The area of spintronics has witnessed tremendous progress in the 21st century. During the 1980s and 1990s, the Giant and Tunnel Magnetoresistance effect dominated spintronics research with room-temperature ferromagnets(FM), metals, and insulators. Since then, the observation of several spin-based phenomena in heavy non-magnetic materials such as the Spin Hall Effects and the discovery of topological insulators have broadened the scope of spintronics research. Strong spin-orbit coupling (SOC) in topological insulators is expected to induce strong spin-orbit torques on proximal magnetic moments. This has motivated much recent interest in FM/TI systems with applications in spintronic memory and sensing. In this work, magnetron sputtered large-area Co/Bi2Se3 thin films were investigated with a custom-built magnetotransport setup. When current is passed predominantly through the Co layer we observe typical Co anisotropic magnetoresistance, but by promoting higher current density through the interface, we observe unidirectional magnetoresistance with a much larger change in resistance than Co alone. We also observe an unusual inverse current dependence. To test the contributions of each constituent material, Co/Ta and Cr/Bi2Se3 were prepared as controls, and similar observations were made in both materials, but not Co/Cr, suggesting that high SOC in the overlayer may be the driving force. While a proper understanding of our magnetoresistance data is not available at this point, the results broadly highlight the exciting prospects of observing novel phenomena in bilayer spintronic systems at room temperature.

Intercalation is known to be an efficient method for tuning the band structure of layered materials to bring out superconductivity, without significantly altering the crystal structure of the host material. Graphite intercalation compounds and intercalated transitional metal dichalcogenides (TMDs) are two most studied representatives. This thesis presents an experimental study of several new superconductors obtained by intercalation of layered materials, including MoS2, black phosphorus and a topological insulator Bi2Se3. Polymorphism is an essential feature of MoS2. While, superconductivity in doped 2H-MoS2 has been extensively studied. Superconductivity in its 1T and 1T' counterparts has been neither observed, nor even predicted theoretically. In this thesis, we have investigated potassium (K)-intercalated MoS2 and found that doping with K induces both structural and superconducting phase transitions. We demonstrate that all three phases of MoS2 - 2H, 1T and 1T'- become superconducting as a result of intercalation, with critical temperature Tc of 6.9 K, 2.8 K and 4.6 K, respectively. Black phosphorus has been 'rediscovered' in the last few years due to its layered structure and unique electronic properties. This thesis describes successful intercalation of black phosphorus with several alkali metals (Li, K, Rb, Cs) and alkaline earth metal Ca, with all five compounds showing superconductivity. Importantly, and very unexpectedly, the found superconductivity of intercalated black phosphorus is independent of the intercalant, with all five compounds having exactly the same superconducting characteristics (Tc, critical fields, anisotropy). We suggest that the superconductivity is due to heavily doped phosphorene layers, with alkali metal atoms acting mainly as charge reservoirs. Superconducting topological insulators, such as Bi2Se3, are regarded as the most promising candidates for topological superconductivity. However, the nature of superconductivity in doped Bi2Se3, such as CuxBi2Se3, SrxBi2Se3 and NbxBi2Se3, remains controversial and so far no convincing evidence of topological superconductivity has been reported for these materials. In this thesis, we report superconductivity in a new family of superconductors derived from Bi2Se3, by intercalation with K, Rb and Cs metals. All three superconductors exhibit qualitatively identical but highly anomalous behaviour of magnetisation, with several new features consistent with the properties of topological superconductors. Specifically, the new materials exhibit a highly unusual extra diamagnetic screening in the Meissner state and two coexisting superconducting phase, including surface superconductivity that we attribute to heavily doped surface states of the original topological insulator (Bi2Se3). This work provides a new platform in the study of the interplay between the topological and superconducting orders. In conclusion, superconductivity has been induced in MoS2, black phosphorus and Bi2Se3 through alkali or alkaline earth metal intercalation. The study of these new superconducting materials has been summarised in the thesis.

