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The long theorized two-dimensional allotrope of SiC has remained elusive amid the exploration of graphenelike honeycomb structured monolayers. It is anticipated to possess a large direct band gap (2.5 eV), ambient stability, and chemical versatility. While sp2 bonding between silicon and carbon is energetically favorable, only disordered nanoflakes have been reported to date. Here we demonstrate largearea, bottom-up synthesis of monocrystalline, epitaxial monolayer honeycomb SiC atop ultrathin transition metal carbide films on SiC substrates. We find the 2D phase of SiC to be almost planar and stable at high temperatures, up to 1200 degrees C in vacuum. Interactions between the 2D-SiC and the transition metal carbide surface result in a Dirac-like feature in the electronic band structure, which in the case of a TaC substrate is strongly spin-split. Our findings represent the first step towards routine and tailored synthesis of 2D-SiC monolayers, and this novel heteroepitaxial system may find diverse applications ranging from photovoltaics to topological superconductivity., Funding Agencies|Swedish Foundation for Strategic Research (SSF) [GMT14-0077, RMA15-0024]; Chalmers Excellence Initiative Nano, the Swedish Research council [2021-05252, 2019-00068]; Chalmers-MAX IV collaboration program; Swedish Research council [2018-07152]; Swedish Governmental Agency for Innovation Systems [2018-04969]; Formas [2019-02496]

In light of their unique physicochemical properties two-dimensional metals are of interest in the development of next-generation sustainable sensing and catalytic applications. Here we showcase results of the investigation of the substrate effect on the formation and the catalytic activity of representative 2D gold layers supported by non-graphenized and graphenized SiC substrates. By performing comprehensive density functional theory (DFT) calculations, we revealed the epitaxial alignment of gold monolayer with the underlying SiC substrate, regardless of the presence of zero-layer graphene or epitaxial graphene. This is explained by a strong binding energy (similar to 4.7 eV) of 2D Au/SiC and a pronounced charge transfer at the interface, which create preconditions for the penetration of the related electric attraction through graphene layers. We then link the changes in catalytic activity of substrate-supported 2D Au layer in hydrogen evolution reaction to the formation of a charge accumulation region above graphenized layers. Gold intercalation beneath zero-layer graphene followed by its transformation to quasi-free-standing epitaxial graphene is found to be an effective approach to tune the interfacial charge transfer and catalytic activity of 2D Au. The sensing potential of substrate-supported 2D Au was also tested through exploring the adsorption behaviour of NH3, NO2 and NO gas molecules. The present results can be helpful for the experimental design of substrate-supported 2D Au layers with targeted catalytic activity and sensing performance., Funding Agencies|Angpannefoereningens Forskningsstiftelse [21-112]; Linkoeping University

We report a reliable and scalable fabrication method for producing electrical contacts to two-dimensional (2D) materials based on the tri-layer resist system. We demonstrate the applicability of this method in devices fabricated on epitaxial graphene on silicon carbide (epigraphene) used as a scalable 2D material platform. For epigraphene, data on nearly 70 contacts result in median values of the one-dimensional (1D) specific contact resistances pc 67 omega center dot im and follow the Landauer quantum limit pc n-1/2, consistently reaching values pc < 50 omega center dot im at high carrier densityn. As a proof of concept, we apply the same fabrication method to the transition metal dichalcogenide (TMDC) molybdenum disulfide (MoS2). Our edge contacts enable MoS2 field-effect transistor (FET) behavior with an ON/OFF ratio of >106 at room temperature (>109 at cryogenic temperatures). The fabrication route demonstrated here allows for contact metallization using thermal evaporation and also by sputtering, giving an additional flexibility when designing electrical interfaces, which is key in practical devices and when exploring the electrical properties of emerging materials., Funding Agencies|Swedish Foundation for Strategic Research (SSF) [GMT14-0077, RMA15-0024, FFL21-0129]; Chalmers Area of Advance Nano, Chalmers Area of Advance Energy, 2D TECH VINNOVA competence Center [2019-00068]; Marie Sklodowska-Curie [766025]; Knut and Alice Wallenberg Foundation [2019.0140]; Swedish Research Council VR [2021-05252, 2018-04962]

