Our vision is as yet unsurpassed by machines because of the sophisticated representations of objects in our brains. This representation is vastly different from a pixel-based representation used in machine storages. It is this sophisticated representation that enables us to perceive two faces as very different, i.e, they are far apart in the “perceptual space”, even though they are close to each other in their pixel-based representations. Neuroscientists have proposed distances between responses of neurons to the images (as measured in macaque monkeys) as a quantification of the “perceptual distance” between the images. Let us call these neuronal dissimilarity indices of perceptual distances. They have also proposed behavioural experiments to quantify these perceptual distances. Human subjects are asked to identify, as quickly as possible, an oddball image embedded among multiple distractor images. The reciprocal of the search times for identifying the oddball is taken as a measure of perceptual distance between the oddball and the distractor. Let us call such estimates as behavioural dissimilarity indices. In this thesis, we describe a decision-theoretic model for visual search that suggests a connection between these two notions of perceptual distances. In the first part of the thesis, we model visual search as an active sequential hypothesis testing problem. Our analysis suggests an appropriate neuronal dissimilarity index which correlates strongly with the reciprocal of search times. We also consider a number of alternative possibilities such as relative entropy (Kullback-Leibler divergence), the Chernoff entropy and the L1-distance associated with the neuronal firing rate profiles. We then come up with a means to rank the various neuronal dissimilarity indices based on how well they explain the behavioural observations. Our proposed dissimilarity index does better than the other three, followed by relative entropy, then Chernoff entropy and then L1 distance. In the second part of the thesis, we consider a scenario where the subject has to find an oddball image, but without any prior knowledge of the oddball and distractor images. Equivalently, in the neuronal space, the task for the decision maker is to find the image that elicits firing rates different from the others. Here, the decision maker has to “learn” the underlying statistics and then make a decision on the oddball. We model this scenario as one of detecting an odd Poisson point process having a rate different from the common rate of the others. The revised model suggests a new neuronal dissimilarity index. The new dissimilarity index is also strongly correlated with the behavioural data. However, the new dissimilarity index performs worse than the dissimilarity index proposed in the first part on existing behavioural data. The degradation in performance may be attributed to the experimental setup used for the current behavioural tasks, where search tasks associated with a given image pair were sequenced one after another, thereby possibly cueing the subject about the upcoming image pair, and thus violating the assumption of this part on the lack of prior knowledge of the image pairs to the decision maker. In conclusion, the thesis provides a framework for connecting the perceptual distances in the neuronal and the behavioural spaces. Our framework can possibly be used to analyze the connection between the neuronal space and the behavioural space for various other behavioural tasks.

No description available.

No description available.

No description available.

This thesis is devoted to the optical properties of low-dimensional structures based on such two-dimensional materials as graphene, silicene and phosphorene. We investigate optical properties of a variety of quasi-one dimensional and quasi-zero-dimensional structures, which are promising for future optoelectronics. Primarily we focus on their low-energy optical properties and how these properties are influenced by the structures’ geometry, external fields, intrinsic strain and edge disorder. As a consequence of this endeavor, we find several interesting effects such as correlation between the optical properties of tubes and ribbons whose periodic and ‘hard wall’ boundary conditions are matched and a universal value of matrix element in narrow-gap tubes and ribbons characterizing probability of transitions across the band gap opened up by intrinsic strain originating from the tube’s surface curvature or ribbon’s edge relaxation. The analytical study of the gapped 2D Dirac materials such as silicene and germanene, which have some similarity to the aforementioned quasi-one-dimensional systems in terms of physical description, reveals a valley- and polarization-dependent selection rules. It was also found that absorption coefficient should change in gapped materials with increasing frequency and become a half of its value for gap edge transitions when the spectrum is linear. Our analysis of the electronic properties of flat clusters of silicene and phosphorene relates the emergence and the number of the peculiar edge states localized at zero energy, so-called zero-energy states, which are know to be of topological origin, to the cluster’s structural characteristics such as shape and size. This allows to predict the presence and the number of such states avoiding complicated topological arguments and provides a recipes for design of metallic and dielectric clusters. We show that zero-energy states are optically active and can be efficiently manipulated by external electric field. However, the edge disorder is important to take into account. We present a new fractal-based methodology to study the effects of the edge disorder which can be applied also to modeling of composite materials. These finding should be useful in design of optoelectronic devices such as tunable emitters and detectors in a wide region of electromagnetic spectrum ranging form the mid-infrared and THz to the optical frequencies.

