O presente trabalho trata do estudo sistemático acerca de supercondutividade em soluções sólidas de monoboretos formados por nióbio e zircônio. Amostras policristalinas de Nb1-xZrxB, com 0 ≤ x ≤ 0,2, de boretos ricos em nióbio Nb1-zBz e ricos em boro NbB1+δ foram preparadas através de um forno a arco elétrico sobre uma base de Cu refrigerada e sob atmosfera de Argônio de alta pureza, ao misturar os elementos Nb em lâminas, flocos de B e pedaços de Zr metálico, com alta pureza. Adicionalmente, algumas amostras foram introduzidas em uma ampola de quartzo com pressão parcial de Argônio e tratadas termicamente à temperatura de 1100 °C durante 150 h. As caracterizações das propriedades físicas dessas amostras foram conduzidas através de medidas de difração de raios-X, dependência com a temperatura e campos magnéticos da magnetização dc M(T, H), resistência elétrica R(T, H) e calor específico Cp(T, H). Também foram obtidas micrografias de algumas amostras, ao utilizar microscopia eletrônica de varredura (MEV). Pequenas perdas de massa foram observadas em todas as amostras como fundidas, ocasionando a formação de soluções sólidas do tipo Nb-B (Nbss) e/ou Nb1-yZry como fases secundárias, apresentando pequenas frações volumétricas. O limite de solubilidade de Zr na matriz NbB é sugerido estar próximo à concentração de 10 %at. Zr. Com exceção do composto rico em boro NbB1,2, todas amostras, como fundidas ou tratadas termicamente, apresentaram propriedades supercondutoras, sendo que o composto estequiométrico NbB exibe uma temperatura crítica supercondutora Tc ~ 9 K, que por sua vez é muito similar àquela conhecida para o nióbio elementar, com Tc ~ 9,2 K. Algumas inconsistências surgem caso a fase ortorrômbica Nb1-xZrxB seja considerada supercondutora, apesar de ser confirmada como a fase majoritária nos padrões de difração de raios-X dessas amostras. Tal fato é sugerido pela enorme diferença entre as frações Meissner nas curvas de susceptibilidade magnética χ(T) de amostras volumétricas e pulverizadas, baixos valores do salto no calor específico em comparação com o previsto pela teoria BCS com acoplamento fraco e a ausência de supercondutividade em um espécime (NbB1,2) no qual a fase NbB é preponderante. Deste modo, os resultados aqui discutidos sugerem que o composto NbB não é supercondutor, em oposição ao que fora reportado previamente, e que as propriedades supercondutoras da solução sólida Nb1-xZrxB são governadas pela presença de fases secundárias supercondutoras do tipo Nbss/Nb1-yZry. / This work is presented as a systematically study regarding superconductivity in niobium-zirconium monoborides and their solid solutions. Polycrystalline samples of Nb1-xZrxB, with 0 ≤ x ≤ 0.2, niobium rich Nb1-zBz and boron rich NbB1+δ borides were arc-melted on a water-cooled Cu hearth under high purity Argon atmosphere, by mixing high purity Nb foils, B flakes and metallic Zr pieces. Some arc-melted samples were placed in a quartz ampoule with Argon partial pressure and heat treated at 1100 °C during 150 h. The samples were characterized by means of X-ray diffraction XRD, temperature and magnetic field dependence of dc magnetization M(T, H), electrical resistance R(T, H) and heat capacity Cp(T, H). Micrographs of few samples were also obtained by scanning electron microscopy (SEM). Small weight losses were observed in all as-cast samples, leading to the formation of Nb-B (or Nbss) and/or Nb1-yZry solid solutions as secondary phases, all of them with low volume fractions. The solubility limit of Zr within Nb1-xZrxB lattice was found to be close to 10 at. % Zr. Except the boron-rich compound NbB1.2, every sample, as-cast or heat treated, exhibited superconducting properties below Tc ~ 9 K, a temperature very close to that known for pure, superconducting niobium of Tc ~ 9.2 K. Some internal discrepancies within the obtained data arise when the orthorhombic phase Nb1-xZrxB is assumed to be superconducting, despite it being the majority phase in the XRD patterns of the samples. This is suggested by a huge difference between the Meissner fraction in magnetic susceptibility χ(T) curves of bulk and powdered samples, small values of specific heat jumps in comparison with the expected within the weak-coupling BCS theory and lack of superconductivity in a specimen (NbB1.2) in which the main phase is NbB. By combining all the experimental results obtained in over two dozen samples studied, we argue that the NbB compound is not a superconducting material, as opposed to what has been reported previously. Also, the superconducting properties found in Nb1-xZrxB alloys are then associated with the occurrence of extra phases Nbss and/or Nb1-yZry which are present in all superconducting samples.

