XPS Analysis of FexNiyPS3 vdW Materials Used in the Hydrogen Evolution Processes.

In response to the global demand for sustainable energy solutions, the quest for stable and cost-effective hydrogen production has garnered significant attention in recent decades. Here, the emergence of layered metal phosphorus trichalcogenides (MPX3, M: transition metal, X: chalcogen) materials and their two-dimensional counterparts with customizable composition and electronic structure holds great promise for such purposes. In the present study, we successfully synthesized large-scale and high-quality FePS3, NiPS3, and an alloyed counterpart, Fe0.5Ni0.5PS3. Subsequent systematic investigations were conducted to probe their respective electronic structures and assess their hydrogen evolution reaction (HER) properties. Remarkably, our results unveiled the successful modulation of the bandgap for FexNiyPS3, ultimately bestowing it with the most favorable HER performance for Fe0.5Ni0.5PS3 when compared to the other two samples. Furthermore, our exploration into the evolution of the X-ray photoelectron spectroscopy (XPS) spectra demonstrated that the charge conversions of metal cations play a pivotal role in the HER reactions. This critical insight further enriches our understanding of the fundamental mechanisms governing the performance of the prepared layered MPX3-based electrocatalysts, thus facilitating a comprehensive and detailed analysis of the pre- and post-HER reactions. This work not only sheds light on the intricate interplay between composition, electronic structure, and catalytic performance in the realm of novel electrocatalysts, but also contributes to the broader scientific community's pursuit of sustainable and efficient hydrogen production.

Electronic Correlations in FexNiyPS3 Van der Waals Materials: Insights from Angle-Resolved Photoelectron Spectroscopy and DFT.

Recently layered antiferromagnetic materials with different magnetic orderings attract increased attention. It was found that these properties can be preserved down to the monolayer limit opening large perspectives for their applications in (opto)spintronics and sensing, however, lacking the experimental results on electronic structure studies. Here the results of angle-resolved photoelectron spectroscopy (ARPES) studies accompanied by DFT calculations for FexNiyPS3 layered van der Waals (vdW) alloys are presented, addressing the effects of electronic correlations in these materials. It is demonstrated that in the case of FePS3 the top of the valence band is formed by the hybrid Fe 3d-S 3p states and is of pure S 3p character for NiPS3, respectively, whereas for the mixed Fe-Ni-based vdW alloy the electronic structure is a sum of contributions from the parent compounds. The obtained results give a clear understanding of the nature of the insulating state in studied MPX3 materials and pave the way on their applications in different areas.

Probing Active Sites on Pristine and Defective MnPX3 (X: S and Se) Monolayers for Electrocatalytic Water Splitting.

The state-of-the-art density functional theory approach was used to study the structural and electronic properties of pristine and defective MnPX3 monolayers as well as their activity toward water and hydrogen evolution reaction (HER) catalytic performance. The adsorption behavior of H2O on a pristine MnPX3 structure is of physisorption nature, whereas the adsorption energy is significantly increased for the defective structures. At the same time, the water dissociation process is more energetically favorable, and the reactivity of MnPX3 is determined by the vacancy configuration. Following Nørskov's approach, the HER catalytic performance is evaluated by calculating the hydrogen adsorption free energy on the respective MnPX3 surface. Our calculation results demonstrate that defective 2D MnPX3 with low coordinated P shows significantly higher HER performance compared to the pristine counterpart.

Realization of a New Graphene-Ferromagnet Interface with Dirac Linear Band Dispersion.

The integration of graphene in spintronics applications requires its close contact with ferromagnetic materials, promoting effective spin injection. At the same time, the linear energy vs wave-vector dependence for the charge carriers in the vicinity of the Fermi level for graphene has to be conserved. Here, motivated by recent theoretical predictions, we present the experimental realization on the synthesis of graphene/ferromagnetic-Mn5Ge3/semiconducting-Ge heterostructures using the intercalation of Mn in the epitaxial graphene/Ge interfaces. Different in situ and ex situ methods confirm the formation of such heterosystems, where graphene is in close contact with ferromagnetic Mn5Ge3, as the Curie temperature reaches room temperature. Despite the expected small distance between graphene and Mn5Ge3 causing the strong interaction at interfaces, our angle-resolved photoelectron spectroscopy experiments for the formed graphene/Mn5Ge3 interfaces confirm the linear band dispersion around the Fermi level for the carriers in graphene. These findings open up an interesting perspective for the integration of graphene in modern semiconductor technology with possible implications for spintronics device fabrication.

