arXiv subjects

Arkady V. Krasheninnikov

Publications and source records attributed to Arkady V. Krasheninnikov.

At least 19 recordsLinked to original sources

arXiv2026

Bottom-up Synthesis of Metastable 2D Hexagonal Copper(I) Iodide on Monolayer and within Bilayer Graphene

Copper(I) iodide (CuI) is a wide-bandgap semiconductor crystallizing in the 3D $γ$-phase under ambient conditions; its layered van der Waals bulk phase $β$-CuI is stable only between 643 and 673 K. The two-dimensional (2D) h-CuI form has been obtained via liquid-phase exfoliation of mechanochemically prepared precursors and via encapsulation between graphene sheets, whereas bottom-up growth of 2D h-CuI on open surfaces has not yet been demonstrated. Here, we report a vapor-phase synthesis of h-CuI directly on low-defect, large-area monolayer and within bilayer reduced oxo-graphene (r-oxo-G) at low temperatures. Using a copper TEM grid as the solid-state precursor for copper, HI-vapor exposure at 40 $°$C initiates nucleation, while annealing at 180 $°$C promotes the growth of extended h-CuI domains. Aberration-corrected HRTEM resolves the atomic structure, local twist angles, and lattice anisotropy of the CuI/r-oxo-G nanohybrid, while STEM-EDX yields a Cu:I ratio consistent with 1:1. First-principles calculations show that van der Waals adhesion to graphene stabilizes the supported hexagonal layer. Under the presented low-temperature precursor conditions, pathways for nucleation of the $γ$-phase are not available, allowing the hexagonal phase to form selectively at the graphene interface. Ab initio molecular dynamics simulations show that the heterostructure retains its hexagonal lattice order at 600 K, including on an open monolayer graphene support. The lateral extent of the growth is limited mainly by remaining interfacial adsorbates. These results establish a route to metastable 2D h-CuI on a chemically inert graphene template, which may be useful for wide-bandgap electronic and optoelectronic devices.

cond-mat.mtrl-sci↗

arXiv2026

Sonochemically Boosted Hydrogen Evolution Activity of Janus TMD Monolayers

2D electrocatalysts that enable hydrogen evolution at low overpotentials offer an attractive alternative to expensive platinum-based systems. Here, we report the growth of Janus transition metal dichalcogenide (TMD) monolayers (MLs), SeMoS and SeWS, on Au foils using chemical vapor deposition, and systematically compare their catalytic properties in the context of hydrogen evolution reaction (HER) with those of their parent TMDs. The Janus MLs exhibited significantly enhanced catalytic performance relative to the parent TMDs. Furthermore, these MLs on Au foils were subjected to sonochemical treatment in polar and non-polar solvents, in which the treatment with polar solvents led to a substantial improvement in the HER activity of Janus MLs. In particular, SeMoS MLs treated with water showed a low overpotential of ~63 mV, a Tafel slope of ~42 mV/dec, and an exchange current density of ~10$^{-3}$ mA cm$^{- 2}$, approaching that of platinum. Analyses indicate that enhanced electrocatalytic activity is associated with tensile strain induced by Au surface restructuring and the formation of defects in Janus MLs, as shown by experimental observations and by density functional theory calculations. The enhancement in catalytic performance due to sonochemical treatment emphasizes the importance of our results for developing novel catalytic systems for HER based on Janus 2D materials.

cond-mat.mtrl-sci↗

arXiv2026

Atomic-Scale Detection of Néel Vector Switching in the Single-Layer A-type Antiferromagnet Cr2S3-2D