Controlling the electronic structure and requisite charge transfer at and across interfaces is a grand challenge of materials science. Despite decades of research and numerous successes in the fields microelectronics and photovoltaics much work remains to be done. In many applications, whether they be in microelectronics, photovoltaics or display technology there is a demand for multiple functions at a single interface. Historically, existent materials were either discarded as an option due to known properties or tested with some application based figure of merit in mind. Following this, the quality of the material and/or the preparation of the surface/interface to which the material would be deposited was optimized. As the microelectronics and photovoltaics industries have matured, continued progress (faster, lower power transistors and more efficient, cheaper, abundant solar cells) will require new materials (possibly not previously existent) that are fundamentally better for their application than their highly optimized existent counter parts. The manifestation of this has been seen in the microelectronics field with introduction of hafnium silicates to replace silica (which had previously been monumentally successful) as the gate dielectrics for the most advanced transistors. Continued progress in efficient, cheap, abundant photovoltaics will require similar advances. Advances will be needed in the area of new abundant absorbers that can be deposited cheaply which result in materials with high efficiencies. In addition, selective contacts capable of extracting charge from efficient absorbers with low ohmic losses and low recombination rates will be needed. Presented here are two approaches to the multifunctional interface problem, first the use of amorphous alloys that open up the accessible composition space of thin films significantly and second the use of bilayers that loosen the requirements of a single film at an interface.

The supramolecular chemistry and crystal structures of four Bis(imidazolium 2,4,6-pyridinetricarboxylate) metal(II)dihydrate complexes, where M=Co2+, Ni2+, Cu2+, or Zn2+ (1-4, respectively), are reported. These complexes serve as supramolecular building blocks that self-assemble when crystallized to generate a single, well defined structure in the solid state. 2,4,6-Pyridinetricarboxylate anions and imidazolium cations form strong ionic hydrogen bonds that dominate crystal packing in compounds 1-4 by forming three-dimensional (3-D) networks of molecules. These networks consist of hydrogen-bonded layers of molecules defined by N-H…O interactions that are joined in the third dimension by O-H…O interactions. This 3-D network provides a supramolecular framework with which to control and predict molecular packing by design for engineering the structures of crystals. Furthermore, compounds 1-4 create a robust organic host lattice that accommodates a range of different transition metals without significantly altering the molecular packing. Growth of crystals from solutions that contain two or more different metal complexes results in the formation of mixed crystals in which the different metal complexes are incorporated into the crystalline lattice in the same relative molar ratio present in solution. Epitaxial growth of crystals involving deposition of one metal complex on the surface of a seed crystal that contains a second metal complex generates composite crystals in which the different metal complexes are segregated into different regions of the crystals. Compounds 1-4 form crystalline solids that represent a new class of modular materials in which the organic ligands serve as a structural component that defines a single packing arrangement that persists over a range of structures, and in which the metal serves as an interchangeable component with which vary the physical properties of material.

Thesis. 1978. Ph.D.--Massachusetts Institute of Technology. Dept. of Physics. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Bibliography: leaves 225-239. / Ph.D.

Atomically thin two-dimensional materials, such as graphene and semiconductor transition metal dichalcogenides (TMDCs), exhibit remarkable and desirable optical and electronic properties. This dissertation focuses on the excitonic properties of monolayer TMDCs taken first in isolation and then in contact with another material. We begin with a study of the exciton binding energy in two monolayer TMDCs, WS₂ and MoS₂. We observe excited states of the exciton by two different optical spectroscopy techniques: reflectance contrast and photoluminescence excitation (PLE) spectroscopy. We fit a hydrogenic model to the energies associated with the excited states and infer a binding energy, which is an order of magnitude higher than the bulk material. In the second half of this work, we study two types of two-dimensional vertical heterostructures. First, we investigate heterostructures composed of monolayer WS₂ partially capped with graphene one to four layers thick. Using reflectance contrast to measure the spectral broadening of the excitonic features, we measure the decrease in the coherence lifetime of the exciton in WS₂ due to charge and energy transfer when in contact with graphene. We then compare our results with the exciton lifetime in MoS₂/WS₂ and MoSe₂/WSe₂ heterostructures. In TMDC/TMDC heterostructures, the decrease in exciton lifetime is twice that in WS₂/graphene heterostructures and due predominantly to charge transfer between the layers. Finally, we probe the band alignment in MoS₂/WS₂ heterostructures using scanning tunneling microscopy (STM) and spectroscopy (STS).We confirm the monolayer band gaps and the predicted type II band alignment in the heterostructure. Drawing from all the research presented, we arrive at a favorable conclusion about the viability of TMDC based devices.

