Multiple morphologies and their transformation of a polystyrene-block-poly(4-vinylpyridine) block copolymer

We report the multiple morphologies and their transformation of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) in low-alkanol solvents. In order to improve the solubility of polystyrene block in alcohol solvents, the solution of block copolymer sample was treated at a higher temperature, and then the influence of rate of decreasing temperature on multiple morphologies (including spheres, rods, vesicles, porous vesicles, large compound vesicles, and large compound micelles) was observed. The transformation of spheres to rods, to tyre-shaped large compound micelles, and to sphere-shaped large compound micelles was also realized. The formation mechanisms of the multiple morphologies and their transformation are discussed briefly.

Observation of inverted phases in poly(styrene-b-butadiene-b-styrene) triblock copolymer by solvent-induced order-disorder phase transition

We report observation of inverted phases consisting of spheres and/or cylinders of the majority fraction block in a poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer by solvent-induced order-disorder phase transition (ODT). The SBS sample has a molecular weight of 140K Da and a polystyrene (PS) weight fraction of 30%. Tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were utilized to study the copolymer microstructure of a set of solution-cast SBS films dried with different solvent evaporation rates, R. The control with different R leads to kinetic frozen-in of microstructures corresponding to a different combination parameter chi (eff)Z of the drying films (where chi (eff) is the effective interaction parameter of the polymer solution in the cast film and Z the number of "blobs" of size equal to the correlation length one block copolymer chain contains), for which faster evaporation rates result in microstructures of smaller chi (eff)Z. As R was decreased from rapid evaporations (similar to0.1 mL/h), the microstructure evolved from a totally disordered one sequentially to inverted phases consisting of spheres and then cylinders of polybutadiene (PB) in a PS matrix and finally reached the equilibrium phase, namely cylinders of PS in a PB matrix. We interpret the formation of inverted phases as due to the increased relative importance of entropy as chi (eff)Z is decreased, which may dominate the energy penalty for having a bigger interfacial area between the immiscible blocks in the inverted phases.

Factor analysis used to peak position optimization and spectral interference correction in inductively coupled plasma atomic emission spectrometry

Target transformation factor analysis was used to correct spectral interference in inductively coupled plasma atomic emission spectrometry (ICP-BES) for the determination of rare earth impurities in high purity thulium oxide. Data matrix was constructed with pure and mixture vectors and background vector. A method based on an error evaluation function was proposed to optimize the peak position, so the influence of the peak position shift in spectral scans on the determination was eliminated or reduced. Satisfactory results were obtained using factor analysis and the proposed peak position optimization method.

Lanthanide ion induced formation of stripes domain structure in phospholipid Langmuir-Blodgett monolayer film observed by atomic force microscopy

Long-range ordered stripes domain structures were observed in Dipalmitoylphosphatidylcholine (DPPC) Langmuir-Blodgett monolayer film which was spread on the subphase of lanthanide ion (Eu3+) solution and transferred to a freshly cleaved mica substrate by vertical deposition. This novel phenomenon was discussed in terms of the competitive interaction of dipole-dipole and electrostatic interactions of the DPPC molecules combined with lanthanide ions with those DPPC molecules free of lanthanide ions.

APPLICATION OF FACTOR-ANALYSIS TO CORRECTION OF SPECTRAL OVERLAP INTERFERENCE IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

Correction of spectral overlap interference in inductively coupled plasma atomic emission spectrometry by factor analysis is attempted. For the spectral overlap of two known lines, a data matrix can be composed from one or two pure spectra and a spectrum of the mixture. The data matrix is decomposed into a spectra matrix and a concentration matrix by target transformation factor analysis. The component concentration of interest in a binary mixture is obtained from the concentration matrix and interference from the other component is eliminated. This method is applied to correcting spectral interference of yttrium on the determination of copper and aluminium: satisfactory results are obtained. This method may also be applied to correcting spectral overlap interference for more than two lines. Like other methods of correcting spectral interferences, factor analysis can only be used for additive spectral overlap. Results obtained from measurements on copper/yttrium mixtures with different white noise added show that random errors in measurement data do not significantly affect the results of the correction method.

