Light concentration and electron transfer in plasmonic-photonic Ag,Au modified Mo-BiVO4 inverse opal photoelectrocatalysts.

Plasmonic photocatalysis based on metal-semiconductor heterojunctions is considered a key strategy to evade the inherent limitations of poor light harvesting and charge separation of semiconductor photocatalysts. It can be profitably combined with three-dimensional photonic crystals (PCs) that offer an ideal scaffold for loading plasmonic nanoparticles and a unique architecture to intensify photon capture. In this work, Mo-doped BiVO4 inverse opals were applied as visible light-responsive photonic hosts of Ag and/or Au plasmonic nanoparticles in order to exploit the synergy of plasmonic and photonic amplification effects with interfacial charge transfer for the photoelectrocatalytic degradation of recalcitrant pharmaceutical contaminants under visible light. Photoelectrochemical evaluation indicated a major contribution from hot spot-assisted local field enhancement, most pronounced for Ag/Mo-BiVO4 PCs due to the spectral overlap of the localized surface plasmon resonance with the electronic absorption and blue-edge slow photon region of Mo-BiVO4 PCs, in contrast to weak plasmonic sensitization effects for the Au-modified PCs. The diverse band alignment at the metal-semiconductor interfaces resulted in the enhanced photoelectrocatalytic degradation of tetracycline broad spectrum antibiotic by Ag/Mo-BiVO4 and the refractory ibuprofen drug by (Ag,Au)/Mo-BiVO4, attributed to the enhanced charge separation by electron transfer toward Ag nanoparticles. Combination of visible light activated semiconductor PCs and plasmonic nanoparticles with suitable band alignment and photonic band gap may provide a versatile approach for the rational design of efficient plasmonic-photonic photoeletrocatalysts.

Exploiting the Close-to-Dirac Point Shift of the Fermi Level in the Sb2Te3/Bi2Te3 Topological Insulator Heterostructure for Spin-Charge Conversion.

Properly tuning the Fermi level position in topological insulators is of vital importance to tailor their spin-polarized electronic transport and to improve the efficiency of any functional device based on them. Here, we report the full in situ metal organic chemical vapor deposition (MOCVD) and study of a highly crystalline Bi2Te3/Sb2Te3 topological insulator heterostructure on top of large area (4″) Si(111) substrates. The bottom Sb2Te3 layer serves as an ideal seed layer for the growth of highly crystalline Bi2Te3 on top, also inducing a remarkable shift of the Fermi level to place it very close to the Dirac point, as visualized by angle-resolved photoemission spectroscopy. To exploit such ideal topologically protected surface states, we fabricate the simple spin-charge converter Si(111)/Sb2Te3/Bi2Te3/Au/Co/Au and probe the spin-charge conversion (SCC) by spin pumping ferromagnetic resonance. A large SCC is measured at room temperature and is interpreted within the inverse Edelstein effect, thus resulting in a conversion efficiency of λIEEE ∼ 0.44 nm. Our results demonstrate the successful tuning of the surface Fermi level of Bi2Te3 when grown on top of Sb2Te3 with a full in situ MOCVD process, which is highly interesting in view of its future technology transfer.

Co-assembled MoS2-TiO2 Inverse Opal Photocatalysts for Visible Light-Activated Pharmaceutical Photodegradation.

Heterostructured photocatalytic materials in the form of photonic crystals have been attracting attention for their unique light harvesting ability that can be ideally combined with judicious compositional modifications toward the development of visible light-activated (VLA) photonic catalysts, though practical environmental applications, such as the degradation of pharmaceutical emerging contaminants, have been rarely reported. Herein, heterostructured MoS2-TiO2 inverse opal films are introduced as highly active immobilized photocatalysts for the VLA degradation of tetracycline and ciprofloxacin broad-spectrum antibiotics as well as salicylic acid. A single-step co-assembly method was implemented for the challenging incorporation of MoS2 nanosheets into the nanocrystalline inverse opal walls. Compositional tuning and photonic band gap engineering of the MoS2-TiO2 photonic films showed that integration of low amounts of MoS2 nanosheets in the inverse opal framework maintains intact the periodic macropore structure and enhances the available surface area, resulting in efficient VLA antibiotic degradation far beyond the performance of benchmark TiO2 films. The combination of broadband MoS2 visible light absorption and photonic-assisted light trapping together with the enhanced charge separation that enables the generation of reactive oxygen species via firm interfacial coupling between MoS2 nanosheets and TiO2 nanoparticles is concluded as a competent approach for pharmaceutical abatement in water bodies.

Engineering Heat Transport Across Epitaxial Lattice-Mismatched van der Waals Heterointerfaces.

