Direct visualization of stacking-selective self-intercalation in epitaxial Nb1+xSe2 films.

Two-dimensional (2D) van der Waals (vdW) materials offer rich tuning opportunities generated by different stacking configurations or by introducing intercalants into the vdW gaps. Current knowledge of the interplay between stacking polytypes and intercalation often relies on macroscopically averaged probes, which fail to pinpoint the exact atomic position and chemical state of the intercalants in real space. Here, by using atomic-resolution electron energy-loss spectroscopy in a scanning transmission electron microscope, we visualize a stacking-selective self-intercalation phenomenon in thin films of the transition-metal dichalcogenide (TMDC) Nb1+xSe2. We observe robust contrasts between 180°-stacked layers with large amounts of Nb intercalants inside their vdW gaps and 0°-stacked layers with little detectable intercalants inside their vdW gaps, coexisting on the atomic scale. First-principles calculations suggest that the films lie at the boundary of a phase transition from 0° to 180° stacking when the intercalant concentration x exceeds ~0.25, which we could attain in our films due to specific kinetic pathways. Our results offer not only renewed mechanistic insights into stacking and intercalation, but also open up prospects for engineering the functionality of TMDCs via stacking-selective self-intercalation.

Quantum Confinement in Epitaxial Armchair Graphene Nanoribbons on SiC Sidewalls.

The integration of graphene into devices necessitates large-scale growth and precise nanostructuring. Epitaxial growth of graphene on SiC surfaces offers a solution by enabling both simultaneous and targeted realization of quantum structures. We investigated the impact of local variations in the width and edge termination of armchair graphene nanoribbons (AGNRs) on quantum confinement effects using scanning tunneling microscopy and spectroscopy (STM, STS), along with density-functional tight-binding (DFTB) calculations. AGNRs were grown as an ensemble on refaceted sidewalls of SiC mesas with adjacent AGNRs separated by SiC(0001) terraces hosting a buffer layer seamlessly connected to the AGNRs. Energy band gaps measured by STS at the centers of ribbons of different widths align with theoretical expectations, indicating that hybridization of π-electrons with the SiC substrate mimics sharp electronic edges. However, regardless of the ribbon width, band gaps near the edges of AGNRs are significantly reduced. DFTB calculations successfully replicate this effect by considering the role of edge passivation, while strain or electric fields do not account for the observed effect. Unlike idealized nanoribbons with uniform hydrogen passivation, AGNRs on SiC sidewalls generate additional energy bands with non-pz character and nonuniform distribution across the nanoribbon. In AGNRs terminated with Si, these additional states occur at the conduction band edge and rapidly decay into the bulk of the ribbon. This agrees with our experimental findings, demonstrating that edge passivation is crucial in determining the local electronic properties of epitaxial nanoribbons.

Observation of ultrafast interfacial Meitner-Auger energy transfer in a Van der Waals heterostructure.

Atomically thin layered van der Waals heterostructures feature exotic and emergent optoelectronic properties. With growing interest in these novel quantum materials, the microscopic understanding of fundamental interfacial coupling mechanisms is of capital importance. Here, using multidimensional photoemission spectroscopy, we provide a layer- and momentum-resolved view on ultrafast interlayer electron and energy transfer in a monolayer-WSe2/graphene heterostructure. Depending on the nature of the optically prepared state, we find the different dominating transfer mechanisms: while electron injection from graphene to WSe2 is observed after photoexcitation of quasi-free hot carriers in the graphene layer, we establish an interfacial Meitner-Auger energy transfer process following the excitation of excitons in WSe2. By analysing the time-energy-momentum distributions of excited-state carriers with a rate-equation model, we distinguish these two types of interfacial dynamics and identify the ultrafast conversion of excitons in WSe2 to valence band transitions in graphene. Microscopic calculations find interfacial dipole-monopole coupling underlying the Meitner-Auger energy transfer to dominate over conventional Förster- and Dexter-type interactions, in agreement with the experimental observations. The energy transfer mechanism revealed here might enable new hot-carrier-based device concepts with van der Waals heterostructures.