EVALUATION OF THE EFFECT OF WAVELENGTH POSITIONING ERRORS ON KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This work evaluates the effect of wavelength positioning errors in spectral scans on analytical results when the Kalman filtering technique is used for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a positioning accuracy of 0.1 pm is required in order to obtain accurate and precise estimates for analyte concentrations. The positioning error in sample scans is more crucial than that in model scans. The relative bias in measured analyte concentration originating from a positioning error in a sample scan increases linearly with an increase in the magnitude of the error and the peak distance of the overlapping lines, but is inversely proportional to the signal-to-background ratio. By the use of an optimization procedure for the positions of scans with the innovations number as the criterion, the wavelength positioning error can be reduced and, correspondingly, the accuracy and precision of analytical results improved.

IMPROVEMENT OF SELECTIVITY WITH NUMERICAL DERIVATIVE TECHNIQUES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

One of the most attractive features of derivative spectrometry is its higher resolving power. In the present power, numerical derivative techniques are evaluated from the viewpoint of increase in selectivity, the latter being expressed in terms of the interferent equivalent concentration (IEC). Typical spectral interferences are covered, including flat background, sloped background, simple curved background and various types of line overlap with different overlapping degrees, which were defined as the ratio of the net interfering signal at the analysis wavelength to the peak signal of the interfering line. the IECs in the derivative spectra are decreased by one to two order of magnitudes compared to those in the original spectra, and in the most cases, assume values below the conventional detection limits. The overlapping degree is the dominant factor that determines whether an analysis line can be resolved from an interfering line with the derivative techniques. Generally, the second derivative technique is effective only for line overlap with an overlapping degree of less than 0.8. The effects of other factors such as line shape, data smoothing, step size and the intensity ratio of analyte to interferent on the performance of the derivative techniques are also discussed. All results are illustrated with practical examples.

Determination of fractional energy loss of waves in nearshore waters using an improved high-order Boussinesq-type model

Fractional energy losses of waves due to wave breaking when passing over a submerged bar are studied systematically using a modified numerical code that is based on the high-order Boussinesq-type equations. The model is first tested by the additional experimental data, and the model's capability of simulating the wave transformation over both gentle slope and steep slope is demonstrated. Then, the model's breaking index is replaced and tested. The new breaking index, which is optimized from the several breaking indices, is not sensitive to the spatial grid length and includes the bottom slopes. Numerical tests show that the modified model with the new breaking index is more stable and efficient for the shallow-water wave breaking. Finally, the modified model is used to study the fractional energy losses for the regular waves propagating and breaking over a submerged bar. Our results have revealed that how the nonlinearity and the dispersion of the incident waves as well as the dimensionless bar height (normalized by water depth) dominate the fractional energy losses. It is also found that the bar slope (limited to gentle slopes that less than 1:10) and the dimensionless bar length (normalized by incident wave length) have negligible effects on the fractional energy losses.

Inorganic glasses, glass-forming liquids and amorphizing solids

Greaves, George; Sen, S., (2007) 'Inorganic glasses, glass-forming liquids and amorphizing solids', Advances in Physics 56(1) pp.1-166 RAE2008

Conversion as transformative experience: a sociological study of identity formation and transformation processes

This thesis contributes to the understanding of the processes involved in the formation and transformation of identities. It achieves this goal by establishing the critical importance of ‘background’ and ‘liminality’ in the shaping of identity. Drawing mainly from the work of cultural anthropology and philosophical hermeneutics a theoretical framework is constructed from which transformative experiences can be analysed. The particular experience at the heart of this study is the phenomenon of conversion and the dynamics involved in the construction of that process. Establishing the axial age as the horizon from which the process of conversion emerged will be the main theme of the first part of the study. Identifying the ‘birth’ of conversion allows a deeper understanding of the historical dynamics that make up the process. From these fundamental dynamics a theoretical framework is constructed in order to analyse the conversion process. Applying this theoretical framework to a number of case-studies will be the central focus of this study. The transformative experiences of Saint Augustine, the fourteenth century nun Margaret Ebner, the communist revolutionary Karl Marx and the literary figure of Arthur Koestler will provide the material onto which the theoretical framework can be applied. A synthesis of the Judaic religious and the Greek philosophical traditions will be the main findings for the shaping of Augustine’s conversion experience. The dissolution of political order coupled with the institutionalisation of the conversion process will illuminate the mystical experiences of Margaret Ebner at a time when empathetic conversion reached its fullest expression. The final case-studies examine two modern ‘conversions’ that seem to have an ideological rather than a religious basis to them. On closer examination it will be found that the German tradition of Biblical Criticism played a most influential role in the ‘conversion’ of Marx and mythology the best medium to understand the experiences of Koestler. The main ideas emerging from this study highlight the fluidity of identity and the important role of ‘background’ in its transformation. The theoretical framework, as constructed for this study, is found to be a useful methodological tool that can offer insights into experiences, such as conversion, that otherwise would remain hidden from our enquiries.

