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Radio frequency (RF) cavities are the foundational infrastructure which facilitates much of the fundamental research conducted in high energy particle physics. These RF cavities utilize their unique shape to produce resonant electromagnetic fields used to accelerate charged particles. Beside their core role in fundamental physics research, RF cavities have found application in other disciplines including material science, chemistry and biology which take advantage of their unique light sources. Industry has been keen on taking advantage of accelerator technology for a multitude of applications. Particle accelerators like the one found at Jefferson Lab’s Continuous Electron Beam Accelerator Facility must produce stable beams of high energy particles which is an incredibly costly endeavor to pursue. With the gargantuan size of these facilities, the cost of high-quality beam production is a matter of great importance. The quest to find highly efficient RF cavities has resulted in the widespread use of superconducting radio frequency (SRF) cavities which are the most efficient resonators that exploit a superconductor’s incredibly low AC surface resistance. While metals like Cu are up to the demanding job of RF cavity particle acceleration, their efficiency at transferring RF power to the particle beam is low when they are compared with SRF Nb cavities. Nb is the standard material for all SRF cavity technology particularly for its reproducibly low surface resistance, comparatively high transition temperature and thermodynamic critical field. Using superconducting Nb is not without its drawbacks. Keeping hundreds of Nb cavities in their superconducting state under extreme RF conditions is quite a daunting task. It requires the normal state not nucleate during operation. This is achieved by producing high-quality cavities with as few defects and impurities as possible while also keeping the cavities at low temperature, usually 2K. Again, due to the sheer scale of the facilities, hundred million-dollar cryogenic plants are required to handle the heat loads during SRF cavity operation. This means even small increases in maximum accelerating gradients or decrease in cavity surface resistance results in a sizably reduced operation cost. Considerable effort has been put forth to increase the efficiency of Nb cavities toward and even beyond the theoretical maximum accelerating gradients and quality factor for a clean superconductor. Recently, a new method to produce high quality factor cavities has emerged that involves nitrogen doping the cavity. The mechanism by which N doping causes the improvement is still not well understood, but the experimental research described in this dissertation shines some light into the mechanisms behind such a drastic improvement. These insights are universal for all superconductors and may prove useful for SRF cavities beyond Nb. With Nb approaching its fundamental limits, new materials are being proposed to increase the performance of future SRF cavities which MgB2 finds itself among. MgB2 is a two-band superconductor that possesses many properties that are very attractive for the next generation of SRF cavities. One of the most important properties is MgB2’s comparatively large critical temperature which in part predicts it will have a lower surface resistance than Nb at higher operating temperatures. Such behavior of MgB2 may unlock the possibility of using cryocoolers instead of costly liquid helium plants for large scale industrial use. This dissertation starts with an introduction to superconductivity, its theory, and application to SRF cavities as well as the open questions that can be addressed in Nb and the next generation of SRF materials. A description of the experimental techniques of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy is presented. Our experimental investigation into Nb SRF cavity cutouts starts with a discussion of the material’s limitations for SRF applications with an emphasis on the proximity effect which arises at the surface of this material due to its myriad of naturally forming oxides. The results of our scanning tunneling microscopy measurements for typically prepared Nb and nitrogen doped Nb follows and comparisons are made which show that the surface oxides are fundamentally different between these samples likely resulting in the profound enhancement of the cavity’s quality factor. Experimental investigation into the native oxide of hot spot nitrogen doped Nb shows a degraded oxide and superconducting properties as compared with the cold spot. The dissertation continues with a brief introduction to MgB2, followed by our scanning tunneling and electron tunneling insights into MgB2. The dissertation is concluded with a summary of our investigations and broader impact of our research on the SRF community. / Physics