In Topologischen Isolatoren (TI) werden metallische Zustände an der Oberfläche beobachtet, während die entsprechenden Volumenzustände eine Bandlücke aufweisen. Der Volumenbeitrag zur Leitfähigkeit von TI-Materialien macht eine Synthese von Nanokristallen bzw. eine Dotierung nötig. Der Fokus der Untersuchungen dieser Arbeit liegt dabei auf der Erzeugung von Nanokristallen der TI-Materialien Bi2Te3- und Bi2Te2Se sowie dotierter Bi2Se3-Nanokristallen. Die Synthese der Nanokristalle erfolgte durch den Gasphasentransport im geschlossenen System über den Mechanismus einer Zersetzungssublimation bzw. unter dem Einsatz eines Transportmittels. Für eine erfolgreiche Erzeugung der Nanokristalle sind im Vorfeld thermodynamische Modellierungen des Gasphasentransports sowie Versuche zum chemischen Transport für die quasibinären Systeme Bi2Se3-Bi2Te3, Bi2Se3-Sb2Se3 und Bi2Se3-FeSe sowie für das ternäre System Mn-Bi-Se durchgeführt worden. Durch Versuche zum chemischen Transport konnten die Aussagen der Modellierung bestätigt und im Weiteren der Dotandengehalt in den abgeschiedenen Kristallen sowie der Einlagerungsmechanismus durch Ergebnisse aus XRD- und ICP-OES-Untersuchungen beschrieben werden. Die Synthese bzw. Dotierung der Nanokristalle wurde hauptsächlich durch die Transportrate und den Dampfdruck des Dotanden bestimmt. In den Systemen Bi2Se3-Bi2Te3 und Bi2Se3-Sb2Se3 ist ein Gasphasentransport über eine Zersetzungssublimation durchführbar und resultierte in einer erfolgreichen Darstellung von Bi2Te3- und Bi2Te2Se-Nanokristallen sowie von dotierten (SbxBi1-x)2Se3-Nanokristallen. Entgegen dessen erfolgte der Gasphasentransport in den Systemen Bi2Se3-FeSe und Mn-Bi-Se unter Verwendung eines Transportmittels. Hierbei verringerten die gesteigerten Transportraten das Wachtum von Nanokristallen. Im Weiteren gelang es dotierte (Fe,Mn)xBi2-xSe3-Volumenkristalle sowie MnBi2Se4-Einkristalle darzustellen und mittels XRD, ICP-OES, magnetischer Messungen sowie elektrischem Transport zu charakterisieren.

Topological Insulator (TI) is new classes of materials with gapless surface states and insulating bulk. The topological connection can be traced back to the discovery of Integer Quantum Hall Effect in 1980. In the last decade, new categories of topological insulators were predicted and later discovered, that have gained a lot of attraction for room-temperature applications. Since the experimental observation of single Dirac cone on the surface states of Bismuth selenide (Bi2Se3) in 2009, it has emerged as the prototype. Bismuth Selenide has one of the highest bulk band gaps of 0.3 eV among all TI materials. While its single crystal properties are well documented, thin films are producing equally exciting discoveries. In this work, Bi2Se3 thin films were synthesized using magnetron sputtering method and a diverse set of physical properties, such as structural, optical, and electronic, are investigated. In particular, properties of few-layer (ultra-thin) Bi2Se3 thin films are studied. Optical properties of Bi2Se3 was particularly revealing. We observed a sharp increase (blue shift) in the bulk band gap of Bi2Se3 by almost 0.5 eV as it approached the two-dimensional limit. Strong thickness-dependent structural and transport properties were also observed.

