Epitaxial multilayer h-BN(0001) heterostructures and graphene/h-BN heterostructures have many potential applications in spintronics. The use of h-BN and graphene require atomically precise control and azimuthal alignment of the individual layers in the structure. These in turn require fabrication of devices by direct scalable methods rather than physical transfer of BN and graphene flakes, and such scalable methods are also critical for industrially compatible development of 2D devices. The growth of h-BN(0001) multilayers on Co and Ni, and graphene/h-BN(0001) heterostructures on Co have been studied which meet these criteria. Atomic Layer Epitaxy (ALE) of BN was carried out resulting in the formation of macroscopically continuous h-BN(0001) multilayers using BCl3 and NH3 as precursors. X-ray photoemission spectra (XPS) show that the films are stoichiometric with an average film thickness linearly proportional to the number of BCl3/NH3 cycles. Molecular beam epitaxy (MBE) of C yielded few layer graphene in azimuthal registry with BN/Co(0001) substrate. Low energy electron diffraction (LEED) measurements indicate azimuthally oriented growth of both BN and graphene layers in registry with the substrate lattice. Photoemission data indicate B:N atomic ratios of 1:1. Direct growth temperatures of 600 K for BN and 800 to 900 K for graphene MBE indicate multiple integration schemes for applications in spintronics.

Submitted by Maike Costa (maiksebas@gmail.com) on 2016-03-15T13:17:25Z No. of bitstreams: 1 arquivototal.pdf: 5498676 bytes, checksum: 4a307b30b2c4f45e565cf9923519ec7f (MD5) / Made available in DSpace on 2016-03-15T13:17:25Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 5498676 bytes, checksum: 4a307b30b2c4f45e565cf9923519ec7f (MD5) Previous issue date: 2015-02-20 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Investigating the stability and electronic structure of nanomaterials is essential for their application in electronic devices. In this thesis were analysed two types of nanostructures, a derivative of h-BN and the other of graphene. This analysis was performed using first-principles calculations by Density Functional Theory (DFT), implemented by the SIESTA code. First we investigated two kinds of stacks of h-BN bilayer with impurities and by means of the calculation of interaction and formation energies was identified the most stable bilayers, both due to the nature of the stack and to the type impurity introduced. We also note that the combination of these two effects cause considerable variations in the gaps of energy and impurity. We also use an electric field perpendicular to the plane of the bilayer and observe different changes in the electronic structure related to the permanent electric dipole moment of each nanostructure. The second nanomaterial investigated in this work, the Carbon bicones have been proposed based on the experimental observation of nanocones. The possibility of bicones are experimentally obtained was analyzed by comparing the stability of these nanostructures with existing cones. It was found that some of them are as stable as the cones, which, at least theoretically, enables the synthesis of these nanomaterials. The effect of the electric field and impurities on the electronic structure of bicones were also analyzed, resulting in significant changes in the state density, evidenced by the emergence of new states near the Fermi level / Investigar a estabilidade e a estrutura eletrônica dos nanomateriais é imprescindível para a aplicação dos mesmos em dispositivos eletrônicos. Nesta tese foram analisados dois tipos de nanoestruturas, uma derivada do h-BN e a outra do grafeno. Tal análise foi realizada utilizando cálculos de primeiros princípios, através da Teoria do Funcional da Densidade (DFT), implementados pelo código SIESTA. Primeiramente investigamos dois tipos de empilhamentos de bicamadas de h-BN com impurezas e por meio das energias de interação e formação calculadas, identificamos as bicamadas mais estáveis, tanto em função da natureza do empilhamento, quanto em relação ao tipo de impureza introduzida. Constatamos também que a combinação destes dois efeitos, causa consideráveis variações nos gaps de energia e de impureza. Aplicamos ainda um campo elétrico perpendicular ao plano das bicamadas e observamos diferentes modificações na estrutura eletrônica, relacionadas ao momento de dipolo elétrico permanente de cada nanoestrutura. O segundo nanomaterial investigado neste trabalho, os bicones de Carbono, foram propostos tomando por base a constatação experimental dos nanocones. A possibilidade dos bicones serem obtidos experimentalmente foi analisada comparando a estabilidade destas nanoestruturas com a dos cones já existentes. Foi possível constatar que alguns deles são tão estáveis quanto os cones, o que, ao menos teoricamente, viabiliza a sintetização destes nanomateriais. O efeito do campo elétrico e das impurezas sobre a estrutura eletrônica dos bicones também foram analisados, resultando em mudanças relevantes na densidade de estado, evidenciadas através do surgimento de novos estados próximos ao nível de Fermi.