The detection of Néel vector switching in a single-layer A-type antiferromagnet marks an important step toward functional two-dimensional spintronics. Here, Cr$_2$S$_3$-2D, grown on graphene on Ir(110), is established as a first single-layer A-type antiferromagnet. Spin-polarized scanning tunneling microscopy reveals hysteresis loops with a large switching field and a pronounced dependence on island size. X-ray magnetic circular dichroism at the Cr L$_{2,3}$ edges exhibits a tiny signal with a linear magnetic field dependence, consistent with a nearly compensated antiferromagnetic ground state and a Néel temperature of about 160 K. Quantitative analysis of the island-size dependence of the switching field, together with first principles calculations, indicates a slight imbalance between the magnetic moments of the two Cr planes of Cr$_2$S$_3$-2D when supported on a substrate. This imbalance results in a net magnetization for the A-type antiferromagnet, which enables the 180$^\circ$ rotation of the Néel vector. Moreover, Cr$_2$S$_3$-2D retains its magnetic properties after several days of exposure to air.

cond-mat.mes-hall↗

arXiv2026

Robust phonon engineering and symmetry-selective lattice dynamics in CrSBr$_{1-x}$Cl$_{x}$

Atomic substitution provides a controlled route to engineer lattice dynamics in low-symmetry two-dimensional materials. Here, by combining polarization-resolved Raman spectroscopy and first-principles calculations, we investigate the evolution of phonon characteristics in CrSBr$_{1-x}$Cl$_{x}$ ($0 \leq x \leq \sim 0.5$) upon partial substitution of Br with Cl atoms. Progressive Cl substitution of Br induces systematic shifts of parent CrSBr out-of-plane $A_\textrm{g}$ phonon modes and activates additional Raman features. These features persist across different polarization configurations and excitation energies, reflecting substitution-induced symmetry lowering and local lattice perturbations. Explicit supercell phonon calculations combined with Raman $Γ$-density-of-states simulations identify these features as symmetry-lowered descendants of parent modes arising from alloy disorder. Complementary strain-dependent calculations reveal that anisotropic lattice compression plays a key role in renormalizing Cr-S dominated phonons. Under near-resonant excitation, stimulated Raman scattering-like amplification remains observable with increasing Cl content, highlighting the resilience of anisotropic electron-phonon coupling in this system.

cond-mat.mtrl-sci↗

arXiv2026

Creation and Microscopic Origins of Single-Photon Emitters in Transition Metal Dichalcogenides and Hexagonal Boron Nitride

We highlight recent advances in the controlled creation of single-photon emitters in van der Waals materials and in the understanding of their atomistic origin. We focus on quantum emitters created in monolayer transition-metal dichalcogenide semiconductors, which provide spectrally sharp single-photon emission at cryogenic temperatures, and the ones in insulating hBN, which provide bright and stable single-photon emission up to room temperature. After introducing the different classes of quantum emitters in terms of band-structure properties, we review the defect creation methods based on electron and ion irradiation as well as local strain engineering and plasma treatments. A main focus of the review is put on discussing the microscopic origin of the quantum emitters as revealed by various experimental platforms, including optical and scanning probe methods.

cond-mat.mes-hall↗

arXiv2025

Which chromium-sulfur compounds exist as 2D material?

Two-dimensional (2D) chromium-sulfides are synthesized by molecular beam epitaxy using graphene as a substrate. Structure characterization by employing scanning tunneling microscopy and low energy electron diffraction indicates that there are two 2D phases, Cr$_2$S$_3$-2D and Cr$_{2\frac{2}{3}}$S$_4$-2D, which have not been reported before. Cr$_{2\frac{2}{3}}$S$_4$-2D is related to bulk Cr$_5$S$_6$, but thinner than a bulk unit cell. For Cr$_2$S$_3$-2D, an even thinner material, no bulk counterpart exists. Both 2D materials are found to be structurally stable under ambient conditions and exhibit interesting electronic properties. Extensive first-principles calculations provide further insight into the electronic structure of these systems and indicate that they should be magnetic. Although single layers of CrS$_2$ were predicted to be stable by density functional theory calculations and reported in previous experimental studies, we were unable to synthesize CrS$_2$ under our range of experimental conditions.

cond-mat.mtrl-sci↗

arXiv2025

Defect migration and phase transformations in 2D iron chloride inside bilayer graphene