Submitted by Livia Mello (liviacmello@yahoo.com.br) on 2016-10-11T19:57:49Z No. of bitstreams: 1 TeseHMNV.pdf: 4404722 bytes, checksum: 1983a667805c061a711a3694028b17b0 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-21T12:45:43Z (GMT) No. of bitstreams: 1 TeseHMNV.pdf: 4404722 bytes, checksum: 1983a667805c061a711a3694028b17b0 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-21T12:45:59Z (GMT) No. of bitstreams: 1 TeseHMNV.pdf: 4404722 bytes, checksum: 1983a667805c061a711a3694028b17b0 (MD5) / Made available in DSpace on 2016-10-21T12:46:06Z (GMT). No. of bitstreams: 1 TeseHMNV.pdf: 4404722 bytes, checksum: 1983a667805c061a711a3694028b17b0 (MD5) Previous issue date: 2016-03-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / In this work, we discuss the growth of Fe containing Bi2 Se3epilayers on the GaAs(111) substrate by molecular beam epitaxy (MBE) with Fe contents of in the 8- 20% range. It is shown that Bi2 Se3 film thin are grown with quality and the Fe form a phase segregation of Fe x Sey material that may have different stoichiometries possibity, leading to magnetic and superconducting results. Despite the composite structure, the surface state of Bi2 Se3 is preserved as shown with persistence of Dirac Cone of the Γ point by Angle-Resolved Photoemission Spectroscopy (ARPES). It was observed that higher Fe content deposited is increased formation of compound responsible for ferrimagnetic layers together with the superconducting phase supposed. The Fe3Se 4 was the most abundant type of segregation in all samples, with the results ferrimagnetic these samples at temperatures around 315 K. / Neste trabalho, abordamos o crescimento de Bi2 Se3 com adição de Fe em substrato de GaAs(111) por meio de epitaxia de feixe molecular (MBE), variando o teor de Fe depositado de 8% até 20%. É mostrado que os filmes de Bi2 Se3 são crescidos com qualidade e o Fe juntamente com o Se formam uma segregação de fases Fex Sey , material que pode ter diferentes estequiometrias levando a resultados magnéticos e possivelmente supercondutor. Apesar da estrutura compósita, a estrutura superficial do Bi2 Se3 é preservada como mostrado pela persistência do cone de Dirac no ponto Γ nas medidas de espectroscopia de fotoemissão de resolução angular (ARPES). Foi possível observar que quanto maior o teor de Fe depositado, ocorre uma maior formação de compostos responsável pela fase ferrimagnética em conjunto com a fase supostamente supercondutora. O Fe3Se 4 foi o tipo de segregação mais abundante em todas as amostras, levando a resultados ferrimagnéticos nessas amostras em temperaturas em torno de 315 K.

abstract: This dissertation presents research findings on the three materials systems: lateral Si nanowires (SiNW), In₂Se₃/Bi₂Se₃ heterostructures and graphene. The first part of the thesis was focused on the growth and characterization of lateral SiNW. Lateral here refers to wires growing along the plane of substrate; vertical NW on the other hand grow out of the plane of substrate. It was found, using the Au-seeded vapor – liquid – solid technique, that epitaxial single-crystal SiNW can be grown laterally along Si(111) substrates that have been miscut toward [11− 2]. The ratio of lateral-to-vertical NW was found to increase as the miscut angle increased and as disilane pressure and substrate temperature decreased. Based on this observation, growth parameters were identified whereby all of the deposited Au seeds formed lateral NW. Furthermore, the nanofaceted substrate guided the growth via a mechanism that involved pinning of the trijunction at the liquid/solid interface of the growing nanowire. Next, the growth of selenide heterostructures was explored. Specifically, molecular beam epitaxy was utilized to grow In₂Se₃ and Bi₂Se₃ films on h-BN, highly oriented pyrolytic graphite and Si(111) substrates. Growth optimizations of In₂Se₃ and Bi₂Se₃ films were carried out by systematically varying the growth parameters. While the growth of these films was demonstrated on h-BN and HOPG surface, the majority of the effort was focused on growth on Si(111). Atomically flat terraces that extended laterally for several hundred nm, which were separated by single quintuple layer high steps characterized surface of the best In₂Se₃ films grown on Si(111). These In₂Se₃ films were suitable for subsequent high quality epitaxy of Bi₂Se₃ . The last part of this dissertation was focused on a recently initiated and ongoing study of graphene growth on liquid metal surfaces. The initial part of the study comprised a successful modification of an existing growth system to accommodate graphene synthesis and process development for reproducible graphene growth. Graphene was grown on Cu, Au and AuCu alloys at varioua conditions. Preliminary results showed triangular features on the liquid part of the Cu metal surface. For Au, and AuCu alloys, hexagonal features were noticed both on the solid and liquid parts. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2014