Στην παρούσα Διδακτορική Διατριβή διερευνώνται αριθμητικά δομές οι οποίες μπορούν να λειτουργήσουν ως φωνονικά ή φωτονικά υλικά. Βασικό χαρακτηριστικό των φωτονικών και των φωνονικών υλικών είναι η ύπαρξη χασμάτων συχνοτήτων στη διάδοση των ηλεκτρομαγνητικών και των ελαστικών κυμάτων αντίστοιχα διαμέσου των δομών αυτών. Αρχικά διερευνήθηκαν αριθμητικά δύο δομές οι οποίες έχουν ήδη χρησιμοποιηθεί ως φωτονικά υλικά και για τις οι οποίες εξετάστηκε κατά πόσο είναι εφικτή λειτουργία τους ως φωνονικά υλικά. Η πρώτη δομή είναι η πολύ γνωστή δομή κατά στρώσεις και η δεύτερη ένας ηχητικός κυματοδηγός «λωρίδα» (slot waveguide) επάνω στον οποίο δομείται ένας φωνονικός κρύσταλλος. Για τους αριθμητικούς υπολογισμούς χρησιμοποιήθηκε η μέθοδος των πεπερασμένων διαφορών στο πεδίο του χρόνου και υπολογίστηκαν το Φάσμα Μετάδοσης καθώς και το διάγραμμα Διασποράς. Στην μελέτη αυτή περιελήφθησαν αρκετά διαφορετικά υλικά όπως το πυρίτιο, η εποξειδική ρητίνη και το βολφράμιο. Διερευνήθηκε επίσης η επίδραση όλων των γεωμετρικών παραμέτρων των δομών. Τα αποτελέσματα έδειξαν ότι οι δομές αυτές φαίνεται να έχουν πολύ ελπιδοφόρα χαρακτηριστικά ως φωνονικοί κρύσταλλοι. Υπό ορισμένες προϋποθέσεις μάλιστα μπορεί να προκύψει πλήρες τρισδιάστατο χάσμα. Λαμβάνοντας υπόψη ότι η συγκεκριμένες δομές είναι ήδη γνωστές για τη χρήση τους ως φωτονικοί κρύσταλλοι, η πεποίθηση για τη χρήση τους ταυτόχρονα ως φωτονικοί και φωνονικοί κρύσταλλοι καθίσταται βάσιμη. Στην συνέχεια, χρησιμοποιώντας ξανά τη μέθοδο των πεπερασμένων διαφορών στο πεδίο του χρόνου, μελετήθηκαν ενδεχόμενες εφαρμογές που θα μπορούσαν οι δομές αυτές να έχουν. Πιο συγκεκριμένα διερευνήθηκε αρχικά η ενδεχόμενη χρήση των φωνονικών κρυστάλλων ως αισθητήρες. Οι Ευαισθησίες αυτών των δομών υπολογίστηκαν από τις αλλαγές στα όρια των αντίστοιχων φωνονικών χασμάτων όταν ένα λεπτό φιλμ νερού (για την περίπτωση του αισθητήρα υγρασίας) προστεθεί στη δομή ή όταν οι δομές εμβαπτιστούν σε κάποιο υγρό (αισθητήρες υγρών). Μελετήθηκε επίσης για πρώτη φορά συγκεκριμένη ελαστοδυναμική συμπεριφορά της τρισδιάστατης δομής κατά στρώσεις. Τα αποτελέσματα που προέκυψαν παρουσιάζουν μια υψηλή τιμή στον λόγο της διαμήκους προς την εγκάρσια ταχύτητα του ήχου και μια ιδανική συμπεριφορά pentamode σε ένα εύρος συχνοτήτων. Τα αποτελέσματα δείχνουν σαφώς ότι η δομή κατά στρώσεις μπορεί να αποτελέσει και ένα πολύ σημαντικό ελαστοδυναμικό μεταϋλικό. Στην επόμενη ενότητα της Διδακτορικής διατριβής χρησιμοποιώντας την θεωρία συναρτησιακών πυκνότητας μελετήθηκε η φωνονική πυκνότητα καταστάσεων για υλικά τύπου γραφενίου όπως το silicene (σιλικένιο) και το germanene (γερμανένιο). Εξετάστηκαν οι περιπτώσεις στις οποίες άτομα πυριτίου ή γερμανίου στις δομές τύπου γραφενίου αντικαταστάθηκαν από άλλα άτομα της Ομάδας IV του Περιοδικού Πίνακα και διερευνήθηκε κατά πόσο οι προκύπτουσες δομές μπορούν να λειτουργήσουν ως φωνονικοί κρύσταλλοι με την εμφάνιση φωνονικών χασμάτων στην φωνονική πυκνότητα καταστάσεών τους. Εξετάστηκαν επίσης νανοσωλήνες άνθρακα και κυρίως οι ομοιότητές τους με τα υλικά τύπου γραφενίου. Βρέθηκε πως, για τις περιπτώσεις όπου η διάμετρος των νανοσωλήνων ξεπερνά το 1nm, παρουσιάζονται αρκετές ομοιότητες με τα υλικά τύπου γραφενίου. Στην τελευταία ενότητα της διατριβής διερευνώνται δομές στις οποίες μπορεί να παρατηρηθεί εντοπισμός