The combination of wide-band gap semiconductors such as zinc oxide (ZnO) and graphene quantum dots (GQDs) is a promising strategy to tune the optoelectronic properties of GQDs and develop new functionalities. Here we report on a theoretical design of not-yet-synthesized hybrid materials composed of ZnO clusters surrounded by carbon moieties, hereinafter referred to as ZnO-embedded graphene quantum dots. Their structure and light absorption properties are presented, with an in-depth analysis of the nature of the photoexcited states. The stability of the (ZnO)(n)C96-2n system with n = 1, 3, 4, 7, 12 and 27 is investigated by performing vibrational mode analysis and estimating cohesive energy and zinc vacancy formation energy. A strong dependence of the structural and optoelectronic properties of the hybrid material on the amount of ZnO pairs is revealed and discussed. Strong light absorption and unexpected enhancement of Raman modes related to the vibrations in carbon moiety are observed for the highly symmetric (ZnO)(27)C-42 system that makes it an ideal study subject. Complementary excited state analysis, charge density difference (CDD) analysis and interfragment charge transfer analysis present insights deep into the nature of the excited states. An equal contribution of doubly degenerate locally excited states and charge transfer states in broadband light absorption by (ZnO)(27)C-42 is identified. The present results are helpful to elucidate the nature of the fundamental internal mechanisms underlying light absorption in ZnO-embedded graphene quantum dots, thereby providing a scientific background for future experimental study of low-dimensional metal-oxygen-carbon material family., Funding Agencies|Angpanneforeningens Forskningsstiftelse [21-112]; Linkoping University

Here we investigate the interface properties of gold (Au) decorated graphenized surfaces of 4H-SiC intended for electrochemical electrodes. These are fabricated using a two-step process: discontinuous Au layers with a nominal thickness of 2 nm are sputter-deposited onto 4H-SiC substrates with different graphenization extent—zero-layer graphene (ZLG) and monolayer epitaxial graphene) —followed by thermal annealing. By performing combined morphometric analysis, Raman mapping analysis, conductive atomic force microscopy, and electrochemical impedance spectroscopy measurements, we shed light on the relationship between physical processes (Au intercalation, particle re-shaping, and de-wetting) caused by thermal annealing and the intrinsic properties of graphenized SiC (vertical electron transport, charge-transfer properties, vibrational properties, and catalytic activity). We find that the impedance spectra of all considered structures exhibit two semicircles in the high and low frequency regions, which may be attributed to the graphene/ZLG/SiC (or Au/graphene/ZLG/SiC) and SiC/ZLG/graphene/electrolyte (or SiC/ZLG//Au/electrolyte) interfaces, respectively. An equivalent circuit model is proposed to estimate the interface carrier transfer parameters. This work provides an in-depth comprehension of the way by which the Au/2D carbon/SiC interaction strength influences the interface properties of heterostructures, which can be helpful for developing high performance catalytic and sensing devices., QC 20230711