A narrow bandwidth extreme ultra-violet light source for time- and angle-resolved photoemission spectroscopy.

Here, we present a high repetition rate, narrow bandwidth, extreme ultraviolet photon source for time- and angle-resolved photoemission spectroscopy. The narrow bandwidth pulses Δ E = 9 , 14 , and 18 meV for photon energies h ν = 10.8 , 18.1 , and 25.3 eV are generated through high harmonic generation using ultra-violet drive pulses with relatively long pulse lengths (461 fs). The high harmonic generation setup employs an annular drive beam in tight focusing geometry at a repetition rate of 250 kHz. Photon energy selection is provided by a series of selectable multilayer bandpass mirrors and thin film filters, thus avoiding any time broadening introduced by single grating monochromators. A two stage optical-parametric amplifier provides < 100 fs tunable pump pulses from 0.65 µm to 9 µm. The narrow bandwidth performance of the light source is demonstrated through angle-resolved photoemission measurements on a series of quantum materials, including high-temperature superconductor Bi-2212, WSe2, and graphene.

Influence of Porosity of Sulfide-Based Artificial Solid Electrolyte Interphases on Their Performance with Liquid and Solid Electrolytes in Li and Na Metal Batteries.

Realization of all-solid-state batteries combined with metallic Li/Na is still hindered due to the unstable interface between the alkali metal and solid electrolytes, especially for highly promising thiophosphate materials. Artificial and uniform solid-electrolyte interphases (SEIs), serving as thin ion-conducting films, have been considered as a strategy to overcome the issues of such reactive interfaces. Here, we synthesized sulfide-based artificial SEIs (LixSy and NaxSy) on Li and Na by solid/gas reaction between the alkali metal and S vapor. The synthesized films are carefully characterized with various chemical/electrochemical techniques. We show that these artificial SEIs are not beneficial from an application point of view since they either contribute to additional resistances (Li) or do not prevent reactions at the alkali metal/electrolyte interface (Na). We show that NaxSy is more porous than LixSy, supported by (i) its rough morphology observed by focused ion beam-scanning electron microscopy, (ii) the rapid decrease of Rinterface (interfacial resistance) in NaxSy-covered-Na symmetric cells with liquid electrolyte upon aging under open-circuit potential, and (iii) the increase of Rinterface in NaxSy-covered-Na solid-state symmetric cells with Na3PS4 electrolyte. The porous SEI allows the penetration of liquid electrolyte or alkali metal creep through its pores, resulting in a continuous chemical reaction. Hence, porosity of SEIs in general should be carefully taken into account in the application of batteries containing both liquid electrolyte and solid electrolyte.

Assembling Metal Organic Layer Composites for High-Performance Electrocatalytic CO2 Reduction to Formate.

2D metal-organic-framework (MOF) based composites have emerged as promising candidates for electrocatalysis due to their high structural flexibility and fully exposed active sites. Herein, a freestanding metal-organic layer (MOL) with a 2D kgd (kagome dual) lattice was constructed with abundant surface oxygenate groups serving as anchoring sites to immobilize diverse guests. Taking Bi as an example, tetragonal Bi2 O3 nanowires can be uniformly grown on MOLs after solvothermal treatment, the structural evolution of which was followed by ex situ electron microscopy. The as-prepared Bi2 O3 /MOL exhibits excellent CO2 electroreduction activity towards formate reaching a specific current of 2.3 A mgBi -1 and Faradaic efficiencies of over 85 % with a wide potential range from -0.87 to -1.17 V, far surpassing Bi2 O3 /UiO (a 3D Zr6 -oxo based MOF) and Bi2 O3 /AB (Acetylene Black). Such a post-synthetic modification strategy can be flexibly extended to develop versatile MOL composites, highlighting the superiority of optimizing MOL-based composites for electrocatalysis.

Topological Surface State in Epitaxial Zigzag Graphene Nanoribbons.

