The topic of this work is the structural characterization and theoretical modeling of organic single and heterolayers. The growth of sub-monolayers and monolayers (ML) of the two polycyclic aromatic hydrocarbons quaterrylene (QT) and hexa-peri-hexabenzocoronene (HBC) on Ag(111) and Au(111) was investigated. A transition from a disordered, isotropic phase to an ordered phase with increasing coverage was found. The lattice of the ordered phase turned out to be coverage dependent. The intermolecular potential was modeled including Coulomb and van der Waals interaction by a force-field approach. The postulated repulsive character of the potential could be connected to the non-uniform intramolecular charge distribution and to a screening of the van der Waals forces. Furthermore, the influence of the variable lattice constant on the epitaxial growth of HBC was studied. The second part of this work deals with a ML of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on a ML of HBC. In dependency on the initial lattice constant of HBC, a total of three line-on-line (LOL) and point-on-line coincident phases of PTCDA (with respect to HBC) was found. Following an analysis of the general properties of LOL coincident systems via force-field calculations, a new method to predict the structure of such systems is introduced.:1 Introduction 2 Experimental Methods 2.1 Organic molecular beam epitaxy 2.2 Scanning tunneling microscopy (STM) 2.3 Low-energy electron diffraction (LEED) 2.4 Molecules and substrates: Basic properties and literature review 2.4.1 3,4,9,10-Perylenetetracarboxylic dianhydride 2.4.2 Hexa-peri-hexabenzocoronene 2.4.3 Quaterrylene 2.4.4 Metal substrates: Au(111) and Ag(111) 3 Theory and Modeling 3.1 Reciprocal space and LEED 3.1.1 Fourier transform and geometrical LEED theory 3.1.2 Kinematic and dynamic LEED theory 3.1.3 Further applications of the Fourier transform 3.2 Computational chemistry 3.2.1 Calculating molecular properties 3.2.2 The atomic force-field method 3.2.3 Potential energy calculations in extended systems 4 Epitaxy in terms of potential energy 5 Interaction of QT and HBC at Sub-ML and ML Coverage 5.1 Experimental results 5.2 Modeling technique 5.3 Results of the model calculation 5.4 Discussion of results 5.5 Conclusion 6 The Ordered Phases of HBC on Ag(111) and Au(111 6.1 Geometrical analysis of epitaxy 6.2 Energetic gain of epitaxial structures 6.3 Comparison to experiment 6.4 Influence of the Au(111) surface reconstruction 6.5 Conclusion 7 Organic Heterosystems of PTCDA and HBC on Au(111) 7.1 PTCDA on Au(111) revisited 7.2 LEED and STM on PTCDA/HBC/Au(111) samples 7.2.1 A “compact” HBC layer substrate 7.2.2 A “loosely packed” HBC layer substrate 7.2.3 Summary of LEED results 7.2.4 STM results 7.3 Epitaxial relations in the system PTCDA/HBC/Au(111) 7.3.1 Geometrical analysis of epitaxy 7.3.2 Energetic gain of epitaxial structures 7.3.3 Mutual alignment of lattices 7.4 Heterosystems of PTCDA and HBC with inverted stacking sequence 8 General Properties of POL and LOL Epitaxy 8.1 A new coordinate system 8.2 Specific properties of the substrate-adsorbate potential 8.3 The “natural order” of the lattice lines 8.4 Prediction of epitaxial growth - a “LOL predictor” 8.4.1 Method 8.4.2 Results 9 General Conclusions and Future Perspectives 9.1 Conclusion 9.2 Outlook Appendix A.1 Conductance in a STM: The 1D WKB model A.2 Extraction of the DOS from STS measurements by means of the 1D WKB model A.3 Practical application of the 1D WKB model A.4 The normalized differential conductivity A.5 A new normalization method / Thema dieser Arbeit ist die strukturelle Charakterisierung von organischen Einfach- und Heterolagen sowie deren theoretische Beschreibung und