The intercalation of metal chlorides, and particularly iron chlorides, into graphitic carbon structures has recently received lots of attention, as it can not only protect this two-dimensional (2D) magnetic system from the effects of the environment, but also substantially alter the magnetic, electronic, and optical properties of both intercalant and host material. At the same time, the intercalation can result in the formation of structural defects, or defects can appear under external stimuli, which can affect materials performance. These aspects have received so far little attention in the dedicated experiments. In this study, we investigate the behavior of atomic-scale defects in iron chlorides intercalated into bilayer graphene (BLG) by using scanning transmission electron microscopy (STEM) and first-principles calculations. We observe transformations between the FeCl2 and FeCl3 phases and elucidate the role of defects in the transformations. Specifically, three types of defects are identified: Fe vacancies in FeCl2 domains, Fe adatoms and interstitials in FeCl3 domains, each exhibiting distinct dynamic behaviors. We also observed a crystalline phase with an unusual stoichiometry of Fe5Cl18 which has not been reported before. Our findings not only advance the understanding of intercalation mechanism of 2D materials but also highlight the profound impact of atomic-scale defects on their properties and potential technological applications.

cond-mat.mtrl-sci↗

arXiv2025

Bilayer graphene as a template for manufacturing novel 2D materials

Recent intensive research on two-dimensional materials (2DMs) rekindle the interest in the intercalation of various atoms and molecules into layered compounds as a tool to manufacture 2DMs and tune their optoelectronic, magnetic and catalytic properties. Intercalation into free-standing bilayer graphene (BLG) has received special attention, as graphene is stable, chemically inert and enables one to study the atomic structure of the intercalated 2DM using high-resolution transmission electron microscopy. It was also discovered that the protecting action of graphene sheets makes it possible to not only stabilize the encapsulated single sheets of marginally stable layered materials, but also synthesize completely new 2D systems inside BLG, which in comparison to the bulk graphite allows for easier intercalation and much larger increase in the inter-layer separation of the sheets. In this review, we summarize the recent progress in this area, with a special focus on new materials created inside BLG. We compare the experimental findings to the theoretical predictions, pay special attention to the discrepancies and outline the challenges in the field. Finally, we discuss unique opportunities offered by the intercalation into 2DMs beyond graphene and their heterostructures.

cond-mat.mes-hall↗

arXiv2025

Quantifying the creation of negatively charged boron vacancies in He-ion irradiated hexagonal boron nitride

Hexagonal boron nitride (hBN) hosts luminescent defects possessing spin qualities compatible with quantum sensing protocols at room temperature. Vacancies, in particular, are readily obtained via exposure to high-energy ion beams. While the defect creation mechanism via such irradiation is well understood, the occurrence rate of optically active negatively charged vacancies ($V_B^-$) is an open question. In this work, we exploit focused helium ions to systematically generate optically active vacancy defects in hBN flakes at varying density. By comparing the density-dependent spin splitting measured by magnetic resonance to calculations based on a microscopic charge model, in which we introduce a correction term due to a constant background charge, we are able to quantify the number of $V_B^-$ defects generated by the ion irradiation. We find a lower bound for the fraction (0.2%) of all vacancies in the optically active, negatively charged state. Our results provide a protocol for measuring the generation efficiency of $V_B^-$, which is necessary for understanding and optimizing luminescent centers in hBN.

cond-mat.mes-hall↗

arXiv2024

Probing the band splitting near the $Γ$ point in the van der Waals magnetic semiconductor CrSBr

