The ability to form multiple component heterostructures of two-dimensional materials promises to provide access to hybrid materials with tunable properties different from those of the bulk materials or two-dimensional constituents. By taking advantage of the unique properties of different constituents, numerous applications are possible for which none of the individual components are viable. The synthesis of multiple component heterostructures, however, is nontrivial, relying on either the cleaving and stacking of bulk materials in a “scotch tape” type technique or finding coincidentally favorable growth conditions which allow layers to be grown epitaxially on each other in any order. In addition, alloying of miscible materials occurs when the modulation wavelength is small. These synthetic challenges have limited the ability of scientists to fully utilize the potential of multiple component heterostructures. An alternative synthetic route to multiple component heterostructures may be found through expansion of the modulated elemental reactant technique which allows access to metastable products, known as ferecrystals, which are otherwise inaccessible. This work focuses on the expansion of the modulated elemental reactants technique for the formation of ferecrystals containing multiple constituents. As a starting point, the synthesis of the first alloy ferecrystals (SnSe)1.16-1.09([NbxMo1-x]Se2) will be discussed. The structural and electrical characterization of these compounds will then be used to determine the intermixing of the first three component ferecrystal heterojunction ([SnSe]1+δ)([{MoxNb1-x}Se2]1+γ)([SnSe]1+δ)({NbyMo1-y}Se2). Then, by synthesizing ([SnSe]1+δ)m([{MoxNb1-x}Se2]1+γ)1([SnSe]1+δ)m({NbxMo1-x}Se2)1 (m = 0 - 4) compounds with increasing thicknesses of SnSe, the interdiffusion of miscible constituents in ferecrystals will be studied. In addition, by comparison of the ([SnSe]1+δ)m ([{MoxNb1-x}Se2]1+γ)1([SnSe]1+δ)m({NbxMo1-x}Se2)1 (m = 0 - 4) compounds to the ([SnSe]1+δ)m(NbSe2)1 (m = 1 - 8) compounds the electronic interactions of the MoSe2 and NbSe2 layers will be determined. Finally, the effects of different alloying strategies and the interdiffusion of miscible constituents will be further examined by the synthesis of ordered ([SnSe]1.15)1([TaxV1-x]Se2)1([SnSe]1.15)1([VyTa1-y]Se2)1 and ([SnSe]1+δ) ([TaxV1-x]Se2) compounds with the effect of isoelectric doping on the charge density wave transition in (SnSe)1.15(VSe2) also being explored. This work contains previously published and unpublished co-authored material.

Exploring the properties of layered materials as a function of thickness has largely been limited to semiconducting materials as thin layers of metallic materials tend to oxidize readily in atmosphere. This makes it challenging to further understand properties such as superconductivity and charge density waves as a function of layer thickness that are unique to metallic compounds. This dissertation discusses a set of materials that use the modulated elemental reactants technique to isolate 1 to 3 layers of VSe2 in a superlattice in order to understand the role of adjacent layers and VSe2 thickness on the charge density wave in VSe2. The modulated elemental reactants technique was performed on a custom built physical vapor deposition to prepare designed precursors that upon annealing will self assemble into the desired heterostructure. First, a series of (PbSe)1+δ(VSe2)n for n = 1 – 3 were synthesized to explore if the charge density wave enhancement in the isovalent (SnSe)1.15VSe2 was unique to this particular heterostructure. Electrical resistivity measurements show a large change in resistivity compared to room temperature resistivity for the n = 1 heterostructure. The overall change in resistivity was larger than what was observed in the analogous SnSe heterostructure. v A second study was conducted on (BiSe)1+δVSe2 to further understand the effect of charge transfer on the charge density wave of VSe2. It was reported that BiSe forms a distorted rocksalt layer with antiphase boundaries. The resulting electrical resistivity showed a severely dampened charge density wave when compared to both analogous SnSe and PbSe containing heterostructures but was similar to bulk. Finally, (SnSe2)1+δVSe2 was prepared to further isolate the VSe2 layers and explore interfacial effects on the charge density wave by switching from a distorted rocksalt structure to 1T-SnSe2. SnSe2 is semiconductor that is used to prevent adjacent VSe2 layers from coupling and thereby enhancing the quasi two-dimensionality of the VSe2 layer. Electrical characterization shows behavior similar to that of SnSe and PbSe containing heterostructures. However, structural characterization shows the presence of a SnSe impurity that is likely influencing the overall temperature dependent resistivity. This dissertation includes previously published and unpublished co-authored materials.