Ab initio calculations of group 4 metallocene reaction mechanisms: atomic layer deposition and bond activation catalysis

Thin film dielectrics based on titanium, zirconium or hafnium oxides are being introduced to increase the permittivity of insulating layers in transistors for micro/nanoelectronics and memory devices. Atomic layer deposition (ALD) is the process of choice for fabricating these films, as it allows for high control of composition and thickness in thin, conformal films which can be deposited on substrates with high aspect-ratio features. The success of this method depends crucially on the chemical properties of the precursor molecules. A successful ALD precursor should be volatile, stable in the gas-phase, but reactive on the substrate and growing surface, leading to inert by-products. In recent years, many different ALD precursors for metal oxides have been developed, but many of them suffer from low thermal stability. Much promise is shown by group 4 metal precursors that contain cyclopentadienyl (Cp = C5H5-xRx) ligands. One of the main advantages of Cp precursors is their thermal stability. In this work ab initio calculations were carried out at the level of density functional theory (DFT) on a range of heteroleptic metallocenes [M(Cp)4-n(L)n], M = Hf/Zr/Ti, L = Me and OMe, in order to find mechanistic reasons for their observed behaviour during ALD. Based on optimized monomer structures, reactivity is analyzed with respect to ligand elimination. The order in which different ligands are eliminated during ALD follows their energetics which was in agreement with experimental measurements. Titanocene-derived precursors, TiCp*(OMe)3, do not yield TiO2 films in atomic layer deposition (ALD) with water, while Ti(OMe)4 does. DFT was used to model the ALD reaction sequence and find the reason for the difference in growth behaviour. Both precursors adsorb initially via hydrogen-bonding. The simulations reveal that the Cp* ligand of TiCp*(OMe)3 lowers the Lewis acidity of the Ti centre and prevents its coordination to surface O (densification) during both of the ALD pulses. Blocking this step hindered further ALD reactions and for that reason no ALD growth is observed from TiCp*(OMe)3 and water. The thermal stability in the gas phase of Ti, Zr and Hf precursors that contain cyclopentadienyl ligands was also considered. The reaction that was found using DFT is an intramolecular α-H transfer that produces an alkylidene complex. The analysis shows that thermal stabilities of complexes of the type MCp2(CH3)2 increase down group 4 (M = Ti, Zr and Hf) due to an increase in the HOMO-LUMO band gap of the reactants, which itself increases with the electrophilicity of the metal. The reverse reaction of α-hydrogen abstraction in ZrCp2Me2 is 1,2-addition reaction of a C-H bond to a Zr=C bond. The same mechanism is investigated to determine if it operates for 1,2 addition of the tBu C-H across Hf=N in a corresponding Hf dimer complex. The aim of this work is to understand orbital interactions, how bonds break and how new bonds form, and in what state hydrogen is transferred during the reaction. Calculations reveal two synchronous and concerted electron transfers within a four-membered cyclic transition state in the plane between the cyclopentadienyl rings, one π(M=X)-to-σ(M-C) involving metal d orbitals and the other σ(C-H)-to-σ(X-H) mediating the transfer of neutral H, where X = C or N. The reaction of the hafnium dimer complex with CO that was studied for the purpose of understanding C-H bond activation has another interesting application, namely the cleavage of an N-N bond and resulting N-C bond formation. Analysis of the orbital plots reveals repulsion between the occupied orbitals on CO and the N-N unit where CO approaches along the N-N axis. The repulsions along the N-N axis are minimized by instead forming an asymmetrical intermediate in which CO first coordinates to one Hf and then to N. This breaks the symmetry of the N-N unit and the resultant mixing of MOs allows σ(NN) to be polarized, localizing electrons on the more distant N. This allowed σ(CO) and π(CO) donation to N and back-donation of π*(Hf2N2) to CO. Improved understanding of the chemistry of metal complexes can be gained from atomic-scale modelling and this provides valuable information for the design of new ALD precursors. The information gained from the model decomposition pathway can be additionally used to understand the chemistry of molecules in the ALD process as well as in catalytic systems.

