Disorder-induced electronic, magnetic, and optoelectronic properties of two-dimensional materials

Technological advancement has been in cadence with material development by improving the purity of single crystals and, at the same time, controlling their imperfections. These capabilities have been especially vital for developing new technolo-gies based on two-dimensional (2D) van der Waals (vdW) materials for future electronic and optoelectronic applications. This is because the inherent properties of 2D vdW materials is highly susceptible to the presence of intrinsic structural defects and ex-trinsic disorders due to large surface-area-to-volume ratio. The successful reduction of these disorders has significantly im-proved material properties and led to the discovery of novel physical phenomena in vdW materials. On the other hand, structural defects â for instance, 0-dimensional point defects â can induce completely new properties that are otherwise absent in the pre-fect lattice. To harness the full potential of vdW materials, it is thus essential to produce high-quality crystals and understand how the disorder affects their material properties, which is the central idea of this dissertation.In this dissertation, we first present the work of high-quality epitaxial growth of NbS2. Based on atmospheric-pressure chemical vapor deposition, we have successfully synthesized the two polymorphs (2H and 3R) of NbS2 with the largest lateral size grown to date. Their distinct superconducting and metallic properties were examined under low-temperature charge transport, respectively. Our finding demonstrates the practical synthesis method for phase-controllable growth of 2D transition metal dichalcogenides and can benefit future studies in mesoscopic devices and large-area applications of 2D superconductors. Secondly, we present the work of discovering defect-induced novel properties in ultrathin layers of PtSe2. Although bulk PtSe2 is non-magnetic, we observe the appearance of magnetism in monolayer and bilayer PtSe2. We were able to measure the magnetoresistance (MR) of mono- and bilayer PtSe2 under perpendicular magnetic fields using proximitized graphene, and found antiferromagnetic and ferromagnetic MR responses for mono- and bilayer, respectively. The appearance of such different magnetic states is theoretically explained by the first-principle density functional theory calculation, suggesting the origin of induced-magnetic moments from intrinsic Pt vacancies for both layers. Moreover, we also found that structural disorder in PtSe2 can induce bulk photovoltaic effect (BPVE). The second-order optical nonlinear effects, such as BPVE, require broken structural inversion symmetry and crystal symmetry can be reduced by the presence of structural defects. The broken local inversion symmetry from structural disorder in centrosymmetric PtSe2 is manifested by the generation of zero-biased photo-current under homogenous illumination. We observe linear and circular polarization-dependent photocurrents in defective PtSe2, which is largely absent in the pristine crystal. Our findings in PtSe2 emphasize the importance of the structural disorder for generating completely new properties and stress the need for defect-engineering for realizing the practical use of PtSe2 in spintronic and photovoltaic applications.

Spin-valley optoelectronics based on two-dimensional materials

Dmitrii Unuchek

Two-dimensional (2D) materials, in particular graphene and transition metal dichalcogenides (TMDC), have attracted great scientific interest over the last decade, revealing exceptional mechanical, electrical and optical properties. Owing to their layered nature, subnanometer-thick single-layer forms of these crystals can be chemically grown or mechanically isolated, representing an ultimately scaled-down platform for further miniaturization of electronic devices. Indeed, the large family of 2D materials contains hundreds of members, including metals, semiconductors, insulators, and others, covering the whole spectrum of potential applications. Availability of all necessary building blocks for the construction of all-2D solid-state devices makes this platform ideal for fabrication of ultrathin, transparent and flexible devices. Extensively investigated graphene has demonstrated excellent electrical properties. However, the absence of a bandgap is an obstacle for its interaction with light and therefore limits applications in optics. In this aspect, atomically thin TMDC semiconductors appear to be an alternative, more promising platform, as they possess a direct band gap in the visible range in the monolayer form. Despite being only three atoms thick, these semiconductors demonstrate exceptionally large light absorption, efficient light emission, and strong light-matter interaction, attracting justified interest from the optics community. We will focus on their potential applications for optoelectronics in Chapter 4. Even more, broken inversion symmetry and strong spin-orbit coupling in single-layer TMDC crystals reveal a new quantum number, the so-called valley index. Indeed, this unique degree of freedom of charge carriers is known for some materials since the 1970s. However, in the case of 2D semiconductors, spin-valley locking mechanism and valley contrasting optical selection rules open new ways for addressing, manipulation and sensing of this pseudospin, opening the whole new field of valleytronics. Due to the large splitting of the valence band, spin and valley degree of freedom become locked in these atomically thin materials. We employ this unique feature in Chapter 5 for indirect injection of spins into graphene by pumping valley polarized carriers in an adjacent TMDC monolayer. Being gapless, graphene does not allow direct optical injection of spins. Another striking feature of 2D materials is their unique ability to be stacked in vertical heterostructures with strong electrical coupling between layers. The weak van der Waals force, which keeps components together, provides freedom in the assembly process, so that a lattice mismatch or a twist angle becomes unimportant in the first approximation. This provides a novel platform for harvesting complementary properties of the constituent materials, allowing the engineering of new artificial meta-materials as we demonstrate in Chapter 6. Furthermore, synergistic effects in van der Waals heterostructures enable completely new properties and phenomena, which do not exist in the single materials, with twist angle being an important knob for tuning these effects. We observe and exploit such novel phenomena arising in heterostructures of 2D semiconductors in the last chapter of this thesis. On the way to the realization of practical optoelectronic and valleytronic applications, this thesis studies fundamental aspects of rich spin-valley physics of atomically thin semiconductors

