In this work we examine Ag-Au and Ni-Cu nanoclusters: their structural,compositional, and morphological characteristics are investigated in detail. The clusters are produced by the inert gas aggregation (IGA) method from magnetron sputtered alloy targets, in an UHV compatible system. The design of the system is optimized for production and deposition of the clusters with size in the range 5 nm < D < 10 nm. In order to increase the flux of sub-5 nm clusters in the system, we conducted modeling and experimental studies of cluster motion: the simulations showed that skimmers with wider internal angles might significantly improve the flux of smaller nanoclusters; however, the experimental study revealed a major influence of the background gas on scattering of such nanoclusters which consequently led to the loss of their flux. A comprehensive study of Ag0:85Au0:15 nanoclusters was conducted over a period of more than 2 years. Nanoclusters with sizes in the range 3 nm < D < 10 nm were deposited onto a-C films at various surface coverages and systematically investigated by transmission electron microscopy. We found that Ag-Au nanoclusters initially exhibited icosahedral and decahedral structural motifs, with a very small fraction of face centered cubic nanoclusters present. This may suggest that the source conditions used in the experiments (primarily Ar flow) left Ag-Au nanoclusters kinetically trapped in structures which correspond to local thermodynamic minima, rather than global energetically favoured atomic configurations. When left exposed to ambient conditions, over time Ag-Au nanoclusters exhibited structural, morphological, and compositional changes: core-shell and Janus nanoclusters were observed in aged samples, as well as fragmentation of bigger particles. We attribute these changes to oxidation of the Ag component and increased diffusion of Ag₂O over the substrates. The final morphology of aged nanocluster-based thin films is governed by a combination of diffusion, Ostwald ripening, and the Plateau-Rayleigh instability. High resolution transmission electron microscopy confirmed the presence of fivefold symmetric structures in Ni-Cu nanoclusters; however, their higher oxidation rate may have influenced the structures from the outset. In addition, when these nanoclusters were exposed to the electron beam, crystalline artifacts (nanochimneys)started to grown on them, with a structure corresponding to the NiO structure. Ni-Cu nanoclusters are subsequently used as catalysts in a pilot study of carbon nanotube synthesis which confirmed that such alloy nanoclusters are catalytically active for single-wall and multi-wall carbon nanotube growth.

Rapidly expanding research in nanotechnology has led to exciting progress in a versatile array of applications from medical diagnostics to photocatalytic fuel cells. Such success is due to the ability of researchers to manipulate the desired properties of nanomaterials by controlling their size, shape, and composition. Among the most thriving areas of nanoparticle research has been the synthesis and characterization of stable metallic nanoclusters capped by thiolate ligands. Our group has extended this research to study copper, silver, and gold clusters with remarkable stability and energetics, which was achieved by using dithiolates as the ligand stabilizers. In addition to the enhanced stability offered by the chelate effect, the use of dithiolate ligands instead of monothiolates is proposed to provide an alternate interfacial bond structure that is shown to strongly influence energetic properties of nanoclusters, with strong evidence of metal-ligand charge transfer. Energetic properties were characterized by spectroscopic and electrochemical methods.

Nanoclusters have special importance in nanotechnology because of their low dimensionality, which provides electronic, chemical, and magnetic properties that differ from those of the equivalent bulk materials. Suitably controllable self-assembly methods are required in order to incorporate nanoclusters into useful devices. The self-assembly method used in this study employs V-grooves as a template element for nanocluster device fabrication. The V-grooves are fabricated by optical lithography on SiO2/Si wafers and KOH wet etching. Bi clusters deposited on a V-groove form a self-assembled conducting wire. The clusters are produced using an inert gas aggregation source inside an ultra high vacuum compatible system. In order to characterise the assembly process, Bi clusters with different average sizes and velocities are deposited on V-grooves with different widths. The cluster bouncing was found to be the main process in forming the cluster wires. The bouncing angles were smaller than the incident angle, and they are dependent on the cluster size and velocity. For a certain bouncing angle, the wire width reflects the V-groove width because of the fixed bouncing angle. Nanocluster devices were fabricated by depositing the clusters on V-grooves with pre-formed Au/NiCr electrical contacts. The amount of the deposited material required to form an electrically conducting wire was found to be a function of the V-groove width and the wire length. The two point I(V) measurements in the voltage range between -1 and +1V showed linear characteristics for low resistance wires (kΩ), and non-linear characteristics for the high resistance ones (MΩ). The silicon substrate was used as a back gate. Applying a voltage to the gate was found to modify the electrical conduction of the cluster wire. The temperature dependence of the resistance of the nanocluster wires was studied in the temperature range of 4.2-473K, and all of the measured wires showed a negative temperature coefficient of resistance. These measurements allowed a detailed study of the conduction mechanisms through the cluster wires. The study showed that Bi clusters can be used for device fabrication. To size select the clusters prior to using them for the device fabrication, a high transmission mass filter is required. This transmission can be obtained using the von Issendorff and Palmer mass filter if it is operated using the optimum operation conditions. The mass filter consists of two pairs of parallel plates with horizontal openings in Plates 1 and 2, and it operates on the time of flight principle. During this project, the operation conditions of this mass filter were studied using both experiment and simulation. The study showed that the beam deflection angle is a critical factor in optimising the mass filter transmission efficiency. This angle is dependent on the accelerating voltage, ion mass, and the horizontal velocity of the ions. The optimum operation conditions for the mass filter were found and used to study the mass distribution of Pd ions produced by a magnetron sputtering source with variable cluster aggregation length.