In this work, we present the results of measurements of the Raman spectrum of the root 3x root 3R30 degrees reconstruction of graphene grown on 4H-SiC(0001), the so-called buffer layer. The extracted Raman spectrum of the buffer layer shows bands, different from those of graphene, which can be attributed to the interaction of the buffer layer with the SiC substrate. In particular, in the high-wavenumber region, at least three bands are observed in the wavenumber regions 1,350-1,420, 1,470-1,490 and 1,520-1,570 cm-1. The assignment of the buffer layer bands is supported here by tight-binding simulations of the one-phonon density of states for structures with a sufficiently large number of Si-C bilayers for reaching convergence. The converged phonon density of states is found to be in semi-quantitative agreement with the latter two bands, and therefore, the tight-binding predictions of the lattice dynamics of the structure can be used for their assignment to buffer layer vibrations. Namely, the Raman band at about 1,550 cm-1 can be assigned to modified in-plane optical phonon branches of graphene, while the Raman band at about 1,490 cm-1 can be assigned to modified folded parts of these branches inside the Brillouin zone of the buffer layer and can be considered as a Raman fingerprint of the buffer layer. We present the results of measurements of the Raman spectrum of the root 3x root 3R30 degrees reconstruction of graphene grown on 4H-SiC(0001), the so-called buffer layer (BL) in the wavenumber region 1,200-1,650 cm-1. The assignment of the BL bands is supported by tight-binding simulations of the one-phonon density of states (DOS) for structures with a sufficiently large number of Si-C bilayers for reaching convergence. The converged phonon DOS is found to be in semi-quantitative agreement with the experimental Raman spectra.image, Funding Agencies|National Science Fund of Bulgaria; [KP-06-H58/2-16.11.2021]

Exploiting low-cost, highly active, and robust oxygen evolution reaction (OER) electrocatalysts based on earth-abundant elements by a simple synthesis approach holds paramount importance for green hydrogen production through water electrolysis. In this work, the NiO, Co3O4 and NiCo2O4 nanoparticle layers with identical surface morphologies are prepared under same deposition conditions by a simple spray pyrolysis method and their OER activities are comparatively investigated. Among all these three electrocatalysts, NiCo2O4 shows the lowest overpotential of 420 mV to drive benchmark current density of 10 mA cm(-2) and the smallest Tafel slope (84.1 mV dec(-1)), which are comparable to the OER performance of the benchmark commercial RuO2 electrocatalyst. The high OER activity of NiCo2O4 is attributed to the synergy effect and the modulation of electronic properties between Co and Ni atoms, which drastically reduces the overpotential required to drive OER activities. Therefore, it is believed that the NiCo2O4 synthesized by this simple method would be a competitive candidate as an industrial electrocatalyst with high-efficiency and low cost for large-scale green hydrogen production via water electrolysis., Funding Agencies|Swedish Research Council (Vetenskapsradet) [2018-04670, 2020-04400]; Swedish Foundation for International Cooperation in Research and Higher Education (STINT) [CH2016-6722]; Olle Engkvists Stiftelse [220-0222, 221-0259]

Graphene pn-junctions offer a rich portfolio of intriguing physical phenomena. They stand as the potential building blocks for a broad spectrum of future technologies, ranging from electronic lenses analogous to metamaterials in optics, to high-performance photodetectors important for a variety of optoelectronic applications. The production of graphene pn-junctions and their precise structuring at the nanoscale remains to be a challenge. In this work, a scalable method for fabricating periodic nanoarrays of graphene pn-junctions on a technologically viable semiconducting SiC substrate is introduced. Via H-intercalation, 1D confined armchair graphene nanoribbons are transformed into a single 2D graphene sheet rolling over 6H-SiC mesa structures. Due to the different surface terminations of the basal and vicinal SiC planes constituting the mesa structures, different types of charge carriers are locally induced into the graphene layer. Using angle-resolved photoelectron spectroscopy, the electronic band structure of the two graphene regions are selectively measured, finding two symmetrically doped phases with p-type being located on the basal planes and n-type on the facets. The results demonstrate that through a careful structuring of the substrate, combined with H-intercalation, integrated networks of graphene pn-junctions could be engineered at the nanoscale, paving the way for the realization of novel optoelectronic device concepts., Funding Agencies|Deutsche Forschungsgemeinschaft (DFG)German Research Foundation (DFG) [Sta315/9-1, Te386/13-1, Te386/12-1]; Projekt DEAL