Solid state synthesis of layered, rotationally disordered intergrowths consisting of rock salt (MX) and hexagonal (TX2) constituents in various sequences [(MX)1+δ]m[TX2]n is carried out by developing structural and compositional prototypes of the desired product, using fine control of the elemental reactants and then annealing at low temperature to facilitate self-assembly. (M = Sn, La, Eu; T = V, Mo.) The remarkable rotational disorder in these systems - in contrast to traditional misfits - and their proven applications in thermal, electrical and thermoelectric disciplines make them a useful group of materials for demonstrating control of reaction pathways of solid state reactions using low temperatures and short times. The synthesized materials are structurally characterized using X-ray diffraction (XRD), X-ray reflectivity (XRR), and Scanning Transmission Electron Microscopy (STEM). Electrical characterization is carried out on patterned samples using the Van der Pauw method of resistivity and the Hall effect method. Composition of the samples is determined using wavelength dispersive electron probe microanalysis (EPMA). Time domain thermoreflectance is used to determine the cross plane thermal conductivity. The family of [(SnSe)1.05]m(MoSe2)n (m = n = 1, 2, 3, 4), which possess the same composition but different unit cell thicknesses, shows that there is no correlation between c-axis unit cell thickness and cross plane thermal conductivity. The family of structural isomers [(SnSe)1.05]4[MoSe2]4, [(SnSe)1.05]3[MoSe2]3[(SnSe)1.05]1[MoSe2]1, [(SnSe)1.05]3[MoSe2]2[(SnSe)1.05]1[MoSe2]2, [(SnSe)1.05]2[MoSe2]3[(SnSe)1.05]2[MoSe2]1,[(SnSe)1.05]2[MoSe2]1[(SnSe)1.05]1[MoSe2]2[(SnSe)1.05]1[MoSe2]1 and [(SnSe)1.05]2[MoSe2]2[(SnSe)1.05]1[MoSe2]1[(SnSe)1.05]1[MoSe2]1 have the same c-axis lattice thickness and absolute composition but have different numbers of [(SnSe)1.05]/[MoSe2] interfaces. Thermal conductivity studies carried out on these showed no correlation with the interface density. (LaSe1-x)1.17(VSe2-y)n (n = 2, 3, 4) feature a family of compounds that self-assemble at higher than usual temperatures. They form non-stoichiometric moieties with unique structural proclivities including La vacancies and V interstitials compared to other ferecrystals or previous misfits. The designable electrical properties show evidence of charge transfer. (EuSe)1+δ(VSe2)n (n = 1, 2, 3) is a family of materials that complements the investigation of Ln-based ferecrystals. They show evidence of multiple M oxidation states. These compounds highlight the use of rational design of structure and composition to tune properties. This dissertation includes previously published and unpublished co-authored material. / 10000-01-01

The controlled and targeted synthesis of new solid materials is still a challenge difficult to overcome. Slow diffusion rates and long diffusion lengths require long reaction times and high synthesis temperatures, resulting in limited control over the reaction pathway. The Modulated Elemental Reactants (MER) method uses compositionally modulated precursors with atomically thin elemental layers that form amorphous alloys upon annealing while maintaining composition modulation. In this amorphous intermediate, nucleation, not diffusion, control the formation of the product, enabling kinetic control of the reaction, and the synthesis of new metastable compounds, heterostructures with designed nanoarchitecture, and thin films with a high degree of texturing. This dissertation uses experimental and computational methods to investigate compounds synthesized by the MER method. Firth, the MER method is used to synthesize ferromagnetic CuCr2Se4 films that show a large degree of crystallographic alignment and interesting magnetic properties such as temperature-dependent easy axes and negative magnetoresistivity. The second part investigates ferecrystals, rotationally disordered members of the misfit layer compounds family. The MER method’s ability to control the nanoarchitecture of the products is used to synthesize a new type of structural isomers, allowing for the synthesis of thousands of ternary compounds using the same elements. Experimental methods are also used to monitor the formation of ferecrystalline compounds using [(SnSe)1+δ][VSe2] as a model system. Despite the vast number of compounds available, however, explaining the properties and stability of ferecrystals is still in its infancy. In the last part of this dissertation, ab initio methods are employed to investigate the components in our ferecrystals. Specifically, isolated layers of VSe2 with its structural distortions due to a charge density wave, SnSe with its thickness-dependent structures, and BiSe with its flexible lattice and anti-phase boundaries are investigated to complement experimental results. Some properties, such as the structural distortion in VSe2 and the different stabilities of BiSe layers, can be explained very well using this simplified model, but others, such as the structure of SnSe layers, are not exclusively determined by their dimensionality, underlining the complex nature of the interactions in ferecrystals. This dissertation includes previously published and unpublished co-authored material.

