Christopher T. Parzyck

We demonstrate the epitaxial growth of tetragonal platinum monoxide (PtO) on MgO, TiO2, and β-Ga2O3 single-crystalline substrates by ozone molecular-beam epitaxy. We provide synthesis routes and derive a growth diagram under which PtO films can be synthesized by physical vapor deposition. A combination of electrical transport and photoemission spectroscopy measurements, in conjunction with density functional theory calculations, reveal PtO to be a degenerately doped p-type semiconductor with a bandgap of Eg ≈ 1.6 eV. Spectroscopic ellipsometry measurements are used to extract the complex dielectric function spectra, indicating a transition from free-carrier absorption to higher photon energy transitions at E ≈ 1.6 eV. Using tetragonal PtO as an anode contact, we fabricate prototype Schottky diodes on n-type Sn-doped β-Ga2O3 substrates and extract Schottky barrier heights of ϕB > 2.2 eV.

The discovery of superconductivity in La₃Ni₂O₇ under pressure has motivated the investigation of a parent spin density wave (SDW) state, which could provide the underlying pairing interaction. Here, we employ resonant soft x-ray scattering and polarimetry on thin films of bilayer La₃Ni₂O₇ to determine that the magnetic structure of the SDW forms unidirectional diagonal spin stripes with moments lying within the NiO₂ plane and perpendicular to Q_SDW, but without evidence of the strong charge disproportionation typically associated with other nickelates. These stripes form anisotropic domains with shorter correlation lengths perpendicular versus parallel to Q_SDW, revealing nanoscale rotational and translational symmetry breaking analogous to the cuprate and Fe-based superconductors, with possible Bloch-like antiferromagnetic domain walls separating orthogonal domains.

We report evidence for superconductivity with onset temperatures up to 11 K in thin films of the infinite-layer nickelate parent compound NdNiO 2 . A combination of oxide molecular beam epitaxy and atomic hydrogen reduction yields samples with high crystallinity and low residual resistivities, a substantial fraction of which exhibit superconducting transitions. We survey a large series of samples with a variety of techniques, including electrical transport, scanning transmission electron microscopy, x-ray absorption spectroscopy, and resonant inelastic x-ray scattering, to investigate the possible origins of superconductivity. We propose that superconductivity could be intrinsic to the undoped infinite-layer nickelates but suppressed by disorder due to a possibly sign-changing order parameter, a finding which would necessitate a reconsideration of the nickelate phase diagram. Another possible hypothesis is that the parent materials can be hole doped from randomly dispersed apical oxygen atoms, which would suggest an alternative pathway for achieving superconductivity.

The growing interest in the growth and study of thin films of low-dimensional metallic delafossites, with the general formula ABO2, is driven by their potential to exhibit electronic and magnetic characteristics that are not accessible in bulk systems. The layered structure of these compounds introduces unique surface states as well as electronic and structural reconstructions, making the investigation of their surface behavior pivotal to understanding their intrinsic electronic structure. In this work, we study the surface phenomena of epitaxially grown PtCoO2, PdCoO2, and PdCrO2 films, utilizing a combination of molecular-beam epitaxy and angle-resolved photoemission spectroscopy. Through precise control of surface termination and treatment, we discover a pronounced 3×3 surface reconstruction in PtCoO2 films and PdCoO2 films, alongside a 2 × 2 surface reconstruction observed in PdCrO2 films. These reconstructions have not been reported in prior studies of delafossites. Furthermore, our computational investigations demonstrate the BO2 surface’s relative stability compared to the A-terminated surface and the significant reduction in surface energy facilitated by the reconstruction of the A-terminated surface. These experimental and theoretical insights illuminate the complex surface dynamics in metallic delafossites, paving the way for future explorations of their distinctive properties in low-dimensional studies.

