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.

First principles modelling of nucleation and growth during atomic layer deposition onto III-V substrates

Atomic layer deposition (ALD) is now used in semiconductor fabrication lines to deposit nanometre-thin oxide films, and has thus enabled the introduction of high-permittivity dielectrics into the CMOS gate stack. With interest increasing in transistors based on high mobility substrates, such as GaAs, we are investigating the surface treatments that may improve the interface characteristics. We focus on incubation periods of ALD processes on III-V substrates. We have applied first principles Density Functional Theory (DFT) to investigate detailed chemistry of these early stages of growth, specifically substrate and ALD precursor interaction. We have modelled the ‘clean-up’ effect by which organometallic precursors: trimethylaluminium (TMA) or hafnium and titanium amides clean arsenic oxides off the GaAs surface before ALD growth of dielectric commences and similar effect on Si3N4 substrate. Our simulations show that ‘clean-up’ of an oxide film strongly depends on precursor ligand, its affinity to the oxide and the redox character of the oxide. The predominant pathway for a metalloid oxide such as arsenic oxide is reduction, producing volatile molecules or gettering oxygen from less reducible oxides. An alternative pathway is non-redox ligand exchange, which allows non-reducible oxides (e.g. SiO2) to be cleaned-up. First principles study shows also that alkylamides are more susceptible to decomposition rather than migration on the oxide surface. This improved understanding of the chemical principles underlying ‘clean-up’ allows us to rationalize and predict which precursors will perform the reaction. The comparison is made between selection of metal chlorides, methyls and alkylamides precursors.

Multi-scale modelling of atomic layer deposition

High-permittivity ("high-k") dielectric materials are used in the transistor gate stack in integrated circuits. As the thickness of silicon oxide dielectric reduces below 2 nm with continued downscaling, the leakage current because of tunnelling increases, leading to high power consumption and reduced device reliability. Hence, research concentrates on finding materials with high dielectric constant that can be easily integrated into a manufacturing process and show the desired properties as a thin film. Atomic layer deposition (ALD) is used practically to deposit high-k materials like HfO2, ZrO2, and Al2O3 as gate oxides. ALD is a technique for producing conformal layers of material with nanometer-scale thickness, used commercially in non-planar electronics and increasingly in other areas of science and technology. ALD is a type of chemical vapor deposition that depends on self-limiting surface chemistry. In ALD, gaseous precursors are allowed individually into the reactor chamber in alternating pulses. Between each pulse, inert gas is admitted to prevent gas phase reactions. This thesis provides a profound understanding of the ALD of oxides such as HfO2, showing how the chemistry affects the properties of the deposited film. Using multi-scale modelling of ALD, the kinetics of reactions at the growing surface is connected to experimental data. In this thesis, we use density functional theory (DFT) method to simulate more realistic models for the growth of HfO2 from Hf(N(CH3)2)4/H2O and HfCl4/H2O and for Al2O3 from Al(CH3)3/H2O.Three major breakthroughs are discovered. First, a new reaction pathway, ’multiple proton diffusion’, is proposed for the growth of HfO2 from Hf(N(CH3)2)4/H2O.1 As a second major breakthrough, a ’cooperative’ action between adsorbed precursors is shown to play an important role in ALD. By this we mean that previously-inert fragments can become reactive once sufficient molecules adsorb in their neighbourhood during either precursor pulse. As a third breakthrough, the ALD of HfO2 from Hf(N(CH3)2)4 and H2O is implemented for the first time into 3D on-lattice kinetic Monte-Carlo (KMC).2 In this integrated approach (DFT+KMC), retaining the accuracy of the atomistic model in the higher-scale model leads to remarkable breakthroughs in our understanding. The resulting atomistic model allows direct comparison with experimental techniques such as X-ray photoelectron spectroscopy and quartz crystal microbalance.

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.

Chemical vapour deposition of complex ferroic oxide thin films

Herein is presented a novel chemical vapour deposition (CVD) route for the fabrication of oxide ferroelectrics. A versatile layer-by-layer growth mode was developed to prepare naturally super-latticed bismuth based materials belonging to the Aurivillius phase family, with which good control over composition and crystal structure was achieved. In chapter 3, the effect of epitaxial strain on one of the very simple oxide materials TiO2 was studied. It has been found that the ultra-thin TiO2 films demonstrate ferroelectric behaviour when grown on NdGaO3 substrates. TiO2 exists in various crystal phases, but none of them show ferroelectric behaviour. The epitaxial strain due to the substrate, changes the crystal structure from tetragonal to orthorhombic which in turn leads to ferroelectric behaviour. In chapter 4, a unique growth method for multiferroic BiFeO3 (BFO) thin films is shown, where a phase pure BFO thin films can be prepared even in the presence of excess bismuth precursor during the growth process. This type of growth is usually called adsorption controlled growth and can be used for growing various bismuth containing compounds, where the volatility of bismuth can create various types of defects. Chapter 5 describes the growth of Bi4Ti3O12 thin films in a layer-by-layer growth mode. In this section, the effect of Bi and Ti precursor flows on the growth of thin films is discussed and it is shown that how change in precursor flows leads to out-ofphase boundary defects during the layer-by-layer growth mode. In chapter 6, the growth of a compound Bi5Ti3FeO15, which is a 1:1 mixture of BiFeO3 and Bi4Ti3O12, is presented. The growth mechanism of Bi5Ti3FeO15 thin films is presented, where the Fe precursor flow was controlled from zero to the insertion of one full BiFeO3 perovskite unit cell into the Bi4Ti3O12 structure in addition, the effect of iron precursor flow on crystalline properties is demonstrated. The methods presented in this thesis can be adopted to grow ferroelectric and multiferroic films for industrial applications.