του φωτός σε περιοχές κλίμακας νανομέτρων. Ένα σύστημα αποτελούμενο από δύο δίσκους πυριτίου με διάκενο να τους χωρίζει μερικά δέκατα του νανομέτρου μελετήθηκε πρώτο. Ο κανονικοποιημένος, αδιάστατος ενεργός όγκος καταστάσεων, V_eff, υπολογίστηκε για τους δύο χαμηλότερους συντονισμούς. Ο ενεργός όγκος καταστάσεων μειώνεται σημαντικά καθώς το χάσμα μεταξύ των δίσκων μεγαλώνει. Μελετάται επίσης μια δομή αποτελούμενη από έναν κυκλικό κυματοδηγό σχισμή ο οποίος σχηματίζεται μέσα σε έναν κυκλικό συντονιστή πυριτίου. Όπως προκύπτει από τα αριθμητικά αποτελέσματα η προτεινόμενη δομή μπορεί να εμφανίσει συντονισμούς με υψηλές τιμές του παράγοντα Q, αυξάνοντας έτσι την πεποίθηση πως η προτεινόμενη δομή μπορεί να αποτελέσει βάση για εφαρμογές σε οπτικές τηλεπικοινωνίες. / This thesis explores numerically structures that can act as phononic or photonic materials. A key feature of photonic and phononic materials is the existence of frequency gaps in propagation of electromagnetic waves and elastic waves respectively. Initially the functionality of two structures as phononic materials is numerically examined. Those structures have already been used as photonic materials. The first structure is the well-known layer-by-layer structure and the second is an acoustic strip waveguide onto which is considered one phononic crystal. For numerical calculations the Finite Difference Time Domain method was used. The transmission spectra and the band structure were calculated. Several different materials such as silicon, epoxy and tungsten were included in this study. It was also investigated the effect of all the geometric parameters of the structures. The results showed that these structures appear to have very promising features as phononic crystals. Under certain conditions it may even exists a full three-dimensional phononic band gap. Considering that those structures are already known for their use as photonic crystals, the belief for their use as both photonic crystals and phononic crystals becomes valid. Then, again using the Finite Difference Time Domain method, potential applications that these structures could have were also examined. Initially it was investigated the potential use of phononic crystals as sensors. The sensitivities of these structures were calculated from the changes in the boundaries of the respective phononic band gaps when a thin film of water (in the case of the humidity sensor) was added to the structure or when those structures immersed in a liquid (liquid sensors). Also studied for the first time the three-dimensional layer-by-layer structure for specific elastodynamic behavior. The results show a high value of the ratio of the longitudinal to the transverse speed of sound and an ideal pentamode behavior for a specific frequency range. The results clearly show that the layer-by-layer structure could be a very important elastodynamic metamaterial. In the next section of this thesis, the phonon density of states of graphene-like materials such as silicene and germanene is examined using density functional theory. Cases were silicon or germanium atoms on graphene-like structures are replaced by other group IV atoms and how these new structures could perform as nanoscale phononic crystals, creating phononic band gaps in their phonon