Protected and spin-polarized transport channels are the hallmark of topological insulators, coming along with an intrinsic strong spin-orbit coupling. Here we identified such corresponding chiral states in epitaxially grown zigzag graphene nanoribbons (zz-GNRs), albeit with an extremely weak spin-orbit interaction. While the bulk of the monolayer zz-GNR is fully suspended across a SiC facet, the lower edge merges into the SiC(0001) substrate and reveals a surface state at the Fermi energy, which is extended along the edge and splits in energy toward the bulk. All of the spectroscopic details are precisely described within a tight binding model incorporating a Haldane term and strain effects. The concomitant breaking of time-reversal symmetry without the application of external magnetic fields is supported by ballistic transport revealing a conduction of G = e2/h.

One-dimensional confinement and width-dependent bandgap formation in epitaxial graphene nanoribbons.

The ability to define an off state in logic electronics is the key ingredient that is impossible to fulfill using a conventional pristine graphene layer, due to the absence of an electronic bandgap. For years, this property has been the missing element for incorporating graphene into next-generation field effect transistors. In this work, we grow high-quality armchair graphene nanoribbons on the sidewalls of 6H-SiC mesa structures. Angle-resolved photoelectron spectroscopy (ARPES) and scanning tunneling spectroscopy measurements reveal the development of a width-dependent semiconducting gap driven by quantum confinement effects. Furthermore, ARPES demonstrates an ideal one-dimensional electronic behavior that is realized in a graphene-based environment, consisting of well-resolved subbands, dispersing and non-dispersing along and across the ribbons respectively. Our experimental findings, coupled with theoretical tight-binding calculations, set the grounds for a deeper exploration of quantum confinement phenomena and may open intriguing avenues for new low-power electronics.

Overdoping Graphene beyond the van Hove Singularity.

At very high doping levels the van Hove singularity in the π^{*} band of graphene becomes occupied and exotic ground states possibly emerge, driven by many-body interactions. Employing a combination of ytterbium intercalation and potassium adsorption, we n dope epitaxial graphene on silicon carbide past the π^{*} van Hove singularity, up to a charge carrier density of 5.5×10^{14} cm^{-2}. This regime marks the unambiguous completion of a Lifshitz transition in which the Fermi surface topology has evolved from two electron pockets into a giant hole pocket. Angle-resolved photoelectron spectroscopy confirms these changes to be driven by electronic structure renormalizations rather than a rigid band shift. Our results open up the previously unreachable beyond-van-Hove regime in the phase diagram of epitaxial graphene, thereby accessing an unexplored landscape of potential exotic phases in this prototype two-dimensional material.

Semiconductor to metal transition in two-dimensional gold and its van der Waals heterostack with graphene.

The synthesis of two-dimensional (2D) transition metals has attracted growing attention for both fundamental and application-oriented investigations, such as 2D magnetism, nanoplasmonics and non-linear optics. However, the large-area synthesis of this class of materials in a single-layer form poses non-trivial difficulties. Here we present the synthesis of a large-area 2D gold layer, stabilized in between silicon carbide and monolayer graphene. We show that the 2D-Au ML is a semiconductor with the valence band maximum 50 meV below the Fermi level. The graphene and gold layers are largely non-interacting, thereby defining a class of van der Waals heterostructure. The 2D-Au bands, exhibit a 225 meV spin-orbit splitting along the [Formula: see text] direction, making it appealing for spin-related applications. By tuning the amount of gold at the SiC/graphene interface, we induce a semiconductor to metal transition in the 2D-Au, which has not yet been observed and hosts great interest for fundamental physics.

Solid Electrolyte Interphase Evolution on Lithium Metal in Contact with Glyme-Based Electrolytes.

The formation of a stable solid electrolyte interphase (SEI) is a prerogative for functional lithium metal batteries. Herein, the formation and evolution of such SEI in contact with glyme-based electrolytes is investigated under open circuit voltage and several constant current cycles. An important conclusion of the study is that Lix Sy species are nonbeneficial SEI components, compared to the Li3 N counterpart. In addition, chemical (X-ray photoelectron spectroscopy, XPS) and electrochemical (impedance spectroscopy) evolution of SEI under galvanostatic conditions are comprehensively tracked.