Atomic layer deposition of copper for CMOS interconnects

This work concerns the atomic layer deposition (ALD) of copper. ALD is a technique that allows conformal coating of difficult topographies such as narrow trenches and holes or even shadowed regions. However, the deposition of pure metals has so far been less successful than the deposition of oxides except for a few exceptions. Challenges include difficulties associated with the reduction of the metal centre of the precursor at reasonable temperatures and the tendency of metals to agglomerate during the growth process. Cu is a metal of special technical interest as it is widely used for interconnects on CMOS devices. These interconnects are usually fabricated by electroplating, which requires the deposition of thin Cu seed layers onto the trenches and vias. Here, ALD is regarded as potential candidate for replacing the current PVD technique, which is expected to reach its limitations as the critical dimensions continue to shrink. This work is separated into two parts. In the first part, a laboratory-scale ALD reactor was constructed and used for the thermal ALD of Cu. In the second part, the potentials of the application of Cu ALD on industry scale fabrication were examined in a joint project with Applied Materials and Intel. Within this project precursors developed by industrial partners were evaluated on a 300 mm Applied Materials metal-ALD chamber modified with a direct RF-plasma source. A feature that makes ALD a popular technique among researchers is the possibility to produce high- level thin film coatings for micro-electronics and nano-technology with relatively simple laboratory- scale reactors. The advanced materials and surfaces group (AMSG) at Tyndall National Institute operates a range of home-built ALD reactors. In order to carry out Cu ALD experiments, modifications to the normal reactor design had to be made. For example a carrier gas mechanism was necessary to facilitate the transport of the low-volatile Cu precursors. Precursors evaluated included the readily available Cu(II)-diketonates Cu-bis(acetylacetonate), Cu-bis(2,2,6,6-tetramethyl-hepta-3,5-dionate) and Cu-bis(1,1,1,5,5,5-hexafluoacetylacetonate) as well as the Cu-ketoiminate Cu-bis(4N-ethylamino- pent-3-en-2-onate), which is also known under the trade name AbaCus (Air Liquide), and the Cu(I)- silylamide 1,3-diisopropyl-imidazolin-2-ylidene Cu(I) hexamethyldisilazide ([NHC]Cu(hmds)), which was developed at Carleton University Ottawa. Forming gas (10 % H2 in Ar) was used as reducing agent except in early experiments where formalin was used. With all precursors an extreme surface selectivity of the deposition process was observed and significant growth was only achieved on platinum-group metals. Improvements in the Cu deposition process were obtained with [NHC]Cu(hmds) compared with the Cu(II) complexes. A possible reason is the reduced oxidation state of the metal centre. Continuous Cu films were obtained on Pd and indications for saturated growth with a rate of about 0.4 Å/cycle were found for deposition at 220 °C. Deposits obtained on Ru consisted of separated islands. Although no continuous films could be obtained in this work the relatively high density of Cu islands obtained was a clear improvement as compared to the deposits grown with Cu(II) complexes. When ultra-thin Pd films were used as substrates, island growth was also observed. A likely reason for this extreme difference to the Cu films obtained on thicker Pd films is the lack of stress compensation within the thin films. The most likely source of stress compensation in the thicker Pd films is the formation of a graded interlayer between Pd and Cu by inter-diffusion. To obtain continuous Cu films on more materials, reduction of the growth temperature was required. This was achieved in the plasma assisted ALD experiments discussed in the second part of this work. The precursors evaluated included the AbaCus compound and CTA-1, an aliphatic Cu-bis(aminoalkoxide), which was supplied by Adeka Corp.. Depositions could be carried out at very low temperatures (60 °C Abacus, 30 °C CTA-1). Metallic Cu could be obtained on all substrate materials investigated, but the shape of the deposits varied significantly between the substrate materials. On most materials (Si, TaN, Al2O3, CDO) Cu grew in isolated nearly spherical islands even at temperatures as low as 30 °C. It was observed that the reason for the island formation is the coalescence of the initial islands to larger, spherical islands instead of forming a continuous film. On the other hand, the formation of nearly two-dimensional islands was observed on Ru. These islands grew together forming a conductive film after a reasonably small number of cycles. The resulting Cu films were of excellent crystal quality and had good electrical properties; e.g. a resistivity of 2.39 µΩ cm was measured for a 47 nm thick film. Moreover, conformal coating of narrow trenches (1 µm deep 100/1 aspect ratio) was demonstrated showing the feasibility of the ALD process.

