Rozprawy doktorskie na temat „STRUCTURAL INTERFACE PROPERTIES”

Für die Effektivität organischer Halbleiter spielen die Grenzflächen zwischen den konjugierten, organischen Molekülen und den Metallelektroden eine entscheidende Rolle. Inhalt dieser Arbeit ist die Untersuchung dieser Grenzflächen bezüglich ihrer strukturellen und elektronischen Eigenschaften. Besonders interessant sind dabei molekulare Systeme, welche Selbstaggregation aufweisen. Ein kritischer Parameter ist dabei das Verhältnis der inter-molekularen zu den Molekül-Metall Wechselwirkungsstärken. Um verschiedene Aspekte der molekularen Selbstaggregation zu beleuchten, wurden vier verschiedene Systeme untersucht. (i) Das defekt-gesteuerte Wachstum selbstaggregierender Molekülschichten wird betrachtet. Es wird gezeigt, dass durch Alkylierung der Moleküle das Wechselwirkungsverhältnis deutlich verändert werden kann. (ii) Weiterhin wird anhand der Orientierungsänderungen der Moleküle der mit zunehmender Schichtdicke schnell abnehmende Einfluss des Substrats nachgewiesen. (iii) Es wird gezeigt, dass durch Fluorination von Molekülen starke chemische Wechselwirkungen mit dem Substrat erzeugt werden können. (iv) Ein neuartiger Ansatz zur Entkopplung von Molekülen von dem Metall wird vorgestellt. Dies geschieht mit Hilfe einer molekularen Vorbeschichtung. Aus experimentellen und theoretischen Daten geht hervor, dass auf diese Art die Wechselwirkung zwischen Molekül und Metall verhindert wird, bei gleichzeitigem Erhalt der metallischen Eigenschaften des Substrats. Weiterhin wirkt die Vorbeschichtung auch als strukturelle Maske. Zur Erkundung der verschiedenen Eigenschaften der molekularen Systeme kamen komplementäre experimentelle Techniken zum Einsatz. Die strukturellen Eigenschaften wurden dabei mit Hilfe von Rastersondenmikroskopie (STM und AFM), Beugung niederenergetischer Elektronen (LEED) und Röntgen-Nahkanten-Absorptions-Spektroskopie (NEXAFS) ermittelt. Eine Bestimmung der elektronischen Eigenschaften erfolgte mittels Photoelektronenspektroskopie (UPS und XPS).
The interfaces between conjugated organic molecules and metal electrodes play an important role for the performance of organic devices. In this thesis the structural and electronic properties at these interfaces are investigated. In particular, the focus of this work is given to molecular systems which undergo self-assembly. The critical parameter which drives the ordering behavior at the interface is the balance between the inter-molecular and molecule-metal interaction strength. To highlight different aspects of the self-assembled growth of molecules, four different molecular systems were investigated. (i) The defect mediated growth of directed self-assembled molecular layers is explored. It will be shown, that addition of short alkyl chains to molecules leads to significant changes in the interaction balance. (ii) The fast attenuation of the substrate''s influence on the molecular ordering with increasing thickness of the molecular layer will be evidenced by the observation of changes in the molecular orientation. (iii) The initiation of strong chemical interactions with the metal substrate by fluorination of molecules is demonstrated by conducting annealing time dependent experiments. (iv) A novel attempt to decouple molecules from the metal substrate is presented. This is achieved by the insertion of a molecular template layer. Experimental and theoretical results prove the successful prevention of molecule-metal interactions, while at the same time metallic properties of the substrate are conserved. Furthermore, the inserted layer acts as a structural template. To explore the properties of the molecular systems, several complementary experimental techniques were used. Structural properties were investigated by scanning probe microscopy (STM and AFM), low energy electron diffraction (LEED) and near edge X-ray absorption fine structure spectroscopy (NEXAFS). The electronic properties were discovered by using photoelectron spectroscopy (UPS and XPS).

Complex-oxides have seen an enormous amount of attention in the realm of Condensed Matter Physics and Materials Science/Engineering over the last several decades. Their ability to host a wide variety of novel physical properties has even caused them to be exploited commercially as dielectric, metallic and magnetic materials. Indeed, since the discovery of high temperature superconductivity in the “Cuprates” in the late 1980’s there has been an explosion of activity involving complex-oxides. Further, as the experimental techniques and equipment for fabricating thin films and heterostructures of these materials has improved over the last several decades, the search for new and more exotic properties has intensified. These properties stem from the interfaces formed by depositing these materials onto one another. Whether it be interfacial strain induced by the mismatch between the crystal structures, modified exchange interactions, or some combination of these and other interactions, thin films and heterostuctures provide an invaluable tool the modern condensed matter community. Simply put, a “complex-oxide” is any compound that contains Oxygen and at least two other elements; or one atom in two different oxidation states. Transition Metal Oxides (TMO’s) are a subset of complex-oxides which are of particular interest because of their strong competition between their charge, spin and orbit degrees of freedom. As we progress down the periodic table from 3d to 4d to 5d transition metals, the crystal field, electron correlation and spin-orbit energies become more and more comparable. Therefore, TMO thin films and heterostructures are indispensable to the search for novel physical properties. KTaO3 (KTO) is a polar 5d TMO which has been investigated for its high-k dielectric properties. It is a band insulator with a cubic perovskite crystal structure which is isomorphic to SrTiO3 (STO). This is important because non-polar STO is famous for forming a highly mobile, 2-Dimensional Electron Gas (2DEG) at the hetero-interface with polar LaAlO3 (LAO) as a result of the so-called “polar catastrophe”. Here, I use this concept of polarity to ask an important question: “What happens at hetero-interfaces where two different polar complex oxides meet?” From this question we propose that a hetero-interface between two polar complex-oxides with opposite polarity (I-V/III-III) should be impossible because of the strong Coulomb repulsion between the adjacent layers. However, we find that despite this proposed conflict we are able to synthesize KTO thin films on (110) oriented GdScO3 (GSO) substrates and the conflict is avoided through atomic reconfiguration at the hetero-interface. SrRuO3 (SRO) is a 4d TMO, and an itinerant ferromagnet that is used extensively as an electrode material in capacitor and transistor geometries and proof-of-concept devices. However, in the thin film limit the ferromagnetic transition temperature, TC, and conductivity drop significantly and even become insulating and lose their ferromagnetic properties. Therefore, we ask “Are the transport properties of SRO thin films inherently inferior to single crystals, or is there a way to maintain and/or enhance the metallic properties in the thin film limit?” We have fabricated SRO thin films of various thickness on GSO substrates (tensile strain) and find that all of our samples have enhanced metallic properties and even match those of single crystals. Finally, we ask “Can these enhanced metallic properties in SRO thin films allow us to observe evidence of a topological phase without the complexity of off-stoichiometry and/or additional hetero-structural layers?” Recent reports of oxygen deficient EuO films as well as hetero-structures and superlattices of SRO mixed with SrIrO3 or La0.7Sr0.3MnO3 have suggested that a magnetic skyrmion phase may exist in these systems. By measuring the Hall resistivity, we are able to observer a topological Hall effect which is likely a result of a magnetic skyrmion. We find that of the THE exists in a narrow temperature range and the proposed magnetic skyrmions range in size from 20-120 nm. Therefore, the SRO/GSO system can provide a more viable means for investigating magnetic skyrmions and their fundamental interactions.

The opportunity of using the organic molecules in spintronic devices appeared challenging since these materials, having nominally high spin relaxation times, are suitable for coherent spin manipulation. The spin behaviour in these molecular spintronic devices has been demonstrated to strongly depend on the nature of the chemical bonds between the organic molecules and the magnetic electrodes affecting also the magnetic response of both molecular and metallic sides. In particular, the adsorption of an organic molecule on a ferromagnetic layer has been proved to change the local magnetism of a magnetic substrate. In spite of their technological interest, the investigation of such effect in the case of the polycrystalline magnetic thin film is still lacking. My work contributes to filling this gap by studying the structural, morphological and magnetic properties of ultrathin polycrystalline cobalt films covered by the well-known buckminsterfullerene organic molecule (C60). The combined investigation by AFM, TEM, SQUID magnetometry and anisotropic magnetoresistance allowed to correlate the sample microstructure with the magnetic response and to identify the main mechanism responsible for spin transport in these FM layers. Analysed films are composed of polycrystalline cobalt grains decoupled by non-crystalline amorphous regions. The volume ratio between crystalline grains and amorphous regions increases by increasing the film thickness. As expected, the values of saturation magnetisation decrease as the crystallinity decreases and a typical blocking behaviour is present. The cobalt layers are also subjected to oxidation at the interface with the single crystal oxide substrate. The presence of amorphous phase in polycrystalline cobalt ultrathin film impacts the analysis of transport properties: the anisotropic magnetoresistance slightly depends on the crystalline phase while it is mainly inherent to the amorphous component.

