Critical transport properties of random metals in large magnetic fields

The threshold behavior of the transport properties of a random metal in the critical region near a metal–insulator transition is strongly affected by the measuring electromagnetic fields. In spite of the randomness, the electrical conductivity exhibits striking phase-coherent effects due to broken symmetry, which greatly sharpen the transition compared with the predictions of effective medium theories, as previously explained for electrical conductivities. Here broken symmetry explains the sign reversal of the T → 0 magnetoconductance of the metal–insulator transition in Si(B,P), also previously not understood by effective medium theories. Finally, the symmetry-breaking features of quantum percolation theory explain the unexpectedly very small electrical conductivity temperature exponent α = 0.22(2) recently observed in Ni(S,Se)2 alloys at the antiferromagnetic metal–insulator transition below T = 0.8 K.

Synthesis and Characterisation of Functional Magnetic and Plasmonic Nanomaterials

The main aim of this thesis is the controlled and reproducible synthesis of functional materials at the nanoscale. In the first chapter, a tuning of morphology and magnetic properties of magnetite nanoparticles is presented. It was achieved by an innovative approach, which involves the use of an organic macrocycle (calixarene) to induce the oriented aggregation of NPs during the synthesis. This method is potentially applicable to the preparation of other metal oxide NPs by thermal decomposition of the respective precursors. Products obtained, in particular the multi-core nanoparticles, show remarkable magnetic and colloidal properties, making them very interesting for biomedical applications. The synthesis and functionalisation of plasmonic Au and Ag nanoparticles is presented in the second chapter. Here, a supramolecular approach was exploited to achieve a controlled and potentially reversible aggregation between Au and Ag NPs. This aggregation phenomena was followed by UV - visible spectroscopy and dynamic light scattering. In the final chapters, the conjugation of plasmonic and magnetic functionalities was tackled through the preparation of dimeric nanostructures. Au - Fe oxide heterodimeric nanoparticles were prepared and their magnetic properties thoroughly characterised. The results demonstrate the formation of FeO (wustite), together with magnetite, during the thermal decomposition of the iron precursor. By an oxidation process that preserves Au in the dimeric structures, wustite completely disappeared, with the formation of either magnetite and / or maghemite, much better from the magnetic point of view. The plasmon resonance of Au results damped by the presence of the iron oxide, a material with high refractive index, but it is still present if the Au domain of the nanoparticles is exposed towards the bulk. Finally, remarkable hyperthermia, also in vitro, was found for these structures.

(Table 1) Magnetic characteristic properties of selected samples of ODP Hole 134-831B

During Ocean Drilling Program Leg 134 (Vanuatu), geological high sensitivity magnetic tools (GHMT) developed by CEA-LETI and TOTAL were used at two drill sites. GHMT combine two sensors, a proton magnetometer for total magnetic field measurements with an operational accuracy of 0.1 nanoteslas (nT), and a highly sensitive induction tool to measure the magnetic susceptibility with an operational accuracy of a few 10**-6 SI units. Hole 829A was drilled through an accretionary prism and the downhole measurements of susceptibility correlate well with other well-log physical properties. Sharp susceptibility contrasts between chalk and volcanic silt sediment provide complementary data that help define the lithostratigraphic units. At Hole 831B magnetic susceptibility and total field measurements were performed through a 700-m reef carbonate sequence of a guyot deposited on top of an andesitic volcano. The downhole magnetic susceptibility is very low and the amplitude of peak-to-peak anomalies is less than a few 10**-5 SI units. Based on the repeatability of the measurements, the accuracy of the magnetic logging measurements was demonstrated to be excellent. Total magnetic field data at Hole 831B reveal low magnetic anomalies of 0.5 to 5 nT and the measurement of a complete repeat section indicates an accuracy of 0.1 to 0.2 nT. Due to the inclination of the earth's magnetic field in this area (~-40°) and the very low magnetic susceptibility of the carbonate, the contribution of the induced magnetization to the total field measured in the hole is negligible. Unfortunately, because the core recovery was extremely poor (<5%) no detailed comparison between the core measurements and the downhole magnetic data could be made. Most samples have a diamagnetic susceptibility and very low intensity of remanent magnetization (< 10**-4 A/m), but a few samples have a stable remanent magnetization up to 0.005 A/m. These variations of the intensity of the remanent magnetization suggest a very heterogeneous distribution of the magnetization in the carbonate sequence that could explain the magnetic field anomalies measured in these weakly magnetized rocks.