EPFL2019

Three-dimensionality of field-induced magnetism in a high-temperature superconductor

Henrik Moodysson Rønnow

Many physical properties of high-temperature superconductors are two-dimensional phenomena derived from their square-planar CuO2 building blocks. This is especially true of the magnetism from the copper ions. As mobile charge carriers enter the CuO2 layers, the antiferromagnetism of the parent insulators, where each copper spin is antiparallel to its nearest neighbours(1), evolves into a fluctuating state where the spins show tendencies towards magnetic order of a longer periodicity. For certain charge-carrier densities, quantum fluctuations are sufficiently suppressed to yield static long-period order(2-6), and external magnetic fields also induce such order(7-12). Here we show that, in contrast to the chemically controlled order in superconducting samples, the field-induced order in these same samples is actually three-dimensional, implying significant magnetic linkage between the CuO2 planes. The results are important because they show that there are three-dimensional magnetic couplings that survive into the superconducting state, and coexist with the crucial inter-layer couplings responsible for three-dimensional superconductivity. Both types of coupling will straighten the vortex lines, implying that we have finally established a direct link between technical superconductivity, which requires zero electrical resistance in an applied magnetic field and depends on vortex dynamics and the underlying antiferromagnetism of the cuprates.

2005

Theoretical investigations of magnetic properties of MRI contrast agents and carbon nanostructures

Oleg Yazyev

The phenomenon of magnetism is one of the key components of today's technological progress. Magnetic interactions and magnetic materials are essential for the scientific disciplines of physics, chemistry and biology, making this subject truly multidisciplinary. This thesis is devoted to magnetic properties of two classes of substances. The first class represents the complexes of the ions of paramagnetic metals, primarily of the gadolinium(III) ion. These molecular compounds have an important application as magnetic resonance imaging (MRI) contrast agents for medical diagnostics. The design of more efficient MRI contrast agents requires a detailed knowledge of their magnetic properties. The other part of the thesis considers the broad class of recently discovered carbon nanostructures and materials. Their extraordinary physical properties foretell future applications of these materials in electronics, medicine and other fields. For instance, carbon nanotubes loaded with gadolinium(III) ion clusters are highly efficient MRI contrast agents. By using accurate density functional theory calculations in combination with classical molecular dynamics simulations, we determine hyperfine and quadrupole coupling constants on the nuclei of a first coordination sphere water molecule in gadolinium(III) aqua complexes. These parameters play a crucial role in the description of the key function, relaxivity, of MRI contrast agents. We found that the spin-polarization effect induced by the paramagnetic gadolinium(III) ion results in a Fermi contact hyperfine coupling of both the 1H and 17O nuclear spins and affects the dipole hyperfine coupling of the 17O nuclear spin of the inner coordination sphere water molecule. The 17O quadrupole coupling parameters of a coordinated water molecule are found to be very similar to that of neat water. We also apply the methodology of first principles molecular dynamics in order to perform realistic simulations of paramagnetic metal ions in water solution. This allows us to assess structure, dynamics and hyperfine interactions on the water molecules in the inner and outer coordination spheres of two metal ions: chromium(III) and gadolinium(III). In order to perform such calculations, we develop a novel approach for the evaluation of hyperfine coupling constants in pseudopotential electronic structure techniques. Our method takes into account the contribution of core electrons. In the second part of the thesis, we consider magnetic properties of a broad class of carbon nanostructures derived from two-dimensional graphene. We find that in metallic carbon nanotubes, an isotropic Knight shift, a hyperfine contribution to the nuclear magnetic resonance chemical shift, shows a regular dependence on the nanotube diameter. By using a more general approach, we reveal systematic dependences of magnetic interactions between arbitrarily distributed spin-polarized conduction electrons and nuclear spins in the carbon nanostructures derived from graphene. This knowledge is important for interpreting the results of magnetic resonance experiments and for evaluating the performance of carbon nanostructures as materials for alternative approaches in electronics, spintronics and quantum information processing based on electron and nuclear spins. In addition, we study magnetism in graphene induced by single-atom defects. The predicted itinerant magnetism due to the defect-induced states in graphenic materials may account for the experimental observations of ferromagnetism in irradiated graphite which has potential applications in technology. Finally, our first principles molecular dynamics study reveals the mechanisms of the irradiation-induced defect formation. We show that certain defect structures in layered carbon materials can be created selectively by irradiation at predefined conditions.