Li₂MnSiO₄/All₂O₃ cathode material over the pristine Li₂MnSiO₄ material can be attributed to the alumina nanoparticle surface coating which considerably reduced the structural instability intrinsic to the pristine Li₂MnSiO₄ cathode material and improved the charge transfer kinetics.

Femtosecond time-resolved photoelectron spectroscopy (fsTRPES) experiments have been used to study the photoelectron energy spectra of simple molecules since the 1980’s. Analysis of these spectra provides information about the ultrafast internal conversion dynamics of the parent ions. However, ultraviolet pulses must be used for these pump-probe experiments in order to ionize the molecules. Since current solid state lasers, such as the Ti:sapphire laser, typically produce pulses centered at 800nm, it is necessary to generate UV pulses with nonlinear frequency mixing techniques. I therefore constructed an optical setup to generate the 3rd and 4th harmonics, at 266.7nm and 200nm, respectively, of a Ti:sapphire (Ti:sa) chirped-pulse amplified (CPA) laser system that produces 35fs pulses centered at 800nm. Thin Beta-Barium Borate (β-BaB2O4 or BBO) crystals were chosen to achieve a compromise between short pulse durations and reasonable conversion efficiencies, since ultrashort pulses are quite susceptible to broadening from group velocity dispersion (GVD). Output energies of around 11μJ and 230nJ were measured for the 266.7nm and 200nm pulses, respectively. The transform limits of the 3rd and 4th harmonic pulse lengths were calculated from their measured spectral widths. We found that the 266.7nm bandwidth was large enough to support sub-30fs pulses, and due to cutting at the lower-wavelength end of the 200nm spectrum, we calculated an upper limit of 38fs. The pulses were compressed with pairs of CaF2 prisms to compensate for dispersion introduced by transmissive optics. Two-photon absorption (TPA) intensity autocorrelations revealed fully compressed pulse lengths of 36 ± 2 fs and 42 ± 4 fs for the 3rd and 4th harmonics, respectively.

The reactivity of oxide surfaces and metal-oxide interfaces play an important role in many technological applications such as corrosion, heterogeneous catalysis, and microelectronics. The focus of this research was (1) understanding the effects of water vapor exposure of ultrathin aluminum oxide films under non-ultrahigh vacuum conditions (>10-9 Torr) and (2) characterization of Pt growth modes on ultrathin Ta silicate and silicon dioxide films and the effects of growth modes on adhesion of a Cu overlayer. These studies were conducted with X-ray photoelectron spectroscopy (XPS). Ni3Al(110) was oxidized (10-6 Torr O2, 800K) followed by annealing (1100K). The data indicate that the annealed oxide film is composed of NiO, Al2O3 and an intermediate phase denoted here as "AlOx". Upon exposure of the oxide film at ambient temperature to increasing water vapor pressure (10-6 - 5 Torr), a shift in both the O(1s) and Al(2p)oxide peak maxima to lower binding energies is observed. In contrast, exposure of Al2O3/Al(polycrystalline) to water vapor under the same conditions results in a high binding energy shoulder in the O(1s) spectra which indicates hydroxylation. Spectral decomposition provides further insight into the difference in reactivity between the two oxide films. The corresponding trends of the O(1s)/Ni0(2p3/2) and Al(2p)/Ni0(2p3/2) spectral intensity ratios suggest conformal changes of the oxide film on Ni3Al(110). The growth behavior of sputter deposited Pt at ~300K on Ta silicate and SiO2 ultrathin films formed on Si(100) was investigated. The XPS data show that Pt deposition results in uniform growth or "wetting" on Ta silicate and 2-D cluster growth on SiO2. Electroless Cu deposition on ~11 monolayers (ML) Pt/Ta silicate film results in an adherent Cu film which passed the Scotch tape test. In contrast, electroless Cu deposition on ~11ML Pt/SiO2 results in a non-adherent Cu film due to weak Pt/SiO2 interaction.

The TaSiO6 films, ~8Å thick, were formed by sputter deposition of Ta onto ultrathin SiO2 substrates at 300 K, followed by annealing to 600 K in 2 torr O2. X-ray photoelectron spectroscopy (XPS) measurements of the films yielded a Si(2p) binding energy at 102.1 eV and Ta(4f7/2) binding energy at 26.2 eV, indicative of Ta silicate formation. O(1s) spectra indicate that the film is substantially hydroxylated. Annealing the film to > 900 K in UHV resulted in silicate decomposition to SiO2 and Ta2O5. The Ta silicate film is stable in air at 300K. XPS data show that sputter-deposited Cu (300 K) displays conformal growth on Ta silicate surface (TaSiO6) but 3-D growth on the annealed and decomposed silicate surface. Initial Cu/silicate interaction involves Cu charge donation to Ta surface sites, with Cu(I) formation and Ta reduction. The results are similar to those previously reported for air-exposed TaSiN, and indicate that Si-modified Ta barriers should maintain Cu wettability under oxidizing conditions for Cu interconnect applications. XPS has been used to study the reaction of tert-butylimino tris(diethylamino) tantalum (TBTDET) with atomic hydrogen on SiO2 and organosilicate glass (OSG) substrates. The results on both substrates indicate that at 300K, TBTDET partially dissociates, forming Ta-O bonds with some precursor still attached. Subsequent bombardment with atomic hydrogen at 500K results in stoichiometric TaN formation, with a Ta(4f7/2) feature at binding energy 23.2 eV and N(1s) at 396.6 eV, leading to a TaN phase bonded to the substrate by Ta-O interactions. Subsequent depositions of the precursor on the reacted layer on SiO2 and OSG, followed by atomic hydrogen bombardment, result in increased TaN formation. These results indicate that TBTDET and atomic hydrogen may form the basis for a low temperature atomic layer deposition (ALD) process for the formation of ultraconformal TaNx or Ru/TaNx barriers. The interactions of sputter-deposited ruthenium with OSG at 300 K have been studied by XPS for Ru coverages from ~ 0.1 monolayer to several monolayers, using in-situ sample transfer between the deposition and analysis chambers. The results indicate Stranski-Krastanov (SK) type growth, with the completion of the first layer of Ru at an average thickness corresponding to 1 monolayer average coverage. Ru(0) is the only electronic state present. XPS core level spectra indicate weak chemical interactions between Ru and the substrate. A less pronounced tendency towards SK growth was observed for Ru deposition on parylene. Deposition of Ru on OSG followed by electroless deposition of Cu resulted in the formation of a shiny copper film that failed the Scotch® tape test. Results indicate failure mainly at the Ru/OSG interface.