density of states, are numerically investigated. Nanotubes were also examined and their similarities, especially for cases with diameters above 1nm, with the graphene-like materials were found. In the final section of this thesis structures which could confine light in nanometer areas were numerically examined. A system consisting of two silicon disks with in plane separation of a few tens of nanometers has been studied first. The normalized unitless effective mode volume, Veff, has been calculated for the two lowest whispering gallery modes resonances. The effective mode volume is reduced significantly as the gap between the disks decreases. It is also numerically examined a structure consisting of a circular slot waveguide which is formed into a silicon disk resonator. It is shown that the proposed structure could have high Q resonances thus raising the belief that it is a very promising candidate for optical interconnects applications.

The popularity of graphene owing to its unique properties has triggered huge interest in other two-dimensional (2D) nanomaterials. Among them, silicene shows considerable promise for electronic devices due to the expected compatibility with silicon electronics. However, the high-end potential application of silicene in electronic devices is limited owing to the lack of an energy band gap. Hence, the principal objective of this research is to tune the electronic and magnetic properties of silicene related nanomaterials through first-principles models. I first explored the impact of edge functionalization and doping on the stabilities, electronic, and magnetic properties of silicene nanoribbons (SiNRs) and revealed that the modified structures indicate remarkable spin gapless semiconductor and half-metal behaviors. In order to open and tune a band gap in silicene, SiNRs were perforated with periodic nanoholes. It was found that the band gap varies based on the nanoribbon’s width, nanohole’s repeat periodicity, and nanohole’s position due to the quantum confinement effect. To continue to take advantage of quantum confinement, I also studied the electronic and magnetic properties of hydrogenated silicene nanoflakes (SiNFs). It was discovered that half-hydrogenated SiNFs produce a large spin moment that is directly proportional to the square of the flake’s size. Next, I studied the adsorption behavior of various gas molecules on SiNRs. Based on my results, the SiNR could serve as a highly sensitive gas sensor for CO and NH3 detection and a disposable gas sensor for NO, NO2, and SO2. I also considered adsorption behavior of toxic gas molecules on boron carbide (BC3) and found that unlike graphene, BC3 has good sensitivity to the gas molecules due to the presence of active B atoms. My findings divulged the promising potential of BC3 as a highly sensitive molecular sensor for NO and NH3 detection and a catalyst for NO2 dissociation. Finally, I scrutinized the interactions of CO2 with lithium-functionalized germanene. It was discovered that although a single CO2 molecule was weakly physisorbed on pristine germanene, a significant improvement on its adsorption energy was found by utilizing Li-functionalized germanene as the adsorbent. My results suggest that Li-functionalized germanene shows promise for CO2 capture.