Triphenylene-Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge-Transfer Complexes with Common Unoccupied Molecular States.

Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule-substrate interactions. Here, the formation of a monolayer thick blend of triphenylene-based organic donor and acceptor molecules from 2,3,6,7,10,11-hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low-energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self-assembled charge-transfer complexes.

Electronic properties of single-layer tungsten disulfide on epitaxial graphene on silicon carbide.

This work reports an electronic and micro-structural study of an appealing system for optoelectronics: tungsten disulfide (WS2) on epitaxial graphene (EG) on SiC(0001). The WS2 is grown via chemical vapor deposition (CVD) onto the EG. Low-energy electron diffraction (LEED) measurements assign the zero-degree orientation as the preferential azimuthal alignment for WS2/EG. The valence-band (VB) structure emerging from this alignment is investigated by means of photoelectron spectroscopy measurements, with both high space and energy resolution. We find that the spin-orbit splitting of monolayer WS2 on graphene is of 462 meV, larger than what is reported to date for other substrates. We determine the value of the work function for the WS2/EG to be 4.5 ± 0.1 eV. A large shift of the WS2 VB maximum is observed as well, due to the lowering of the WS2 work function caused by the donor-like interfacial states of EG. Density functional theory (DFT) calculations carried out on a coincidence supercell confirm the experimental band structure to an excellent degree. X-ray photoemission electron microscopy (XPEEM) measurements performed on single WS2 crystals confirm the van der Waals nature of the interface coupling between the two layers. In virtue of its band alignment and large spin-orbit splitting, this system gains strong appeal for optical spin-injection experiments and opto-spintronic applications in general.

Interplay of Chemical and Electronic Structure on the Single-Molecule Level in 2D Polymerization.

Single layers of covalently linked organic materials in the form of two-dimensional (2D) polymers constitute structures complementary to inorganic 2D materials. The electronic properties of 2D polymers may be manipulated through a deliberate choice of the organic precursors. Here we address the changes in electronic structure-from precursor molecule to oligomer-by scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy. For this purpose, we introduce the polymerization reaction of 1,3,5-tris(4-carboxyphenyl)benzene via decarboxylation on Cu(111), which is thoroughly characterized by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We present a comprehensive study of a contamination-free on-surface coupling scheme and study how dehydrogenation, decarboxylation, and polymerization affect the electronic structure on the molecular level.

Phonon-pump extreme-ultraviolet-photoemission probe in graphene: anomalous heating of Dirac carriers by lattice deformation.

We modulate the atomic structure of bilayer graphene by driving its lattice at resonance with the in-plane E_{1u} lattice vibration at 6.3 µm. Using time- and angle-resolved photoemission spectroscopy (tr-ARPES) with extreme-ultraviolet (XUV) pulses, we measure the response of the Dirac electrons near the K point. We observe that lattice modulation causes anomalous carrier dynamics, with the Dirac electrons reaching lower peak temperatures and relaxing at faster rate compared to when the excitation is applied away from the phonon resonance or in monolayer samples. Frozen phonon calculations predict dramatic band structure changes when the E_{1u} vibration is driven, which we use to explain the anomalous dynamics observed in the experiment.

Population inversion in monolayer and bilayer graphene.

The recent demonstration of saturable absorption and negative optical conductivity in the Terahertz range in graphene has opened up new opportunities for optoelectronic applications based on this and other low dimensional materials. Recently, population inversion across the Dirac point has been observed directly by time- and angle-resolved photoemission spectroscopy (tr-ARPES), revealing a relaxation time of only ∼130 femtoseconds. This severely limits the applicability of single layer graphene to, for example, Terahertz light amplification. Here we use tr-ARPES to demonstrate long-lived population inversion in bilayer graphene. The effect is attributed to the small band gap found in this compound. We propose a microscopic model for these observations and speculate that an enhancement of both the pump photon energy and the pump fluence may further increase this lifetime.