In Topologischen Isolatoren (TI) werden metallische Zustände an der Oberfläche beobachtet, während die entsprechenden Volumenzustände eine Bandlücke aufweisen. Der Volumenbeitrag zur Leitfähigkeit von TI-Materialien macht eine Synthese von Nanokristallen bzw. eine Dotierung nötig. Der Fokus der Untersuchungen dieser Arbeit liegt dabei auf der Erzeugung von Nanokristallen der TI-Materialien Bi2Te3- und Bi2Te2Se sowie dotierter Bi2Se3-Nanokristallen. Die Synthese der Nanokristalle erfolgte durch den Gasphasentransport im geschlossenen System über den Mechanismus einer Zersetzungssublimation bzw. unter dem Einsatz eines Transportmittels. Für eine erfolgreiche Erzeugung der Nanokristalle sind im Vorfeld thermodynamische Modellierungen des Gasphasentransports sowie Versuche zum chemischen Transport für die quasibinären Systeme Bi2Se3-Bi2Te3, Bi2Se3-Sb2Se3 und Bi2Se3-FeSe sowie für das ternäre System Mn-Bi-Se durchgeführt worden. Durch Versuche zum chemischen Transport konnten die Aussagen der Modellierung bestätigt und im Weiteren der Dotandengehalt in den abgeschiedenen Kristallen sowie der Einlagerungsmechanismus durch Ergebnisse aus XRD- und ICP-OES-Untersuchungen beschrieben werden. Die Synthese bzw. Dotierung der Nanokristalle wurde hauptsächlich durch die Transportrate und den Dampfdruck des Dotanden bestimmt. In den Systemen Bi2Se3-Bi2Te3 und Bi2Se3-Sb2Se3 ist ein Gasphasentransport über eine Zersetzungssublimation durchführbar und resultierte in einer erfolgreichen Darstellung von Bi2Te3- und Bi2Te2Se-Nanokristallen sowie von dotierten (SbxBi1-x)2Se3-Nanokristallen. Entgegen dessen erfolgte der Gasphasentransport in den Systemen Bi2Se3-FeSe und Mn-Bi-Se unter Verwendung eines Transportmittels. Hierbei verringerten die gesteigerten Transportraten das Wachtum von Nanokristallen. Im Weiteren gelang es dotierte (Fe,Mn)xBi2-xSe3-Volumenkristalle sowie MnBi2Se4-Einkristalle darzustellen und mittels XRD, ICP-OES, magnetischer Messungen sowie elektrischem Transport zu charakterisieren.

In this thesis, we investigate the quantum transport properties of disordered three dimensional topological insulator (3DTI) nanostructures of BiSe and BiTe in detail. Despite their intrinsic bulk conductivity, we show the possibility to study the specific transport properties of the topological surface states (TSS), either with or without quantum confinement. Importantly, we demonstrate that unusual transport properties not only come from the Dirac nature of the quasi-particles, but also from their spin texture. Without quantum confinement (wide ribbons), the transport properties of diffusive 2D spin-helical Dirac fermions are investigated. Using high magnetic fields allows us to measure and separate all contributions to charge transport. Band bending is investigated in BiSe nanostructures, revealing an inversion from upward to downward bending when decreasing the bulk doping. This result points out the need to control simultaneously both the bulk and surface residual doping in order to produce bulk-depleted nanostructures and to study TSS only. Moreover, Shubnikov-de-Haas oscillations and transconductance measurements are used to measure the ratio of the transport length to the electronic mean free path ltr/le. This ratio is measured to be close to one for bulk states, whereas it is close to 8 for TSS, which is a hallmark of the anisotropic scattering of spin-helical Dirac fermions. With transverse quantum confinement (narrow wires or ribbons), the ballistic transport of quasi-1D surface modes is evidenced by mesoscopic transport measurements, and specific properties due to their topological nature are revealed at very low temperatures. The metallic surface states are directly evidenced by the measure of periodic Aharonov-Bohm oscillations (ABO) in 3DTI nanowires. Their exponential temperature dependence gives an unusual power-law temperature dependence of the phase coherence length, which is interpreted in terms of quasi-ballistic transport and decoherence in the weak-coupling regime. This remarkable finding is a consequence of the enhanced transport length, which is comparable to the perimeter. Besides, the ballistic transport of quasi-1D surface modes is further evidenced by the observation of non-universal conductance fluctuations in a BiSe nanowire, despite the long-length limit (L > ltr) and a high metallicity (many modes). We show that such an unusual property for a mesoscopic conductor is related to the limited mixing of the transverse modes by disorder, as confirmed by numerical calculations. Importantly, a model based on the modes' transmissions allows us to describe our experimental results, including the full temperature dependence of the ABO amplitude.