Aujourd'hui se pose une question fondamentale sur le futur de l'électronique actuelle. De plus en plus, des circuits hybrides intégrant de nouvelles fonctionnalités sont fabriqués. On envisage même, à plus long terme, des circuits basés sur une technologie différente de l'approche CMOS utilisée actuellement. Une de ces technologies est la spintronique qui tire profit du spin, degré de liberté supplémentaire de l'électron. Elle a rapidement fait ses preuves par le passé dans le stockage non volatile binaire (disques durs) et s'oriente aujourd'hui vers de nouvelles mémoires magnétiques ultra-performantes et basse consommation les MRAMs (Magnetic Random Access Memories). En parallèle, une nouvelle catégorie de matériaux à fort potentiel a émergé : les matériaux bidimensionnels (2D). Ces matériaux, dont le fer de lance est le graphène (une couche d'un atome d'épaisseur de graphite), offrent de nouvelles propriétés inégalées. Leur combinaison via la fabrication d'hétérostructures et la capacité d'avoir un contrôle de leur épaisseur à l'échelle atomique pourrait devenir un atout majeur en électronique et plus particulièrement en spintronique. L'objectif de cette thèse a été l'étude de l'intégration et la démonstration du potentiel en termes de fonctionnalités et de performances de ces nouveaux matériaux 2D au sein de jonctions tunnel magnétiques (MTJs), le dispositif prototype de la spintronique. Au cours de cette thèse, nous avons poursuivi les travaux initiés au laboratoire sur l'intégration dans des MTJs du graphène obtenu via une méthode de dépôt CVD (dépôt chimique en phase vapeur) directe sur l’électrode ferromagnétique inférieure. Nous avons démontré que les propriétés de filtrage en spin et de membrane protectrice contre l'oxydation de l'électrode ferromagnétique (FM) sous-jacente s'étendaient à une unique couche de graphène. Par ailleurs, nous avons aussi pu étudier et améliorer significativement l'amplitude du filtrage en spin et du signal de magnétorésistance observé via l'optimisation des procédés de croissance et d'intégration et le choix de différentes configurations de matériaux ferromagnétiques (Ni(111), Co...). De forts effets de filtrage de spin ont ainsi pu être observés avec des magnétorésistances allant de -15% à plus de +80%, soit presque trois fois l'état de l'art. En parallèle, nous nous sommes aussi intéressés à un autre matériau 2D, le nitrure de bore hexagonal (h-BN), isolant isomorphe du graphène qui s'apparenterait à une barrière tunnel d'un seul atome d'épaisseur. Afin d’étudier le h-BN dans une MTJ, nous avons décidé d’exploiter à nouveau le principe d’une croissance directe par CVD du matériau 2D sur le matériau FM. Des mesures CT-AFM (Conductive Tip Atomic Force Microscopy) nous ont permis de démontrer les propriétés de barrière tunnel homogène du h-BN ainsi que le contrôle possible de la hauteur de barrière avec le nombre de couches de h-BN. De plus, des mesures électriques et de magnétotransport nous ont permis de confirmer l’intégration réussie de la barrière tunnel h-BN dans notre MTJ. Nous avons pu obtenir les premiers résultats de forte magnétorésistance pour du h-BN avec une amplitude de la magnétorésistance de +50%, plus d'un ordre de grandeur au-dessus de l'état de l'art, révélant le potentiel du h-BN. Nous avons enfin aussi pu démontrer l'importance du couplage entre le h-BN et l'électrode FM offrant un potentiel de contrôle inédit sur les effets de filtrage en spin et allant jusqu'à rendre le h-BN métallique. Lors de cette thèse, nous avons pu montrer que l’intégration du graphène et du h-BN dans des MTJs via la croissance directe par CVD est un procédé privilégié pour tirer pleinement profit de leurs propriétés. Les résultats obtenus de forte magnétorésistance et de filtrage en spin laissent entrevoir le fort potentiel du graphène, du h-BN mais aussi des autres nouveaux matériaux 2D à venir pour les MTJs. Ces études ouvrent une nouvelle