Nanoclusters have special importance in nanotechnology because of their low dimensionality, which provides electronic, chemical, and magnetic properties that differ from those of the equivalent bulk materials. Suitably controllable self-assembly methods are required in order to incorporate nanoclusters into useful devices. The self-assembly method used in this study employs V-grooves as a template element for nanocluster device fabrication. The V-grooves are fabricated by optical lithography on SiO2/Si wafers and KOH wet etching. Bi clusters deposited on a V-groove form a self-assembled conducting wire. The clusters are produced using an inert gas aggregation source inside an ultra high vacuum compatible system. In order to characterise the assembly process, Bi clusters with different average sizes and velocities are deposited on V-grooves with different widths. The cluster bouncing was found to be the main process in forming the cluster wires. The bouncing angles were smaller than the incident angle, and they are dependent on the cluster size and velocity. For a certain bouncing angle, the wire width reflects the V-groove width because of the fixed bouncing angle. Nanocluster devices were fabricated by depositing the clusters on V-grooves with pre-formed Au/NiCr electrical contacts. The amount of the deposited material required to form an electrically conducting wire was found to be a function of the V-groove width and the wire length. The two point I(V) measurements in the voltage range between -1 and +1V showed linear characteristics for low resistance wires (kΩ), and non-linear characteristics for the high resistance ones (MΩ). The silicon substrate was used as a back gate. Applying a voltage to the gate was found to modify the electrical conduction of the cluster wire. The temperature dependence of the resistance of the nanocluster wires was studied in the temperature range of 4.2-473K, and all of the measured wires showed a negative temperature coefficient of resistance. These measurements allowed a detailed study of the conduction mechanisms through the cluster wires. The study showed that Bi clusters can be used for device fabrication. To size select the clusters prior to using them for the device fabrication, a high transmission mass filter is required. This transmission can be obtained using the von Issendorff and Palmer mass filter if it is operated using the optimum operation conditions. The mass filter consists of two pairs of parallel plates with horizontal openings in Plates 1 and 2, and it operates on the time of flight principle. During this project, the operation conditions of this mass filter were studied using both experiment and simulation. The study showed that the beam deflection angle is a critical factor in optimising the mass filter transmission efficiency. This angle is dependent on the accelerating voltage, ion mass, and the horizontal velocity of the ions. The optimum operation conditions for the mass filter were found and used to study the mass distribution of Pd ions produced by a magnetron sputtering source with variable cluster aggregation length.

In this paper, molecular dynamics is used to investigate into the adsorption behaviour of water nanocluster on a solid substrate. The potential function of water molecule is F3C (Flexible three-Centered)model. Water nanocluster with radius of 5Ǻ, 7Ǻ and 10Ǻ were studied. Five adsorption parameters between water molecules and the substrate were used to represent the hydrophilic magnitude. The influences of different size and interaction on adsorption behaviour were investigated. The simulation results indicate that when the hydrophilic magnitude is increasing, the water molecule number of adsorption on solid substrate increases, the water nanocluster tends to spread flatly on the substrate, and the contact angle was very close to zero, which represents better wettability. The larger water nanocluster distribute widely upon a substrate.