The main objective of this work is to research and obtain surface protected topological states in nano-ribbons created from the leaves of Germanene and Silicene. These sheets belong to the class of Topological Insulators and correspond to monolayers of germanium and silicon atoms in a hexagonal arrangement that is similar to the graphene sheet. For this investigation, we conducted a study of the electronic and structural properties of these sheets, as well as their respective nano-ribbons through first-principles calculations based on density functional theory (DFT). In this methodology we use the generalized gradient approximation (GGA) for estimating the exchange and correlation term, and the PAW method for the effective potential and the expansion of plane waves of the Kohn-Sham. We conducted a computer simulation with the aid of the package VASP (Vienna ab-initio Simulation Package). As a starting point for our research, we used the methodology of solid state physics in order to describe the crystalline structure of the leaves as well as their mutual space. Subsequently we analyze the band structure, from which many of its properties can be visualized. For this task, we initially proceeded to investigate the stability of these systems via total energy calculations, in turn obtaining the network parameters that minimizes the energy of the system. We also obtained the energy cutoff, ECUT used in our calculations, or in other words, determining the number of plane waves needed to expand the electronic wave functions on the DFT formalism. We continued our study, with the creation and analysis of two different configurations of nano-ribbons, one that corresponds to a straightforward cut of the sheet with the armchair termination pattern, and the other based on a reconstruction of those edges, which provide an energetically more stable system. Subsequently we obtained electronic structures, and conducted a study of its variation due to the change of the width of the nano-ribbon and ionic relaxation of its edges. In a way, we modified the above parameters in order to obtain a system that would give us a zero gap, or at least insignificant, as well as a specific configuration for the spin texture, in order to verify the evidence of surface protected topological states in these nano-ribbons. / O objetivo principal deste trabalho é a investigação e obtenção dos estados topologicamente protegidos de superfície em nano-fitas criadas a partir das folhas de Germaneno e Siliceno. Estas folhas pertencem a classe dos Isolantes Topológicos e correspondem a monocamadas de átomos de Germânio e Silício, em um arranjo hexagonal que se assemelha a folha do Grafeno. Para esta investigação, realizamos um estudo das propriedades eletrônicas e estruturais destas folhas, bem como de suas respectivas nano-fitas, através de cálculos de primeiros princípios fundamentados na teoria do funcional da densidade (DFT). Nesta metodologia utilizamos a aproximação do gradiente generalizado (GGA) para a estimativa do termo de troca e correlação, e o método PAW para o potencial efetivo e a expansão em ondas planas dos orbitais de Kohn-Sham. Realizamos a simulação computacional com o auxílio do pacote VASP (Vienna ab-initio Simulation Package). Como ponto de partida para nossa pesquisa, utilizamos a metodologia da física do estado sólido com o intuito de descrever a estrutura cristalina das folhas, bem como seu espaço recíproco. Posteriormente analisamos as estruturas de bandas, a partir das quais muitas de suas propriedades podem ser visualizadas. Para esta tarefa, inicialmente procedemos à investigação da estabilidade destes sistemas via cálculos de energia total, obtendo o parâmetro de rede a que minimiza a energia do sistema. Obtivemos também a energia de corte ECUT utilizada em nossos cálculos, ou em outras palavras, a determinação do número de ondas planas necessárias para expandir as funções de onda eletrônicas no formalismo da DFT. Prosseguimos nosso estudo, com a criação e análise de duas distintas configurações de nano-fitas, uma que corresponde a um corte simples e direto da folha com terminação no padrão armchair, e a outra baseada em uma reconstrução destas bordas, que acaba por fornecer um sistema mais estável energeticamente. Posteriormente obtivemos as estruturas eletrônicas, e realizamos um estudo de sua variação em função da alteração da largura da nano-fita e a relaxação iônica de suas bordas. De certa maneira, modificamos os parâmetros acima, de forma a obter um sistema que nos fornecesse um gap nulo, ou pelo menos desprezível, bem como uma determinada configuração para a textura de spin, de modo a verificarmos a evidência de uma proteção topológica nos estados de superfície nestas nano-fitas. / Mestre em Física