Modellierung. Es wurden Submonolagen und Monolagen (ML) der polyzyklischen Kohlenwasserstoffe Quaterrylen (QT) und Hexa-peri-hexabenzocoronen (HBC) auf Ag(111) und Au(111) Einkristallen untersucht und ein Übergang von einer ungeordneten, isotropen Phase zu einer geordneten Phase mit steigender Bedeckung beobachtet. Die geordnete Phase wies dabei bedeckungsabhängige Gitterkonstanten auf. Das intermolekulare Potential wurde unter Berücksichtigung von Coulomb und van der Waals Anteilen mittels Kraftfeldmethoden modelliert. Der postulierte repulsive Charakter des Potentials konnte auf die Ladungsverteilung im Molekül und eine Abschwächung des van der Waals Potentials zurückgeführt werden. Weiterhin wurde der Einfluss der variablen HBC Gitterkonstante auf die epitaktische Relation des Gitters zum Metallsubstrat untersucht. Der zweite Teil der Arbeit widmet sich der Untersuchung einer ML 3,4,9,10-Perylenetetracarboxylic dianhydrid (PTCDA) auf einer ML HBC. Dabei wurden, in Abhängigkeit von der HBC Gitterkonstante, insgesamt drei verschiedene Typen von line-on-line bzw. point-on-line Epitaxie nachgewiesen. Im Anschluss an eine Analyse der generellen Eigenschaften solcher epitaktischer Lagen mittels Kraftfeldrechnungen wird eine neue Methode zur Vorhersage der Struktur konkreter Systeme vorgestellt.:1 Introduction 2 Experimental Methods 2.1 Organic molecular beam epitaxy 2.2 Scanning tunneling microscopy (STM) 2.3 Low-energy electron diffraction (LEED) 2.4 Molecules and substrates: Basic properties and literature review 2.4.1 3,4,9,10-Perylenetetracarboxylic dianhydride 2.4.2 Hexa-peri-hexabenzocoronene 2.4.3 Quaterrylene 2.4.4 Metal substrates: Au(111) and Ag(111) 3 Theory and Modeling 3.1 Reciprocal space and LEED 3.1.1 Fourier transform and geometrical LEED theory 3.1.2 Kinematic and dynamic LEED theory 3.1.3 Further applications of the Fourier transform 3.2 Computational chemistry 3.2.1 Calculating molecular properties 3.2.2 The atomic force-field method 3.2.3 Potential energy calculations in extended systems 4 Epitaxy in terms of potential energy 5 Interaction of QT and HBC at Sub-ML and ML Coverage 5.1 Experimental results 5.2 Modeling technique 5.3 Results of the model calculation 5.4 Discussion of results 5.5 Conclusion 6 The Ordered Phases of HBC on Ag(111) and Au(111 6.1 Geometrical analysis of epitaxy 6.2 Energetic gain of epitaxial structures 6.3 Comparison to experiment 6.4 Influence of the Au(111) surface reconstruction 6.5 Conclusion 7 Organic Heterosystems of PTCDA and HBC on Au(111) 7.1 PTCDA on Au(111) revisited 7.2 LEED and STM on PTCDA/HBC/Au(111) samples 7.2.1 A “compact” HBC layer substrate 7.2.2 A “loosely packed” HBC layer substrate 7.2.3 Summary of LEED results 7.2.4 STM results 7.3 Epitaxial relations in the system PTCDA/HBC/Au(111) 7.3.1 Geometrical analysis of epitaxy 7.3.2 Energetic gain of epitaxial structures 7.3.3 Mutual alignment of lattices 7.4 Heterosystems of PTCDA and HBC with inverted stacking sequence 8 General Properties of POL and LOL Epitaxy 8.1 A new coordinate system 8.2 Specific properties of the substrate-adsorbate potential 8.3 The “natural order” of the lattice lines 8.4 Prediction of epitaxial growth - a “LOL predictor” 8.4.1 Method 8.4.2 Results 9 General Conclusions and Future Perspectives 9.1 Conclusion 9.2 Outlook Appendix A.1 Conductance in a STM: The 1D WKB model A.2 Extraction of the DOS from STS measurements by means of the 1D WKB model A.3 Practical application of the 1D WKB model A.4 The normalized differential conductivity A.5 A new normalization method