Synthesis and Thermoelectric Properties of Bi2Se3 Nanostructures

Bismuth selenide (Bi2Se3) nanostructures were synthesized via solvothermal method. The crystallinity of the as-synthesized sample has been analyzed by X-ray diffraction, which shows the formation of rhombohedral Bi2Se3. Electron microscopy examination indicates that the Bi2Se3 nanoparticles have hexagonal flake-like shape. The effect of the synthesis temperature on the morphology of the Bi2Se3 nanostructures has also been investigated. It is found that the particle size increases with the synthesis temperature. Thermoelectric properties of the Bi2Se3 nanostructures were also measured, and the maximum value of dimensionless figure of merit (ZT) of 0.096 was obtained at 523 K.

The role of impurities in the shape, structure and physical properties of semiconducting oxide nanostructures grown by thermal evaporation

A thermal evaporation method developed in the research group enables to grow and design several morphologies of semiconducting oxide nanostructures, such as Ga_2O_3, GeO_2 or Sb_2O_3, among others, and some ternary oxide compounds (ZnGa_2O_4, Zn_2GeO_4). In order to tailor physical properties, a successful doping of these nanostructures is required. However, for nanostructured materials, doping may affect not only their physical properties, but also their morphology during the thermal growth process. In this paper, we will show some examples of how the addition of impurities may result into the formation of complex structures, or changes in the structural phase of the material. In particular, we will consider the addition of Sn and Cr impurities into the precursors used to grow Ga_2O_3, Zn_2GeO_4 and Sb_2O_3 nanowires, nanorods or complex nanostructures, such as crossing wires or hierarchical structures. Structural and optical properties were assessed by electron microscopy (SEM and TEM), confocal microscopy, spatially resolved cathodoluminescence (CL), photoluminescence, and Raman spectroscopies. The growth mechanisms, the luminescence bands and the optical confinement in the obtained oxide nanostructures will be discussed. In particular, some of these nanostructures have been found to be of interest as optical microcavities. These nanomaterials may have applications in optical sensing and energy devices.

Influence of the sputtering flow regime on the structural properties and magnetic behavior of Fe-Ga thin films (Ga ∼ 30 at.%)

In this paper we analyze the structure of Fe-Ga layers with a Ga content of ∼30 at.% deposited by the sputtering technique under two different regimes. We also studied the correlation between the structure and magnetic behavior of the samples. Keeping the Ar pressure fixed, we modified the flow regime from ballistic to diffusive by increasing the distance between the target and the substrate. X-ray diffraction measurements have shown a lower structural quality when growing in the diffusive flow. We investigated the impact of the growth regime by means of x-ray absorption fine structure (XAFS) measurements and obtained signs of its influence on the local atomic order. Full multiple scattering and finite difference calculations based on XAFS measurements point to a more relevant presence of a disordered A2 phase and of orthorhombic Ga clusters on the Fe-Ga alloy deposited under a diffusive regime; however, in the ballistic sample, a higher presence of D0_3/B2 phases is evidenced. Structural characteristics, from local to long range, seem to determine the magnetic behavior of the layers. Whereas a clear in-plane magnetic anisotropy is observed in the film deposited under ballistic flow, the diffusive sample is magnetically isotropic. Therefore, our experimental results provide evidence of a correlation between flow regime and structural properties and its impact on the magnetic behavior of a rather unexplored compositional region of Fe-Ga compounds.

Growth, Characterization, and Properties of Hybrid Graphene-Carbon Nanotube Films and Related Carbon Nanostructures

Graphene, first isolated in 2004 and the subject of the 2010 Nobel Prize in physics, has generated a tremendous amount of research interest in recent years due to its incredible mechanical and electrical properties. However, difficulties in large-scale production and low as-prepared surface area have hindered commercial applications. In this dissertation, a new material is described incorporating the superior electrical properties of graphene edge planes into the high surface area framework of carbon nanotube forests using a scalable and reproducible technology.