In this thesis, we investigate the quantum transport properties of disordered three dimensional topological insulator (3DTI) nanostructures of BiSe and BiTe in detail. Despite their intrinsic bulk conductivity, we show the possibility to study the specific transport properties of the topological surface states (TSS), either with or without quantum confinement. Importantly, we demonstrate that unusual transport properties not only come from the Dirac nature of the quasi-particles, but also from their spin texture. Without quantum confinement (wide ribbons), the transport properties of diffusive 2D spin-helical Dirac fermions are investigated. Using high magnetic fields allows us to measure and separate all contributions to charge transport. Band bending is investigated in BiSe nanostructures, revealing an inversion from upward to downward bending when decreasing the bulk doping. This result points out the need to control simultaneously both the bulk and surface residual doping in order to produce bulk-depleted nanostructures and to study TSS only. Moreover, Shubnikov-de-Haas oscillations and transconductance measurements are used to measure the ratio of the transport length to the electronic mean free path ltr/le. This ratio is measured to be close to one for bulk states, whereas it is close to 8 for TSS, which is a hallmark of the anisotropic scattering of spin-helical Dirac fermions. With transverse quantum confinement (narrow wires or ribbons), the ballistic transport of quasi-1D surface modes is evidenced by mesoscopic transport measurements, and specific properties due to their topological nature are revealed at very low temperatures. The metallic surface states are directly evidenced by the measure of periodic Aharonov-Bohm oscillations (ABO) in 3DTI nanowires. Their exponential temperature dependence gives an unusual power-law temperature dependence of the phase coherence length, which is interpreted in terms of quasi-ballistic transport and decoherence in the weak-coupling regime. This remarkable finding is a consequence of the enhanced transport length, which is comparable to the perimeter. Besides, the ballistic transport of quasi-1D surface modes is further evidenced by the observation of non-universal conductance fluctuations in a BiSe nanowire, despite the long-length limit (L > ltr) and a high metallicity (many modes). We show that such an unusual property for a mesoscopic conductor is related to the limited mixing of the transverse modes by disorder, as confirmed by numerical calculations. Importantly, a model based on the modes' transmissions allows us to describe our experimental results, including the full temperature dependence of the ABO amplitude.

Over the past twenty-five years, condensed matter physics has been developing materials with novel electronic characteristics for a wide range of future applications. Two research directions have shown particular promise: topological insulators, and high temperature copper based superconductors (cuprates). Topological insulators are a newly discovered class of materials that can be manipulated for spintronic or quantum computing devices. However there is a poor spectroscopic understanding of the current topological insulators and emerging topological insulator candidates. In cuprate superconductors, the challenge lies in raising the superconducting transition temperature to temperatures accessible in non-laboratory settings. This effort has been hampered by a poor understanding of the superconducting mechanism and its relationship with a mysterious pseudogap phase. In this thesis, I will describe experiments conducted on topological insulators and cuprate superconductors using scanning tunneling microscopy and spectroscopy, which provide nanoscale spectroscopic information in these materials. / Physics