Neste trabalho, propusemos um método autoconsistente de espaço direto para o calculo de estrutura eletrônica. O método se baseia no formalismo LNTO -ASA na representação fortemente ligada (light-binding) e no método de recorrência aliado ao terminador de Beer & Pettifor. Neste método o custo computacional cresce linearmente com o numero de átomos não equivalentes na cela primitiva sendo, portanto, ideal para tratar sistemas complexos que não apresentam periodicidade ou que possuem um grande numero de átomos não equivalentes por cela primitiva. Podemos, por exemplo, estudar de forma autoconsistente a estrutura eletrônica das vizinhanças de uma impureza com um custo computacional apenas cinco ou seis vezes maior que o de um metal puro. O método aqui proposto tem a vantagem adicional de ser fisicamente transparente. Para avaliarmos a eficácia do método, comparamos nossos resultados autoconsistentes obtidos para a liga cristalina ZR IND.2FE com os resultados obtidos pelo processo autoconsistente de espaço reciproco. O material em questão tem uma estrutura cristalina simples com seis átomos por cela primitiva e o calculo de estrutura eletrônica pode ser resolvido por métodos usuais de espaço reciproco. A presença do FE com sua banda d estreita e com uma alta densidade de estados no nível de Fermi tornara o processo de convergência não trivial. / In this work we have proposed a first-principles selfconsistent method which allows us to perform electronic structure calculations in real space. The scheme, based on the LNTO ASA formalism and the Recursion Method, enables us to evaluate the electronic structures of complex systems, with good degree of precision and low computational costs. Using Zr 2 Fe as test case, we compare our real-space results with those obtained in reciprocal space using the standard LMTO - ASA procedure. The agreement is very good showing the efficiency of the real-space approach. We note that the real-space method developed here presents advantages for the evaluation of local properties and can be applied for non-periodic systems. For instance, we can describe the electronic structure in a large region around a substitutional impurity with very little cost. lf we consider five shells around the impurity the cost in real-space will be about seven times the cost of the calculation for a mono atomic system.