Die untersuchten Ferekristalle sind neuartige Verwachsungs-Schichtverbindungen aus m Monolagen von Niobdiselenid (NbSe2), die wiederholt mit n atomaren Bilagen von Bleiselenid (PbSe) oder Zinnselenid (SnSe) geschichtet sind. Niobdiselenid als Volumenmaterial besitzt eine Schichtstruktur und ist ein Supraleiter. Aufgrund ihrer gezielt einstellbaren atomar geschichteten Struktur können Ferekristalle als Modellsysteme für geschichtete Supraleiter dienen. In dieser Arbeit werden ihre strukturellen und elektrischen Eigenschaften untersucht. Mittels Transmissionselektronenmikroskopie wird ihre turbostratisch ungeordnete, nanokristalline Struktur nachgewiesen. Die atomare Struktur innerhalb der einzelnen Schichten ist ähnlich wie in den Volumenmaterialien NbSe2, PbSe und SnSe, wobei die kristallographischen c-Achsen parallel zur Stapelrichtung der Ferekristalle zeigen. Eine quantitative Analyse unter Verwendung eines Zwei-Schicht-Modells für den spezifischen Widerstand, Hall-Koeffizienten und Magnetwiderstand liefert ähnliche Ladungsträgersorten, -dichten und –beweglichkeiten in den NbSe2-Schichten, wie sie für isolierte Einzellagen von NbSe2 berichtet wurden. Diese unterscheiden sich von denen des Volumenmaterials NbSe2. Erstmals wurde ein Übergang der Ferekristalle in den supraleitenden Zustand nachgewiesen. Die Sprungtemperaturen sind dabei in etwa auf die Hälfte der Sprungtemperaturen der jeweiligen nicht turbostratisch ungeordneten Misfit-Schichtverbindungen reduziert. Diese Reduzierung kann der turbostratischen Unordnung der Ferekristalle zugeordnet werden. Das Verhältnis zwischen der schichtsenkrechten Ginzburg-Landau-Kohärenzlänge und dem Abstand zwischen den supraleitenden Schichten ist bei den Ferekristallen kleiner als bei den nicht ungeordneten Misfit-Schichtverbindungen, was Ferekristalle zu vielversprechenden Kandidaten für (quasi-)zweidimensionale Supraleiter macht. / The investigated ferecrystals are novel layered intergrowth compounds consisting of m monolayers of niobium diselenide (NbSe2) stacked repeatedly with n atomic bilayers of lead selenide (PbSe) or tin selenide (SnSe). Bulk NbSe2 is a layered compound showing superconductivity. Due to their artificially atomic-scale layered structure, which is tunable on the atomic scale, ferecrystals can serve as model systems for layered superconductors. In this study, their structural and electrical properties are investigated. Using transmission electron microscopy their turbostratically disordered, nanocrystalline structure is revealed. The atomic structure within the individual layers is similar as for bulk NbSe2, PbSe and SnSe, with the crystallographic c-axes parallel to the stacking direction in the ferecrystals. A quantitative analysis using a two-layer model fit for the electrical resistivity, Hall coefficient and magnetoresistance yields a similar carrier type, density and mobility in the NbSe2 layers as reported for isolated NbSe2 monolayers. These values differ from those of bulk NbSe2. For the first time, a normal-to-superconducting transition has been detected in ferecrystals. The transition temperatures of the ferecrystals are reduced to about a half of those of analogous non-disordered misfit layer compounds. This reduction in transition temperature can be correlated to the turbostratic disorder in ferecrystals. The ratio between the cross-plane Ginzburg-Landau coherence length and the cross-plane distance between the NbSe2 layers for the ferecrystals is lower than for non-disordered misfit layer compounds, making ferecrystals promising candidates for (quasi-)two-dimensional superconductors.