Dual Character of the Insulating State in the van der Waals Fe1-xNixPS3 Alloyed Compounds.

The electronic structure of the alloyed transition-metal phosphorus trichalcogenide van der Waals Fe1-xNixPS3 compounds is studied using X-ray absorption spectroscopy and resonant photoelectron spectroscopy combined with intensive density functional theory calculations. Our systematic spectroscopic and theoretical data demonstrate the strong localization of the Fe- and Ni-ions-derived electronic states that leads to the description of the spectroscopic data as belonging simultaneously to Mott-Hubbard and charge-transfer insulators. These findings reveal Fe1-xNixPS3 as unique layered compounds with dual character of the insulating state, pointing to the importance of these results for the description and understanding of the functionality of this class of materials in different applications.

Mixed Insulating State for van der Waals CoPS3.

Large-scale high-quality van der Waals CoPS3 single crystals are synthesized using a chemical vapor transport (CVT) method. The crystallographic structure and electronic properties of this layered material are systematically studied using different spectroscopic methods (XPS, NEXAFS, and resonant photoelectron spectroscopy) accompanied by density functional theory (DFT) calculations. All experimental and theoretical data allow assignment of this material to the class of mixed Mott-Hubbard/charge-transfer insulator with Udd ≅ Δ. All obtained results can enrich the information on the new class of van der Waals materials, transition metal phosphorus trichalcogenides, and help to further effectively exploit their electronic, optical, and transport properties, which are important for adopting this kind of materials into different application areas, such as spintronics and catalysis.

Semiconducting eutectic materials for photocatalysis and photoelectrochemistry applications: a perspective.

The world of semiconductors has drastically improved human lifestyle due to its versatile applications. The demand for new efficient semiconductors is increasing day by day, giving birth to the idea of new synthesis methods. Here, the importance of semiconductor eutectic materials has been presented, as one of the potential candidates for solar-based devices such as photo-anodes for water splitting, along with the micro (µ) pulling method (as a synthesis method for semiconductor eutectic materials). A comparison of the efficiency of the present devices with the eutectic composites has been made, showing semiconductor eutectic materials as a better alternative. In addition, possible changes that can be achieved using the µ-pulling method to enhance the photo(electro)chemical (PEC) properties have focused on semiconducting eutectic materials in this article.

Electronic and Magnetic Properties of the Graphene/Y/Co(0001) Interfaces: Insights from the Density Functional Theory Analysis.

The effect of Y intercalation on the atomic, electronic, and magnetic properties of the graphene/Co(0001) interface is studied using state-of-the-art density functional theory calculations. Different structural models of the graphene/Y/Co(0001) interface are considered: (i) graphene/Y/Co(0001), (ii) graphene/1ML-YCo2/Co(0001), and (iii) graphene/bulk-like-YCo2(111). It is found that the interaction strength between graphene and the substrate is strongly affected by the presence of Y at the interface and the electronic structure of graphene (doping and the appearance of the energy gap) is defined by the Y concentration. For the Co-terminated interfaces between graphene and the metallic support in the considered systems, the electronic structure of graphene is strongly disturbed, leading to the absence of the linear dispersion for the graphene π band; in the case of the Y-terminated interfaces, a graphene layer is strongly n-doped, but the linear dispersion for this band is preserved. Our calculations show that the magnetic anisotropy for the magnetic atoms at the graphene/metal interface is strongly affected by the adsorption of a graphene layer, giving a possibility for one to engineer the magnetic properties of the graphene/ferromagnet systems.