Im ersten Teil der Arbeit werden Graphen sowie von Monolagen von auf Nanometer großen Graphenen basierenden Hexa-peri(Dodekyl)-Hexabenzocoronen-Molekülen (HBC-C12), adsorbiert auf Graphen, mit Rastertunnelmikroskopie und –spektroskopie an der Fest-Flüssig-Grenzfläche untersucht. Nanographen-Moleküle selbstaggregieren epitaktisch zu hochgeordneten Monolagen. Die Einheitszellen der Moleküllagen auf Monolage Graphen, Bilage Graphen und auf Graphit sind ununterscheidbar. Die Strukturen der Moleküllagen auf gewellten und flachen Teilen des Graphens stimmen überein. Strom-Spannungs-Kennlinien an Nanographen auf Graphen und auf Graphit weisen auf sehr ähnliche elektronische Eigenschaften hin. Zusammengefasst sind strukturelle sowie elektronische Eigenschaften der Nanographenlage homogen, stabil und definiert. Graphen erweist sich als bestens als Substrat und gleichzeitig als Elektrode für hochgeordnete Lagen von Nanographen-Molekülen geeignet. Im zweiten Teil der Arbeit wird Graphen mit der Sonde eines Rasterkraftmikroskops im Kontaktmodus mechanisch manipuliert. Es wird gezeigt, dass Graphen in nur einem Manipulationsschritt zu Streifen und Spalt geschnitten werden kann. Dieses Verhalten wird mit einem klassischen Modell des Biegens theoretisch erklärt. Das Schnittverhalten liegt in der 2-Dimensionalität des Graphens sowie in dessen Faltbarkeit auf Grund hinreichender Elastizität begründet. Durch mechanische Manipulation mit der Sonde des Rasterkraftmikroskops im Kontaktmodus unter atmosphärischen Bedingungen wird eine Flüssigkeitsschicht zwischen Graphen und dem Siliziumdioxidsubstrat nachgewiesen, welche eine mögliche Erklärung des stark kraftabhängigen Materialkontrasts zwischen Graphen und Siliziumdioxid im Amplitudenmodulationsmodus des Rasterkraftmikroskops darstellt. Weiter wird gezeigt, dass das Falten des Graphens durch mechanische Manipulation eine geeignete Methode zur Herstellung nicht epitaktisch aufeinander gestapelter Graphene darstellt. / In the first part of the thesis graphene as well as monolayers of hexa-peri(dodecyl)-hexabenzocoronene molecules (HBC-C12) based on nanometer sized graphenes adsorbed on graphene is investigated by scanning tunnelling microscopy and tunneling spectroscopy at the solid-liquid interface. The nanographene molecules self-assemble on graphene epitaxially to form highly ordered monolayers. The unit cells of the molecular layers on monolayer graphene, bilayer graphene and on graphite appear identical. The structures of the molecular layers occur equal on corrugated and on flat parts of graphene. Current-voltage-characteristics show that the electronic properties of nanographene on graphene and on graphite are very similar. Summarized, structural as well as electronic properties of the nanographene layer are homogeneous, stable and defined. Graphene proves to be excellently qualified for simultaneously being substrate as well as electrode for highly ordered layers of nanographene based molecules. In the second part of the thesis graphene is mechanically manipulated in air in contact mode of a scanning force microscope. It is shown that a single manipulation process can lead to a stripe cut out of graphene. This behaviour is theoretically explained by a classical bending model. The cutting behavior originates from the 2-dimensionality of graphene and its folding ability because of sufficient elasticity. A liquid layer between graphene and the silicon dioxide substrate is verified by mechanical manipulation in contact mode of a scanning force microscope. Hence a possible explanation could be found for the strongly force dependent material contrast between graphene and silicon dioxide in amplitude modulation mode of the scanning force microscope. Further, it is demonstrated that folding graphene by mechanical manipulation is a proper method for the production of graphene stacked on each other non-epitaxially.