This study investigates the electronic band structure of Chromium Sulfur Bromide (CrSBr) through comprehensive photoluminescence (PL) characterization. We clearly identify low-temperature optical transitions between two closely adjacent conduction-band states and two different valence-band states. The analysis of the PL data robustly unveils energy splittings, bandgaps and excitonic transitions across different thicknesses of CrSBr, ranging from monolayer to bulk. Temperature-dependent PL measurements elucidate the stability of the band splitting below the Néel temperature, suggesting that magnons coupled with excitons are responsible for the symmetry breaking and brightening of the transitions from the secondary conduction band minimum (CBM2) to the global valence band maximum (VBM1). Collectively, these results not only reveal band splitting in both the conduction and valence bands, but also point to an intricate interplay between the optical, electronic and magnetic properties of antiferromagnetic two-dimensional van der Waals crystals.

cond-mat.mes-hall↗

arXiv2024

Tip-induced creation and Jahn-Teller distortions of sulfur vacancies in single-layer MoS$_{2}$

We present an atomically precise technique to create sulfur vacancies and control their atomic configurations in single-layer MoS$_{2}$. It involves adsorbed Fe atoms and the tip of a scanning tunneling microscope, which enables single sulfur removal from the top sulfur layer at the initial position of Fe. Using scanning tunneling spectroscopy, we show that the STM tip can also induce two Jahn-Teller distorted states with reduced orbital symmetry in the sulfur vacancies. Density functional theory calculations rationalize our experimental results. Additionally, we provide evidence for molecule-like hybrid orbitals in artificially created sulfur vacancy dimers, which illustrates the potential of our technique for the development of extended defect lattices and tailored electronic band structures.

cond-mat.mtrl-sci↗

arXiv2023

Magnetic State Control of Non-van der Waals 2D Materials by Hydrogenation

Controlling the magnetic state of two-dimensional (2D) materials is crucial for spintronic applications. By employing data-mining and autonomous density functional theory calculations, we demonstrate the switching of magnetic properties of 2D non-van der Waals materials upon hydrogen passivation. The magnetic configurations are tuned to states with flipped and enhanced moments. For 2D CdTiO$_3$ - a nonmagnetic compound in the pristine case - we observe an onset of ferromagnetism upon hydrogenation. Further investigation of the magnetization density of the pristine and passivated systems provides a detailed analysis of modified local spin symmetries and the emergence of ferromagnetism. Our results indicate that selective surface passivation is a powerful tool for tailoring magnetic properties of nanomaterials such as non-vdW 2D compounds.

cond-mat.mtrl-sci↗

arXiv2023

Roadmap for focused ion beam technologies

The focused ion beam (FIB) is a powerful tool for the fabrication, modification and characterization of materials down to the nanoscale. Starting with the gallium FIB, which was originally intended for photomask repair in the semiconductor industry, there are now many different types of FIB that are commercially available. These instruments use a range of ion species and are applied broadly in materials science, physics, chemistry, biology, medicine, and even archaeology. The goal of this roadmap is to provide an overview of FIB instrumentation, theory, techniques and applications. By viewing FIB developments through the lens of the various research communities, we aim to identify future pathways for ion source and instrumentation development as well as emerging applications, and the scope for improved understanding of the complex interplay of ion-solid interactions. We intend to provide a guide for all scientists in the field that identifies common research interests and will support future fruitful interactions connecting tool development, experiment and theory. While a comprehensive overview of the field is sought, it is not possible to cover all research related to FIB technologies in detail. We give examples of specific projects within the broader context, referencing original works and previous review articles throughout.

physics.ins-det↗

arXiv2023

Ferromagnetic interlayer coupling in CrSBr crystals irradiated by ions

Layered magnetic materials are becoming a major platform for future spin-based applications. Particularly the air-stable van der Waals compound CrSBr is attracting considerable interest due to its prominent magneto-transport and magneto-optical properties. In this work, we observe a transition from antiferromagnetic to ferromagnetic behavior in CrSBr crystals exposed to high-energy, non-magnetic ions. Already at moderate fluences, ion irradiation induces a remanent magnetization with hysteresis adapting to the easy-axis anisotropy of the pristine magnetic order up to a critical temperature of 110 K. Structure analysis of the irradiated crystals in conjunction with density functional theory calculations suggest that the displacement of constituent atoms due to collisions with ions and the formation of interstitials favors ferromagnetic order between the layers.

