Excited State Band Mapping and Ultrafast Nonequilibrium Dynamics in Topological Dirac Semimetal 1T-ZrTe2.

We performed time- and polarization-resolved extreme ultraviolet momentum microscopy on the topological Dirac semimetal candidate 1T-ZrTe2. Excited state band mapping uncovers the previously inaccessible linear dispersion of the Dirac cone above the Fermi level. We study the orbital texture of bands using linear dichroism in photoelectron angular distributions. These observations provide hints about the topological character of 1T-ZrTe2. Time-, energy-, and momentum-resolved nonequilibrium carrier dynamics reveal that intra- and interband scattering processes play a major role in the relaxation mechanism, leading to multivalley electron-hole accumulation near the Fermi level. We also show that electrons' inverse lifetime has a linear dependence as a function of their excess energy. Our time- and polarization-resolved XUV photoemission results shed light on the excited state electronic structure of 1T-ZrTe2 and provide valuable insights into the relatively unexplored field of quantum-state-resolved ultrafast dynamics in 3D topological Dirac semimetals.

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.

Anisotropic Thermal Conductivity of Crystalline Layered SnSe2.

The degree of thermal anisotropy affects critically key device-relevant properties of layered two-dimensional materials. Here, we systematically study the in-plane and cross-plane thermal conductivity of crystalline SnSe2 films of varying thickness (16-190 nm) and uncover a thickness-independent thermal conductivity anisotropy ratio of about ∼8.4. Experimental data obtained using Raman thermometry and frequency domain thermoreflectance showed that the in-plane and cross-plane thermal conductivities monotonically decrease by a factor of 2.5 with decreasing film thickness compared to the bulk values. Moreover, we find that the temperature-dependence of the in-plane component gradually decreases as the film becomes thinner, and in the range from 300 to 473 K it drops by more than a factor of 2. Using the mean free path reconstruction method, we found that phonons with MFP ranging from ∼1 to 53 and from 1 to 30 nm contribute to 50% of the total in-plane and cross-plane thermal conductivity, respectively.

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.

Direct versus reverse vertical two-dimensional Mo2C/graphene heterostructures for enhanced hydrogen evolution reaction electrocatalysis.

Mo2C/graphene heterostructures prepared by chemical vapor deposition have demonstrated excellent electrocatalytic activity in a hydrogen evolution reaction (HER). This is attributed to the high catalytic activity of Mo2C while the high electrical conductivity of graphene facilitates charge transfer. In the as-grown direct vertical order, graphene is placed above the Mo2C film. This reduces the catalytic activity of the heterostructure, since graphene in chemically inert. Here, a simple transfer method is proposed that results in the reverse order deposition of the heterostructure on the electrode. This method places graphene at the interface between Mo2C and the electrode, enhancing charge transfer between them, which results in an overpotential of 440 mV at 10 mA cm-2 and corresponds to ∼65 mV overpotential reduction as compared to the direct heterostructure. At the same time, when a direct Cu/Mo2C/graphene junction with a Cu catalyst substrate is used as a working electrode, the improvement of the heterostructure HER activity is observed which is manifested in an overpotential of 275 mV at 10 mA cm-2 with a correspondent ∼230 mV reduction. All above performances are accompanied with excellent endurance.

Mo2C/graphene heterostructures: low temperature chemical vapor deposition on liquid bimetallic Sn-Cu and hydrogen evolution reaction electrocatalytic properties.

Thin 2D Mo2C/graphene vertical heterostructures have attracted significant attention due to their potential application as electrodes in the hydrogen evolution reaction (HER) and energy storage. A common drawback in the chemical vapor deposition synthesis of these structures is the demand for high temperature growth, which should be higher than the melting temperature of the metal catalyst. The most common metallic catalyst is Cu, which has a melting temperature of 1084 °C. Here, we report the growth of thin, ∼200 nm in thickness, semitransparent micrometer-sized Mo2C domains and Mo2C/graphene heterostructures at lower temperatures using liquid Sn-Cu alloys. No Sn-associated defects are observed, making the alloy an appealing growth substrate. Raman spectroscopy reveals the vertical interaction between graphene and Mo2C, as shown by the variation in the strain of the graphene film. The results demonstrate the capability to grow continuous nanometer-thin Mo2C films at temperatures as low as 880 °C, without sacrificing the growth rate. Mo2C films are proven to be efficient electrocatalysts for the HER. Moreover, we demonstrate the beneficial role of graphene overgrown on Mo2C in reducing the HER overpotential values, which is attributed to more efficient charge transfer kinetics, compared to pure Mo2C films.

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.

Visible Light Trapping against Charge Recombination in FeOx-TiO2 Photonic Crystal Photocatalysts.