This dissertation works out the vibrational properties of epitaxial silicene, which was discovered by Vogt et al. in 2012 by the epitaxial synthesis on the silver substrate. Its two-dimensional (2D) character is modified in comparison to the free-standing silicene due to its epitaxial nature, since the underlying substrate alters the physical properties of silicene as a result of the strong hybridization of the electronic levels of the substrate and adlayer. The growth of silicene layers is complicated by the sensitivity of the Si structures to the experimental conditions, mainly temperature, resulting in the formation of several seemingly different surface reconstructions. Another Si structure appears on the Ag surface at a supramonolayer coverage. The Raman spectroscopy was utilized to understand the relation between different Si structures and reveal their origin as well as to investigate the phonon-related physical properties of two-dimensional Si sheets. The central core of this work is the growth and characterization of these 2D silicene monolayers on the Ag (111) surface as well as the formation of silicene multilayer structures. The characterization of these materials was performed using in situ surface-sensitive measurement methods such as Raman spectroscopy and low-energy electron diffraction under ultra-high vacuum conditions due to high chemical reactivity of epitaxial silicene. Additional characterization was done ex situ by means of scanning force microscopy. The experimentally determined spectral signature of the prototypical epitaxial (3x3)/(4x4) silicene structure was confirmed by ab initio calculations, in collaboration with theory groups. The Raman signatures of the other 2D and 3D Si phases on Ag (111) were determined which allowed us to provide a clear picture of their formation depending on the preparation conditions. The monitoring of the silicene multi-layer growth yielded the vibrational signature of the top layer, reconstructed in a (√3x√3) fashion. It was compared to the inverse, (√3x√3)-Ag/Si(111), system showing the vast amount of similarities, which suggest that the (√3x√3) reconstruction belong to the silver layer. The chemical and physical properties of this surface structure additionally strengthen this equivalence. The possibility of functionalization of epitaxial silicene was demonstrated via exposure to the atomic hydrogen under UHV conditions. The adsorbed hydrogen covalently bonds to the silicene lattice modifying it and reducing its symmetry. As shown by Raman spectroscopy, such modification can be reversed by thermal desorption of hydrogen. The excitation-dependent Raman measurements also suggest the change of the electronic properties of epitaxial silicene upon hydrogenation suggesting that its originally semi-metallic character is modified into a semiconducting one. / Die experimentellen Forschungsarbeiten zum Thema Silicen basieren auf den 2012 von Vogt et al. durchgeführten Untersuchungen zu dessen Synthese auf Silbersubstraten. Diese Untersuchungen lieferten die Grundlage, auf der zweidimensionales (2D) epitaktisches Silicen sowie weitere 2D Materialien untersucht werden konnten. In den anfänglichen Arbeiten konnte dabei gezeigt werden, dass sich die Eigenschaften von epitaktischem Silicen gegenüber den theoretischen Vorhersagen von frei-stehendem Silicen unterscheiden. Darüber hinaus verkomplizieren sich die experimentellen Untersuchungen dieses 2D Materials, da auf dem Ag(111) Wachstumssubstrat sechs verschiedene 2D Si Polytypen existieren. Eine detaillierte Darstellung dieser Untersuchungen findet sich in dem einführenden Kapitel der vorliegen Promotionsschrift. Der zentrale Kern dieser Arbeit beschäftigt sich mit dem Wachstum und