Molten salts attracted the attention of the scientific community several times during the last century. This interest is motivated by the physico-chemical properties of these systems. In fact, usually molten salts show chemical and thermal stability, i.e. they do not easily decompose or react. Furthermore, these compounds remain liquid over an extended range of temperatures, in which they show also a remarkably low volatility. The fact that molten salts are composed solely by ions, and can have a quite wide electrochemical window, make them very interesting as electrolytes[1]. The main disadvantage in the usage of molten salts in any practical process, is their high melting point (for example as high as 800°C for NaCl), which severely limits the number of reactions that can be done in these media and reduces the possibility of industrial scaling, due to the high energy required to maintain those high temperatures. Since the '70s lower temperature molten salts has been synthesised, like chloroaluminate eutectic mixtures, having melting points around 100°C or even lower, but the real turning point that boosted the research field has been the development of the first water-stable low melting point molten salts, that is what are now usually named room temperature ionic liquids, or simply ionic liquids. Ionic liquids are usually composed by a big organic cation and a bulky inorganic, water stable, anion: the bulkiness and the complex asymmetric structure of the ions prevent an efficient packaging, leading to a lowering of the coulombic cohesive energy and so of the melting point. Ionic liquids maintain all the characteristics of the high temperature molten salts, but they are usually liquid at room temperature. This fact induced a renewed interest in the field, as is proved by the several thousand papers published on the topic in 2011. The community of chemists devoted a great effort to the study of ionic liquids, because of the potential use of those liquids as solvents. Ionic liquids are complex systems, that usually are organised in polar and apolar domains, and can dissolve both polar and apolar species. In addition, there are virtually unlimited choices of ions, and each choice changes the physico-chemical characteristics of the systems: this allows to tailor the properties of the ionic liquids (like miscibility, density, viscosity...), in order to match specific tasks. The characteristics of ionic liquids, last but not least their low vapour pressure, promote them as good solvents for the growing field of the Green Chemistry, in substitution of the volatile organic compounds. Ionic liquids are also promising as lubricants, in particular in micro- and nano- -electromechanical devices (NEMSs and NEMSs)[2, 3] as well as electrolytes in photoelectrochemical devices used for energy storage and energy production such as supercapacitors[4, 5] or Grätzel solar cells[6]. In all these cases, the most relevant processes determining the performance of the devices, take place at the liquid/solid interface between ILs and solid surfaces: this is a region only a few nanometers thick where the properties of ILs can be significantly different from those of the bulk. The investigation of the interfacial properties of ILs is therefore of primary importance for their technological exploitation. To date, the (bulk)liquid-vapour and solid- (bulk)liquid ILs interfaces have been studied, mostly by sum-frequency generation spectroscopy[7, 8] and by X-ray photoemission spectroscopy[9]. For imidazolium-based ILs, ordering of the ions at the solid/liquid or liquid/ vapour interface has been inferred from vibrational spectroscopy data. For example Mezger et al.[10] performed a study of the (bulk)liquid/solid interface between a negatively charged sapphire substrate and imidazolium and pyrrolidinium-based ILs. They found strong interfacial layering, with repeated spacing of 0.7-0.8 nm, decaying exponentially into the bulk liquid. Recently the ionic liquid/solid interface has been studied with the surface force apparatus (SFA)[11, 12, 13]. In those experiments thin layers of ionic liquids are compressed between two approaching sheets of mica, while the normal force is recorded. The force vs. distance curves show a characteristic oscillatory profile, extending for few nanometers from the interface and exponentially decaying into the bulk. Only very recently, in order to explore in details the ionic liquid/solid interfaces, more local approaches has been used, i.e. scanning probe microscopies and numerical simulations. Layering at the solid/(bulk)liquid have been found by Atkin[14, 15] performing force spectroscopy with atomic force microscope (AFM). In these kind of measurements, in which the AFM tip is ramped against the interface while measuring the force acting on it, as in SFA experiments, subsequent ruptures of solvation layers are seen, beginning few nanometers above the surface. The group of Atkin, in collaboration with other groups, performed also scanning tunneling microscopy (STM)/AFM study on ionic liquid/Au(111) interface, finding a dependence of the behaviour of the solvation layers upon potential changes[16]. In simulation studies is again evidenced the formation of strong interfacial layering on different surfaces[17, 18], where moreover, the preferential orientation of the ions at the interface can be analysed. The studies previously cited about the interfacial behaviour of the ionic liquids, are mainly focused to the analysis of the bulk ionic liquid/solid interface. To date, a little effort has been devoted to what happens when thin layers of an ionic liquid are put in contact with a solid substrate. In those kind of situations, where the surface/volume ratio is high, it can been argued that the interaction with the surface can greatly change the physico-chemical and structural properties of the ionic liquid. The study of systems with high surface/volume ratio is directly relevant in all those applications in which a thin _lm of ionic liquid is used, e.g. in tribological applications, as well as in photoelectrochemical devices, where the liquid is soaked into a nanoporous matrix: a change of the properties of the ionic liquid in this case can heavily modify the final performance of the devices. My PhD work has been devoted to improving further extend the understanding of the behaviour of thin films of ionic liquids in contact with solid surfaces. At the time when I begun my work, very few studies regarding such systems were published. A pioneering study on thin _lm of [Bmim][PF6] on mica has been published in 2006 by Liu et al.[19]. In this work, performed using an AFM, the ionic liquid has been found to structure in two different ways on substrate: as droplets and as at layers, qualitatively referred to as solid layers. Inspired by the approach of Liu, I decided to study more quantitatively the thin-layer/solid interface, in particular using atomic force microscopy, because this instrument can acquire morphologies with vertical sub-nanometer and lateral nanometric resolution, so giving access to very localised information. Furthermore other kind of maps regarding different physico-chemical properties can be acquired simultaneously to the topography and moreover, force spectroscopy studies can be performed ramping the AFM tip against the surface. In particular I focused my investigation on the interaction of [Bmim][Tf2N], a hydrophobic and almost water-stable liquid, with different substrates, i.e. mica, amorphous silica, single crystal silicon covered by its native oxide, and HOPG graphite. The main part of the work has been performed on those test substrates, because their properties are well known and because they are at, so very suitable for an accurate AFM investigation. With the experience gained on those systems and the results obtained, on the last part of my PhD, the attention has been moved to surfaces more relevant for applications, as the nanostructured silicon oxide, directly synthesised in our lab with supersonic cluster beam deposition (SCBD). In order to perform my investigation, I first obtained very thin ionic liquid layers on the surface, diluting the liquid into a solvent, (methanol, ethanol, chloroform), and then drop-casting few μl of the solution onto a freshly cleaned substrate, letting the evaporation to proceed in air. On all the insulating surfaces studied, the [Bmim][Tf2N] coexists in 2 forms: as liquid micro- and nano- droplets and in at ordered domains. The melting temperature of this particular ionic liquid is ~-4°C, so a fundamental role in the liquid to solid transition has to be played by the interaction with the solid surface. The solid-like terraces appear as at layers, often growing one on top of the other. The hypothesis is that each layer is composed by several layers of cations and anions. By a statistical analysis of the morphological maps acquired, I extrapolated that the height of the best sub-multiple of the solid-like terraces is δ=0.6nm, in good agreement with the result of the simulations. The AFM has also been used to study the mechanical behaviour of the solid-like structures. If imaged in contact mode, the layers tend to be eroded after repeated scans, and in some cases the terraces are removed one by one, as in a lamellar solid. Investigating the resistance to normal loads, saw tooth profiles in force vs. separation curves have been found, highlighting a sequence of ruptures, separated by 1.8-2nm, where the average rupture pressure is ~2-3KBar, very similar to the maximum pressure found in a MD simulation of a tip penetrating in 4nm of [Bmim][Tf2N] on silica[20]. Moreover, the observation that supported IL islands were not disrupted by intense electric fields up to 108-109V/m (applied biasing the AFM with respect to sample during imaging) and that Scanning Nanoscale Impedance Microscopy[21] measurements highlighted a dielectric insulating character of the ordered domains (εr = 3-5 was measured[22]) is consistent with the idea that IL ordered domains behave as solid materials in which the ions are tightly bound. To understand what is the influence of the nanostructure on the formation of the solid-like layers, I realised [Bmim][Tf2N] depositions on nanostructured silica deposited on oxidised silicon by SCBD in our lab. Of particular interest is the case of IL coating on a sub-monolayer deposition of silica nanoparticles. The preliminary results show that the presence of a dense distribution of nanoparticles on the surface of oxidised silicon actually doesn't prevent the growth of multilayered solid-like domains, that are as thick as on at surfaces and densely distributed. The liquid part of the deposition is pinned to the silica clusters, fact that evidences the strong affinity of [Bmim][Tf2N] with silica. The results suggest that the formation of immobilised, possibly solid-like, layers of ionic liquids in contact with nanoporous matrices, is not unlikely and such structures and can strongly affect the properties of the devices in which those interfaces are present. This possibility is also supported by the fact that a small percentage of silica nanoparticles (5 wt%) is enough to induce the gelation in an IL-based electrolyte used for dye sensitised solar cells[23]. The findings of my PhD work highlight the potentialities of scanning probe techniques for the quantitative investigation of the interfacial properties of thin ionic liquid films. My AFM investigation highlights how heterogeneous can be the IL/solid interfaces and so how is of fundamental importance to deal with local and not with average properties. The results of my work show that the behaviour of thin layers of ionic liquid is greatly modified by the influence of the substrate. In particular, I found a coexistence of liquid domains and terraces with elevated structural order. The formation of those structures, not present in the bulk liquid, is clearly induced by the contact with the solid surface. The solid-like terraces are very resistant to normal loads and to intense electric fields and, differently from the bulk, they tend to behave as insulating layers: the development of those structures can then have a crucial influence in the performances of photoelectrochemical devices. The importance of this field of research and the validity of my work, are witnessed by the increasing number of papers studying thin ionic liquid layers appeared just before, but especially during the course of my PhD[24, 25, 26, 27, 28, 15, 16]; in many of these works, the AFM is the instrument of choice for the interfacial investigation because it allows to access to the physico-chemical properties of the system with nanometric or sub-nanometric resolution in all the three dimensions. In the next future the structural behaviour of the ionic liquids in contact with nanostructured surfaces will be further studied, making use of the experience of our group in synthesise the nanostructured oxides and metals. Moreover, we will explore in more details the dielectric properties of thin fillm of ionic liquids, in particular selecting those ILs directly used in supercapacitors and solar cells. Another interesting field that to date is still poorly explored is the interaction of ionic liquids with biological tissue. For this reason, we are going to begin to study the effects of ionic liquids on supported lipid bilayers. Bibliography [1] Wilkis, J. S., Green Chem 4, 73-80, (2002). [2] Qu, J., Truhan, J. J., Dai, S., Luo, H., Blau, P., J. Tribol. Lett. 22, 207-214, (2006). [3] Bhushan, B., Palacio, M., Kinzig, B., J. Coll. and Inter. Sci. 317, 275-287, (2008). [4] Simon, P. and Gogotsi, Y., Nature Materials 7, 845-854, (2008). [5] Appetecchi, G. B., Montanino, M., Carewska, M., Moreno, M., Alessandrini and F., Passerini, S., Electrochimica Acta 56, 1300-1307, (2011). [6] Grätzel, M., Journal of Photochemistry and Photobiology A: Chemistry 164, 3-14, (2004). [7] Santos, C. S., Baldelli, S., J. Phys. Chem. B 111, 4715-4723, (2007). [8] Rollins, J. B., Fitchett, B. D. and Conboy, J. C., J. Phys. Chem. B 111, 4990-4999, (2007). [9] Lovelock, K. R. J., Villar-Garcia, I. J., Maier, F., Steinrück, H. and Licence, P., Chem. Rev. 110, 5158-5190, (2010). [10] Mezger, M., Schröder, H., Reichert, H., Schramm, S., Okasinski, J. S., Schöder, S., Honkimäki, V., Deutsch, M., Ocko, B. M., Ralston, J. And Rohwerder, M., Science 322, 424428, (2008). [11] Ueno, K., Kasuya, M., Watanabe, M., Mizukami, M. and Kurihara, K., Phys. Chem. Chem. Phys. 12, 4066-4071, (2010). [12] Perkin, S., Albrecht, T. and Klein, J., Phys. Chem. Chem. Phys. 12, 1243-1247 (2010). [13] Min, Y., Akbulut, M., Sangoro, J. R., Kremer, F., Prudhomme, R. K. and Israelachvili, J., J. Phys. Chem. C 37, 16445{16449, (2009). [14] Atkin, R. and Warr, G. G., J. Phys. Chem. C, 111, 5162-5168, (2007). [15] Hayes, R., Warr, G. G. and Atkin, R., Phys. Chem. Chem. Phys. 12, 1709-1723, (2010). [16] Atkin, R., Borisenko, N., Drüschler, M., El Abedin, S. Z., Endres, F., Hayes, R., Huber, B. and Roling, B., Phys. Chem. Chem. Phys. 13, 6849-6857, (2011). [17] Sieffert, N., and Wip_, G., J. Phys. Chem. C 112, 19590-19603 (2008). [18] Sha, M., Zhang, F., Wu, G., Fang, H., Wang, C., Chen, S., Zhang, Y., and Hu, J., J. Chem. Phys. 128, 134504, (2008). [19] Liu, Y., Zhang, Y., Wu, G. and Hu, J., J. Am. Chem. Soc. 128, 7456-7457, (2006). [20] Ballone, P., Del Pópolo, M. G., Bovio, S., Podestà, A., Milani, P. and Manini, N., Phys. Chem. Chem. Phys. in press (2011) (arXiv:1101.5424v1). [21] Cassina, V., Gerosa, L., Podestà, A., Ferrari, G., Sampietro, M., Fiorentini, F., Mazza, T., Lenardi, C. and Milani, P., Phys. Rev. B 79, 115422, (2009). [22] M. Galluzzi, Study of morphological and dielectric properties of thin ionic liquid films by Atomic Force Microscopy, Master Thesis, University of Milan, (2010). [23] Wang, P., Zakeeruddin, S. M., Compte, P., Exnar, I. and Grätzel, M., J. Am. Chem. Soc., 125, 1166{1167, (2003). [24] Cremer, T., Killian, M., Gottfried, J. M., Paape, N., Wasserscheid, P., Maier, F. and Steinrück, H.-P., Chem. Phys. Chme. 9, 2185-2190, (2008). [25] Cremer, T., Stark, M., Deyko, A., Steinrück, H.-P. and Maier, F., Langmuir 27, 3662-3671, (2011). [26] Yokota, Y., Harada, T. and Fukui, K., Chem. Commun. 46, 8627-8629, (2010). [27] Zhang, F., Sha, M., Ren, X., Wu, G., Hu, J. and Zhang, Y., Chin. Phys. Lett. 27, 086101, (2010). [28] Kaisei, K., Kobayashi, K., Matsushige, K., Yamada, H., Ultramicroscopy 110, 733-736, (2010).