voie d’exploration pour les MTJs : les 2D-MTJs. / Nowadays a critical issue is raised concerning the future of current electronics. Increasingly, hybrid circuits with new functionalities are manufactured. A longer term approach is even contemplated with circuits based on a technology different from the one currently used (CMOS technology). One of these envisioned technologies is spintronics, which benefits from the spin properties, the electron additional degree of freedom. Spintronics has quickly proven its worth in the past in the field of non volatile data storing (hard drives) and is today moving towards new fast and ultra-low-power magnetic random access memories the MRAMs. Meanwhile, these last few years, a new category of materials with high potential has emerged : the bidimensional materials (2D). These materials, with graphene (one atomically thick layer of graphite) as the forerunner, provide new unrivaled properties. Their combination in the form of heterostructures and the ability to obtain a control of their thickness at the atomic scale could be a major asset for electronics and more specifically spintronics. The purpose of this thesis has been the study of the integration and the demonstration of the potential in terms of functionalities and performances of these new 2D materials inside the prototypical spintronic device: the magnetic tunnel junction (MTJ). During this thesis, we have pursued the work initiated by the laboratory on the integration of graphene in MTJs with direct CVD deposition method (chemical vapor deposition) on the underlying ferromagnetic electrode. We demonstrated that the spin filtering and protective membrane properties (preventing the oxidation of the underlying ferromagnetic electrode (FM)) observed earlier expand to a graphene monolayer. Furthermore, we have also studied and improved significantly the amplitude of the spin filtering and the magnetoresistance signal observed. This was done thanks to the optimization of the growth process, integration, and choice of the different configurations of ferromagnetic materials in our structures (Ni(111), Co...). High spin filtering effects have been observed as a function of the configurations with magnetoristances ranging from -15% to beyond +80%, which is almost three times the state of the art. Meanwhile, we looked at another 2D material, the hexagonal boron nitride (h-BN), an insulating isomorph of graphene which could be considered as an atomically thin tunnel barrier. In order to study h-BN into a MTJ, we took again advantage of direct CVD growth of the 2D material on a ferromagnet. CT-AFM (Conductive Tip Atomic Force Microscopy) measurements allowed us to demonstrate the homogeneous tunnel barrier properties of h-BN and the possible control of the barrier height with the number of h-BN layers. Simultaneously, electrical and magnetotransport measurement in the complete junction allowed us to confirm the achieved integration of the h-BN tunnel barrier into our MTJ. We have been able to obtain the first results of high magnetoresistance for h-BN with values one order of magnitude beyond the state of the art. A magnetoresistance of +50% has been reached, thanks to the optimization of the growth process revealing the potential of h-BN. We have also been able to show the important role of the coupling between h-BN and the FM electrode offering an unprecedented potential of control on the spin filtering effects, ranging up to making the h-BN metallic. During this thesis, we have been able to demonstrate that the integration of graphene and h-BN in MTJs through direct CVD growth is a promising process in order to fully exploit their properties. The results obtained of high magnetoresistance and spin filtering point to the high potential for MTJs of graphene and h-BN but also to all the new 2D materials to come. These studies pave the way for exploring a new path for MTJs : the 2D-MTJs.