Artificially engineered 2D materials offer unique physical properties for thermal management, surpassing naturally occurring materials. Here, using van der Waals epitaxy, we demonstrate the ability to engineer extremely insulating thermal metamaterials based on atomically thin lattice-mismatched Bi2Se3/MoSe2 superlattices and graphene/PdSe2 heterostructures with exceptional thermal resistances (70-202 m2 K/GW) and ultralow cross-plane thermal conductivities (0.012-0.07 W/mK) at room temperature, comparable to those of amorphous materials. Experimental data obtained using frequency-domain thermoreflectance and low-frequency Raman spectroscopy, supported by tight-binding phonon calculations, reveal the impact of lattice mismatch, phonon-interface scattering, size effects, temperature, and interface thermal resistance on cross-plane heat dissipation, uncovering different thermal transport regimes and the dominant role of long-wavelength phonons. Our findings provide essential insights into emerging synthesis and thermal characterization methods and valuable guidance for the development of large-area heteroepitaxial van der Waals films of dissimilar materials with tailored thermal transport characteristics.

Ultrathin epitaxial Bi film growth on 2D HfTe2template.

Among ultrathin monoelemental two-dimensional (2D) materials, bismuthene, the single layer of heavier group-VΑ element bismuth (Bi), has been predicted to have large non trivial gap. Here, we demonstrate the growth of Bi films by molecular beam epitaxy on 2D-HfTe2template. At the initial stage of Bi deposition (1-2 bilayers, BL), both the pseudocubic Bi(110) and the hexagonal Bi(111) phases are formed. When reaching 3 BL Bi, a transformation to pure hexagonal Bi(111) occurs. The electronic band structure of 3 BL Bi(111) films was measured by angle-resolved photoemission spectroscopy showing very good matching with the density functional theory band structure calculations of 3 BL free standing Bi(111). The grown Bi(111) thin film was capped with a protective Al2O3layer and its stability under ambient conditions, necessary for practical applications and device fabrication, was confirmed by x-ray photoelectron spectroscopy and Raman spectroscopy.

Massless Dirac Fermions in ZrTe2 Semimetal Grown on InAs(111) by van der Waals Epitaxy.

Single and few layers of the two-dimensional (2D) semimetal ZrTe2 are grown by molecular beam epitaxy on InAs(111)/Si(111) substrates. Excellent rotational commensurability, van der Waals gap at the interface and moiré pattern are observed indicating good registry between the ZrTe2 epilayer and the substrate through weak van der Waals forces. The electronic band structure imaged by angle resolved photoelectron spectroscopy shows that valence and conduction bands cross at the Fermi level exhibiting abrupt linear dispersions. The latter indicates massless Dirac Fermions which are maintained down to the 2D limit suggesting that single-layer ZrTe2 could be considered as the electronic analogue of graphene.

Epitaxial 2D SnSe2/ 2D WSe2 van der Waals Heterostructures.

van der Waals heterostructures of 2D semiconductor materials can be used to realize a number of (opto)electronic devices including tunneling field effect devices (TFETs). It is shown in this work that high quality SnSe2/WSe2 vdW heterostructure can be grown by molecular beam epitaxy on AlN(0001)/Si(111) substrates using a Bi2Se3 buffer layer. A valence band offset of 0.8 eV matches the energy gap of SnSe2 in such a way that the VB edge of WSe2 and the CB edge of SnSe2 are lined up, making this materials combination suitable for (nearly) broken gap TFETs.

Epitaxial 2D MoSe2 (HfSe2) Semiconductor/2D TaSe2 Metal van der Waals Heterostructures.

Molecular beam epitaxy of 2D metal TaSe2/2D MoSe2 (HfSe2) semiconductor heterostructures on epi-AlN(0001)/Si(111) substrates is reported. Electron diffraction reveals an in-plane orientation indicative of van der Waals epitaxy, whereas electronic band imaging supported by first-principles calculations and X-ray photoelectron spectroscopy indicate the presence of a dominant trigonal prismatic 2H-TaSe2 phase and a minor contribution from octahedrally coordinated TaSe2, which is present in TaSe2/AlN and TaSe2/HfSe2/AlN but notably absent in the TaSe2/MoSe2/AlN, indicating superior structural quality of TaSe2 grown on MoSe2. Apart from its structural and chemical compatibility with the selenide semiconductors, TaSe2 has a workfunction of 5.5 eV as measured by ultraviolet photoelectron spectroscopy, which matches very well with the semiconductor workfunctions, implying that epi-TaSe2 can be used for low-resistivity contacts to MoSe2 and HfSe2.

Observation of surface Dirac cone in high-quality ultrathin epitaxial Bi2Se3 topological insulator on AlN(0001) dielectric.

Bi2Se3 topological insulators (TIs) are grown on AlN(0001)/Si(111) substrates by molecular beam epitaxy. In a one-step growth at optimum temperature of 300 °C, Bi2Se3 bonds strongly with AlN without forming interfacial reaction layers. This produces high epitaxial quality Bi2Se3 single crystals with a perfect registry with the substrate and abrupt interfaces, allowing thickness scaling down to three quintuple layers (QL) without jeopardizing film quality. It is found by angle-resolved photoelectron spectroscopy that, remarkably, Bi2Se3 films maintain the 3D TI properties at very low thickness of 3QL (∼2.88 nm), exhibiting top surface gapless metallic states in the form of a Dirac cone.