Atomic layer deposition of interface control layers for the fabrication of III/V MOS devices

The continued advancement of metal oxide semiconductor field effect transistor (MOSFET) technology has shifted the focus from Si/SiO2 transistors towards high-κ/III-V transistors for high performance, faster devices. This has been necessary due to the limitations associated with the scaling of the SiO2 thickness below ~1 nm and the associated increased leakage current due to direct electron tunnelling through the gate oxide. The use of these materials exhibiting lower effective charge carrier mass in conjunction with the use of a high-κ gate oxide allows for the continuation of device scaling and increases in the associated MOSFET device performance. The high-κ/III-V interface is a critical challenge to the integration of high-κ dielectrics on III-V channels. The interfacial chemistry of the high-κ/III-V system is more complex than Si, due to the nature of the multitude of potential native oxide chemistries at the surface with the resultant interfacial layer showing poor electrical insulating properties when high-κ dielectrics are deposited directly on these oxides. It is necessary to ensure that a good quality interface is formed in order to reduce leakage and interface state defect density to maximise channel mobility and reduce variability and power dissipation. In this work, the ALD growth of aluminium oxide (Al2O3) and hafnium oxide (HfO2) after various surface pre-treatments was carried out, with the aim of improving the high-κ/III-V interface by reducing the Dit – the density of interface defects caused by imperfections such as dangling bonds, dimers and other unsatisfied bonds at the interfaces of materials. A brief investigation was performed into the structural and electrical properties of Al2O3 films deposited on In0.53Ga0.47As at 200 and 300oC via a novel amidinate precursor. Samples were determined to experience a severe nucleation delay when deposited directly on native oxides, leading to diminished functionality as a gate insulator due to largely reduced growth per cycle. Aluminium oxide MOS capacitors were prepared by ALD and the electrical characteristics of GaAs, In0.53Ga0.47As and InP capacitors which had been exposed to pre-pulse treatments from triethyl gallium and trimethyl indium were examined, to determine if self-cleaning reactions similar to those of trimethyl aluminium occur for other alkyl precursors. An improved C-V characteristic was observed for GaAs devices indicating an improved interface possibly indicating an improvement of the surface upon pre-pulsing with TEG, conversely degraded electrical characteristics observed for In0.53Ga0.47As and InP MOS devices after pre-treatment with triethyl gallium and trimethyl indium respectively. The electrical characteristics of Al2O3/In0.53Ga0.47As MOS capacitors after in-situ H2/Ar plasma treatment or in-situ ammonium sulphide passivation were investigated and estimates of interface Dit calculated. The use of plasma reduced the amount of interface defects as evidenced in the improved C-V characteristics. Samples treated with ammonium sulphide in the ALD chamber were found to display no significant improvement of the high-κ/III-V interface. HfO2 MOS capacitors were fabricated using two different precursors comparing the industry standard hafnium chloride process with deposition from amide precursors incorporating a ~1nm interface control layer of aluminium oxide and the structural and electrical properties investigated. Capacitors furnished from the chloride process exhibited lower hysteresis and improved C-V characteristics as compared to that of hafnium dioxide grown from an amide precursor, an indication that no etching of the film takes place using the chloride precursor in conjunction with a 1nm interlayer. Optimisation of the amide process was carried out and scaled samples electrically characterised in order to determine if reduced bilayer structures display improved electrical characteristics. Samples were determined to exhibit good electrical characteristics with a low midgap Dit indicative of an unpinned Fermi level