Private set intersection(PSI) is a two party protocol where both parties possess a private set and at the end of the protocol, one party (client) learns the intersection while other party (server) learns nothing. Motivated by some interesting practical applications, several provably secure and efficient PSI protocols have appeared in the literature in recent past. Some of the proposed solutions are secure in the honest-but-curious (HbC) model while the others are secure in the (stronger) malicious model. Security in the latter is traditionally achieved by following the classical approach of attaching a zero knowledge proof of knowledge (ZKPoK) (and/or using the so-called cut-and-choose technique). These approaches prevent the parties from deviating from normal protocol execution, albeit with significant computational overhead and increased complexity in the security argument, which includes incase of ZKPoK, knowledge extraction through rewinding. We critically investigate a subset of the existing protocols. Our study reveals some interesting points about the so-called provable security guarantee of some of the proposed solutions. Surprisingly, we point out some gaps in the security argument of several protocols. We also discuss an attack on a protocol when executed multiple times between the same client and server. The attack, in fact, indicates some limitation in the existing security definition of PSI. On the positive side, we show how to correct the security argument for the above mentioned protocols and show that in the HbC model the security can be based on some standard computational assumption like RSA and Gap Diffie-Hellman problem. For a protocol, we give improved version of that protocol and prove security in the HbC model under standard computational assumption. For the malicious model, we construct two PSI protocols using deterministic blind signatures i.e., Boldyreva’s blind signature and Chaum’s blind signature, which do not involve ZKPoK or cut-and-choose technique. Chaum’s blind signature gives a new protocol in the RSA setting and Boldyreva’s blind signature gives protocol in gap Diffie-Hellman setting which is quite similar to an existing protocol but it is efficient and does not involve ZKPoK.

À la fin du XVIIIe siècle, l’embauche de Canadiens français, surnommés les voyageurs, s’inscrit dans un système de travail de la traite des fourrures qui s’articule à Montréal autour de contrats notariés. Les engagés se lient pour plusieurs mois, voire plusieurs années à un marchand qui les emploie afin d’acheminer en canot des marchandises dans les territoires du Nord-Ouest et en revenir chargé de pelleteries. Conscients des dangers encourus et de l’imprévoyance de leurs employés, les « négociants des Pays d’en haut » orchestrent une société de secours, dès 1790, appelé le « Fonds des voyageurs ». Ce dernier, atypique dans sa conception et dans son organisation, est le « soutien des voyageurs infirmes, de leurs veuves et des orphelins » dans la détresse. Cette étude a pour but de mettre en exergue l’atypie de cette institution d'aide. Elle apparaît dans une conjoncture de métamorphose sociale et économique du Bas-Canada, ainsi que dans le contexte d’une évolution culturelle de prévoyance et d’un communautarisme émergeant. Cette élite marchande venue d’Écosse est liée à une histoire commune de l’« habitus » avec ses employés. Elle applique les préceptes avant-gardistes des Lumières écossaises dans une société montréalaise confrontée à un courant libéral naissant. Ce faisant, ces bourgeois écossais de la société marchande, souvent décrits comme mercantiles, se présentent en fin de compte comme des membres d'un « monde du voyage » solidaires de leurs semblables. Cette nouvelle perspective invite à un ajustement des interprétations de l’historiographie sur la communauté qui exerce le commerce des fourrures à Montréal entre 1790 et 1821.