Amorphous silicon carbide (a-SiC) and silicon carbonitride thin films have been deposited onto a variety of substrates by Polymer-Source Chemical Vapor Deposition (PS-CVD). The interfacial interaction between the a-SiC films and several substrates including silicon, SiO[subscript 2], Si[subscript 3]N[subscript 4], Cr, Ti and refractory metal-coated silicon has been studied. The effect of thermal annealing on the structural and mechanical properties of the prepared films has been discussed in detail. The composition and bonding states are uniquely characterized with respect to the nitrogen atomic percentage introduced into the a-SiCN:H films. Capacitance-voltage (C-V) measurements were systematically used to evaluate the impurity level of the deposited a-SiC films. The chemical bonding of the films was systematically examined by means of Fourier transform infrared spectroscopy (FTIR). In addition, elastic recoil detection (ERD) and X-ray photoelectron spectroscopy (XPS) techniques were used to determine the elemental composition of the films and of their interface with substrates, while X-ray reflectivity measurements (XRR) were used to account for the film density. Spectral deconvolution was used to extract the individual components of the FTIR and XPS spectra. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were also employed to characterize the surface morphology of the films. In addition, their mechanical properties [(hardness (H) and Young's modulus (E)] were investigated by using the nanoindentation technique. The impurity levels of the a-SiC films were found to be clearly correlated with the nature of the underlying substrates. The Pt-Rh and TiN-coated Si substrates were shown to lead to the lowest impurity level (~ 1×10[superscript 13] cm[superscript -3]) in the PS-CVD grown a-SiC films, while Cr and Ti-coated Si substrates induced much higher impurity concentrations. Such high impurity levels were shown to be a consequence of a strong metallic diffusion of the metallic species (Cr or Ti). In contrast, no diffusion was observed at the interface of a-SiC with either Pt-Rh or TiN. Our results pinpointed TiN-coated Si as the electrode material of choice that satisfied best all criteria required for the integration of a-SiC into opto-electronic devices. FTIR measurements revealed that not only the intensity of a-SiC absorption band linearly increased, but also its position is found to shift to a higher wave number as a result of annealing. In addition, the bond density of Si-C is found to increase from (101.6-224.5)×10[superscript 21] bond[dot]cm[superscript -3] accompanied by a decrease of Si-H bond density from (2.58-0.46)× 10[superscript 21] bond[dot]cm[superscript -3] as a result of increasing the annealing temperature (T[subscript a]) from 750 to 1200 [degrees]C. Annealing-induced film densification is confirmed by the XRR measurements, as the a-SiC film density is found to increase from 2.36 to ~ 2.75 g/cm[superscript -3] when T[subscript a] is raised from 750 to 1200 [degrees]C. In addition, as annealing temperature T[subscript a] is increased from 750 to 1200 [degrees]C, both hardness and Young's modulus are found to increase from 15.5 to 17.6 GPa and 155 to 178 GPa, respectively. On the microstructural level, the increase incorporation of N in the a-SiCN:H films is found not only to lead to C atoms substitution by N atoms in the local Si-C-N environment but also to the formation of a complex structure between Si, C and N. For instance, the FTIR spectra show a remarkable drop in the intensity of Si-C vibration accompanied by the formation of further bonds including Si-N, C-N, C=N, C[identical to]N and N-H with increasing NH[subscript 3]/Ar ratio. Moreover, the XPS spectra showed the existence of different chemical bonds in the a-SiCN:H films such as Si-C, Si-N, C-N, C=N and C=C. Both FTIR and XPS data demonstrate that the chemical bonding in the amorphous matrix is more complicated than a collection of single Si-C, Si-N, or Si-H bonds. Furthermore, the increase incorporation of N in the a-SiCN:H films resulted in an increase of the average R[subcsript rms] surface roughness from 4 to 12 nm. Moreover, the films became porous with pore size and density increase as a result of increasing N at.%. Ultimately, both H and E of the a-SiCN:H films were found to be sensitive to their N content, as they decreased (from ~17 GPa and 160 GPa to ~13 GPa and 136 GPa, respectively) when the N content was increased from 0 to 27 at.%. The formation of Si-N, Si-H, and N-H bonds at the detriment of the more stiffer Si-C bonds are thought to account for the observed lowering of the mechanical properties of the a-SiCN:H films such as their N content increased. Our results confirmed the previously-established constant-plus-linear correlation between the mechanical properties of the a-SiC films and their bond densities.

The adsorbed layer morphology of a series of surfactants under different conditions has been examined primarily using atomic force microscopy (AFM). The morphologies of single and double chained quaternary ammonium surfactants adsorbed to mica have been characterised using AFM at concentrations below the cmc. Mixing these different types of surfactants systematically allowed a detailed examination of the change in adsorbed film curvature from the least curved bilayers through to most curved globules. From this study a novel mesh structure was discovered at curvatures intermediate to bilayers and rods. A mesh was again observed in studies examining the morphology change of adsorbed nonionic surfactant films on silica with variation in temperature. Other surfactant mixtures were also examined including grafting non-adsorbing nonionic surfactants and diblock copolymers into quaternary ammonium surfactant films of different morphologies.

The adsorbed layer morphology of a series of surfactants under different conditions has been examined primarily using atomic force microscopy (AFM). The morphologies of single and double chained quaternary ammonium surfactants adsorbed to mica have been characterised using AFM at concentrations below the cmc. Mixing these different types of surfactants systematically allowed a detailed examination of the change in adsorbed film curvature from the least curved bilayers through to most curved globules. From this study a novel mesh structure was discovered at curvatures intermediate to bilayers and rods. A mesh was again observed in studies examining the morphology change of adsorbed nonionic surfactant films on silica with variation in temperature. Other surfactant mixtures were also examined including grafting non-adsorbing nonionic surfactants and diblock copolymers into quaternary ammonium surfactant films of different morphologies.

In dieser Arbeit wurde die Austrittsarbeit von Graphen, einer vielversprechenden Elektrodenmaterial für (opto)- elektronische Bauteile, durch die Adsorption von luftbeständigen konjugierten organischen Molekülen (KOMs), welche als Akzeptoren und Donatoren fungieren, modifiziert. Die Eigenschaften der Valenz- und Rumpfniveaus sowie die Austrittsarbeitsmodifikation der vakuumverdampften KOMs wurden mit Photoelektronenspektroskopie (PES) untersucht, während die Orientierung der KOMs mit Röntgen-Nahkanten-Absorptions-Spektroskopie (NEXAFS) aufgeklärt wurde. Die Austrittsarbeit von Graphen auf Quartz (G/Qu) lässt sich auf maximal 5.7 eV und minimal 3 eV anpassen, welches aus einem Ladungstransfer direkt an der Grenzfläche resultiert, der keine Ausbildung von kovalenten Bindungen zwischen der molekularen Monolage und dem Graphen beinhaltet. Zudem, für den starken molekularen Akzeptor Hexaazatriphenylen-Hexacarbonitril (HATCN) verläuft die Austrittsarbeitserhöhung über eine Orientierungsänderung der Moleküle im Monolagenbereich. Für alle anderen auf G/Qu abgeschiedenen Akzeptoren (Donatoren) wurde beobachtet, dass der Ladungstransfer eine positive (negative) Oberflächen-ladungsdotierung der Graphen-Schicht bewirkt, welches in einer Austrittsarbeitserhöhung (-erniedrigung) resultiert. Letztere ließ sich jeweils in zwei Beiträge zerlegen: (a) Verschiebung des Vakuumniveaus durch einen Grenzflächendipol an der KOM/Graphen-Grenzfläche und (b) Verschiebung des Fermi-Niveaus durch Oberflächenladungstransferdotierung der Graphen-Schicht. Weiterhin wurde der molekulare Akzeptor Hexafluoro-tetracyano napththoquinodimethan (F6TCNNQ) sowohl auf G/Qu als auch auf Graphen auf Kupfer abgeschieden, wobei sich herausstellte, dass der Ladungstransfer im ersteren Fall vom Graphen stammt, und im letzteren von der Kupferunterlage. Die Ergebnisse werden von Dichtefunktionaltheorieberechnungen gestützt und tragen erheblich zum Verständnis von Graphen/KOM-Grenzflächen bei.
In this thesis, the work function of graphene, a promising electrode for (opto)electronic devices was modified by adsorption of air-stable conjugated organic molecules (COMs) that act as strong molecular acceptors or donors. The valence and core level properties, together with the work function modification of the vacuum-deposited COMs on graphene were investigated with photoelectron spectroscopy (PES), while the orientation of COMs was studied with near edge X-ray fine structure spectroscopy (NEXAFS). The work function of graphene-on-quartz (G/Qu) is modified up to 5.7 eV and down to 3 eV as a result of charge transfer (CT) occurring right at the interface, which does not invoke covalent bond formation between the molecular monolayer and the graphene. In addition to the CT, in the case of the molecular acceptor hexaazatriphenylene-hexacarbonitrile (HATCN), the work function increase proceeded via a density-dependent re-orientation of the molecule in the monolayer regime. For all the other tested molecular acceptors (donors) deposited on graphene-on-quartz, the CT was observed to induce positive (negative) surface CT doping of the graphene layer, leading to a work function increase (decrease) and was disentangled into two contributions: (a) shift of the Vacuum level due to the formation of an interface dipole at the COM/graphene interface and (b) shift of the Fermi level of the graphene due to the surface CT doping. Additionally, the molecular acceptor hexafluoro-tetracyanonapththoquinodimethane (F6TCNNQ) was deposited on both G/Qu and graphene-on-copper, where the CT was found to originate from graphene and copper support respectively. The findings were supported by density functional theory calculations and significantly add to a fundamental understanding of graphene/COM interfaces.

The results of a density functional theory investigations of structural and electronic properties of zig-zag graphene nanoribbons 8-ZGNR/ h-BN(0001) are presented. The peculiarities of the spin state at the Fermi level and the role of the edge effect and the effect of substrate in formation of the band gap (380 meV) in 8-ZGNR/h-BN(0001) system were determined. The contributions of nanoribbon edges and the substrate in formation of the gap have been differentiated. The estimations of local magnetic moments on carbon atoms of the 8-ZGNR nanoribbon are made. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35245

Organic semiconductor interfaces are promising materials for use in next-generation electronic and optoelectronic devices. Current models for metal-organic interfacial electronic structure and dynamics are inadequate for strongly hybridized systems. This work aims to address this issue by identifying the factors most important for understanding chemisorbed interfaces with an eye towards tuning the interfacial properties. Here, I present the results of my research on chemisorbed interfaces formed between thin-films of phthalocyanine molecules grown on monocrystalline Cu(110). Using atomically-resolved nanoscale imaging in combination with surface-sensitive photoemission techniques, I show that single-molecule level interactions control the structural and electronic properties of the interface. I then demonstrate that surface modifications aimed at controlling interfacial interactions are an effective way to tailor the physical and electronic structure of the interface. This dissertation details a systematic investigation of the effect of molecular and surface functionalization on interfacial interactions. To understand the role of molecular structure, two types of phthalocyanine (Pc) molecules are studied: non-planar, dipolar molecules (TiOPc), and planar, non-polar molecules (H2Pc and CuPc). Multiple adsorption configurations for TiOPc lead to configuration-dependent self-assembly, Kondo screening, and electronic energy-level alignment. To understand the role of surface structure, the Cu(110) surface is textured and passivated by oxygen chemisorption prior to molecular deposition, which gives control over thin-film growth and interfacial electronic structure in H2Pc and CuPc films. Overall, the work presented here demonstrates a method for understanding interfacial electronic structure of strongly hybridized interfaces, an important first step towards developing more robust models for metal-organic interfaces, and reliable, predictive tuning of interfacial properties.