Quantum chemical study of the effect of precursor stereochemistry on dissociative chemisorption and surface redox reactions during the atomic layer deposition of the transition metal copper

Using quantum chemical calculations, we investigate surface reactions of copper precursors and diethylzinc as the reducing agent for effective Atomic Layer Deposition (ALD) of Cu. The adsorption of various commonly used Cu(II) precursors is explored. The precursors vary in the electronegativity and conjugation of the ligands and flexibility of the whole molecule. Our study shows that the overall stereochemistry of the precursor governs the adsorption onto its surface. Formation of different Cu(II)/Cu(I)/Cu(0) intermediate complexes from the respective Cu(II) compounds on the surface is also explored. The surface model is a (111) facet of a Cu55 cluster. Cu(I) compounds are found to cover the surface after the precursor pulse, irrespective of the precursor chosen. We provide new information about the surface chemistry of Cu(II) versus Cu(I) compounds. A pair of CuEt intermediates or the dimer Cu2Et2 reacts in order to deposit a new Cu atom and release gaseous butane. In this reaction, two electrons from the Et anions are donated to copper for reduction to metallic form. This indicates that a ligand exchange between the Cu and Zn is important for the success of this transmetalation reaction. The effect of the ligands in the precursor on the electron density before and after adsorption onto the surface has also been computed through population analysis. In the Cu(I) intermediate, charge is delocalized between the Cu precursor and the bare copper surface, indicating metallic bonding as the precursor densifies to the surface.

Computational study of the growth of copper thin films by atomic layer deposition

Copper is the main interconnect material in microelectronic devices, and a 2 nm-thick continuous Cu film seed layer needs to be deposited to produce microelectronic devices with the smallest features and more functionality. Atomic layer deposition (ALD) is the most suitable method to deposit such thin films. However, the reaction mechanism and the surface chemistry of copper ALD remain unclear, which is deterring the development of better precursors and design of new ALD processes. In this thesis, we study the surface chemistries during ALD of copper by means of density functional theory (DFT). To understand the effect of temperature and pressure on the composition of copper with substrates, we used ab initio atomistic thermodynamics to obtain phase diagram of the Cu(111)/SiO2(0001) interface. We found that the interfacial oxide Cu2O phases prefer high oxygen pressure and low temperature while the silicide phases are stable at low oxygen pressure and high temperature for Cu/SiO2 interface, which is in good agreement with experimental observations. Understanding the precursor adsorption on surfaces is important for understanding the surface chemistry and reaction mechanism of the Cu ALD process. Focusing on two common Cu ALD precursors, Cu(dmap)2 and Cu(acac)2, we studied the precursor adsorption on Cu surfaces by means of van der Waals (vdW) inclusive DFT methods. We found that the adsorption energies and adsorption geometries are dependent on the adsorption sites and on the method used to include vdW in the DFT calculation. Both precursor molecules are partially decomposed and the Cu cations are partially reduced in their chemisorbed structure. It is found that clean cleavage of the ligand−metal bond is one of the requirements for selecting precursors for ALD of metals. 2 Bonding between surface and an atom in the ligand which is not coordinated with the Cu may result in impurities in the thin film. To have insight into the reaction mechanism of a full ALD cycle of Cu ALD, we proposed reaction pathways based on activation energies and reaction energies for a range of surface reactions between Cu(dmap)2 and Et2Zn. The butane formation and desorption steps are found to be extremely exothermic, explaining the ALD reaction scheme of original experimental work. Endothermic ligand diffusion and re-ordering steps may result in residual dmap ligands blocking surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. This may lead to very slow growth rate, as was the case in the experimental work. By investigating the reduction of CuO to metallic Cu, we elucidated the role of the reducing agent in indirect ALD of Cu. We found that CuO bulk is protected from reduction during vacuum annealing by the CuO surface and that H2 is required in order to reduce that surface, which shows that the strength of reducing agent is important to obtain fully reduced metal thin films during indirect ALD processes. Overall, in this thesis, we studied the surface chemistries and reaction mechanisms of Cu ALD processes and the nucleation of Cu to form a thin film.