A central concern within the field of molecular magnetism has been the elucidation of magneto-structural correlations. This thesis describes a variety of systems and endeavours to study the relationship between structure and magnetic properties in these systems. The first body of work (chapters 2 and 3) studies CrIII dimers, with the metal centres displaying a dialkoxo bridging moiety and latterly an additional carboxylate bridge to direct the synthesis of ferromagnetic analogues. The second section of work (chapters 4‐6) moves forward to the study of larger, heterometallic 3d‐3d compounds, through the synthesis of a large family of Anderson type MIII 2MII 5 wheels and a subsequent family of (VIVO)2MII 5 wheels. Chapter 2 describes a series of di‐alkoxo bridged Cr(III) dimers, synthesised using the pyridine alcohol ligands 2‐pyridinemethanol (hmpH) and 2‐pyridineethanol (hepH) as well as 2‐picolinic acid (picH). The structures fall into four general categories and are of formula: [Cr2(OMe)2(pic)4], [Cr2(hmp)2(pic)2X2] (where X = Cl, Br), [Cr2(L)2Cl4(A)2] (where L = hmp, A = H2O; L = hmp, A = pyridine; L = hmp, A = 4‐picoline; L = hep, A = H2O), and [Cr(hmp)(hmpH)Cl2. Magnetic studies show relatively weak antiferromagnetic exchange interactions between the Cr(III) centres and DFT calculations are used to develop magneto‐structural correlations, showing that the magnitude and sign of the J value is strongly dependent upon the orientation of the dihedral angle formed between the bridging Cr2O2 plane and the O-R vector of the bridging group, and the Cr-O-Cr-O dihedral angle. Chapter 3 builds on the work from the previous chapter with discussion of a large family of chromium(III) dimers, synthesised using a combination of carboxylate and diethanolamine type ligands. The compounds have the general formula [Cr2(R1‐deaH)2(O2CR2)Cl2]Cl where R1 = Me and R2 = H, Me, CMe3, Ph, 3,5‐(Cl)2Ph, (Me)5Ph, R1 = Et and R2 = H, Ph. The compound [Cr2(Me‐deaH)2Cl4] was also synthesised in order to study the effect of removing/adding the carboxylate bridge to the observed magnetic behaviour. Magnetic studies reveal ferromagnetic exchange interactions between the Cr(III) centres in the carboxylate bridged family with coupling constants in the range +0.37 < J < +8.02 cm‐1. Removal of the carboxylate to produce the dialkoxide‐bridged compound results in antiferromagnetic exchange between the Cr(III) ions. DFT calculations to further develop the magneto-structural correlations reveal the ferromagnetic exchange is the result of an orbital counter-complementarity effect occurring upon introduction of the bridging carboxylate. Chapter 4 reports a family of heterometallic Anderson‐type 'wheels' of general formula [MIII 2MII 5(hmp)12](ClO4)4 (where MIII = Cr or Al and MII = Ni or Zn giving [Cr2Ni5], [Cr2Zn5], [Al2Ni5] and [Al2Zn5]; hmpH = 2‐pyridinemethanol) synthesised solvothermally. The metallic skeleton describes a centred hexagon with the MIII sites disordered around the outer wheel. The structural disorder is characterised via single crystal X‐ray crystallography, 1‐3D 1H and 13C solution‐state NMR spectroscopy of the diamagnetic analogue, and solid‐state 27Al MAS NMR spectroscopy of the Al containing analogues. Alongside ESI mass spectrometry, these techniques show that structure is retained in solution, and that the disorder is present in both the solution and solid‐state. Solid‐state dc susceptibility and magnetisation measurements on [Cr2Zn5] and [Al2Ni5] reveal the Cr‐Cr and Ni‐Ni exchange interactions to be JCr‐Cr = ‐1 cm‐1 and JNi‐Ni,r = ‐5 cm‐1, JNi‐Ni,c = 10 cm‐1. Fixing these values allows us to extract JCr‐Ni,r = ‐1.2 cm‐1, JCr‐Ni,c = 2.6 cm‐1, the exchange between adjacent Ni and Cr ions on the ring is antiferromagnetic and between Cr ions on the ring and the central Ni ion is ferromagnetic. Chapter 5 focusses on planar molecules, espanding the family of heterometallic Anderson‐type 'wheels' discussed in chapter 4 to include MIII = Cr, Al and MII = Co, Fe, Mn, Cu, affording five new species of formulae [Cr2Co5(hmp)12](ClO4)4, [Cr2Fe5(hmp)12](ClO4)4, [Cr2Mn5(hmp)12](ClO4)4, [Cr2Cu5(hmp)12](ClO4)2(NO3)2 and [Al2Co5(hmp)12](ClO4)4. As per previous family members, the two MIII sites are disordered around the outer wheel, with the exception of [Cr2Cu5] where the the CuII sites are localised. A structurally related, but enlarged planar disc possessing a [MIII 6MII] hexagon capped on each edge by a CuII ion is also reported, which is formed only when MIII = Al and MII = Cu. In [AlIII 6CuII 7(OH)12(hmp)12](ClO4)6(NO3)2 the Anderson moiety contains a central, (symmetry‐imposed) octahedral CuII ion surrounded by a wheel of AlIII ions. Solid‐state dc susceptibility and magnetisation measurements reveal the presence of competing exchange interactions in the Anderson wheels family, and weak antiferromagnetic exchange between the CuII ions in [Al6Cu7]. Chapter 6 describes two heterometallic wheels of formula [(VIVO)2MII 5(hmp)10Cl2](ClO4)2∙2MeOH (where MII = Ni or Co) displaying the same Anderson‐type structure as seen in chapters 4 and 5, however the use of the vanadyl moiety has the effect of removing the disorder, with the two vanadyl ions sitting on opposing sides of the ring. The magnetic properties of both show competing antiferroand ferromagnetic interactions.