Electronic systems are an indivisible part of modern life. Every day, new materials, devices, passive components, antennas for wireless communication are needed to be designed and developed. In particular, flexible and biocompatible wearable devices are urgent required for medical and industrial applications. The great hope lies in the materials with high crystalline quality and flexibility such as graphene and other 2D semiconductors and insulators. Doping is a conventional tool for tailoring of the electronic properties of the functional materials. Here we examine application of the widely used the electron donor species to the graphene and hexagonal boron nitride monolayer (h-BN). For each we determine surface-interface properties and the full electronic band structure using the combination of the surface science methods such as angle-integrated and angle resolved photoemission (XPS, ARPES), electron diffraction (LEED) and photo absorption (XAS). As the result we provided insight into mechanisms underlying the doping gating of the graphene h-BN monolayer by the alkali metals. We fully characterized their surface and interface structure. Finally we studied the interplay between electrons and phonons in the doped graphene and we demonstrated that Ca-doped graphene is the promising candidate for realizing superconductivity in graphene.

Electronic systems are an indivisible part of modern life. Every day, new materials, devices, passive components, antennas for wireless communication are needed to be designed and developed. In particular, flexible and biocompatible wearable devices are urgent required for medical and industrial applications. The great hope lies in the materials with high crystalline quality and flexibility such as graphene and other 2D semiconductors and insulators. Doping is a conventional tool for tailoring of the electronic properties of the functional materials. Here we examine application of the widely used the electron donor species to the graphene and hexagonal boron nitride monolayer (h-BN). For each we determine surface-interface properties and the full electronic band structure using the combination of the surface science methods such as angle-integrated and angle resolved photoemission (XPS, ARPES), electron diffraction (LEED) and photo absorption (XAS). As the result we provided insight into mechanisms underlying the doping gating of the graphene h-BN monolayer by the alkali metals. We fully characterized their surface and interface structure. Finally we studied the interplay between electrons and phonons in the doped graphene and we demonstrated that Ca-doped graphene is the promising candidate for realizing superconductivity in graphene.

The present thesis is focused on various methods of controlling electronic and geometrical structure of two-dimensional overlayers adsorbed on metal surfaces exemplified by graphene and hexagonal boron nitride (h-BN) grown on transition metal (TM) substrates. Combining synchrotron-radiation-based spectroscopic and various microscopic techniques with in situ sample preparation, we are able to trace the evolution of overlayer electronic and geometrical properties in overlayer/substrate systems, as well as changes of interfacial interaction in the latter.It is shown that hydrogen uptake by graphene/TM substrate strongly depends on the interfacial interaction between substrate and graphene, and on the geometrical structure of graphene. An energy gap opening in the electronic structure of graphene on TM substrates upon patterned adsorption of atomic species is demonstrated for the case of atomic oxygen adsorption on graphene/TM’s (≥0.35 eV for graphene/Ir(111)). A non-uniform character of adsorption in this case – patterned adsorption of atomic oxygen on graphene/Ir(111) due to the graphene height modulation is verified. A moderate oxidation of graphene/Ir(111) is found largely reversible. Contrary, oxidation of h-BN/Ir(111) results in replacing nitrogen atoms in the h-BN lattice with oxygen and irreversible formation of the B2O3 oxide-like structure.      Pronounced hole doping (p-doping) of graphene upon intercalation with active agents – halogens or halides – is demonstrated, the level of the doping is dependent on the agent electronegativity. Hole concentration in graphene on Ir(111) intercalated with Cl and Br/AlBr3 is as high as ~2×1013 cm-2 and ~9×1012 cm-2, respectively.     Unusual periodic wavy structures are reported for h-BN and graphene grown on Fe(110) surface. The h-BN monolayer on Fe(110) is periodically corrugated in a wavy fashion with an astonishing degree of long-range order, periodicity of 2.6 nm, and the corrugation amplitude of ~0.8 Å. The wavy pattern results from a strong chemical bonding between h-BN and Fe in combination with a lattice mismatch in either [11 ̅1] or [111 ̅] direction of the Fe(110) surface. Two primary orientations of h-BN on Fe(110) can be observed corresponding to the possible directions of lattice match between h-BN and Fe(110).     Chemical vapor deposition (CVD) formation of graphene on iron is a formidable task because of high carbon solubility in iron and pronounced reactivity of the latter, favoring iron carbide formation. However, growth of graphene on epitaxial iron films can be realized by CVD at relatively low temperatures, and the formation of carbides can be avoided in excess of the carbon-containing precursors. The resulting graphene monolayer creates a periodically corrugated pattern on Fe(110): it is modulated in one dimension forming long waves with a period of ~4 nm parallel to the [001] direction of the substrate, with an additional height modulation along the wave crests. The novel 1D templates based on h-BN and graphene adsorbed on iron can possibly find an application in 1D nanopatterning. The possibility for growing high-quality graphene on iron substrate can be useful for the low-cost industrial-scale graphene production.