A fundamental understanding of interfacial charge transfer at donor-acceptor interfaces is very crucial as it is considered among the most important dynamical processes for optimizing performance in many light harvesting systems, including photovoltaics and photo-catalysis. In general, the photo-generated singlet excitons in photoactive materials exhibit very short lifetimes because of their dipole-allowed spin radiative decay and short diffusion lengths. In contrast, the radiative decay of triplet excitons is dipole forbidden; therefore, their lifetimes are considerably longer. The discussion in this thesis primarily focuses on the relevant parameters that are involved in charge separation (CS), charge transfer (CT), intersystem crossing (ISC) rate, triplet state lifetime, and carrier recombination (CR) at silver nanocluster (NCs) molecular-acceptors interfaces. A combination of steady-state and femto- and nanosecond broadband transient absorption spectroscopies were used to investigate the charge carrier dynamics in various donor-acceptor systems. Additionally, this thesis was prolonged to investigate some important factors that influence the charge carrier dynamics in Ag29 silver NCs donor-acceptor systems, such as the metal doping and chemical structure of the nanocluster and molecular acceptors. Interestingly, clear correlations between the steady-state measurements and timeresolved spectroscopy results are found. In the first study, we have investigated the interfacial charge transfer dynamics in positively charged meso units of 5, 10, 15, 20-tetra (1- methyl-4-pyridino)-porphyrin tetra (p-toluene sulfonate) (TMPyP) and neutral charged 5, 10, 15, 20-tetra (4-pyridyl)-porphyrin (TPyP), with negatively charged undoped and gold (Au)- doped silver Ag29 NCs. Moreover, this study showed the impact of Au doping on the charge carrier dynamics of the system. In the second study, we have investigated the interfacial charge transfer dynamics in [Pt2 Ag23 Cl7 (PPh3)10] silver NCs doped with platinum (Pt), with neutral charged 5, 10, 15, 20-tetra (4-pyridyl)-porphyrin (TPyP). Here, we evaluated the effects of Pt (II) doping on the interfacial charge-transfer dynamics between TPyP and silver NCs.

Indiana University-Purdue University Indianapolis (IUPUI) / Semiconductor nanocrystals (SNCs) are a class of material with one dimension <100 nm, which display size, shape, and composition dependent photophysical (absorption and emission) properties. Ultrasmall SNCs are a special class of SNCs whose diameter is <3.0 nm and are strongly quantum confined leading to a high surface to volume ratio. Therefore, their electronic and photophysical properties are fundamentally dictated by their surface chemistry, and as such, even a minute variation of the surface ligation can have a colossal impact on these properties. Since the development of the hot injection-method by Bawendi et al., the synthetic methods of SNCs have evolved from high-temperature, highly toxic precursors to low-temperature, relatively benign precursors over the last 25 years. Unfortunately, optimization of their synthetic methods by appropriate surface ligation is still deficient. The deficiency lies in the incomplete or inappropriate surface passivation during the synthesis and/or post-synthetic modification procedure, which due to the high surface to volume ratio of ultrasmall SNCs, is a significant problem. Currently, direct synthetic methods produce SNCs that are either soluble in an aqueous media or soluble in organic solvents therefore limiting their applicability. In addition, use of insulating ligands hinder SNCs transport properties and thus their potential application in solid state devices. Appropriate choice of surface ligation can provide 1) solubility, 2) stability, and 3) facilitate exciton delocalization. In this dissertation, the effects of appropriate surface ligation on strongly quantum confined ultrasmall SNCs was investigated. Due to their high surface to volume ratio, we are able to highly control their optical and electronic properties through surface ligand modification. Throughout this dissertation, we utilized a variety of ligands (e.g. oleylamine, cadmium benzoate, and PEGn-thiolate) in order to change the solubility of the SNC as well as investigate their optical and electronic properties. First delocalization of the excitonic wave function 1) into the ligand monolayer using metal carboxylates and 2) beyond the ligand monolayer to provide strong inter-SNC electronic coupling using poly(ethylene) glycol (PEG)-thiolate was explored. Passivation of the Se sites of metal chalcogenide SNCs by metal carboxylates provided a two-fold outcome: (1) facilitating the delocalization of exciton wave functions into ligand monolayers (through appropriate symmetry matching and energy alignment) and (2) increasing fluorescence quantum yield (through passivation of midgap trap states). An ~240 meV red-shift in absorbance was observed upon addition of Cd(O2CPh)2, as well as a ~260 meV shift in emission with an increase in PL-QY to 73%. Through a series of control experiments, as well as full reversibility of our system, we were able to conclude that the observed bathochromic shifts were the sole consequence of delocalization, not a change in size or relaxation of the inorganic core, as previously reported. Furthermore, the outstanding increase in PL-QY was found to be a product of both passivation and delocalization effects. Next we used poly(ethylene) glycol (PEG)-thiolate ligands to passivate the SNC and provide unique solubility properties in both aqueous and organic solvents as well as utilized their highly conductive nature to explore inter-SNC electronic coupling. The electronic coupling was studied: 1) as a function of SNC size where the smallest SNC exhibited the largest coupling energy (170 meV) and 2) as a function of annealing temperature, where an exceptionally large (~400 meV) coupling energy was observed. This strong electronic coupling in self-organized films could facilitate the large-scale production of highly efficient electronic materials for advanced optoelectronic device applications. Strong inter-SNC electronic coupling together with high solubility, such as that provided by PEG-thiolate-coated CdSe SNCs, can increase the stability of SNCs during solution-phase electrochemical characterization. Therefore, we utilized these properties to characterize solution-state electrochemical properties and photocatalytic activity of ternary copper indium diselenide (CuInSe2) SNCs as a function of their size and surface ligand chemistry. Electrochemical characterization of our PEG-thiolate-coated SNCs showed that the thermodynamic driving force (-ΔG) for oxygen reduction, which increased with decreasing bandgap, was a major contributor to the overall photocatalytic reaction. Additionally, phenol degradation efficiency was monitored in which the smallest diameter SNC and shortest chain length of PEG provided the highest efficiency. The information provided herein could be used to produce superior SNC photocatalysts for a variety of applications including oxidation of organic contaminants, conversion of water to hydrogen gas, and decomposition of crude oil or pesticides. Therefore, we believe our work will significantly advance quantitative electrochemical characterization of SNCs and allow for the design of highly efficient, sustainable photocatalysts resulting in economic and environmental benefits.