Nanostructured materials are defined as systems composed of single or multiple phases such that at least one of them has characteristic dimensions in the nanometer range (1-100 nm). The strategic importance of nanostructured materials rely on the fact that their structural, electronic, magnetic, catalytic, and optical properties can be tuned and controlled by a careful choice and assembling of their nanoscale elemental building blocks. Clusters, aggregations of a few atoms to a few thousands of atoms, are the building blocks used to synthetize nanostructured materials. Low-Energy Cluster Beam Deposition (LECBD) is a technique of choice for the fabrication of nanostructured systems, since it allows the deposition on a substrate of neutral particles produced in the gas phase and maintaining their properties even after deposition. This has been proven to be a powerful bottom-up approach for the engineering of nanostructured thin films with tailored properties, since it allows in principle the control of the physical and chemical characteristics of the building blocks. Among different approaches to LECBD, supersonic cluster beam deposition (SCBD) present several advantages in terms of deposition rate, lateral resolution compatible with planar microfabrication technologies and neutral particle mass selection by exploiting aerodynamic focusing effects. All these features make SCBD a superior tool to synthesize nanostructured films and their integration on microfabricated platforms. The morphology of cluster-assembled materials is characterized by a hierarchical arrangements of small units in larger and larger features up to a certain critical length-scale, in general determined by the duration of the deposition process. The cluster-assembled film morphology is characterized by high specific area and porosity at the nano and sub-nanometer scale, extending in the bulk of the film. Surface pores and surface specific area, as well as rms roughness, depend on film thickness, and increase with it. All these morphological properties is of great relevance for the use of cluster-assembled film in devices as gas sensor, (photo) catalysis, solar energy conversion and as biocompatible substrates.Recently it has been recognized that nanoscale surface morphology and nanopores play an important role in processes involving the interaction of biological entities (protein, viruses, enzymes) with nanostructured surfaces, via the modulation of electric interfacial properties. In particular, when the nanostructured material is used to produce electrodes and substrates for operation in liquid electrolytes, with given pH and ionic strength, double layer phenomena take place. An important parameter to describe these electrostatic phenomena is the IsoElectric Point (IEP), which corresponds to the pH value at which the net charge of the compact layer is zero. When two interacting surfaces approach to a distance comparable or smaller than the typical screening length of the electrolytic solution (the Debye length, determined by the ionic strength of the solution), the overlap of the charged layers determines complex regulation phenomena that are difficult to describe theoretically. While significant insights have been obtained on the properties of the electric double layers formed between flat smooth surfaces, the case of rough surfaces still represents a severe challenge, hampering analytical, yet approximate, solutions of the double layer equations to be reliably obtained. Anyway, these phenomena have been recently shown to be strongly influenced by the morphological properties of the surface. The quantitative characterization of all these interfacial properties requires imaging and force spectroscopy techniques with a resolution in and beyond the nanometer-scale. Atomic Force Spectroscopy (AFM) is an excellent candidate, since it couples the possibility of scanning with a z-resolution lower than fraction of nanometer and x-y resolution of 1 nm and also of performing very accurate force spectroscopy measurements. The first aim of my PhD work is to characterize by AFM the evolution of morphological properties of transition-metal oxides cluster-assembled materials (in particular nanostructured Titania (ns-TiOx) and nanostructured Zirconia (ns-ZrOx), starting from sub-monolayer regime to thin film, and especially to describe the influence of the building-blocks dimensions on the growth mechanisms and on the final surface morphology and topography. With this information, I have explored the influence of nanoscale morphology on double layer interactions which takes place on these nanostructured interfaces and on the wettability behaviour. The results have been used to highlight the role of morphological and structural surface properties as biophysical signal mediators for protein adsorption processes and cellular adhesion.

This dissertation describes a structural investigation of hyaluronan (HA) with neutron scattering techniques. HA is a natural biopolymer and one of the major components of the extracellular matrix, synovial fluid, and vitreous humor.  It is used in several biomedical applications like tissue engineering, drug delivery, and treatment of osteoarthritis. Although HA is extensively studied, very little is known about its three-dimensional conformation and how it interacts with ions and other molecules. The study aims to understand the bulk structure of a cross-linked HA hydrogel, as well as the conformational arrangement of HA at solid-liquid interfaces. In addition, the structural changes of HA are investigated by simulation of physiological environments, such as changes in ions, interactions with nanoparticles, and proteins etc. Small-angle neutron scattering and neutron reflectivity are the two main techniques applied to investigate the nanostructure of hyaluronan in its original, hydrated state. The present study on hydrogels shows that they possess inhomogeneous structures best described with two correlation lengths, one of the order of a few nanometers and the other in the order of few hundred nanometers. These gels are made up of dense polymer-rich clusters linked to each other. The polymer concentration and mixing governs the connectivity between these clusters, which in turn determines the viscoelastic properties of the gels. Surface-tethered HA at a solid-liquid interface is best described with a smooth varying density profile. The shape of this profile depends on the immobilization chemistry, the deposition protocol, and the ionic interactions. HA could be suitably modified to enhance adherence to metal surfaces, as well as incorporation of proteins like growth factors with tunable release properties. This could be exploited for surface coating of implants with bioactive molecules. The knowledge gained from this work would significantly help to develop future biomaterials and surface coatings of implants and biomedical devices.

Surfaces of metal oxides play a vital role in many technologically important applications. The surfaces of titanium dioxide, in particular, show quite promising properties that can be utilized in solid-state gas sensing and photocatalysis applications. In the first part of this dissertation we investigate these properties of TiO2 surfaces through a vigorous surface scientific approach. In the second part, we investigate the possibilities of modifying the TiO2 surfaces by depositing multi-component transition metal oxide monolayers so that the properties of bare TiO2 surface can be influenced in a beneficial way. For instance, via formation of new surface sites or cations that have different valance states, the chemisorption and catalytic properties can be modified. We use sophisticated experimental surface science techniques that are compatible with ultra-high vacuum technology for surface characterization. All the experimental results, except for the photocatalysis experiments, were compared to and verified by supporting DFT-based theoretical results produced by our theory collaborators. TiO2 based solid-state gas sensors have been used before for detecting trace amounts of explosives such as 2,4-dinitrololuene (DNT), a toxic decomposition product of the explosive 2,4,6-trinitrotoluene (TNT) that have very low vapor pressure. However, the adsorption, desorption and reaction mechanism were not well- understood. Here, we investigate 2,4-DNT adsorption on rutile-TiO2(110) surface in order to gain insight about these mechanisms in an atomistic level and we propose an efficient way of desorbing DNT from the surface through UV-light induced photoreactions. TiO2 exists in different polymorphs and the photocatalytic activity differs from one polymorph to another. Rutile and anatase are the most famous forms of TiO2 in photocatalysis and anatase is known to show higher activity than rutile. The photoactivity also varies depending on the surface orientation for the same polymorph. So far, a reasonable explanation as to why these differences exist was not reported. In our studies, we used high quality epitaxial rutile and anatase thin films which enabled isolating the surface effects from the bulk effects and show that it is the difference between the charge carrier diffusion lengths that causes this difference in activities. In addition to that, using different surface orientations of rutile-TiO2, we show that the anisotropic bulk charge carrier mobility may contribute to the orientation dependent photoactivity. Moreover, we show that different surface preparation methods also affect the activity of the sample and vacuum reduction results in an enhanced activity. In an effort to modify the TiO2 surfaces with monolayer/mixed monolayer oxides, we carried out experiments on (011) orientation of single crystal rutile TiO2 with few of the selected transition metal oxides namely Fe, V, Cr and Ni. We found that for specific oxidation conditions a monolayer mixed oxide is formed for all M (M= Fe, V, Cr, Ni), with one common structure with the composition MTi2O5. For small amounts of M the surface segregates into pure TiO2(011)-2×1 and into domains of MTi2O5indicating that this mixed monolayer oxide is a low energy line phase in a compositional surface phase diagram. The oxygen pressure required for the formation of this unique monolayer structure increases in the order of V2O5 mixed monolayer oxide by DFT-based simulations was verified by X-ray photoemission diffraction measurements performed at a synchrotron facility.

Thesis (Ph.D. in Materials Engineering) -- University of Dayton.
Title from PDF t.p. (viewed 06/23/10). Advisor: Liming Dai. Includes bibliographical references (p. 136-162). Available online via the OhioLINK ETD Center.

Diese Arbeit behandelt elektronische und strukturelle Eigenschaften dünner Schichten aus konjugierten organischen Molekülen (COMs), aufgebracht auf Metalloberflächen per Vakuum-Sublimation. Diese Eigenschaften sind essenziell für Funktionsrealisierung und -optimierung organischer Elektronikbauteile. Teil 1 diskutiert zwei Ansätze zur Energieniveauanpassung (ELA) an Organik-Metall-Grenzflächen zur Einstellung der dortigen Löcherinjektionsbarrieren (HIBs) durch (Über-)Kompensation des abträglichen "Push-back"-Effekts: - Ausnutzung der besonderen ELA bei Chalkogen-Metall-Bindungen, hier gezeigt mit Hilfe von Röntgen- und Ultraviolettphotoelektronenspektroskopie (UPS/XPS) für ein Seleno-funktionalisiertes COM - Einfügen von COMs mit ausgeprägtem Elektronen-Akzeptorcharakter vor dem Aufbringen der aktiven Schicht. UPS-Messungen zeigen, dass beide Ansätze HIBs von ca. 0.3 eV ermöglichen. Teil 2 untersucht ausgewählte organische Heterostrukturen auf Metallen. Die Untersuchungen identifizieren einen Ladungstransfer vom Metall zur Überschicht (MOCT) als verantwortlich dafür, das System bei Ferminiveau-Pinning in den Gleichgewichtszustand zu überführen. Detaillierte Untersuchungen gestatten die Identifikaton von ganzzahligem Ladungstransfer zu einem Teil der Moleküle in der ersten Überschichtlage und den Einfluss der Dipol-Abstoßung in der Überschicht. In Teil 3 dienen Metalloberflächen als Auflage für supramolekulare Architekturen mit dipolaren Bausteinen. Rastertunnelmikroskopie (STM) an einer Serie von teils partiell fluorierten, stäbchenförmigen COMs mit unterschiedlich großen Dipolmomenten ermöglicht die Entflechtung von Dipol-Dipol- und konkurierenden Wechselwirkungen physisorbierter Submonolagen auf Ag(111). Ein anderes, stark dipolares COM bildet bei Monolagenbedeckung auf Au(111) sechs Phasen, alle mit antiferroelektrischer Einheitszellen. UPS-Messungen ergeben eine bevorzugte Ausrichtung der Moleküle in Multilagen.
In this thesis, the electronic and structural properties of thin films of conjugated organic molecules (COMs) vacuum-deposited on metal surfaces are studied. These properties are essential for realization and optimization of device functionalities in the field of organic electronics. Part 1 discusses two approaches for engineering the energy-level alignment (ELA), and, thereby, optimizing hole injection barriers (HIBs), at organic/metal interfaces via (over)compensation of the detrimental "push-back": - Exploiting the peculiar ELA at chalcogen-metal bonds, shown here (with X-ray and ultraviolet photoelectron spectroscopy, UPS/XPS) for a seleno-functionalized COM - inserting electron-accepting COMs prior to deposition of active layers. UPS shows that both approaches realize HIBs into the active COM as low as 0.3 eV. Part 2 studies selected organic/organic heterostructures on metal surfaces. These studies allow to propose that metal to overlayer charge transfer (MOCT), is responsible for achieving electronic equilibrium when such systems are Fermi-level pinned. Detailed investigations allowed identifying integer charge transfer to a fraction of the molecules in the first overlayer and the influence of the dipole-repulsion on the overlayer. In Part 3, metal surfaces are used as support for supramolecular architecture with polar building blocks. Scanning tunneling microscopy (STM) of a series of rod-like COMs with and without partial fluorination and with different dipole moments help disentangling the delicate balance dipole-dipole and competing interactions for sub-monolayer films physisorbed on Ag(111). For another, highly-polar COM at ca. monolayer coverage on Au(111), STM identifies six phases. All phases are found to exhibit anti-ferroelectric unit cells. UPS evidences a preferential alignment of multilayer molecules.