Mott-Hubbard insulating state for the layered van der Waals [Formula: see text] (X: S, Se) as revealed by NEXAFS and resonant photoelectron spectroscopy.

A broad family of the nowadays studied low-dimensional systems, including 2D materials, demonstrate many fascinating properties, which however depend on the atomic composition as well as on the system dimensionality. Therefore, the studies of the electronic correlation effects in the new 2D materials is of paramount importance for the understanding of their transport, optical and catalytic properties. Here, by means of electron spectroscopy methods in combination with density functional theory calculations we investigate the electronic structure of a new layered van der Waals [Formula: see text] (X: S, Se) materials. Using systematic resonant photoelectron spectroscopy studies we observed strong resonant behavior for the peaks associated with the [Formula: see text] final state at low binding energies for these materials. Such observations clearly assign [Formula: see text] to the class of Mott-Hubbard type insulators for which the top of the valence band is formed by the hybrid Fe-S/Se electronic states. These observations are important for the deep understanding of this new class of materials and draw perspectives for their further applications in different application areas, like (opto)spintronics and catalysis.

Topological Quasi-2D Semimetal Co3Sn2S2: Insights into Electronic Structure from NEXAFS and Resonant Photoelectron Spectroscopy.

The electronic structure of the natural topological semimetal Co3Sn2S2 crystals was studied by using near-edge X-ray absorption spectroscopy (NEXAFS) and resonant photoelectron spectroscopy (ResPES). Although, the significant increase of the Co 3d valence band emission is observed at the Co 2p absorption edge in the ResPES experiments, the spectral weight at these photon energies is dominated by the normal Auger contribution. This observation indicates the delocalized character of photoexcited Co 3d electrons and is supported by the first-principle calculations. Our results on the investigations of the element- and orbital-specific electronic states near the Fermi level of Co3Sn2S2 are of importance for the comprehensive description of the electronic structure of this material, which is significant for its future applications in different areas of science and technology, including catalysis and water splitting.

Second Floor of Flatland: Epitaxial Growth of Graphene on Hexagonal Boron Nitride.

In the studies presented here, the subsequent growth of graphene on hexagonal boron nitride (h-BN) is achieved by the thermal decomposition of molecular precursors and the catalytic assistance of metal substrates. The epitaxial growth of h-BN on Pt(111) is followed by the deposition of a temporary Pt film that acts as a catalyst for the fabrication of the graphene sheet. After intercalation of the intermediate Pt film underneath the boron-nitride mesh, graphene resides on top of h-BN. Scanning tunneling microscopy and density functional calculations reveal that the moiré pattern of the van-der-Waals-coupled double layer is due to the interface of h-BN and Pt(111). While on Pt(111) the graphene honeycomb unit cells uniformly appear as depressions using a clean metal tip for imaging, on h-BN they are arranged in a honeycomb lattice where six protruding unit cells enframe a topographically dark cell. This superstructure is most clearly observed at small probe-surface distances. Spatially resolved inelastic electron tunneling spectroscopy enables the detection of a previously predicted acoustic hybrid phonon of the stacked materials. Its' spectroscopic signature is visible in surface regions where the single graphene sheet on Pt(111) transitions into the top layer of the stacking.

Adsorption of water on the pristine and defective semiconducting 2D CrPX3monolayers (X: S, Se).

The effect of vacancy and water adsorption on the electronic structure of semiconducting 2D trichalcogenide material CrPX3(X: S, Se) is studied using state-of-the-art density functional theory (DFT) approach. It is found that chalcogen vacancies play a minor role on the electronic structure of CrPX3in the vicinity of the Fermi level leading to the slightly reduced band gap for these materials, however, inducing strongly localised defect states which are placed in the energy gap formed by the valence band states. Our DFT calculations show that the interaction of water molecules with CrPX3, pristine and defective, can be described as physisorption and the adsorption energy for H2O is insensitive to the difference between pristine and chalcogen-defective surface of trichalcogenide material. These results are the first steps for the theoretical description of the ambient molecules interaction with 2D semiconducting CrPX3material, that is important for its future experimental studies and possible applications.