The objectives of this research were to investigate the growth parameters and mechanisms of a graphene-carbon nanotube hybrid nanomaterial termed “graphenated carbon nanotubes” (g-CNTs), examine the applicability of g-CNT materials for applications in electrochemical capacitors (supercapacitors) and cold-cathode field emission sources, and determine materials characteristics responsible for the superior performance of g-CNTs in these applications. The growth kinetics of multi-walled carbon nanotubes (MWNTs), grown by plasma-enhanced chemical vapor deposition (PECVD), was studied in order to understand the fundamental mechanisms governing the PECVD reaction process. Activation energies and diffusivities were determined for key reaction steps and a growth model was developed in response to these findings. Differences in the reaction kinetics between CNTs grown on single-crystal silicon and polysilicon were studied to aid in the incorporation of CNTs into microelectromechanical systems (MEMS) devices. To understand processing-property relationships for g-CNT materials, a Design of Experiments (DOE) analysis was performed for the purpose of determining the importance of various input parameters on the growth of g-CNTs, finding that varying temperature alone allows the resultant material to transition from CNTs to g-CNTs and finally carbon nanosheets (CNSs): vertically oriented sheets of few-layered graphene. In addition, a phenomenological model was developed for g-CNTs. By studying variations of graphene-CNT hybrid nanomaterials by Raman spectroscopy, a linear trend was discovered between their mean crystallite size and electrochemical capacitance. Finally, a new method for the calculation of nanomaterial surface area, more accurate than the standard BET technique, was created based on atomic layer deposition (ALD) of titanium oxide (TiO2).

Crystallographic and magnetic identification of secondary phase in orientated Bi 5Fe 0.5Co 0.5Ti 3O 15 ceramics

The fabrication of highly-oriented polycrystalline ceramics of Bi 5Fe 0.5Co 0.5Ti 3O 15, prepared via molten salt synthesis and uniaxial pressing of high aspect ratio platelets is reported. Electron backscatter images show a secondary phase within the ceramic which is rich in cobalt and iron. The concentration of the secondary phase obtained from scanning electron microscopy is estimated at less than 2% by volume, below the detection limit of x-ray diffraction (XRD). The samples were characterized by x-ray diffraction, polarization-electric field measurements, superconducting quantum interference device as a function of sample orientation and vibrating sample magnetometry as a function of temperature. It is inferred from the data that the observed ferromagnetic response is dominated by the secondary phase. This work highlights the importance of rigorous materials characterisation in the study of multiferroics as small amounts of secondary phase, below the limit of XRD, can lead to false conclusions.

Magnetic and petrographic properties of ODP Site 120-747 (Table 1)

Carbonate sediments from the Kerguelen Plateau (ODP Leg 120) of Eocene to Pliocene age were investigated with rock magnetic, petrographic and geochemical methods to determine the carriers of remanent magnetization. Magnetic methods showed that the major magnetic minerals were titanomagnetites slightly larger than single domain particles. Submicrometre to micrometre-size grains of titanomagnetite were identified as inclusions in volcanic glass particles or as crystals in lithic clasts. Volcanic fallout ash particles formed the major fraction of the magnetic extract from each sediment sample. Three groups of volcanic ashes were identified: trachytic ashes, basaltic ashes with sideromelane and tachylite shards, and palagonitic ashes. These three groups could be equally well defined based on their magnetic hysteresis properties and alternating field demagnetization curves. The highest coercivities of all samples were found for the tachylite, due to the submicrometre-size titanomagnetite inclusions in the matrix. Trachytic ashes had intermediate magnetic properties between the single-domain-type tachylites and the palagonitic (altered) basaltic ashes with low coercivities. Samples which contained mixtures of these different volcanic ashes could be distinguished from the three types of ashes based on their magnetic characteristics. There was neither evidence of biogenic magnetofossils in the transmission electron micrographs nor did we find magnetic particles derived from continental Antarctica. The presence of dispersed volcanic fallout ashes between visible ash layers suggests continuous explosive volcanic activity on the Kerguelen Plateau in the South Indian Ocean since the early Eocene. The continuous fallout of volcanic ash from explosive volcanism on the Kerguelen Archipelago is the source of the magnetic particles and thus responsible for the magnetostratigraphy of the nannofossil oozes drilled during Leg 120.