Novel two-dimensional materials (2DMs) with balanced electrical conductivity and lithium (Li) storage capacity are desirable for next-generation rechargeable batteries as they may serve as high-performance anodes, improving output battery characteristics. Gaining an advanced understanding of the electrochemical behavior of lithium at the electrode surface and the changes in interior structure of 2DM-based electrodes caused by lithiation is a key component in the long-term process of the implementation of new electrodes into to a realistic device. Here, we showcase the advantages of bilayer-patched epitaxial graphene on 4H-SiC (0001) as a possible anode material in lithium-ion batteries. The presence of bilayer graphene patches is beneficial for the overall lithiation process because it results in enhanced quantum capacitance of the electrode and provides extra intercalation paths. By performing cyclic voltammetry and chronoamperometry measurements, we shed light on the redox behavior of lithium at the bilayer-patched epitaxial graphene electrode and find that the early-stage growth of lithium is governed by the instantaneous nucleation mechanism. The results also demonstrate the fast lithium-ion transport (similar to 4.7-5.6 x 10(-7) cm(2).s(-1)) to the bilayer-patched epitaxial graphene electrode. Raman measurements complemented by in-depth statistical analysis and density functional theory calculations enable us to comprehend the lithiation effect on the properties of bilayer-patched epitaxial graphene and ascribe the lithium intercalation-induced Raman G peak splitting to the disparity between graphene layers. The current results are helpful for further advancement of the design of graphene-based electrodes with targeted performance., Funding Agencies|VR [2018-04962]; SSF [SSF GMT14-0077, SSF RMA15-0024]; Angpanneforeningens Forskningsstiftelse [21-112]

The climate change due to human activities stimulates the research on new energy resources. Hydrogen has attracted interest as a green carrier of high energy density. The sustainable production of hydrogen is achievable only by water electrolysis based on the hydrogen evolution reaction (HER). Graphitic materials are widely utilized in this technology in the role of conductive catalyst supports. Herein, by performing dynamic and steady-state electrochemical measurements in acidic and alkaline media, we investigated the bidirectional electrocatalysis of the HER and hydrogen oxidation reaction (HOR) on metal- and defect-free epigraphene (EG) grown on 4H silicon carbide (4HSiC) as a ground level of structural organization of general graphitic materials. The absence of any signal degradation illustrates the high stability of EG. The experimental and theoretical investigations yield the coherent conclusion on the dominant HER pathway following the Volmer-Tafel mechanism. We ascribe the observed reactivity of EG to its interaction with the underlying SiC substrate that induces strain and electronic doping. The computed high activation energy for breaking the O-H bond is linked to the high negative overpotential of the HER. The estimated exchange current of HER/HOR on EG can be used in the evaluation of complex electrocatalytic systems based on graphite as a conducing support., Funding Agencies|Angpanneforeningens Forskningsstiftelse [16-541, 21-112]; VR [2018-04962]; SSF [RMA 15-0024]

In this paper, we demonstrate the feasibility of fabricating vertical Schottky diodes on bulk cubic silicon carbide (3C-SiC) material obtained by combining sublimation epitaxy and chemical vapor deposition, starting from 4 degrees -off axis 4H-SiC. First, the good quality of the epilayers grown with this method was demonstrated by morphological and structural analyses. Then, fabricated vertical Pt/3C-SiC Schottky diodes exhibited an ideality factor of 1.21 and a barrier height of 0.6 eV, as determined by thermionic emission model. The temperature dependent forward current analysis indicated the formation of an inhomogeneous barrier, which has been related with the presence of conductive surface defects, detected by nanoscale local current measurements. On the other hand, the reverse leakage current could be described by thermionic field emission model, including image force lowering. These findings demonstrate the viability of the proposed approach for bulk 3C-SiC growth for device fabrication. The material quality and the feasibility of fabricating vertical diodes based on 3C-SiC with a low barrier pave the way for the application of this polytype for medium-voltage power devices., Funding Agencies|European project CHALLENGE; [720827]