Correlations in the Electronic Structure of van der Waals NiPS3 Crystals: An X-ray Absorption and Resonant Photoelectron Spectroscopy Study.

The electronic structure of high-quality van der Waals NiPS3 crystals was studied using near-edge X-ray absorption spectroscopy (NEXAFS) and resonant photoelectron spectroscopy (ResPES) in combination with density functional theory (DFT) approach. The experimental spectroscopic methods, being element specific, allow one to discriminate between atomic contributions in the valence and conduction band density of states and give direct comparison with the results of DFT calculations. Analysis of the NEXAFS and ResPES data allows one to identify the NiPS3 material as a charge-transfer insulator. Obtained spectroscopic and theoretical data are very important for the consideration of possible correlated-electron phenomena in such transition-metal layered materials, where the interplay between different degrees of freedom for electrons defines their electronic properties, allowing one to understand their optical and transport properties and to propose further possible applications in electronics, spintronics, and catalysis.

Graphene Layer Morphology as an Indicator of the Metal Alloy Formation at the Interface.

The intercalation of different species in graphene-metal interfaces is widely used to stabilize the artificial phases of different materials, which in some cases leads to the formation of the surface alloys between atoms of the guest metal and the substrate. Here, the interfaces of graphene with Ru(0001) and Ir(111) were modified using intercalation of a thin Mn layer and investigated by means of scanning tunneling microscopy (STM) accompanied by density functional theory (DFT) calculations. It is found that Mn forms a pseudomorphic layer on Ru(0001) under a strongly buckled graphene layer. In the case of Mn intercalation in graphene/Ir(111), a buried thin layer of MnIr alloy is formed beneath the first Ir layer under a flat graphene layer. This unexpected observation is explained on the basis of phase diagram pictures for the Mn-Ru and Mn-Ir systems as well as via comparison of calculated total energies for the respective interfaces.

Intercalation of Mn in graphene/Cu(111) interface: insights to the electronic and magnetic properties from theory.

The effect of Mn intercalation on the atomic, electronic and magnetic structure of the graphene/Cu(111) interface is studied using state-of-the-art density functional theory calculations. Different structural models of the graphene-Mn-Cu(111) interface are investigated. While a Mn monolayer placed between graphene and Cu(111) (an unfavorable configuration) yields massive rearrangement of the graphene-derived [Formula: see text] bands in the vicinity of the Fermi level, the possible formation of a [Formula: see text]Mn alloy at the interface (a favorable configuration) preserves the linear dispersion for these bands. The deep analysis of the electronic states around the Dirac point for the graphene/[Formula: see text]Mn/Cu(111) system allows to discriminate between contributions from three carbon sublattices of a graphene layer in this system and to explain the bands' as well as spins' topology of the electronic states around the Fermi level.

Epitaxial graphene/Ge interfaces: a minireview.

The recent discovery of the ability to perform direct epitaxial growth of graphene layers on semiconductor Ge surfaces led to a huge interest in this topic. One of the reasons for this interest is the chance to overcome several present-day drawbacks on the method of graphene integration in modern semiconductor technology. The other one is connected with the fundamental studies of the new graphene-semiconductor interfaces that might help with the deeper understanding of mechanisms, which governs graphene growth on different substrates as well as shedding light on the interaction of graphene with these substrates, whose range is now spread from metals to insulators. The present minireview gives a timely overview of the state-of-the-art field of studies of the graphene-Ge epitaxial interfaces and draws some conclusions in this research area.

Quantum Well States for Graphene Spin-Texture Engineering.

The modification of graphene band structure, in particular via induced spin-orbit coupling, is currently a great challenge for the scientific community from both a fundamental and applied point of view. Here, we investigate the modification of the electronic structure of graphene (gr) initially adsorbed on Ir(111) via intercalation of one monolayer Pd by means of angle-resolved photoelectron spectroscopy and density functional theory. We reveal that for the gr/Pd/Ir(111) intercalated system, a spin splitting of graphene π states higher than 200 meV is present near the graphene K point. This spin separation arises from the hybridization of the graphene valence band states with spin-polarized quantum well states of a single Pd layer on Ir(111). Our results demonstrate that the proposed approach on the tailoring of the dimensionality of heavy materials interfaced with a graphene layer might lead to a giant spin-orbit splitting of the graphene valence band states.