der Charakterisierung dieser 2D Silicen Monolagen auf Ag(111) Oberflächen sowie der Bildung von Silicen- Multilagen Strukturen. Die Charakterisierung dieser Materialien wurde in situ mit oberflächenempfindlichen Messmethoden wie der Raman Spektroskopie und der niederenergetischen Elektronenbeugung unter Ultrahochvakuum-Bedingungen durchgeführt. Eine zusätzliche Charakterisierung erfolgte ex situ mittels Raster-KraftMikroskopie. Die experimentell bestimmte spektrale Raman-Signatur der prototypischen epitaktischen (3x3)/(4x4) Silicene Struktur wurde durch ab initio Rechnungen, in Zusammenarbeit mit Theoriegruppen, bestätigt. Durch diesen Vergleich wir die zweidimensionale Natur der epitaktischen Silicen-Schichten vollständig bestätigt, wodurch andere mögliche Interpretationen ausgeschlossen werden können. Darüber hinaus wurden die Ramans-Signaturen der weiteren 2D und 3D Siliziumphasen auf Ag(111) bestimmt, wodurch sich ein klares Bild der Bildung dieser Strukturen in Abhängigkeit von den Präparationsbedingungen ergibt. Um die Möglichkeit der Funktionalisierung von Silicen und der weiteren 2D Si Strukturen zu testen, wurden diese unter UHV Bedingungen atomarem Wasserstoff ausgesetzt. Durch die Bindung zu den Wasserstoffamen wird die kristalline Struktur der Silicen-Schichten modifiziert und die Symmetrie reduziert, was sich deutlich in der spektralen Raman-Signatur zeigt. Wie mittels Raman Spektroskopie gezeigt werden konnte, kann diese Modifikation durch thermische Desorption des Wasserstoffs rückgängig gemacht werden, ist also reversibel. Raman Messungen mit verschiedenen Anregungswellenlängen deuten darüber hinaus auf die Änderung der elektronischen Eigenschaften der Silicen-Schichten durch die Hydrierung hin. Der ursprüngliche halbmetallische Charakter der epitaktischen Silicen-Schicht geht möglicherweise in einen halbleitenden Zustand über. Das Wachstum von Silicen Multilagen wurde ebenfalls mit in situ Ramanspektroskopie verfolgt. Die sich dabei ergebene Raman-Signatur wurde mit der Raman-Signatur von Ag terminiertem Si(111) verglichen. Hier zeigen sich große Ähnlichkeiten, die auf eine ähnliche atomare Struktur hindeuten und zeigen, dass Ag Atome für die Ausbildung der Oberflächenstruktur während des Wachstums der Si-Lagen verantwortlich sind. Die chemischen und physikalischen Eigenschaften dieser Struktur bestärken zusätzlich diese Äquivalenz.

This dissertation works out the vibrational properties of epitaxial silicene, which was discovered by Vogt et al. in 2012 by the epitaxial synthesis on the silver substrate. Its two-dimensional (2D) character is modified in comparison to the free-standing silicene due to its epitaxial nature, since the underlying substrate alters the physical properties of silicene as a result of the strong hybridization of the electronic levels of the substrate and adlayer. The growth of silicene layers is complicated by the sensitivity of the Si structures to the experimental conditions, mainly temperature, resulting in the formation of several seemingly different surface reconstructions. Another Si structure appears on the Ag surface at a supramonolayer coverage. The Raman spectroscopy was utilized to understand the relation between different Si structures and reveal their origin as well as to investigate the phonon-related physical properties of two-dimensional Si sheets. The central core of this work is the growth and characterization of these 2D silicene monolayers on the Ag (111) surface as well as the formation of silicene multilayer structures. The characterization of these materials was performed using in situ surface-sensitive measurement methods such as Raman spectroscopy and low-energy electron diffraction under ultra-high vacuum conditions due to high chemical reactivity of epitaxial silicene. Additional characterization was done ex situ by means of scanning force microscopy. The experimentally determined spectral signature of the prototypical epitaxial (3x3)/(4x4) silicene structure was confirmed by ab initio calculations, in collaboration with theory groups. The Raman signatures of the other 2D and 3D Si phases on Ag (111) were determined which allowed us to provide a clear picture of their formation depending on the preparation conditions. The