Superconductivity enhancement in phase-engineered molybdenum carbide/disulfide vertical heterostructures.

Stacking layers of atomically thin transition-metal carbides and two-dimensional (2D) semiconducting transition-metal dichalcogenides, could lead to nontrivial superconductivity and other unprecedented phenomena yet to be studied. In this work, superconducting α-phase thin molybdenum carbide flakes were first synthesized, and a subsequent sulfurization treatment induced the formation of vertical heterolayer systems consisting of different phases of molybdenum carbide-ranging from α to γ' and γ phases-in conjunction with molybdenum sulfide layers. These transition-metal carbide/disulfide heterostructures exhibited critical superconducting temperatures as high as 6 K, higher than that of the starting single-phased α-Mo2C (4 K). We analyzed possible interface configurations to explain the observed moiré patterns resulting from the vertical heterostacks. Our density-functional theory (DFT) calculations indicate that epitaxial strain and moiré patterns lead to a higher interfacial density of states, which favors superconductivity. Such engineered heterostructures might allow the coupling of superconductivity to the topologically nontrivial surface states featured by transition-metal carbide phases composing these heterostructures potentially leading to unconventional superconductivity. Moreover, we envisage that our approach could also be generalized to other metal carbide and nitride systems that could exhibit high-temperature superconductivity.

Transformation of 2D group-III selenides to ultra-thin nitrides: enabling epitaxy on amorphous substrates.

The experimental realization of two-dimensional (2D) gallium nitride (GaN) has enabled the exploration of 2D nitride materials beyond boron nitride. Here we demonstrate one possible pathway to realizing ultra-thin nitride layers through a two-step process involving the synthesis of naturally layered, group-III chalcogenides (GIIIC) and subsequent annealing in ammonia (ammonolysis) that leads to an atomic-exchange of the chalcogen and nitrogen species in the 2D-GIIICs. The effect of nitridation differs for gallium and indium selenide, where gallium selenide undergoes structural changes and eventual formation of ultra-thin GaN, while indium selenide layers are primarily etched rather than transformed by nitridation. Further investigation of the resulting GaN films indicates that ultra-thin GaN layers grown on silicon dioxide act as effective 'seed layers' for the growth of 3D GaN on amorphous substrates.

Carbon doping of WS2 monolayers: Bandgap reduction and p-type doping transport.

Chemical doping constitutes an effective route to alter the electronic, chemical, and optical properties of two-dimensional transition metal dichalcogenides (2D-TMDs). We used a plasma-assisted method to introduce carbon-hydrogen (CH) units into WS2 monolayers. We found CH-groups to be the most stable dopant to introduce carbon into WS2, which led to a reduction of the optical bandgap from 1.98 to 1.83 eV, as revealed by photoluminescence spectroscopy. Aberration corrected high-resolution scanning transmission electron microscopy (AC-HRSTEM) observations in conjunction with first-principle calculations confirm that CH-groups incorporate into S vacancies within WS2. According to our electronic transport measurements, undoped WS2 exhibits a unipolar n-type conduction. Nevertheless, the CH-WS2 monolayers show the emergence of a p-branch and gradually become entirely p-type, as the carbon doping level increases. Therefore, CH-groups embedded into the WS2 lattice tailor its electronic and optical characteristics. This route could be used to dope other 2D-TMDs for more efficient electronic devices.

Three-dimensional atomic scale electron density reconstruction of octahedral tilt epitaxy in functional perovskites.

Octahedral tilts are the most ubiquitous distortions in perovskite-related structures that can dramatically influence ferroelectric, magnetic, and electronic properties; yet the paradigm of tilt epitaxy in thin films is barely explored. Non-destructively characterizing such epitaxy in three-dimensions for low symmetry complex tilt systems composed of light anions is a formidable challenge. Here we demonstrate that the interfacial tilt epitaxy can transform ultrathin calcium titanate, a non-polar earth-abundant mineral, into high-temperature polar oxides that last above 900 K. The comprehensive picture of octahedral tilts and polar distortions is revealed by reconstructing the three-dimensional electron density maps across film-substrate interfaces with atomic resolution using coherent Bragg rod analysis. The results are complemented with aberration-corrected transmission electron microscopy, film superstructure reflections, and are in excellent agreement with density functional theory. The study could serve as a broader template for non-destructive, three-dimensional atomic resolution probing of complex low symmetry functional interfaces.

Thermal Conductivity in the Radial Direction of Deformed Polymer Fibers.

Thermal conductivity of polymer fibers in the axial direction has been extensively studied while thermal conductivity in the radial direction Λ remains unknown. In this work, polymer fibers with different molecular arrangements (crystalline, liquid crystalline, and amorphous) were plastically deformed. Λ was measured at engineering strains ε = 0.2-2.3 using time-domain thermoreflectance. Λ decreases with increasing strains for polyethylene (PE) and poly(p-phenylene-2,6-benzobisoxazole) (PBO) fibers and is independent of strain for poly(methyl methacrylate) (PMMA) fibers. The extrapolated thermal conductivity at zero strain is Λ0 ≈ 0.27 Wm-1 K-1 for crystalline PE, Λ0 ≈ 0.29 Wm-1 K-1 for liquid crystalline PBO, and Λ0 ≈ 0.18 Wm-1 K-1 for amorphous PMMA. Λ of PE drops to Λ ≈ 0.14 Wm-1 K-1 at ε = 1.9; Λ of PBO drops to Λ ≈ 0.12 Wm-1 K-1 at ε = 2.1. We attribute the decrease of Λ with ε in crystalline and liquid crystalline fibers to structural disorder induced by plastic deformation. The combination of structural disorder and phonon focusing effects produces a thermal conductivity in deformed PE and PBO fibers that is lower than amorphous PMMA.