Die vorliegende Arbeit behandelt Fragestellungen aus der Organischen Elektronik, in der die Ladungsträgerinjektion in alle Arten von Bauteilen kritisch von der elektronischen und morphologischen Struktur der Grenzflächen zwischen Elektrode und den konjugierten organischen Molekülen (KOM) abhängt. Näher betrachtet wurden: die Energieniveauanpassung mit starken (i) Elektronendonatoren und (ii) -akzeptoren und (iii) die dichteabhängige Umorientierung einer molekularen Monolage. Zur Analyse wurden Photoelektronen- und Reflektionsabsorptionsinfrarotspektroskopie angewandt. Weitere Informationen konnten durch Modellierung mit Dichtefunktionaltheory gewonnen werden, die über Kollaborationen zur Verfügung standen. (i) Das Konzept der optimierten Energieniveauanpassung mit starken Elektronenakzeptoren konnte auf Donatoren erweitert und damit erfolgreich von der Anode zur Kathode transferiert werden. Auch hier führte der Ladungstransfer zu einem Dipol über die Grenzfläche, womit die Austrittsarbeit um bis zu 2.2 eV reduziert wurde. Als Resultat konnte die Elektroneninjektionsbarriere in nachfolgende Materialien entscheidend verringert werden (bis zu 0.8 eV). (ii) Ein bis dato unerforschter starker Elektronenaktzeptor [hexaaza-triphenylene-hexacarbonitrile (HATCN)] wurde vollständig verschiedenen Elektroden charakterisiert. HATCN zeigte dabei eine bessere Performance verglichen mit derzeit üblichen Materialien (starke Austrittsarbeitsanhebung und Verringerung der Lochinjektionsbarriere um bis zu 1.0 eV). (iii) Zusätzlich konnte mit HATCN gezeigt werden, dass eine liegende molekulare Monolage durch Erhöhung der Moleküldichte in eine stehende Monolage umgewandelt werden kann. Dies führte zu einer Änderung der chemischen Bindung zum Metall und damit zu einer starken Modifikation der elektronischen Struktur der Grenzfläche. Die vorliegende Arbeit liefert damit wertvolle Informationen für das Verständnis der Grenzfläche zwischen Elektrode und KOM in der Organischen Elektronik.
The present work is embedded in the field of organic electronics, where charge injection into devices is critically determined by the electronic and structural properties of the interfaces between the electrodes and the conjugated organic materials (COMs). Three main topics are addressed: energy level tuning with new and strong electron (i) donor and (ii) acceptor materials and (iii) the density dependent re-orientation of a molecular monolayer and its impact on the energy level alignment. To study these topics photoelectron and reflection absorption infrared spectroscopy were used. Moreover, additional information was obtained from density functional theory modelling, which was available through collaboration. (i) A concept of optimizing the energy level alignment at interfaces with strong molecular acceptors was extended to donor materials and thus successfully transferred from the anode to the cathode side of the device. Also in this case, charge transfer leads to a chemisorbed molecular monolayer. Due to the dipole across the interface, the work function of the electrode is reduced by up to 2.2 eV. Consequently, a reduced electron injection barrier into subsequently deposited materials is achieved (up to 0.8 eV). (ii) A yet unexplored strong electron acceptor material [i.e. hexaazatriphenylene- hexacarbonitrile (HATCN)] is thoroughly investigated on various surfaces. HATCN shows superior performance as electron acceptor material compared to presently used materials (e.g. work function modification and hole injection barrier reduction by up to 1 eV). (iii) Also with HATCN, the orientation of a molecular monolayer is observed to change from a face-on to an edge-on depending on layer density. This is accompanied by a re-hybridization of molecular and metal electronic states, which significantly modifies the interface electronic properties. All findings presented are valuable for the understanding of electrode-COM interfaces in organic electronics.

Soft interfaces play a fundamental role in many biological and industrial processes. In this work, atomistic simulations were used to study the structural properties of the interfaces between water and five organic solvents, with special attention devoted to the 1,2-dichloroethane-water system. This system is widely used in sensing applications currently in development, and was used as a prototypical case to study the effect of ions on interfacial structure and to gain insight into their transfer mechanism.

In this study, we have fabricated an Al/Colchicine/p-Si structure and have investigated its current– voltage (I–V) and capacitance–voltage (C–V) characteristics at room temperature. The barrier height and ideality factor values of 0.68 eV and 3.22, respectively, have been obtained from the I-V plot. The value of the barrier height was compared with the barrier height value of 0.50 eV of a conventional Al/p-Si diode. This was attributed to the Colchicine organic film modifying the effective barrier height by affecting the space charge region of the inorganic Si semiconductor substrate. By using C – 2-V characteristics the diffusion potential value has been extracted as 1.32 V. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35140

Nous avons épitaxié des tri-couches Cr\Fe\Cr sur les substrats de MgO et SrTiO3 (100) par pulvérisation cathodique. Leurs propriétés structurales et magnétiques s’améliorent lorsque la température de dépôt du Fe décroît, mais il y a formation d’oxydes de Fe et de Cr aux interfaces. Nous avons donc choisi de continuer l’élaboration des tri-couches par MBE. Nous avons varié l’épaisseur de tri-couches déposées par MBE pour extraire le moment moyen et sa modification aux interfaces. La contribution des interfaces ont le signe et l’ordre de grandeur prédits par Daniel Stoeffler en liaisons fortes. Les phénomènes d’interdiffusion dans ces multicouches ont été étudiés par des recuits isochrones et isothermes. La gamme de température intéressante pour les recuits est de 400 à 500°C. Les recuits isothermes montrent la présence de plusieurs régimes. Les profils de concentration simulés par Monte-Carlo révèlent une diffusion asymétrique
We have epitaxied Cr/Fe/Cr tri-layers on the MgO and SrTiO3 (100) substrates by magnetron sputtering. Their structural and magnetic properties improve when the deposition temperature of Fe decreases, but Fe and Cr oxides form at the interfaces. We therefore chose to continue with the multi-layers growth using MBE. We varied the thickness of three layers deposited by MBE to extract the average moment and its modification at the interfaces. The contribution of the interfaces has the sign and order of magnitude predicted by Daniel Stoeffler using tight-binding. The interdiffusion phenomenain these multilayers have been studied by isochronous and isothermal annealings. The temperature range of interest for annealing is 400 to 500°C. Isothermal annealing shows the presence of several regimes. The concentration profiles simulated by Monte Carlo reveal an asymmetric diffusion

The paper presents the results of capacitance-voltage (C-V) characterization of metal-oxidesemiconductor (MOS) structure, namely Pd/Al2O3/ In0.53Ga0.47As/InP. It is shown that MOS structure under study exhibit both electron and hole trapping with permanent and temporary charge trapping contributions. The interfacial transition layer between the high-k oxide and InGaAs has the greatest influence on this charge trapping phenomenon. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35048

Cette etude porte sur les proprietes interfaciales du polycrylamide hydrolyse adsorbe sur un aluminosilicate de synthese. La cinetique d'adsorption resultant d'interactions attractives a courtes distances est fortement influencee par l'existence de potentiels electrostatiques a longue portee. L'adsorption induit la creation de charges positives en surface, charges instantanement compensees par un transfert d'anions de la solution vers la zone interfaciale

With the semiconductor industry racing toward a historic transition, nano chips with less than 45 nm features demand I/Os in excess of 20,000 with multi-core processors aggregately providing highest bandwidth at lowest power. On the other hand, emerging mixed signal systems are driving the need for 3D packaging with embedded active components and ultra-short interconnections. Being able to provide several fold increase in the chip-to-package vertical interconnect density is essential for garnering the true benefits of nanotechnology that will utilize nano-scale devices. Electrical interconnections are multi-functional materials that must also be able to withstand complex, sustained and cyclic thermo-mechanical loads. Device- to- system board interconnections are typically accomplished today with either wire bonding or solders. Both of these are incremental and run into either electrical or mechanical barriers as they are extended to higher interconnections densities. Downscaling traditional solder bump interconnect will not satisfy the thermo-mechanical reliability requirements at very fine pitches. Other approaches such as compliant interconnects require lengthy connections and are limited in terms of electrical properties. A novel chip-package interconnection technology is developed to address the IC packaging requirements and to introduce innovative design and fabrication concepts that will further advance the performance of the chip, the package, and the system board. The nano-structured interconnect technology simultaneously packages all the ICs intact in wafer form with quantum jump in the number of interconnections with the lowest electrical parasitics. The intrinsic properties of nano materials also enable several orders of magnitude higher interconnect densities with the best mechanical properties for the highest reliability and yet provide higher current and heat transfer densities. This thesis investigates the electrical and mechanical performance of nano-structured interconnections through modeling and test vehicle fabrication. Test vehicles with nano-interconnections were fabricated using low cost electro-deposition techniques and assembled with various bonding interfaces. Interconnections were fabricated at 200 micron pitch to compare with the existing solder joints and at 50 micron pitch to demonstrate fabrication processes at fine pitches. Experimental and modeling results show that the proposed nano-interconnections could enhance the reliability and potentially meet all the system performance requirements for the emerging micro/nano-systems.