The SRV test rig was used to evaluate the friction and wear properties of a lubricant in a laboratory setup. Normally, the coefficient of friction and the amount of wear that occurred are measured while the wear scar surface is also evaluated. Special attention was paid to factors that affect the repeatability. The test fluid was subjected to a friction and wear test on the SRV test rig in order to determine what factors affect the repeatability of the coefficient of friction, the amount of wear that occurred and the wear scar appearance. The test fluid used was based on rapeseed oil and white mineral oil. The fluid also contained an extreme pressure additive in the form of sulphurised ester. This was also compared for the same test fluid with dispersed hexagonal-boron nitride (h-BN) nanoparticles. The standard test method as described by ASTM D 6425, was used as test method. Instead of the standard temperature, the block temperature was increased to 100 °C in order to simulate harsher operating environments. The load was set at 200 N It was found that:  The rapid load increase from 50 to 200 N at the end of the running-in period (as described in the standard test method) caused poor repeatability. The test was modified with a more gradual load application for the duration of the running-in period (30 N/min), which resulted in improvement in the repeatability of the tests conducted.  The moisture content in the atmosphere also affected the repeatability of the friction and wear tests. This was most likely due to the formation of a corrosion layer that involves water and by keeping the relative humidity constant, a further improvement in the repeatability was observed. The addition of the h-BN nanoparticles resulted in an improvement of the repeatability of the coefficient of friction (COF), wear scar surface (WSS) and wear scar volume (WSV), since the wear scar surfaces indicated that the particles remove the corrosion layers. This could have led to more consistent wear surfaces for the duration of the test.  The particles also influenced the corrosion layer formation. For both fluids, Raman spectroscopy indicated that greigite (Fe3S4) and goethite (α-FeOOH) were found on the surface, while additional corrosion products were found on the wear scar surface for the test fluid with dispersed particles. These compounds were melanterite (FeSO4.7H2O) and rozenite (FeSO4.4H2O). All these corrosion products were most likely formed due to the reaction of iron from the specimens with sulphurised esters in the test fluid. / Dissertation (MEng)--University of Pretoria, 2015. / tm2015 / Chemical Engineering / MEng / Unrestricted

Zweidimensionale (2D) Materialien bieten eine Vielzahl von neuartigen Eigenschaften und sind aussichtsreich Kandidaten für ein breites Spektrum an Anwendungen. Da hexagonales Bornitrid (h-BN) für eine Integration in Heterostrukturen mit anderen 2D Materialien geeignet ist, erweckte dieses in letzter Zeit großes Interesse. Insbesondere van-der-Waals-Heterostrukturen, welche h-BN und Graphen verbinden, weisen viele potenzielle Vorteile auf, verbleiben in ihrer großflächigen Herstellung von kontinuierlichen Filmen allerdings problematisch. Diese Dissertation stellt eine Untersuchung betreffend des Wachstums von h-BN und vertikalen Heterostrukturen von Graphen und h-BN auf Ni-Substraten durch Molekularstrahlepitaxie (MBE) vor. Zuerst wurde das Wachstum von h-BN mittels elementarer B- und N-Quellen auf Ni als Wachstumssubstrat untersucht. Kristalline h-BN-Schichten konnten durch Raman-spektroskopie nachgewiesen werden. Wachstumsparameter für kontinuierliche und atomar dünne Schichten wurden erlangt. Das Keimbildungs- und Wachstumsverhalten so wie die strukturelle Güte von h-BN wurden mittels einer systemischen Veränderung der Wachstumstemperatur und -dauer untersucht. Die entsprechenden Beobachtungen wie der Änderungen der bevorzugten Keimbildungszentren, der Kristallgröße und der Bedeckung des h-BN wurden diskutiert. Ein Wachstum von großflächigen vertikalen h-BN/Graphen Heterostrukturen (h-BN auf Graphen) konnte mittels einem neuartigen, MBE-basierenden Verfahren demonstriert werden, welche es h-BN und Graphen jeweils erlaubt sich in der vorteilhaften Wachstumsumgebung, welche von Ni bereitgestellt wird, zu