Ballistic bipolar junctions in chemically gated graphene ribbons.

The realization of ballistic graphene pn-junctions is an essential task in order to study Klein tunneling phenomena. Here we show that intercalation of Ge under the buffer layer of pre-structured SiC-samples succeeds to make truly nano-scaled pn-junctions. By means of local tunneling spectroscopy the junction width is found to be as narrow as 5 nm which is a hundred times smaller compared to electrically gated structures. The ballistic transmission across the junction is directly proven by systematic transport measurements with a 4-tip STM. Various npn- and pnp-junctions are studied with respect to the barrier length. The pn-junctions are shown to act as polarizer and analyzer with the second junction becoming transparent in case of a fully ballistic barrier. This can be attributed to the almost full suppression of electron transmission through the junction away from normal incidence.

Non-equilibrium Dirac carrier dynamics in graphene investigated with time- and angle-resolved photoemission spectroscopy.

We have used time- and angle-resolved photoemission spectroscopy (tr-ARPES) to assess the influence of many-body interactions on the Dirac carrier dynamics in graphene. From the energy-dependence of the measured scattering rates we directly determine the imaginary part of the self-energy, visualizing the existence of a relaxation bottleneck associated with electron-phonon coupling. A comparison with static line widths obtained by high-resolution ARPES indicates that the dynamics of photo-excited carriers in graphene are solely determined by the equilibrium self-energy. Furthermore, the subtle interplay of different many-body interactions in graphene may allow for carrier multiplication, where the absorption of a single photon generates more than one electron-hole pair via impact ionization. We find that, after photo-excitation, the number of carriers in the conduction band along the ΓK-direction keeps increasing for about 40 fs after the pump pulse is gone. A definite proof of carrier multiplication in graphene, however, requires a more systematic study, carefully taking into account the contribution of momentum relaxation on the measured rise time.

Snapshots of non-equilibrium Dirac carrier distributions in graphene.

The optical properties of graphene are made unique by the linear band structure and the vanishing density of states at the Dirac point. It has been proposed that even in the absence of a bandgap, a relaxation bottleneck at the Dirac point may allow for population inversion and lasing at arbitrarily long wavelengths. Furthermore, efficient carrier multiplication by impact ionization has been discussed in the context of light harvesting applications. However, all of these effects are difficult to test quantitatively by measuring the transient optical properties alone, as these only indirectly reflect the energy- and momentum-dependent carrier distributions. Here, we use time- and angle-resolved photoemission spectroscopy with femtosecond extreme-ultraviolet pulses to directly probe the non-equilibrium response of Dirac electrons near the K-point of the Brillouin zone. In lightly hole-doped epitaxial graphene samples, we explore excitation in the mid- and near-infrared, both below and above the minimum photon energy for direct interband transitions. Whereas excitation in the mid-infrared results only in heating of the equilibrium carrier distribution, interband excitations give rise to population inversion, suggesting that terahertz lasing may be possible. However, in neither excitation regime do we find any indication of carrier multiplication, questioning the applicability of graphene for light harvesting.

Phase boundary propagation in large LiFePO4 single crystals on delithiation.

Large single crystals of LiFePO(4) have been chemically delithiated. The relevance of chemical oxidation in comparison with electrochemical delithiation is discussed. Analyses of the Li content and profiles were done by electron energy loss spectroscopy and secondary ion mass spectrometry. The propagation of the FePO(4) phase growing on the surface of the large single crystal was followed by in situ optical microscopy as a function of time. The kinetics were evaluated in terms of linear irreversible thermodynamics and found to be characterized by an induction period followed by parabolic growth behavior of the FePO(4) phase indicating transport control. The growth rate was shown to depend on the crystallographic orientation. Scanning electron microscopy images showed cracks and a high porosity of the FePO(4) layer due to the significant changes in the molar volumes. The transport was found to be greatly enhanced by the porosity and crack formation and hence greatly enhanced over pure bulk transport, a result which is supposed to be very relevant for battery research if coarse-grained powder is used.