Über die besonders hohe Effizienz von Halid-Perowskit (HaP)-basierten optoelektronischen Bauteilen wurde bereits in der Literatur berichtet. Um die Entwicklung dieser Bauteile voranzutreiben, ist ein umfassendes und verlässliches Verständnis derer elektronischen Struktur, sowie der Energielevelanordnung (ELA) an HaP Grenzflächen von größter Bedeutung. Demzufolge beschäftigt sich die vorliegende Arbeit mit der Untersuchung i) der Bandstruktur von Perowskit-Einkristallen, um ein solides Fundament für die Darlegung der elektronischen Eigenschaften von polykristallinen Dünnschichten zu erarbeiten, und mit ii) den Einflüssen von Oberflächenzuständen auf die elektronische Struktur der Oberfläche, sowie deren Rolle bei der Kontrolle von ELA an HaP Grenzflächen. Die Charakterisierung erfolgt überwiegend mithilfe von Photoelektronenspektroskopie (PES) und ergänzenden Messmethoden wie Beugung niederenergetischer Elektronen an Oberflächen, UV-VIS-Spektroskopie, Rasterkraftmikroskopie und Kelvin-Sonde. Erstens weist die Banddispersion von zwei prototypischen Perowskit-Einkristallen eine starke Dispersion des jeweiligen oberen Valenzbandes (VB) auf, dessen globales Maximum in beiden Fällen am R-Punkt in der Brillouin-Zone liegt. Dabei wird eine effektive Lochmasse von 0.25 m0 für CH3NH3PbBr3, bzw. von ~0.50 m0 für CH3NH3PbI3 bestimmt. Basierend auf diesen Ergebnissen werden die elektronischen Spektren von polykristallinen Dünnschichten konstruiert und es wird dadurch aufgezeigt, dass eine Bestimmung der Valenzbandkantenposition ausgehend von einer logarithmischen Intensitätsskala aufgrund von geringer Zustandsdichte am VB Maximum vorzuziehen ist. Zweitens stellt sich bei der Untersuchung der elektronischen Struktur von frisch präparierten Perowskit-Oberflächen heraus, dass die n-Typ Eigenschaft eine Folge der Bandverbiegung ist, welche durch donatorartige Oberflächenzustände hervorgerufen wird. Des Weiteren weisen die PES-Messungen an Perowskiten mit unterschiedlichen Zusammensetzungen aufgrund von Oberflächenphotospannung eine Anregungslichtintensitätsabhängigkeit der Energieniveaus von bis zu 0.7 eV auf. Darüber hinaus wird die Kontrolle von ELA durch gezielte Variation der Oberflächenzustandsdichte gezeigt, wodurch sich unterschiedliche ELA-Lagen (mit Abweichungen von über 0.5 eV) an den Grenzflächen mit organischen Akzeptormolekülen erklären lassen. Die vorliegenden Ergebnisse verhelfen dazu, die starke Abweichung der in der Literatur berichteten Energieniveaus zu erklären und somit ein verfeinertes Verständnis des Funktionsprinzips von perowskit-basierten Bauteilen zu erlangen.
Optoelectronic devices based on halide perovskites (HaPs) and possessing remarkably high performance have been reported. To push the development of such devices even further, a comprehensive and reliable understanding of their electronic structure, including the energy level alignment (ELA) at HaPs interfaces, is essential but presently not available. In an attempt to get a deep insight into the electronic properties of HaPs and the related interfaces, the work presented in this thesis investigates i) the fundamental band structure of perovskite single crystals, in order to establish solid foundations for a better understanding the electronic properties of polycrystalline thin films and ii) the effects of surface states on the surface electronic structure and their role in controlling the ELA at HaPs interfaces. The characterization is mostly performed using photoelectron spectroscopy, together with complementary techniques including low-energy electron diffraction, UV-vis absorption spectroscopy, atomic force microscopy and Kelvin probe measurements. Firstly, the band structure of two prototypical perovskite single crystals is unraveled, featuring widely dispersing top valence bands (VB) with the global valence band maximum at R point of the Brillouin zone. The hole effective masses there are determined to be ~0.25 m0 for CH3NH3PbBr3 and ~0.50 m0 for CH3NH3PbI3. Based on these results, the energy distribution curves of polycrystalline thin films are constructed, revealing the fact that using a logarithmic intensity scale to determine the VB onset is preferable due to the low density of states at the VB maximum. Secondly, investigations on the surface electronic structure of pristine perovskite surfaces conclude that the n-type behavior is a result of surface band bending due to the presence of donor-type surface states. Furthermore, due to surface photovoltage effect, photoemission measurements on different perovskite compositions exhibit excitation-intensity dependent energy levels with a shift of up to 0.7 eV. Eventually, control over the ELA by manipulating the density of surface states is demonstrated, from which very different ELA situations (variation over 0.5 eV) at interfaces with organic electron acceptor molecules are rationalized. Our findings further help to explain the rather dissimilar reported energy levels at perovskite surfaces and interfaces, refining our understanding of the operational principles in perovskite related devices.

Les matériaux cellulaires font l'objet de beaucoup de recherches du fait de leurs remarquables propriétés. Celles-ci proviennent de la structure interne du matériau, dans lequel des inclusions cellulaires sont compactées dans une matrice solide. Comprendre et contrôler l'organisation des cellules dans la phase continue est donc primordial pour pouvoir contrôler les propriétés finales du solide poreux. L'influence des propriétés d'objets sur leur organisation dans un volume a souvent été étudiée pour des systèmes granulaires durs monodisperses, où la friction entre deux grains implique que l'arrangement global sera désorganisé, ou pour des systèmes mous comme les bulles dans les mousses aqueuses, où la très faible friction aux interfaces conduit à un empilement organisé et compact de sphères. Une question importante est de comprendre comment s'empilent des objets déformables présentant de la friction à l'interface. Pour répondre à cela, nous nous intéressons ici à un système modèle de gouttes de PEG (polyéthylèneglycol) dispersées dans une phase continue de PDMS (polydiméthylsiloxane). La coalescence entre les gouttes est empêchée grâce à une réaction à l'interface qui crée un gel de polymère à la surface des gouttes au contact avec le PDMS. Cette peau de polymères induit de la friction et de l'adhésion entre les gouttes. Pour étudier l'influence des propriétés de la peau sur la sédimentation des gouttes, nous caractérisons la fraction volumique finale sous gravité grâce à la tomographie sous rayons X. Nous montrons que la présence de friction et d'adhésion à l'interface induit une organisation non-conventionnelle des gouttes en comparaison avec celle d'émulsions stabilisées par des tensioactifs. Nous examinons ensuite les propriétés mécaniques et adhésives des émulsions solides, composées de gouttes liquides dans une matrice solide, avec un test de probe-tack. Nous étudions l'impact de la taille ainsi que de la densité de gouttes sur l'augmentation des dissipations d'énergie dans le volume
Macro-cellular polymers are highly searched-for materials thanks to their rich physical properties. These arise from the internal structuration of the material, in which discrete cells of gas or liquid are tightly packed within a continuous polymeric solid. The size and organization of these cells have an important influence on the overall material properties. The influence of the properties of spheres on their final packing morphology has led to numerous studies usually dealing with either hard frictional or soft frictionless grains, which are the two extremes of the spectrum of possible systems. An important question remains as to what happens for systems which are in-between these extremes, i.e. highly deformable grains presenting a frictional surface. To tackle this problem, we work with a model system of ultra-stable emulsions which consist of PEG (polyethyleneglycol) drops which are dispersed in a continuous phase of PDMS (polydimethylsiloxane). Coalescence of the drops is prohibited by a reactive blending approach which creates a solid-like skin around the PEG drops upon contact with the PDMS. This skin creates adhesion and friction between the drops. To study the influence of the skin properties on the sedimentation of the drops, we characterize the final drop packing under gravity using absorption contrast X-Ray. We show that the presence of friction and adhesion at the interface makes the liquid drops pack unconventionally regarding density and organization compared to classic surfactant stabilized emulsions. We then investigated the adhesive properties of the solid emulsions i.e. elastomers containing liquid drops in their substructure, using a probe-tack test. We studied the impact of the drop size and density on the increase of the bulk's dissipations of energy which enhance the adhesive properties of the material

Cette thèse porte sur les propriétés de transport anormal des oxydes de métaux de transition, en particulier de la surface de SrTiO₃ ou de l’interface entre SrTiO₃ et LaAlO₃. Dans ces systèmes on observe l’apparition de gaz d’électrons bidimensionnels. Des mesures d’Effet Hall non linéaire indiquent que ces gaz sont constitués de plusieurs sortes de porteurs de charge, et que leurs populations varient de manière non monotone sous l’effet du dopage électrostatique. L’effet des propriétés électrostatiques et des corrélations électroniques sur ces variations sont discutées. Celles-ci sont à l’origine de réponses remarquables en ce qui concerne la conversion du spin en charge dans ces systèmes à l’aide d’un modèle de liaisons fortes et de la théorie de la réponse linéaire. Les effets conjoints du spin-orbite atomique et de la brisure de symétrie d’inversion à l’interface verrouille les nombres quantiques de spin, de caractère orbital et d’impulsion des électrons, et induit des textures de spin complexe dans l’espace réciproque. Ces textures sont responsables de l’apparition des effets Edelstein et Hall de spin dans ces hétérostructures et sont caractéristiques de la nature multi-orbitale de ces systèmes électroniques. Enfin nous conduirons une étude ab initio des hétérostructures STO/LAO/STO pour expliquer les observations expérimentales de nouvelles manières de former un gaz d’électrons à ces interfaces d’oxydes. Nous discuterons des rôles respectifs de la chimie, de l’électrostatique et des défauts dans l’apparition de ce gaz
The anomalous transport properties of transition metal oxides, in particular the surface of SrTiO₃ or at the interface between SrTiO₃ and LaAlO₃ is investigated in this thesis. These systems host two-dimensional electron gases. Nonlinear Hall Effect measurements suggest that several species of carriers are present in these systems, and that their population is varying on a nontrivial manner upon electrostatic doping. The role of the electrostatics properties of the electron gas and of the electronic correlations are discussed in this light. Next we discuss the spin to charge conversion of these systems thanks to tight-binding modeling and linear response theory. The complex interplay between atomic spin-orbit coupling and the inversion symmetry breaking at the interface leads to a complex spin-orbital-momentum locking of the electrons, inducing spin textures. These spin textures are responsible for the appearance of the Edelstein and Spin Hall Effect in these heterostructures and are characteristic of the multi-orbital character of these electronic systems. Finally an ab initio study of STO/LAO/STO heterostructures is performed to explain experimental evidence of new ways to produce an electron gas at this interface. The respective roles of the chemistry, electrostatics and defects are discussed