Tip-Induced Inversion of the Chirality of a Molecule's Adsorption Potential Probed by the Switching Directionality.

The switching behavior of surface-supported molecular units excited by current, light, or mechanical forces is determined by the shape of the adsorption potential. The ability to tailor the energy landscape in which a molecule resides at a surface gives the possibility of imposing a desired response, which is of paramount importance for the realization of molecular electronic units. Here, by means of scanning tunneling microscopy, a triazatruxene (TAT) molecule on Ag(111) is studied, which shows a switching behavior characterized by transitions of the molecule between three states, and which is attributed to three energetically degenerate bonding configurations. Upon tunneling current injection, the system can be excited and continuously driven, showing a switching directionality close to 100%. Two surface enantiomers of TAT show opposite switching directions pointing at the chirality of the energy landscape of the adsorption potential as a key ingredient for directional switching. Further, it is shown that by tuning the tunneling parameters, the symmetry of the adsorption potential can be controllably adjusted, leading to a suppression of the directionality or an inversion of the switching direction. The findings represent a molecule-surface model system exhibiting unprecedented control of the shape of its adsorption potential.

Electronic, magnetic and optical properties of MnPX3 (X = S, Se) monolayers with and without chalcogen defects: a first-principles study.

Based on density functional theory (DFT), we performed first-principles studies on the electronic structure, magnetic state and optical properties of two-dimensional (2D) transition-metal phosphorous trichalcogenides MnPX3 (X = S and Se). The calculated interlayer cleavage energies of the MnPX3 monolayers indicate the energetic possibility to be exfoliated from the bulk phase, with good dynamical stability confirmed by the absence of imaginary contributions in the phonon spectra. The MnPX3 monolayers are both Néel antiferromagnetic (AFM) semiconductors with direct band gaps falling into the visible optical spectrum. Magnetic interaction parameters were extracted within the Heisenberg model to investigate the origin of the AFM state. Three in-plane magnetic exchange parameters play an important role in the robust AFM configuration of Mn ions. The Néel temperatures (T N) were estimated by means of Monte Carlo simulations, obtaining theoretical T N values of 103 K and 80 K for 2D MnPS3 and MnPSe3, respectively. With high spin state Mn ions arranged in honeycomb lattices, the spin-degenerated band structures exhibit valley polarisation and were investigated in different biaxial in-plain strains, considering the spin-orbital coupling (SOC). 2D MnPX3 monolayers show excellent performance in terms of the optical properties, and the absorption spectra were discussed in detail to find the transition mechanism. Different amounts and configurations of chalcogen vacancies were introduced into the MnPX3 monolayers, and it was found that the electronic structures are heavily affected depending on the vacancy geometric structure, leading to different magnetic state and absorption spectra of defected MnPX3 systems.

Unoccupied electronic band structure of pentagonal Si nanoribbons on Ag(110).

Silicon nanoribbons - one dimensional silicon structures with a pentagonal atomic structure and mixed sp2- and sp3-hybridisation - grow on Ag(110) upon deposition of silicon. These nanostructures are viewed as promising candidates for modern day electronics as they are comprised of the same element as today's semiconductor devices. Even though they have been studied extensively over the last decade, only little is known about their unoccupied band structure which is important for possible future optoelectronics, semiconductor, and spintronics applications. In order to elucidate the unoccupied band structure of the nanoribbons, k-resolved inverse photoemission spectroscopy (KRIPES) studies were performed on both nanoribbon structures reported in the literature as well as on the bare Ag(110) substrate within the energy range of E-EF = 0-6.5 eV. The obtained experimental results are compared to density functional theory (DFT) calculated band structures to assign individual spectral features to specific bands. Since even small changes in the structural model of the nanoribbons lead to a change in the calculated band structure, this comparison allows us to assess the validity of the proposed structural models.