Search Results (8)

Nitrate electroreduction reaction to ammonia (NO₃ER) holds great promise for both nitrogen pollution removal and valuable ammonia synthesis, which are still dependent on transition-metal-based catalysts at present. However, metal-free catalysts with multiple advantages for such processes have been rarely reported. Herein, by means of density functional theory (DFT) computations, in which the Perdew–Burke–Ernzerhof (PBE) functional is obtained by considering the possible van der Waals (vdW) interaction using the DFT+D3 method, we explored the potential of several two-dimensional (2D) silicon carbide monolayers as metal-free NO₃ER catalysts. Our results revealed that the excellent synergistic effect between the three Si active sites within the Si₃C monolayer enables the sufficient activation of NO₃⁻ and promotes its further hydrogenation into NO₂^*, NO^*, and NH₃, making the Si₃C monolayer exhibit high NO₃ER activity with a low limiting potential of −0.43 V. In particular, such an electrochemical process is highly dependent on the pH value of the electrolytes, in which acidic conditions are more favorable for NO₃ER. Moreover, ab initio molecular dynamics (AIMD) simulations demonstrated the high stability of the Si₃C monolayer. In addition, the Si₃C monolayer shows a low formation energy, excellent electronic properties, a superior suppression effect on competing reactions, and high stability, offering significant advantages for its experimental synthesis and practical applications in electrocatalysis. Thus, a Si₃C monolayer can perform as a promising NO₃ER catalyst, which would open a new avenue to further develop novel metal-free catalysts for NO₃ER. Full article

Silicon carbide has structural strength, high electronic conductivity, low diffusion barrier and high storage capacity, which are suitable for engineering applications such as lithium-ion batteries, electric vehicles, uninterruptible power supplies and SiC diodes. In particular, 3C-SiC monolayers oriented along the (1 1 0) crystallographic direction that could have symmetric surfaces have been poorly studied, as have the effects of surface passivation on their physical and electronic properties. In this work, we investigate the influence of lithium on the electronic properties of hydrogenated surfaces in 3C-SiC monolayers using density functional theory. We examine the electronic properties of surfaces fully passivated with hydrogen with those of surfaces fully passivated with lithium and those with mixed passivation. Our results show that only fully hydrogenated surfaces exhibit a direct band-gap, while the full Li, CH+SiLi, and H+Li${}_c$ passivations exhibit metallic behavior. The CLi+SiH, H+1LiC, and H+1LiSi passivation systems decrease the band-gap compared to the hydrogenated case and show an indirect band-gap. The formation energy of the system shows that the most stable arrangement is full-H, followed by H+1LiC, and the most unstable system is full-Li, which has a positive formation energy. Full article

Sp²-hybridized monolayer semiconductors (e.g., planar group III-V and IV-IV binary compounds) with inversion symmetry breaking (ISB) display piezoelectricity governed by their σ- and π-bond electrons. Here, we studied their bond-orbital-resolved electronic piezoelectricity (i.e., the σ- and π-piezoelectricity). We formulated a tight-binding piezoelectric model to reveal the different variations of σ- and π-piezoelectricity with the ISB strength ($\Delta$). As $\Delta$ varied from positive to negative, the former decreased continuously, but the latter increased piecewise and jumped at $\Delta =0$ due to the criticality of the π-electrons’ ground-state geometry near this quantum phase-transition point. This led to a piezoelectricity predominated by the π-electrons for a small $|\Delta |$. By constructing an analytical model, we clarified the microscopic mechanisms underlying the anomalous π-piezoelectricity and its subtle relations with the valley Hall effect. The validation of our models was justified by applying them to the typical sp² monolayers including hexagonal silicon carbide, Boron-X (X = N, P, As, Ab), and a BN-doped graphene superlattice. Full article

The micromechanism of the low-cycle fatigue of mono- and multilayer PVD coatings on cutting tools was investigated. Multilayer nanolaminate (TiAlCrSiY)N/(TiAlCr)N and monolayer (TiAlCrSiY)N PVD coatings were deposited on the cemented carbide ball nose end mills. Low-cycle fatigue resistance was studied using the cyclic nanoindentation technique. The obtained results were compared with the behaviour of the polycrystalline silicon reference sample. The fractal analysis of time-resolved curves for indenter penetration depth demonstrated regularities of damage accumulation in the coatings at the early stage of wear. The difference in low-cycle fatigue of the brittle silicon and nitride wear-resistant coatings is shown. It is demonstrated that when distinguished from the single layer (TiAlCrSiY)N coating, the nucleation and growth of microcracks in the multilayer (TiAlCrSiY)N/(TiAlCr)N coating is accompanied by acts of microplastic deformation providing a higher fracture toughness of the multilayer nanolaminate (TiAlCrSiY)N/(TiAlCr)N. Full article