formen. In diesem Verfahren formt sich Graphen an der Schnittstelle von h-BN und Ni durch Präzipitation von zuvor in der Ni-Schicht eingebrachten C-Atomen. Schließlich konnte noch ein großflächiges Wachstum von Graphen/h-BN-Heterostrukturen (Graphen auf h-BN) durch das direkte abscheiden von C auf MBE-gewachsenen h-BN gezeigt werden. / Two-dimensional (2D) materials offer a variety of novel properties and have shown great promise to be used in a wide range of applications. Recently, hexagonal boron nitride (h-BN) has attracted significant attention due to its suitability for integration into heterostructures with other 2D materials. In particular, van der Waals heterostructures combining h-BN and graphene offer many potential advantages, but remain difficult to produce as continuous films over large areas. This thesis presents an investigation regarding the growth of h-BN and vertical heterostructures of graphene and h-BN on Ni substrates using molecular beam epitaxy (MBE). The growth of h-BN from elemental sources of B and N was investigated initially by using Ni as the growth substrate. The presence of crystalline h-BN was confirmed using Raman spectroscopy. Growth parameters resulting in continuous and atomically thin h-BN films were obtained. By systematically varying the growth temperature and time the structural quality as well as the nucleation and growth behavior of h-BN was studied. Corresponding observations such as changes in preferred nucleation site, crystallite size, and coverage of h-BN were discussed. Growth of h-BN/graphene vertical heterostructures (h-BN on graphene) over large areas was demonstrated by employing a novel MBE-based technique, which allows both h-BN and graphene to form in the favorable growth environment provided by Ni. In this technique, graphene forms at the interface of h-BN/Ni via the precipitation of C atoms previously dissolved in the thin Ni film. No evidence for the formation of BCN alloy could be found. Additionally, the suitability of ultraviolet Raman spectroscopy for characterization of h-BN/graphene heterostructures was demonstrated. Finally, growth of large-area graphene/h-BN heterostructures (graphene on h-BN) was demonstrated via the direct deposition of C on top of MBE-grown h-BN.

Two-dimensional layered materials, namely monolayer hexagonal boron nitride and graphene were grown by CVD on various transition metals. The physical and chemical properties of these systems were characterized systematically using synchrotron-based spectroscopic techniques, scanning tunneling microscopy and low energy electron diffraction. It is learned that the overlayer–substrate interaction is caused by the overlayer π–substrate d band hybridization. The physical properties of these overlayers depend on the strength of interaction and the degree of lattice matching at the interface. The strength of interaction between the boron nitride and graphene overlayers and the transition metal substrates is increasing from Pt(111)–Ir(111)–Rh(111)–Ru(0001). For overlayers adsorbed on Rh and Ru, the interplay between these two parameters can result in corrugation of the overlayer, i.e. a surface with bonding and non-bonding areas. The amplitude of corrugation is increasing with the strength of interfacial interaction. The corrugated BN overlayer (BN nanomesh) was used as a template for the growth of two-dimensional and highly dispersive Au nanoparticles. In addition, the inert BN nanomesh was used as a substrate for the deposition of pentacene molecules that conform to the corrugated surface while preserving the herringbone crystal structure. The coadsorption of oxygen and Co clusters on the nanomesh was investigated. Oxygen was utilized to lower the Co surface energy, i.e. to prevent Co agglomeration. It is observed that the smaller Co clusters intercalate through the BN overlayer upon soft annealing. Beside the surface structure, the substrate induced surface reactivity of the MG overlayer was employed to promote the hydrogenation of graphene on Pt, Ir and Ni. The graphene layer adsorbed on Pt and Ir shows higher H uptake than MG/Ni. Furthermore the uptake increases with the size of the bonded graphene. The small H uptake for MG/Ni was attributed to the electron localization in the C-Ni bonds.