Tailoring metal oxide photocatalysts in the form of heterostructured photonic crystals has spurred particular interest as an advanced route to simultaneously improve harnessing of solar light and charge separation relying on the combined effect of light trapping by macroporous periodic structures and compositional materials' modifications. In this work, surface deposition of FeOx nanoclusters on TiO2 photonic crystals is investigated to explore the interplay of slow-photon amplification, visible light absorption, and charge separation in FeOx-TiO2 photocatalytic films. Photonic bandgap engineered TiO2 inverse opals deposited by the convective evaporation-induced co-assembly method were surface modified by successive chemisorption-calcination cycles using Fe(III) acetylacetonate, which allowed the controlled variation of FeOx loading on the photonic films. Low amounts of FeOx nanoclusters on the TiO2 inverse opals resulted in diameter-selective improvements of photocatalytic performance on salicylic acid degradation and photocurrent density under visible light, surpassing similarly modified P25 films. The observed enhancement was related to the combination of optimal light trapping and charge separation induced by the FeOx-TiO2 interfacial coupling. However, an increase of the FeOx loading resulted in severe performance deterioration, particularly prominent under UV-Vis light, attributed to persistent surface recombination via diverse defect d-states.

Heterostructured CoOx-TiO2 Mesoporous/Photonic Crystal Bilayer Films for Enhanced Visible-Light Harvesting and Photocatalysis.

Heterostructured bilayer films, consisting of co-assembled TiO2 photonic crystals as the bottom layer and a highly performing mesoporous P25 titania as the top layer decorated with CoOx nanoclusters, are demonstrated as highly efficient visible-light photocatalysts. Broadband visible-light activation of the bilayer films was implemented by the surface modification of both titania layers with nanoscale clusters of Co oxides relying on the chemisorption of Co acetylacetonate complexes on TiO2, followed by post-calcination. Tuning the slow photon regions of the inverse opal supporting layer to the visible-light absorption of surface CoOx oxides resulted in significant amplification of salicylic-acid photodegradation under visible and ultraviolet (UV)-visible light (Vis), outperforming benchmark P25 films of higher titania loading. This enhancement was related to the spatially separated contributions of slow photon propagation in the inverse opal support layer assisted by Bragg reflection toward the CoOx-modified mesoporous P25 top layer. This effect indicates that photonic crystals may be highly effective as both photocatalytically active and backscattering layers in multilayer photocatalytic films.

Graphene Quantum Dot-TiO2 Photonic Crystal Films for Photocatalytic Applications.

Photonic crystal structuring has emerged as an advanced method to enhance solar light harvesting by metal oxide photocatalysts along with rational compositional modifications of the materials' properties. In this work, surface functionalization of TiO2 photonic crystals by blue luminescent graphene quantum dots (GQDs), n-π* band at ca. 350 nm, is demonstrated as a facile, environmental benign method to promote photocatalytic activity by the combination of slow photon-assisted light trapping with GQD-TiO2 interfacial electron transfer. TiO2 inverse opal films fabricated by the co-assembly of polymer colloidal spheres with a hydrolyzed titania precursor were post-modified by impregnation in aqueous GQDs suspension without any structural distortion. Photonic band gap engineering by varying the inverse opal macropore size resulted in selective performance enhancement for both salicylic acid photocatalytic degradation and photocurrent generation under UV-VIS and visible light, when red-edge slow photons overlapped with the composite's absorption edge, whereas stop band reflection was attenuated by the strong UVA absorbance of the GQD-TiO2 photonic films. Photoelectrochemical and photoluminescence measurements indicated that the observed improvement, which surpassed similarly modified benchmark mesoporous P25 TiO2 films, was further assisted by GQDs electron acceptor action and visible light activation to a lesser extent, leading to highly efficient photocatalytic films.

Advanced Photocatalysts Based on Reduced Nanographene Oxide-TiO2 Photonic Crystal Films.

Surface functionalization of TiO2 inverse opals by graphene oxide nanocolloids (nanoGO) presents a promising modification for the development of advanced photocatalysts that combine slow photon-assisted light harvesting, surface area, and mass transport of macroporous photonic structures with the enhanced adsorption capability, surface reactivity, and charge separation of GO nanosheets. In this work, post-thermal reduction of nanoGO-TiO2 inverse opals was investigated in order to explore the role of interfacial electron transfer vs. pollutant adsorption and improve their photocatalytic activity. Photonic band gap-engineered TiO2 inverse opals were fabricated by the coassembly technique and were functionalized by GO nanosheets and reduced under He at 200 and 500 °C. Comparative performance evaluation of the nanoGO-TiO2 films on methylene blue photodegradation under UV-VIS and visible light showed that thermal reduction at 200 °C, in synergy with slow photon effects, improved the photocatalytic reaction rate despite the loss of nanoGO and oxygen functional groups, pointing to enhanced charge separation. This was further supported by photoluminescence spectroscopy and salicylic acid UV-VIS photodegradation, where, in the absence of photonic effects, the photocatalytic activity increased, confirming that fine-tuning of interfacial coupling between TiO2 and reduced nanoGO is a key factor for the development of highly efficient photocatalytic films.

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.