monitoring of the silicene multi-layer growth yielded the vibrational signature of the top layer, reconstructed in a (√3x√3) fashion. It was compared to the inverse, (√3x√3)-Ag/Si(111), system showing the vast amount of similarities, which suggest that the (√3x√3) reconstruction belong to the silver layer. The chemical and physical properties of this surface structure additionally strengthen this equivalence. The possibility of functionalization of epitaxial silicene was demonstrated via exposure to the atomic hydrogen under UHV conditions. The adsorbed hydrogen covalently bonds to the silicene lattice modifying it and reducing its symmetry. As shown by Raman spectroscopy, such modification can be reversed by thermal desorption of hydrogen. The excitation-dependent Raman measurements also suggest the change of the electronic properties of epitaxial silicene upon hydrogenation suggesting that its originally semi-metallic character is modified into a semiconducting one. / Die experimentellen Forschungsarbeiten zum Thema Silicen basieren auf den 2012 von Vogt et al. durchgeführten Untersuchungen zu dessen Synthese auf Silbersubstraten. Diese Untersuchungen lieferten die Grundlage, auf der zweidimensionales (2D) epitaktisches Silicen sowie weitere 2D Materialien untersucht werden konnten. In den anfänglichen Arbeiten konnte dabei gezeigt werden, dass sich die Eigenschaften von epitaktischem Silicen gegenüber den theoretischen Vorhersagen von frei-stehendem Silicen unterscheiden. Darüber hinaus verkomplizieren sich die experimentellen Untersuchungen dieses 2D Materials, da auf dem Ag(111) Wachstumssubstrat sechs verschiedene 2D Si Polytypen existieren. Eine detaillierte Darstellung dieser Untersuchungen findet sich in dem einführenden Kapitel der vorliegen Promotionsschrift. Der zentrale Kern dieser Arbeit beschäftigt sich mit dem Wachstum und der Charakterisierung dieser 2D Silicen Monolagen auf Ag(111) Oberflächen sowie der Bildung von Silicen- Multilagen Strukturen. Die Charakterisierung dieser Materialien wurde in situ mit oberflächenempfindlichen Messmethoden wie der Raman Spektroskopie und der niederenergetischen Elektronenbeugung unter Ultrahochvakuum-Bedingungen durchgeführt. Eine zusätzliche Charakterisierung erfolgte ex situ mittels Raster-KraftMikroskopie. Die experimentell bestimmte spektrale Raman-Signatur der prototypischen epitaktischen (3x3)/(4x4) Silicene Struktur wurde durch ab initio Rechnungen, in Zusammenarbeit mit Theoriegruppen, bestätigt. Durch diesen Vergleich wir die zweidimensionale Natur der epitaktischen Silicen-Schichten vollständig bestätigt, wodurch andere mögliche Interpretationen ausgeschlossen werden können. Darüber hinaus wurden die Ramans-Signaturen der weiteren 2D und 3D Siliziumphasen auf Ag(111) bestimmt, wodurch sich ein klares Bild der Bildung dieser Strukturen in Abhängigkeit von den Präparationsbedingungen ergibt. Um die Möglichkeit der Funktionalisierung von Silicen und der weiteren 2D Si Strukturen zu testen, wurden diese unter UHV Bedingungen atomarem Wasserstoff ausgesetzt. Durch die Bindung zu den Wasserstoffamen wird die kristalline Struktur der Silicen-Schichten modifiziert und die Symmetrie reduziert, was sich deutlich in der spektralen Raman-Signatur zeigt. Wie mittels Raman Spektroskopie gezeigt werden konnte, kann diese Modifikation durch thermische Desorption des Wasserstoffs rückgängig gemacht werden, ist also reversibel. Raman Messungen mit verschiedenen Anregungswellenlängen deuten darüber hinaus auf die Änderung der elektronischen Eigenschaften der Silicen-Schichten durch die Hydrierung hin. Der ursprüngliche halbmetallische Charakter der epitaktischen Silicen-Schicht geht möglicherweise in einen halbleitenden Zustand über. Das Wachstum von Silicen Multilagen wurde ebenfalls mit in situ Ramanspektroskopie verfolgt. Die sich dabei ergebene Raman-Signatur wurde mit der Raman-Signatur von Ag terminiertem Si(111) verglichen. Hier zeigen sich große Ähnlichkeiten, die auf eine ähnliche atomare Struktur hindeuten und zeigen, dass Ag Atome für die Ausbildung der Oberflächenstruktur während des Wachstums der Si-Lagen verantwortlich sind. Die chemischen und physikalischen Eigenschaften dieser Struktur bestärken zusätzlich diese Äquivalenz.