Molecular electronics based on bottom-up electronic circuit design is a potential solution to meet the continuous need to miniaturize electronic devices. The development of highly conductive molecular wires, especially for long distance charge transfer, is a major milestone in the molecular electronics roadmap. A challenge presented by single molecule conductance is to define the relative influence of the molecular "core" and the molecular "interconnects" on the observed currents. Much focus has been placed on designing conductive, conjugated molecules. However, the electrode-molecule contacts can dominate the responses of metal-molecule-metal devices. We have experimentally and theoretically probed charge transfer through single phenyleneethynylene molecules terminated with thiol and carbodithioate linkers, using STM break-junction and non-equilibrium Green's function methods. The STM break-junction method utilizes repeatedly formed circuits where one or a few molecules are trapped between two electrodes, at least one of which has nanoscale dimensions. The statistical analysis of thousands of measurements yields the conductance of single molecules. Experimental data demonstrate that the carbodithioate linker not only augments electronic coupling to the metal electrode relative to thiol, but reduces the barrier to charge injection into the phenyleneethynylene bridge. The theoretical analysis shows that sulfur hybridization provides the genesis for the order-of-magnitude increased conductance in carbodithioate-terminated systems relative to those that feature the thiol linker. Collectively, these data emphasize the promising role for carbodithioate-based connectivity in molecular electronics applications involving metallic and semi-conducting electrodes. One of the strategies for building molecular wires that can transfer charge over long distance is to incorporate metal ions into the conductive molecular core. Peptide nucleic acid (PNA) is a great candidate for this purpose. Studying the conductivity of PNA can not only contribute to a better understanding of charge transfer through biomolecules, but can also help develop better molecular wires and other building blocks of molecular electronics. We study the charge transfer of PNA molecules using the STM break-junction technique and compare with traditional macroscopic voltammetric measurements. By measuring the resistance of different PNA molecules, we hope to develop a deep understanding of how charge transport though PNA is affected by factors such as the number and type of natural and artificial bases, embedded metal ions, pH, etc. Self-assembled monolayers (SAMs) of porphyrins are of great interest due to their diverse applications, including molecular devices, nano-templates, electrocatalysis, solar cells, and photosynthesis. We combined a molecular level study of the redox reactions using electrochemical scanning tunneling microscopy (EC-STM) with a macroscopic electrochemical technique, cyclic voltammetry (CV), to study two redox active porphyrin molecules, TPyP (5,10,15,20-Tetra(4-Pyridyl)-21H,23H-Porphine) and 5, 10, 15, 20-tetrakis (4-carboxylphenyl)-21H, 23H-porphine (TCPP). We showed that the adsorbed oxidized TPyP molecules slowly change to brighter contrast, consistent with the appearance of the reduced form of TPyP, under reduction condition (0.0VSCE). The time scale of the slow reduction is in the order of tens of minutes at 0.0VSCE, but accelerates at more negative potentials. We propose that protonation and deprotonation processes play an important role in the surface redox reaction due to geometric restriction of the molecules adsorbed on the surface. EC-STM and CV experiments were performed at various pH values to investigate the mechanism of this anomalously slow redox reaction. Our results show that the increased concentration of H+ hinders the reduction of porphyrins, a feature that has not been reported preciously. This provides insight into the details of the surface redox reaction. / Chemistry

In recent years, two-dimensional (2D) van der Waals (vdW) materials have aroused much interest for their unique structural, thermal, optical, and electronic properties and have become a hot topic in condensed matter physics and material science. Many research methods, including scanning tunneling microscopy (STM), transmission electron microscopy (TEM), optical and transport measurements, have been used to investigate these unique properties. Among them, STM stands out as a powerful characterization tool with atomic resolution and is capable of simultaneously revealing both atomic structures and local electronic properties. This dissertation focuses on scanning tunneling microscopy and spectroscopy (STM/S) investigation of 2D metal chalcogenides and heterostructures. The first part of the dissertation focuses on the continuous interface in WS2/MoS2 heterostructures grown by the chemical vapor deposition (CVD) method. We observed a closed interface between the MoS2 monolayer and the heterobilayer with atomic resolution. Furthermore, our scanning tunneling spectroscopy (STS) results