<p> </p> <p>  Mass spectrometry (MS) plays an important role in nanomaterials research by facilitating the discovery of superatomic clusters and fullerenes, enabling the identification of atomically substituted clusters, and contributing to understanding mechanisms of cluster formation. In this dissertation, we used different mass spectrometry methods as well as ion soft-landing to address some of the ongoing challenges in cluster science. The first challenge is to extend the atom-by-atom substitution method, which is a promising strategy for designing new cluster-based materials, to a wider range of molecular clusters. Due to challenges associated with the synthesis, purification, and crystallization, this approach has been achieved only for a handful of gold and silver clusters. We extended this approach to enable the substitution of the first-row transitional metals into the core of Co6S8(PEt3)6 cluster, a well-defined metal chalcogenide superatomic cluster and a popular building block for designing novel 2D materials. This cluster is widely used in energy and electronic applications and is an excellent model system for computational studies of cluster-based materials. High-resolution MS analysis identified the formation of Co5MS8(PEt3)6+ (M=Mn, Fe, Ni) clusters, indicating that only Mn, Fe, and Ni atoms can be incorporated into the Co6S8 core using our synthetic method. A combination of mass spectrometric analysis and theoretical studies reaved that each heteroatom has different impact on the relative stability, core-ligand interaction, as well as optical, magnetic, and electrochemical properties of the cluster. </p> <p>Another challenge in the cluster science addressed in this work is the controlled activation of fully ligated clusters by ligand removal. Conventional activation methods such as thermolysis or chemical treatment do not provide sufficient control of the number of the removed ligands and often suffer from sintering of NCs as a result of excessive ligand removal and degradation of the destabilized NC cores. Using a specially-designed ion soft-landing instrument, we achieved a controlled removal of one or two phosphine ligands form the synthesized cobalt sulfide clusters using collision-induced dissociation (CID). The resulting fragments were mass selected and soft-landed onto surfaces. We found out that the reactivity of the fragment ions on surfaces may be controlled by altering the composition of the cluster core and ligand binding energy to the cluster. Although some of the fragments formed by removing one ligand including Co5FeS8(PEt3)5+ and Co6S8L(PPh3)5+ remain unreactive on surfaces, other fragments including Co6S8(PEt3)5+, Co5NiS8(PEt3)5+, and Co6S8(PEt3-xPhx) (x=1-2) undergo selective dimerization.  We observe that the reactivity of fragment ions produced by removing one surface ligand is controlled by the relative stability of the corresponding precursor ions towards fragmentation. In particular, fragment ions generated from more stable precursors undergo a selective dimerization reaction. In contrast, fragment ions produced from the least stable precursors remain largely unreactive on surfaces. In addition, we found that fragments generated by removing two surface ligands are highly reactive and undergo several nonselective reactions. This study demonstrates that fragment ions are unique building blocks that may undergo selective reactivity on surfaces to generate compounds that are difficult to prepare using conventional synthetic methods. We believe that the controlled preparation of fragment ions using ion soft-landing is a generalizable method to activate wide range of ligated nanoclusters which opens a direction for materials design and innovation.</p> <p>Finally, soft-landing of well-characterized redox-active polyatomic anions, PW12O403- (WPOM), was carried out to explore the distribution of pure mass selected anions on semiconducting vertically-aligned TiO2 nanotubes, which were used as a model system for 3D semiconductive materials. Energy dispersive X-ray (EDX) mapping analysis revealed that WPOMs form micron-size aggregates on top of the TiO2 NT and only penetrates 1-1.3 µm into the 10 µm-long nanotubes. This aggregation is attributed to the high resistance of TiO2. This is different from what we see on conductive substrates such as carbon nanotubes (CNTs) where a uniform distribution of ions is typically observed. This study provides valuable insight into the functionalization of porous semiconducting surfaces using mass selected ions for applications in energy storage and electronics.</p>

This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO^2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and ≈1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960\'s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain \\lq magic\' angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.

This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO^2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and ≈1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960\'s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain \\lq magic\' angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.