cond-mat.mtrl-sci↗

arXiv2023

Hydrogenic Spin-Valley states of the Bromine donor in 2H-MoTe$_2$

In semiconductors, the identification of doping atomic elements allowing to encode a qubit within spin states is of intense interest for quantum technologies. In transition metal dichalcogenides semiconductors, the strong spin-orbit coupling produces locked spin-valley states with expected long coherence time. Here we study the substitutional Bromine Br\textsubscript{Te} dopant in 2H-MoTe$_2$. Electron spin resonance measurements show that this dopant carries a spin with long-lived nanoseconds coherence time. Using scanning tunneling spectroscopy, we find that the hydrogenic wavefunctions associated with the dopant levels have characteristics spatial modulations that result from their hybridization to the \textbf{Q}-valleys of the conduction band. From a Fourier analysis of the conductance maps, we find that the amplitude and phase of the Fourier components change with energy according to the different irreducible representations of the impurity-site point-group symmetry. These results demonstrate that a dopant can inherit the locked spin-valley properties of the semiconductor and so exhibit long spin-coherence time.

cond-mat.mes-hall↗

arXiv2023

Optical properties of MoSe$_2$ monolayer implanted with ultra-low energy Cr ions

The paper explores the optical properties of an exfoliated MoSe$_2$ monolayer implanted with Cr$^+$ ions, accelerated to 25 eV. Photoluminescence of the implanted MoSe$_2$ reveals an emission line from Cr-related defects that is present only under weak electron doping. Unlike band-to-band transition, the Cr-introduced emission is characterised by non-zero activation energy, long lifetimes, and weak response to the magnetic field. To rationalise the experimental results and get insights into the atomic structure of the defects, we modelled the Cr-ion irradiation process using ab-initio molecular dynamics simulations followed by the electronic structure calculations of the system with defects. The experimental and theoretical results suggest that the recombination of electrons on the acceptors, which could be introduced by the Cr implantation-induced defects, with the valence band holes is the most likely origin of the low energy emission. Our results demonstrate the potential of low-energy ion implantation as a tool to tailor the properties of 2D materials by doping.

cond-mat.mtrl-sci↗

arXiv2022

Electron Holographic Mapping of Structural and Electronic Reconstruction at Mono- and Bilayer Steps of h-BN

Here, by making use of medium and high resolution autocorrected off-axis electron holography, we directly probe the electrostatic potential as well as in-plane and out-of-plane charge delocalization at edges and steps in multilayer hexagonal boron nitride. In combination with ab-initio calculations, the data allows to directly reveal the formation of out-of-plane covalent bonds at folded zig-zag edges and steps comprising two monolayers and the absence of which at monolayer steps. The technique paves the way for studying other charge (de)localization phenomena in 2D materials, e.g., at polar edges, topological edge states and defects.

cond-mat.mtrl-sci↗

arXiv2022

A New Group of Two-Dimensional Non-van der Waals Materials with Ultra Low Exfoliation Energies

The exfoliation energy - quantifying the energy required to extract a two-dimensional (2D) sheet from the surface of a bulk material - is a key parameter determining the synthesizability of 2D compounds. Here, using ab initio calculations, we present a new group of non-van der Waals 2D materials derived from non-layered crystals which exhibit ultra low exfoliation energies. In particular for sulfides, surface relaxations are essential to correctly describe the associated energy gain needed to obtain reliable results. Taking into account long-range dispersive interactions has only a minor effect on the energetics and ultimately proves that the exfoliation energies are close to the ones of traditional van der Waals bound 2D compounds. The candidates with the lowest energies, 2D SbTlO$_3$ and MnNaCl$_3$, exhibit appealing electronic, potential topological, and magnetic features as evident from the calculated band structures making these systems an attractive platform for fundamental and applied nanoscience.

cond-mat.mtrl-sci↗