As a direct wide bandgap semiconducting material, two-dimensional, 2D, silicon carbide has the potential to bring revolutionary advances into optoelectronic and electronic devices. It can overcome current limitations with silicon, bulk SiC, and gapless graphene. In addition to SiC, which is the most stable form of monolayer silicon carbide, other compositions, i.e., ${\mathrm{Si}}_x{\mathrm{C}}_y,$ are also predicted to be energetically favorable. Depending on the stoichiometry and bonding, monolayer ${\mathrm{Si}}_x{\mathrm{C}}_y$ may behave as a semiconductor, semimetal or topological insulator. With different Si/C ratios, the emerging 2D silicon carbide materials could attain novel electronic, optical, magnetic, mechanical, and chemical properties that go beyond those of graphene, silicene, and already discovered 2D semiconducting materials. This paper summarizes key findings in 2D SiC and provides insight into how changing the arrangement of silicon and carbon atoms in SiC will unlock incredible electronic, magnetic, and optical properties. It also highlights the significance of these properties for electronics, optoelectronics, magnetic, and energy devices. Finally, it will discuss potential synthesis approaches that can be used to grow 2D silicon carbide. Full article

Modification of epitaxial graphene on silicon carbide (EG/SiC) was explored by ion implantation using 10 keV nitrogen ions. Fragments of monolayer graphene along with nanostructures were observed following nitrogen ion implantation. At the initial fluence, sp³ defects appeared in EG; higher fluences resulted in vacancy defects as well as in an increased defect density. The increased fluence created a decrease in the intensity of the prominent peak of SiC as well as of the overall relative Raman intensity. The X-ray photoelectron spectroscopy (XPS) showed a reduction of the peak intensity of graphitic carbon and silicon carbide as a result of ion implantation. The dopant concentration and level of defects could be controlled both in EG and SiC by the fluence. This provided an opportunity to explore EG/SiC as a platform using ion implantation to control defects, and to be applied for fabricating sensitive sensors and nanoelectronics devices with high performance. Full article

Due to its excellent physical properties and availability directly on a semiconductor substrate, epitaxial graphene (EG) grown on the (0001) face of hexagonal silicon carbide is a material of choice for advanced applications in electronics, metrology and sensing. The deposition of ultrathin high-k insulators on its surface is a key requirement for the fabrication of EG-based devices, and, in this context, atomic layer deposition (ALD) is the most suitable candidate to achieve uniform coating with nanometric thickness control. This paper presents an overview of the research on ALD of high-k insulators on EG, with a special emphasis on the role played by the peculiar electrical/structural properties of the EG/SiC (0001) interface in the nucleation step of the ALD process. The direct deposition of Al₂O₃ thin films on the pristine EG surface will be first discussed, demonstrating the critical role of monolayer EG uniformity to achieve a homogeneous Al₂O₃ coverage. Furthermore, the ALD of several high-k materials on EG coated with different seeding layers (oxidized metal films, directly deposited metal-oxides and self-assembled organic monolayers) or subjected to various prefunctionalization treatments (e.g., ozone or fluorine treatments) will be presented. The impact of the pretreatments and of thermal ALD growth on the defectivity and electrical properties (doping and carrier mobility) of the underlying EG will be discussed. Full article

Silicon carbide (SiC) has already found useful applications in high-power electronic devices and light-emitting diodes (LEDs). Interestingly, SiC is a suitable substrate for growing monolayer epitaxial graphene and GaN-based devices. Therefore, it provides the opportunity for integration of high-power devices, LEDs, atomically thin electronics, and high-frequency devices, all of which can be prepared on the same SiC substrate. In this paper, we concentrate on detailed measurements on ultralow-density p-type monolayer epitaxial graphene, which has yet to be extensively studied. The measured resistivity ρ_xx shows insulating behavior in the sense that ρ_xx decreases with increasing temperature T over a wide range of T (1.5 K ≤ T ≤ 300 K). The crossover from negative magnetoresistivity (MR) to positive magnetoresistivity at T = 40 K in the low-field regime is ascribed to a transition from low-T quantum transport to high-T classical transport. For T ≥ 120 K, the measured positive MR ratio [ρ_xx(B) − ρ_xx(B = 0)]/ρ_xx(B = 0) at B = 2 T decreases with increasing T, but the positive MR persists up to room temperature. Our experimental results suggest that the large MR ratio (~100% at B = 9 T) is an intrinsic property of ultralow-charge-density graphene, regardless of the carrier type. This effect may find applications in magnetic sensors and magnetoresistance devices. Full article