and density functional theory (DFT) calculations revealed band gaps of the heterobilayer and the MoS2 monolayer agree with previously reported values for MoS2 monolayer and MoS2/WS2 heterobilayer on SiO2 fabricated through the mechanical exfoliation method. The results could deepen our understanding of the growth mechanism, interlayer interactions and electronic structures of 2D transition metal dichalcogenides (TMD) heterostructures synthesized via CVD. The second part of the dissertation focuses on phase transformation in 2D In2Se3. We observed that 2D In2Se3 layers with thickness ranging from single to ~20 layers stabilized at the beta phase with a superstructure at room temperature. After cooling down to around 180 K, the beta phase converted to a more stable beta' phase that was distinct from previously reported phases in 2D In2Se3. The kinetics of the reversible thermally driven beta-to-beta' phase transformation was investigated by temperature dependent transmission electron microscopy and Raman spectroscopy, combined with the expected minimum-energy pathways obtained from our first-principles calculations. Furthermore, DFT calculations reveal in-plane ferroelectricity in the beta' phase. STS measurements show that the indirect bandgap of monolayer beta' In2Se3 is 2.50 eV, which is larger than that of the multilayer form with a measured value of 2.05 eV. Our results on the reversible thermally driven phase transformation in 2D In2Se3 will provide insights to tune the functionalities of 2D In2Se3 and other emerging 2D ferroelectric materials and shed light on their numerous potential applications like non-volatile memory devices. The third part of the dissertation focuses on domain boundaries in 2D ferroelectric In2Se3. The atomic structure of domain boundaries in two-dimensional (2D) ferroelectric beta' In2Se3 is visualized with scanning tunneling microscopy and spectroscopy (STM/S) combined with DFT calculations. A double-barrier energy potential across the 60° tail to tail domain boundaries in monolayer beta' In2Se3 is also revealed. The results will deepen our understanding of domain boundaries in 2D ferroelectric materials and stimulate innovative applications of these materials. / Doctor of Philosophy / Two-dimensional (2D) materials are materials consisting of a single layer or a few layers of atoms. They exhibit unique and interesting properties distinct from their bulk counterparts. Over the past decade, much effort has been devoted to a large family of 2D materials — 2D metal chalcogenides that exhibit fascinating structural and electronic properties. These 2D metal chalcogenides can also be stacked together to form various heterostructures. The scanning tunneling microscope (STM) is a powerful tool to study these materials with atomic resolution and is capable of simultaneously revealing both atomic structures and local electronic properties. It can also be used to manipulate nanometer-scale structures on the material surface. In this dissertation, we use scanning tunneling microscopy and spectroscopy (STM/S) to investigate 2D metal chalcogenides and heterostructures. The first part of the dissertation focuses on WS2/MoS2 heterostructures grown by the chemical vapor deposition (CVD) method. We observed a closed interface between the MoS2 monolayer and the heterobilayer with atomic resolution. Furthermore, our scanning tunneling spectroscopy (STS) results and density functional theory (DFT) calculations revealed band gaps of the heterobilayer and the MoS2 monolayer. The results could deepen our understanding of the growth mechanism, interlayer interactions and electronic structures of 2D transition metal dichalcogenides (TMD) heterostructures synthesized via CVD. The second part of the dissertation focuses on phase transformation in 2D In2Se3. We observed that 2D In2Se3 layers transform from beta phase to a more stable beta' phase when the sample is cooled down from room temperature to 77 K. This thermally driven beta-to-beta' phase transformation was found to be reversible by temperature dependent transmission electron microscopy and Raman spectroscopy, corroborated with the expected minimum-energy pathways obtained from our first-principles calculations. Furthermore, DFT calculations reveal in-plane ferroelectricity in the beta' phase. Our results on the reversible thermally driven phase transformation in 2D In2Se3 will provide insights to tune the functionalities of 2D In2Se3 and other emerging 2D ferroelectric materials. The third part of the dissertation focuses on domain boundaries in 2D ferroelectric In2Se3. The atomic structure of domain boundaries in 2D ferroelectric beta' In2Se3 is visualized by using STM/S combined with DFT calculations. A double-barrier energy potential across the 60° tail to tail domain boundaries in monolayer beta' In2Se3 is also revealed. The results will deepen our understanding of domain boundaries in 2D ferroelectric materials and stimulate innovative applications of these materials.