L'efficacité du processus photovoltaïque dépend du matériau actif à travers la structure de bande et la dynamique des porteurs de charge. Dans cette thèse, nous avons relié les propriétés électroniques et la dynamique de relaxation à la structure atomique des matériaux utilisés pour deux technologies différentes de cellules solaires, celle à base d’hétérostructures de silicium, et celle à base de pérovskites hybrides organiques-inorganiques. Dans les cellules solaires de silicium, nous avons analysé l'influence des défauts sur les propriétés électroniques des hétérostructures de silicium amorphe (a-Si:H/a-SIC:H/c-Si) par spectroscopies des niveaux de coeur et de la bande de valence. En particulier, nous avons quantifié le nombre de liaisons pendantes induites dans la couche a-Si:H par irradiation, et nous avons identifié les états électroniques qui leur sont associés. Enfin nous avons expliqué les transitions précédemment observées par photoluminescence. Dans les cellules solaires à pérovskite hybride, nous avons corrélé la structure atomique, la structure électronique et la dynamique électronique pour des pérovskites bi- et tridimensionnelles. Dans ce but nous avons utilisé tout un panel de techniques complémentaires: diffraction des rayons X, spectroscopie de photoémission résolue en angle, spectroscopie de photoémission inverse et photoémission à deux photons résolue en temps. Pour la pérovskite bidimensionnelle (C₆H₅C₂H₄NH₃)₂PbI₄, nous avons déterminé expérimentalement les bandes de valence et de conduction et nous les avons comparées aux simulations de la fonction spectrale. Pour la pérovskite tridimensionnelle CH₃NH₃PbI₃, nous avons aussi déterminé les structures de bande expérimentale et simulée. Des signatures spectrales très larges ont été observées expérimentalement, ce qui relaxe les conditions de transition optique avec un impact éventuel sur l'efficacité des cellules solaires. Tant dans les expériences que dans les calculs, nous observons que le poids spectral suit une périodicité cubique alors que le système est structurellement dans une phase tétragonale. Cette contradiction apparente s'explique par la largeur spectrale des bandes, qui cache le repliement dû à la distorsion tétragonale. En ce qui concerne la dynamique de relaxation, nous avons observé que les porteurs photoexcités se thermalisent dans une échelle de temps subpicoseconde par couplage aux vibrations des cations organiques. À des échelles de temps plus longues (10~100 picosecondes), la diffusion électronique contrôle la dynamique. Cette dynamique est affectée par les défauts induits par recuit, qui localisent les électrons photoexcités pendant plus de 300 picosecondes
The efficiency of the photovoltaic process depends on the electronic band structure of the active material and the charge carrier dynamics. In this thesis, we have studied how these issues are related to the atomic structure in materials for two different technologies of solar cells, namely silicon heterostructure solar cells, and hybrid organic-inorganic perovskite solar cells. In silicon heterostructure solar cells, we have analyzed the impact of defects on the electronic properties of amorphous silicon heterostructures (a-Si:H/a-SIC:H/c-Si) by core level and valence band spectroscopies. In particular, we have quantified the number of dangling bonds inside a-Si:H layer upon irradiation, we have identified the electronic states associated to them, and we have understood the transitions previously observed by photoluminescence. In perovskite solar cells, we have correlated the atomic structure, the electronic structure and the electronic dynamics for two- and three-dimensional hybrid organic-inorganic perovskites. We have used with this goal a whole panel of complementary techniques: X-ray diffraction, angle-resolved photoemission spectroscopy, inverse photoemission spectroscopy, and time-resolved two-photon photoemission. In the two-dimensional perovskite (C₆H₅C₂H₄NH₃)₂PbI₄, the valence and conduction bands have been determined experimentally and compared to spectral function simulations. In the three-dimensional perovskite CH₃NH₃PbI₃, we have again determined the band structure and simulated it. Very broad spectral features have been experimentally observed, which relax the optical transition conditions impacting in the solarcell efficiencies. In both experiments and calculations, we observe that the spectral weight follows a cubic periodicity while the system is structurally in the tetragonal phase. This apparent contradiction is explained by the band broadness, which hides the band folding of the tetragonal distortion. As for the relaxation dynamics, we have observed that the photoexcited carriers thermalize in a subpicosecond time scale through the coupling to organic cation vibrations. At longer timescales (10~100 picoseconds), the electron diffusion controls the dynamics. This dynamics is affected by the annealing-induced defects, which localize the photoexcited electrons for more than 300 picoseconds

The elastic properties of oil/water/surfactant interfaces play an important role in the phase behaviour of microemulsions and for the stability of macroemulsions. The aim of this thesis is to obtain an understanding of the relationship between the structure of the surfactant molecules, the structure of the interface, and macroscopic interfacial properties. To achieve this aim, we performed molecular simulations of oil/water/surfactant systems. We made a quantitative comparison of various model surfactants to determine how structural changes affect interfacial properties and film rupture. The model consists of water, oil, head, and tail beads, and surfactants are constructed by coupling head and tail beads with harmonic springs. We used a hybrid dissipative particle dynamics-Monte Carlo scheme. The former was used to simulate particle trajectories and the Monte Carlo scheme was used to mimic experimental conditions: bulk-interface phase equilibrium, tensionless interfaces in microemulsions, and the surface force apparatus.

A detailed comparison of various non-ionic model surfactants showed how structural changes affect interfacial properties:

Comparison between linear and branched surfactants showed that the efficiency of adsorption is higher for linear surfactants, although branched surfactants are more efficient at a given surface density. Linear surfactants can be more efficient also at the same surface density if the head group is sufficiently soluble in oil, because low head-oil repulsion makes the branched isomers stagger at the interface. The bending rigidity is higher for linear surfactants. Furthermore, branched surfactants make oil droplets coalesce more easily than linear surfactants do, but linear and branched surfactants have roughly the same effect on water droplet coalescence.

Comparison of linear surfactants with varying chain lengths showed that longer surfactants have a lower surface tension and higher bending rigidity. The increase in rigidity with chain length follows a power law, but the exponent is higher for surfactant monolayers at a fixed density than at a fixed tension. Longer tails and/or denser monolayers influence the stability of water droplets in a positive direction, and the stability of oil droplets in a negative direction.

Addition of cosurfactant showed that mixed monolayers have a lower bending rigidity than pure monolayers at the same average chain length and tension. Cosurfactants have a negative effect on the stability of water droplets, and a positive effect on the stability of oil droplets.

Paper I reprinted with kind permission of EDP Sciences. Paper III reprinted with kind permission of the American Institute of Physics. Paper IV reprinted with kind permission of the American Physics Society.

Predictive models of structures containing frictional joints presently suffer from poor descriptions of interface behaviour at the joints. This thesis aims to address this shortfall by furthering the physical understanding of parameters affecting interface behaviour such as friction and contact stiffness. Aspects of friction and contact stiffness relevant to the characterisation of fretting joints are investigated by a combined modelling and experimental approach. Friction and wear behaviour in gross-slip fretting are investigated by in-line and rotational fretting tests. New 3D topography parameters are found to be useful in the analysis of surfaces during fretting. Wear-scar shape is found to be dependent on material. A phenomenon whereby friction increases during the gross-slip phase of individual cycles is found to be due to wear-scar interaction primarily through the interference of local features distributed over the contact area. These features are similar in size to the applied fretting stroke. A simple model to explain the behaviour is put forward which shows that wear-scar shape determines the form of the friction variation. A finite-element (FE) model of the interaction of an elastic-plastic asperity junction is used to predict sliding friction coefficients. The modelling differs from previous work by: permitting greater asperity overlaps, enforcing an interface shear strength, and allowing material failure. The results are also used to predict friction coefficients for a stochastic rough surface. The magnitudes of the predicted friction coefficients are generally representative of experimental measurements. Results suggest that friction arises from both plasticity and tangential interface adhesion. Contact stiffness is studied for both fretting and non-fretting. A technique to isolate the true interface stiffness from results derived from load-deflection data is developed by comparing experimental and FE results. In the fretting wear case, comparison of tangential contact stiffness results in the literature with FE results reveals an interface whose compliance dominates the response to the extent that stiffness is proportional to contact area. In fretting tests such as this, wear debris is thought to be a factor contributing to high interface compliance. Non-fretting experiments performed here show that, at higher pressures, interface domination is reduced as the contact approaches the smooth case. Experiments are performed where contact stiffness is measured simultaneously by both ultrasound and digital image correlation. The effect of normal and tangential loading upon the contact stiffness (normal and tangential) is investigated. Experimental evidence showing that ultrasound measures an ‘unloading’ stiffness while DIC measures a ‘loading’ stiffness is obtained for the case of tangential loading where the ‘DIC stiffness’ decreases with increasing tangential load whereas the ‘ultrasound stiffness’ remains approximately constant. On average, ultrasound gives magnitudes 3.5 and 2.5 times stiffer than the DIC results for the normal and tangential stiffness cases, respectively. The difference in magnitudes can largely be physically explained, and is relatively small considering the significant differences between the techniques. Therefore, both methods can claim to give valid measurements of contact stiffness – though each has its own limitations which are outlined herein.