Two-dimensional materials such as graphene, boron nitride and transition metal dichalcogenides have attracted significant research interest due to their unique optoelectronic properties. Transition metal dichalcogenides (TMDCs) are a family of two-dimensional semiconductors which exhibit strong light-matter interaction and show great promise for applications ranging from more efficient LEDs to quantum computing. One of the most intriguing qualities of TMDCs is their ability to be stacked on top of one another to tailor devices with specific properties and exploit interlayer phenomena to develop new characteristics. One such interlayer interaction is the generation of charge transfer excitons which span the interface between two different TMDC monolayers. This work aims to study the intrinsic optical properties of charge transfer excitons in TMDC heterostructures. We must first start by investigating methods to protect and isolate our sample of interest from its chemical and electrostatic environment. We demonstrate that near intrinsic photoluminescence (PL) linewidth and exciton emission homogeneity from monolayer TMDCs can be achieved using a combination of BN encapsulation and passivation of substrate hydroxyl groups. Next, we develop clean stacking techniques and incorporate low defect density source crystals to maintain intrinsic properties and ensure a sufficiently high quality heterostructure interface to study characteristics of charge transfer excitons in 2D TDMCs. Strong photoluminescence emission from charge transfer excitons is realized and is shown to persist to room temperature. Charge transfer exciton lifetime is measured to be two orders of magnitude longer than previously reported. Using these high quality heterostructures, we study the behavior of charge transfer excitons under high excitation density. We observe the dissociation of charge transfer excitons into spatially separated electron-hole plasmas under optical excitation. We then probe properties of charge transfer exciton emission enhancement due resonant coupling to surface plasmon modes of gold nanorods.

E. Michael Gyorgy. / "May 25, 1953." "This report is based on a thesis submitted to the Department of Physics ... for the degree of Doctor of Philosophy." / Bibliography: p. 33-34. / Army Signal Corps Contract DA36-039 sc-100 Project 8-102B-0 Dept. of the Army Project 3-99-10-022

The main subject of this thesis is the study of electronic and magnetic properties of materials containing 3d transition metal atoms. Our motivation stems mainly from the modern fields of spintronic computing and solar energy conversion. The two primary goals of this work are to determine (i) why certain transition metal impurities in certain semiconductors can induce magnetic properties suitable for spintronic computing applications, and (ii) how transition metal impurities can be used to modify the electronic band gaps of semiconductors and insulators in ways useful for harnessing solar energy and for other applications. To accomplish these goals, we have applied both experimental and theoretical tools. We studied high quality materials prepared by advanced synthesis techniques using x-ray spectroscopy methods at synchrotron light sources. The results of these experiments were interpreted using a variety of theoretical techniques, primarily using computational software developed as part of this thesis and discussed herein. Regarding the study of introducing transition metal impurities into semiconductors to induce magnetic properties, we first developed and demonstrated a method to determine the location of impurity atoms within the host semiconductor lattice. This allowed to us explain the presence and absence of ferromagnetism in samples prepared under only slightly different synthesis conditions, which helped to address some long--standing issues in the spintronics field. We then studied an advanced and promising material -- indium (III) oxide with iron impurities -- to determine how magnetic ordering was maintained up to room temperatures. Our techniques unveiled that a portion of the iron atoms were coupled to oxygen vacancies in the material to create conditions which propelled the observed magnetism. This finding confirmed some earlier theoretical predictions by others in the field. For the study of electronic band gap modifications in semiconductors and insulators via the incorporation of transition metal atoms, we investigated a wide range of materials synthesized using different techniques. Again, we used experimental techniques to determine the location of impurity atoms within the materials, and used this to understand how band gaps were modified upon the introduction of the impurities. For Ti implantation into SiO2, Ni substitution into ZnO, and a new material, MnNCN, we have determined the electronic band gaps and used our techniques to explain how the values for the gaps arise. Finally, an additional outcome of this thesis work is a software program capable of simulating x-ray spectra using various advanced quantum models. We rewrote and built upon powerful existing programs and applied the result to the above studies. Our software was further applied in a collaborative effort with other researchers at the Canadian Light Source to study the differences in two experimental techniques for measuring x-ray absorption: partial and inverse partial fluorescence yields. By using the proper absorption and scattering formalisms to simulate each technique, we were able to explain the differences between the experimental spectra obtained from each. We explain fluorescence yield deviations using an analysis based on the spin configuration of different states, suggesting that the technique can be further extended as a quantitative spin state probe. These results could have significant implications for the field of soft x-ray absorption spectroscopy.