The development of metals that can overcome the strength-ductility-weight trade-off has been an ongoing challenge in engineering for many decades. A promising option for making such materials are Metal matrix composites (MMCs). MMCs contain dispersions of reinforcement in the form of fibers, particles, or platelets that significantly improve their thermal, electrical, or mechanical performance. This dissertation focuses on reinforcement with two-dimensional (2D) materials due to their unprecedented mechanical properties. For instance, compared to steel, the most well-studied 2D material, graphene, is nearly forty times stronger (130 GPa) and five times stiffer (1 TPa). Examples of reinforcement by graphene have achieved increases in strength of 60% due to load transfer at the metal/graphene interface and dislocation blocking by the graphene. However, the superior mechanical properties of graphene are not fully transferred to the matrix in conventional MMCs, a phenomenon known as the "valley of death." In an effort to develop key insight into how the relationships between composite design, processing, structure, properties, and mechanics can be used to more effectively transfer the intrinsic mechanical properties of reinforcements to bulk composite materials, nanolayered composite systems made of Ni, Cu, and NiTi reinforced with graphene or 2D hexagonal boron nitride h-BN is studied using experimental techniques and molecular dynamics (MD) simulations. / Doctor of Philosophy / The design of new metals with concurrently improved strength and ductility has been an enduring goal in engineering for many decades. The utilization of components made with these new materials would reduce the weight of structures without sacrificing their performance. Such materials have the potential to revolutionize many industries, from electronics to aerospace. Traditional methods of improving the properties of metals by thermomechanical processing have approached a point where only minor performance improvements can be achieved. The development of Metal matrix composites (MMCs) is among the best approaches to achieving the strength-ductility goal. Metal matrix composites are a class of materials containing reinforcements of dissimilar materials that significantly improve their thermal conductivity, electrical conductivity, or mechanical performance. Reinforcements are typically in the form of dispersed fibers, particles, or platelets. The ideal reinforcement materials have superior mechanical properties compared to the metal matrix, a high surface area, and a strong interfacial bond with the matrix. Two-dimensional (2D) materials (materials made up of a single to a few layers of ordered atoms) are attractive for reinforcement in composite materials because they possess unprecedented intrinsic properties. The most well-studied 2D material, graphene, is made of a single layer of carbon atoms arranged in a hexagonal honeycomb pattern. It is nearly forty times stronger (130 GPa) and five times stiffer (1 TPa) than steel. Examples of graphene reinforcing have shown increases in strength of 60% due to load transfer at the metal/graphene interface and dislocation blocking by the graphene. Despite their exceptional mechanical properties, the superior mechanical properties of graphene are not fully transferred to the matrix when incorporated into conventional metal matrix composites. This phenomenon, known as the "valley of death," refers to the loss of mechanical performance at different length scales. One cause of this phenomenon is the difficulty of evenly dispersing the reinforcements in the matrix using traditional fabrication techniques. Another is the presence of dislocations in the metal matrix, which cause very large local lattice strains in the graphene. This atomistic-scale deformation at the interface between the metal and the graphene can significantly weaken it, leading to failure at low strains before reaching its intrinsic failure stress and strain. This dissertation aims to provide insight into how the relationships between composites' design, processing, structure, properties, and mechanics can be used to transfer intrinsic mechanical properties of reinforcements to bulk composite materials more effectively. For this, nanolayered composite systems of Ni and Cu reinforced with graphene or 2D h-BN were studied using experimental techniques and molecular dynamics (MD) simulations to elucidate the underlying mechanisms behind the composites' material structure and mechanical behavior. Additionally, we explore the incorporation of graphene in a metallic matrix that does not deform through dislocations (or shear bands), such as the shape memory alloy nickel-titanium ( Nitinol or NiTi), to avoid low strain failure of the metal/graphene interface. This theoretical strengthening mechanism is investigated by designing and fabricating NiTi/graphene composites.