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

Atomic layer deposition of copper – study through density functional theory

The wonder of the last century has been the rapid development in technology. One of the sectors that it has touched immensely is the electronic industry. There has been exponential development in the field and scientists are pushing new horizons. There is an increased dependence in technology for every individual from different strata in the society. Atomic Layer Deposition (ALD) is a unique technique for growing thin films. It is widely used in the semiconductor industry. Films as thin as few nanometers can be deposited using this technique. Although this process has been explored for a variety of oxides, sulphides and nitrides, a proper method for deposition of many metals is missing. Metals are often used in the semiconductor industry and hence are of significant importance. A deficiency in understanding the basic chemistry at the nanoscale for possible reactions has delayed the improvement in metal ALD. In this thesis, we study the intrinsic chemistry involved for Cu ALD. This work reports computational study using Density Functional Theory as implemented in TURBOMOLE program. Both the gas phase and surface reactions are studied in most of the cases. The merits and demerits of a promising transmetallation reaction have been evaluated at the beginning of the study. Further improvements in the structure of precursors and coreagent have been proposed. This has led to the proposal of metallocenes as co-reagents and Cu(I) carbene compounds as new set of precursors. A three step process for Cu ALD that generates ligand free Cu layer after every ALD pulse has also been studied. Although the chemistry has been studied under the umbrella of Cu ALD the basic principles hold true for ALD of other metals (e.g. Co, Ni, Fe ) and also for other branches of science like thin film deposition other than ALD, electrochemical reactions, etc.

Cooperation between adsorbates accounts for the activation of atomic layer deposition reactions

Atomic layer deposition (ALD) is a technique for producing conformal layers of nanometre-scale thickness, used commercially in non-planar electronics and increasingly in other high-tech industries. ALD depends on self-limiting surface chemistry but the mechanistic reasons for this are not understood in detail. Here we demonstrate, by first-principle calculations of growth of HfO2 from Hf(N(CH3)2)4–H2O and HfCl4–H2O and growth of Al2O3 from Al(CH3)3–H2O, that, for all these precursors, co-adsorption plays an important role in ALD. By this we mean that previously-inert adsorbed fragments can become reactive once sufficient numbers of molecules adsorb in their neighbourhood during either precursor pulse. Through the calculated activation energies, this ‘cooperative’ mechanism is shown to have a profound influence on proton transfer and ligand desorption, which are crucial steps in the ALD cycle. Depletion of reactive species and increasing coordination cause these reactions to self-limit during one precursor pulse, but to be re-activated via the cooperative effect in the next pulse. This explains the self-limiting nature of ALD.

Precursor adsorption on copper surfaces as the first step during the deposition of copper: a density functional study with van der Waals correction

Copper dimethylamino-2-propoxide [Cu(dmap)2] is used as a precursor for low-temperature atomic layer deposition (ALD) of copper thin films. Chemisorption of the precursor is the necessary first step of ALD, but it is not known in this case whether there is selectivity for adsorption sites, defects, or islands on the substrate. Therefore, we study the adsorption of the Cu(dmap)2 molecule on the different sites on flat and rough Cu surfaces using PBE, PBE-D3, optB88-vdW, and vdW-DF2 methods. We found the relative order of adsorption energies for Cu(dmap)2 on Cu surfaces is Eads (PBE-D3) > Eads (optB88-vdW) > Eads (vdW-DF2) > Eads (PBE). The PBE and vdW-DF2 methods predict one chemisorption structure, while optB88-vdW predicts three chemisorption structures for Cu(dmap)2 adsorption among four possible adsorption configurations, whereas PBE-D3 predicts a chemisorbed structure for all the adsorption sites on Cu(111). All the methods with and without van der Waals corrections yield a chemisorbed molecule on the Cu(332) step and Cu(643) kink because of less steric hindrance on the vicinal surfaces. Strong distortion of the molecule and significant elongation of Cu–N bonds are predicted in the chemisorbed structures, indicating that the ligand–Cu bonds break during the ALD of Cu from Cu(dmap)2. The molecule loses its initial square-planar structure and gains linear O–Cu–O bonding as these atoms attach to the surface. As a result, the ligands become unstable and the precursor becomes more reactive to the coreagent. Charge redistribution mainly occurs between the adsorbate O–Cu–O bond and the surface. Bader charge analysis shows that electrons are donated from the surface to the molecule in the chemisorbed structures, so that the Cu center in the molecule is partially reduced.

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.