A very important role is played by metal oxides in many areas of chemistry, physics, and materials science. Transition metal and rare-earth metal elements are able to form a large diversity of oxide compounds which can adopt an ample array of atomic structures and electronic properties that can exhibit metallic, semiconductor, or insulator characteristics. In technological applications, metal oxides are used in the fabrication of microelectronic components, sensors, fuel cells, coatings to protect surfaces against corrosion, and as catalysts. In this thesis we have decided to study two known catalytic materials Zirconia-Titania and Ceria-Titania mixed oxides. For both materials bibliography principally concerns powders thus in order to better study their interfaces, of which a deeper study is still lacking, we decided to deposit zirconia and ceria as thin films onto rutile TiO2(110). We first studied the zirconia-titania system by depositing an ultra-thin film of zirconium oxide via a metal-organic precursor: Zirconium Tetra tert-Butoxide. The deposition was carried at three different substrate temperatures 677 K, 738 K, 773 K in five stages of a minute each and the results were traced by using XPS. The chemical characterization via XPS showed an interesting chemistry undergoing on the substrate’s surface and we have observed the formation of carbonaceous species at the interface. Zirconium appeared to be at its highest oxidation state while titanium was seen to undergo reduction with each successive deposited layer. The ratio of the Zr/Ti signals showed that zirconia didn’t completely wet the surface. Furthermore, no long range order was observed via LEED. XPD measurements showed that zirconia does not form a substitutional oxide with titania. However with the aid of computer simulation we deduced that very likely zirconia forms nanochains on the surface of TiO2(110). This surface was exposed to 100 L of pyridine to test its acidity. In the case of ceria, we have deposited the oxide on a heated TiO2(110) substrate via metal evaporation from a Mo crucible since the process is rather easy and garners clean deposits. During deposition the substrate was kept at 677 K and in an O2 environment of 5.2•10-6mbar, and, in order to obtain an ordered homogeneous surface the sample was further annealed in the same environment at 900 K. Through LEED imaging different phases were observed and were dependent on sample history and film thickness. Via computer simulation these phases were then referred to the parent oxide in order to better comprehend the difference in respect to the bulk phase. All films showed cerium present at Ce(III). Ultra-violet Photoelectron Spectroscopy showed the electronic properties of the film showing a binding energy shift and the population of Ce4f states due to stabilization of Ce(III) by TiO2(110). The reactivity of the ceria-titania system was the probed by using methanol and ethanol. Results showed that the addition of ceria opened the dehydrogenation path from alcohol to aldehyde. We have observed that oxygen pre-oxidation of the CeOx-TiO2(110) system had an impact on its selectivity by opening also a dehydration path from methanol and ethanol to respectively, methane and ethylene. This alternative path was viable only for low cerium oxide coverages as interaction with the substrate was needed for dehydration to occur. Aldehyde formation was seen to occur at mild temperatures (330 K) and was independent of film thickness. Subsequently, ceria-titania mixed oxide powders were characterized via XPS and we have observed that for increasing amount of cerium the element gradually became present at its highest oxidation state Ce(IV). By XPS we have also determined the formation of a very intimate composite between the two oxides by observing the increasing the full width at half maximum of the Ti2p peak for increasing amounts of cerium. Furthermore, compositional calculation showed that cerium had the tendency to disperse within the titania particles. These data helped to uncover a possibly good recipe for the formation of cerium titanate a composite with good oxygen storage capacity.
Un ruolo molto importante è svolto dagli ossidi metallici in molti settori della chimica, fisica e scienza dei materiali. I metalli di transizione e le terre rare sono in grado di formare una grande diversità di composti ossidici che possono adottare un'ampia gamma di strutture atomiche ed proprieta’ elettroniche che possono esibire caratteristiche metalliche, semiconduttrici o isolanti. In applicazioni tecnologiche, gli ossidi metallici sono impiegati nella fabbricazione di componenti microelettronici, sensori, celle a combustibile, rivestimenti per proteggere le superfici dalla corrosione, e come catalizzatori. In questa tesi abbiamo deciso di studiare due noti materiali catalitici: gli ossidi misti di Zirconia-Titania Ceria-Titania. Per entrambi i materiali la bibliografia riguarda principalmente le polveri quindi, al fine di studiare meglio le loro interfacce, di cui uno studio più approfondito e’ tuttora neccessario, abbiamo deciso di depositare film sottili di ossido di zirconio e ossido di cerio su rutilo TiO2(110). Abbiamo prima studiato il sistema zirconia-titania depositando un film ultra-sottile di ossido di zirconio mediante un precursore metallo-organico: Zirconio Tetra tert-butossido. La deposizione è stata effettuata a tre diverse temperature del substrato 677. K, 738 K, 773 K in cinque fasi di un minuto ciascuno. La caratterizzazione mediante XPS ha mostrato una chimica interessante sulla superficie del substrato e abbiamo osservato la formazione di specie carboniose all'interfaccia. Lo zirconio sembrava essere nel suo piu’ alto stato di ossidazione mentre il titanio è stato visto gradualmente ridursi con ogni successive strato di deposito. Il rapporto dei segnali Zr/Ti ha mostrato che la zirconia non ha completamente coperto la superficie. Inoltre,tramite LEED non si e’ osservato nessun ordine a lungo raggio. Misure XPD ha mostrato che la zirconia non forma un ossido di sostituzione con la titania. Tuttavia, con l'ausilio di simulazione al computer abbiamo dedotto che la zirconia forma, molto probabilmente nanocatene sulla superficie di TiO2(110). Questa superficie è stato esposta a 100 L di pyridinina per testarne la acidita’. Nel caso di ceria, abbiamo depositato l'ossido su un substrato riscaldato di TiO2 (110) tramite evaporazione del metallo da un crogiolo Mo poiché il processo è piuttosto facile e fornisce depositi puliti. Durante la deposizione il substrato è stata mantenuto a 677 K in un ambiente di 5,2 • 10 -6 mbar di O2, e, al fine di ottenere una superficie omogenea e ordinata il campione è stato ulteriormente sottoposto a trattamento termico nello stesso ambiente a 900 K. Tramite la tecnica LEED sono state osservate differenti fasi dipendenti dalla storia del campione e dallo spessore del film. Tramite simulazione al computer queste fasi sono stati poi riferite rispetto al biossido di cerio per meglio comprendere le differenze rispetto alla fase massiva. Tutti i film hanno mostrato cerio presenti come Ce(III). La Spettroscopia Fotoelettronica a Ultravioletti ha mostrato le proprietà elettroniche del film che mostra uno spostamento in energia di legame e un popolamento degli stati Ce4f. Questo e’ dovuto alla stabilizzazione di Ce (III) da parte di TiO2 (110). Si e’ volute osservare la reattività del sistema ceria-titania nei confronti di metanolo ed etanolo. I risultati hanno mostrato che l'aggiunta di ceria ha aperto il percorso della deidrogenazione degli alcoli ad aldeidi. Abbiamo osservato che la pre-ossidazione con ossigeno del sistema CeOx-TiO2(110) ha avuto un impatto sulla sua selettività aprendo anche un percorso di disidratazione di metanolo ed etanolo rispettivamente a metano ed etilene. Questa via alternativa era valida solo per basse coperture di ossido di cerio avendo osservato che l’interazione con il substrato è stato necessario perche’ avvenga la disidratazione. La formazione di aldeidi fu osservata avvenire a temperature piuttosto (330 K) ed essere indipendente dallo spessore del film. Successivamente sono state caratterizzate tramite XPS delle polveri di ossidi misti di ceria e titania. Abbiamo osservato che per quantità crescenti di cerio l'elemento diventa gradualmente sempre piu’ presente al suo stato di ossidazione più alto Ce (IV). Con XPS abbiamo anche determinato la formazione di un composito molto intimo tra i due ossidi osservando l'aumento della larghezza a metà altezza del picco Ti2p per quantità crescenti di cerio. Inoltre, la determinazione della composizione ha mostrato che il cerio ha la tendenza di disperdersi all'interno delle particelle di titania. Questi dati hanno contribuito a scoprire una possibile buona ricetta per la formazione di cerio titanato; un composito con buona capacità di stoccaggio di ossigeno.

The capabilities of various metal Additive Manufacturing (AM) processes, such as Powder Bed Fusion – Laser (PBF-L) and Direct Energy Deposition (DED) are increasing such that it is becoming ever more common to use them in industrial applications. The ability to print atop a substrate broadens that scope of applications. There is ongoing research regarding the mechanical properties of additively processed materials, but little regarding the interaction between additive material and its substrate. An understanding of the mechanical and performance properties of the AM/substrate interface is imperative. This paper describes a study of the strength properties of AM/substrate interfaces, with respect to torsion and tension, and compares them to their fully wrought and fully additive counterparts. PBF-L and DED are used to produce tensile and torsion test specimens of two different materials, SS316L and M300 steels. This provides sufficient variety in testing for a confident analysis to be made.

Les monofeuillets de dichalcogénures de métaux de transition (TMDC) tels que MoS2 ou WSe2 sont des semiconducteurs bidimensionnels à gap direct, dont les allées K et K' sont inéquivalentes dans la première zone de Brillouin : la levée de dégénérescence induite par le couplage spin-orbite entre les bandes de spin up et dawn est inversée entre les vallées K et K'. Des contacts métalliques magnétiques devraient permettre une injection de spin efficace depuis une électrode magnétique vers un TMDC. Les indices de vallée (Kou K') et de spin (up ou dawn) étant fortement couplés, cela permettrait de sélectionner électriquement l'une ou l'autre des vallées et de réaliser des dispositifs à base de TMDC pour la spintronique (exploitant le spin des électrons) ou pour la valléetronique (exploitant l'indice de vallée des électrons). Dans cette thèse, nous explorons les propriétés physiques des interfaces Co(OOOl)/MoS2 et Ni(lll)/WSe2 par des méthodes de calcul ab-initia basées sur la théorie de la fonctionnelle de la densité. Nous démontrons la nature covalente des liaisons à l'interface entre les monofeuillets de TMDC et les surfaces magnétiques Co(OOOl) et Ni(lll). Nous décrivons la structure atomique de ces interfaces, ainsi que la modification des moments magnétiques induite par des transferts de charge électrique entre atomes. Les liaisons covalentes aux interfaces confèrent aux monofeuillets de MoS2 et de WSe2 un caractère métallique. Nos calculs donnent finalement accès à la polarisation en spin au niveau de Fermi du TMDC connecté à ces électrodes magnétiques, ainsi qu'à la hauteur de la barrière Schottky (différence entre le niveau de Fermi dans la phase métallique du TMDC situé sous le contact magnétique et le bas de la bande de conduction du TMDC pur dans le canal)
Transition metal dichalcogenide (TMDC) single layers like MoS2 or WSe2 are direct band gap two-dimensional semiconductors, with non-equivalent K and K' valleys in the first Brillouin zone. The degeneracy liftingbetween spin-up and spin-down energy bands induced by spin-orbit coupling is inverted between the K and K' valleys . Magnetic metallic contacts should allow spin-injection from a magnetic electrode to a TMDC single layer. The valley (K or K') and spin (up or down) indexes being strongly coupled, this should also allow to electrically select one of the valleys in TMDC-based spintronic or valleytronic deviees. In this Thesis, we have studied the physical properties of the Co(OOOl)/MoS2 and Ni(lll)/WSe2 interfaces with first-principles methods based on the density functional theory. We demonstrated that the TMDC single layers are covalently bound to the Co(OOOl) and Ni(lll) surfaces. We describe the atomic structure of these interfaces and the modification of the magnetic moments induced by charge transfer between interface atomes. The MoS2 and WSe2 single layers become metallic when they are covalently bound to the magnetic metals. We also calculated the spin-polarization at the Fermi level of the TMDC layers connected to th Co and Ni electrodes and the Schottky barrier height (difference between the Fermi level in the metallic phase of the TMDC below the magnetic contact and the bottom of the conduction band in a pure TMDC channel)

Thesis (Ph. D.)--Ohio State University, 2005.
Title from first page of PDF file. Document formatted into pages; contains xvi, 136 p.; also includes graphics (some col.). Includes bibliographical references (p. 125-136). Available online via OhioLINK's ETD Center

Organic and hybrid organic-inorganic photovoltaic (PV) devices have the potential to provide low-cost, large scale renewable energy. Despite the tremendous progress that has been made in this field, device efficiencies remain low. This low efficiency can be partly attributed to the low open-circuit voltages (Voc) generated by organic and hybrid organic-inorganic PV devices. The Voc is critically determined by the energy-level alignment at the interface between the materials forming the device. In this thesis we use first-principles methods to explore the energy-level alignment at the interfaces between the conjugated polymer poly(3-hexylthiophene) (P3HT) and three electron acceptors, zinc oxide (ZnO), gallium arsenide (GaAs) and graphene. We find that Voc reported in the literature for ZnO/P3HT devices is significantly lower than the theoretical maximum and that the interfacial electrostatic dipole plays an important role in the physics underlying the charge transfer at the heterojunction. We note significant charge transfer from the polymer to the semiconductor at GaAs/P3HT interfaces, and use this result to help interpret experimental data. Our findings support the conclusion that charge transferred from P3HT to GaAs nanowires can passivate the surface defect states of the latter and, as a result, account for the observed decrease in photoluminescence lifetimes. Finally, we explore the energy-level alignment at the graphene/P3HT interface and find that Voc reported for experimental devices is in line with the theoretical maximum. The effect of functionalised graphene is also examined, leading to the suggestion that functionalisation might have important consequences for device optimisation.

A flexible nanofibrous PVDF-BaTiO3 composite material is prepared for impact sensing and biomechanical energy harvesting applications. Dielectric polyvinylidene fluoride (PVDF) and barium titanate (BaTiO3)-PVDF nanofibrous composites were made using the electrospinning process based on a design of experiments approach. The ultrasonication process was optimized using a 2k factorial DoE approach to disperse BaTiO3 particles in PVDF solution in DMF. Scanning electron microscopy was used to characterize the microstructure of the fabricated mesh. The FT-IR and Raman analysis were carried out to investigate the crystal structure of the prepared mesh. Surface morphology contribution to the adhesive property of the composite was explained through contact angle measurements. The capacitance of the prepared PVDF- BaTiO3 nanofibrous mesh was a more than 40% increase over the pure PVDF nanofibers. A comparative study of dielectric relaxation, thermodynamics properties and impact analysis of electrospun polyvinylidene fluoride (PVDF) and 3% BaTiO3-PVDF nanofibrous composite are presented. The frequency dependent dielectric properties revealed micro structural features of the composite material. The dielectric relaxation behavior is further supported by complex impedance analysis and Nyquist plots. The temperature dependence of electric modulus shows Arrhenius type behavior. The observed non-Debye dielectric relaxation in electric loss modulus follows a thermally activated process which can be attributed to a small polaron hopping effect. The particle induced crystallization is supported with thermodynamic properties from differential scanning calorimetric (DSC) measurements. The observed increase in piezoelectric response by impact analysis was attributed to the interfacial interaction between PVDF and BaTiO3. The interfacial polarization between PVDF and BaTiO3 was studied using density functional theory calculations and atomic charge density analysis. The results obtained indicates that electrospinning offers a potential way to produce nanofibers with desired crystalline nature which was not observed in molded samples. In addition, BaTiO3 can be used to increase the capacitance, desired surface characteristics of the PVDF nanofibers which can find potential application as flexible piezoelectric sensor mimicking biological skin for use in impact sensing and energy harvesting applications.