It has been suggested that Ba₃In₂O₆ might be a high-T_c superconductor. Experimental investigation of the properties of Ba₃In₂O₆ was long inhibited by its instability in air. Recently epitaxial Ba₃In₂O₆ with a protective capping layer was demonstrated, which finally allows its electronic characterization. The optical bandgap of Ba₃In₂O₆ is determined to be 2.99 eV in-the (001) plane and 2.83 eV along the c-axis direction by spectroscopic ellipsometry. First-principles calculations were carried out, yielding a result in good agreement with the experimental value. Various dopants were explored to induce (super-)conductivity in this otherwise insulating material. Neither A- nor B-site doping proved successful. The underlying reason is predominately the formation of oxygen interstitials as revealed by scanning transmission electron microscopy and first-principles calculations. Additional efforts to induce superconductivity were investigated, including surface alkali doping, optical pumping, and hydrogen reduction. To probe liquid-ion gating, Ba₃In₂O₆ was successfully grown epitaxially on an epitaxial SrRuO₃ bottom electrode. So far none of these efforts induced superconductivity in Ba₃In₂O_6, leaving the answer to the initial question of whether Ba₃In₂O₆ is a high-T_c superconductor to be ‘no’ thus far.

We present an integrated procedure for the synthesis of infinite-layer nickelates using molecular-beam epitaxy with gas-phase reduction by atomic hydrogen. We first discuss challenges in the growth and characterization of perovskite NdNiO3/SrTiO3, arising from post growth crack formation in stoichiometric films. We then detail a procedure for fully reducing NdNiO3 films to the infinite-layer phase, NdNiO2, using atomic hydrogen; the resulting films display excellent structural quality, smooth surfaces, and lower residual resistivities than films reduced by other methods. We utilize the in situ nature of this technique to investigate the role that SrTiO3 capping layers play in the reduction process, illustrating their importance in preventing the formation of secondary phases at the exposed nickelate surface. A comparative bulk- and surface-sensitive study indicates that the formation of a polycrystalline crust on the film surface serves to limit the reduction process.

A hallmark of many unconventional superconductors is the presence of many-body interactions that give rise to broken-symmetry states intertwined with superconductivity. Recent resonant soft X-ray scattering experiments report commensurate 3a₀ charge density wave order in infinite-layer nickelates, which has important implications regarding the universal interplay between charge order and superconductivity in both cuprates and nickelates. Here we present X-ray scattering and spectroscopy measurements on a series of NdNiO_2+x samples, which reveal that the signatures of charge density wave order are absent in fully reduced, single-phase NdNiO₂. The 3a₀ superlattice peak instead originates from a partially reduced impurity phase where excess apical oxygens form ordered rows with three-unit-cell periodicity. The absence of any observable charge density wave order in NdNiO₂ highlights a crucial difference between the phase diagrams of cuprate and nickelate superconductors.

Alkali antimonide semiconductor photocathodes provide a promising platform for the generation of high-brightness electron beams, which are necessary for the development of cutting-edge probes, including x-ray free electron lasers and ultrafast electron diffraction. Nonetheless, to harness the intrinsic brightness limits in these compounds, extrinsic degrading factors, including surface roughness and contamination, must be overcome. By exploring the growth of CsxSb thin films monitored by in situ electron diffraction, the conditions to reproducibly synthesize atomically smooth films of CsSb on 3C–SiC (100) and graphene-coated TiO2 (110) substrates are identified, and detailed structural, morphological, and electronic characterization is presented. These films combine high quantum efficiency in the visible (up to 1.2% at 400 nm), an easily accessible photoemission threshold of 566 nm, low surface roughness (down to 600 pm on a 1 μm scale), and a robustness against oxidation up to 15 times greater than Cs3Sb. These properties lead us to suggest that CsSb has the potential to operate as an alternative to Cs3Sb in electron source applications where the demands of the vacuum environment might otherwise preclude the use of traditional alkali antimonides.

Utilizing the powerful combination of molecular-beam epitaxy (MBE) and angle-resolved photoemission spectroscopy (ARPES), we produce and study the effect of different terminating layers on the electronic structure of the metallic delafossite PdCoO₂. Attempts to introduce unpaired electrons and synthesize new antiferromagnetic metals akin to the isostructural compound PdCrO₂ have been made by replacing cobalt with iron in PdCoO₂ films grown by MBE. Using ARPES, we observe similar bulk bands in these PdCoO₂ films with Pd-, CoO₂-, and FeO₂-termination. Nevertheless, Pd- and CoO₂-terminated films show a reduced intensity of surface states. Additionally, we are able to epitaxially stabilize PdFe_xCo_1−xO₂ films that show an anomaly in the derivative of the electrical resistance with respect to temperature at 20 K, but do not display pronounced magnetic order.