Search

Bulk water exists in many forms, including liquid, vapour and numerous crystalline and amorphous phases of ice, with hexagonal ice being responsible for the fascinating variety of snowflakes (1,2). Much less noticeable but equally ubiquitous is water adsorbed at interfaces and confined in microscopic pores. Such low-dimensional water determines aspects of various phenomena in materials science, geology, biology, tribology and nanotechnology (3-8). Theory suggests many possible phases for adsorbed and confined water (9-17), but it has proved challenging to assess its crystal structure experimentally (17-23). Here we report high-resolution electron microscopy imaging of water locked between two graphene sheets, an archetypal example of hydrophobic confinement. The observations show that the nanoconfined water at room temperature forms 'square ice'--a phase having symmetry qualitatively different from the conventional tetrahedral geometry of hydrogen bonding between water molecules. Square ice has a high packing density with a lattice constant of 2.83 Å and can assemble in bilayer and trilayer crystallites. Molecular dynamics simulations indicate that square ice should be present inside hydrophobic nanochannels independently of their exact atomic nature., Many molecular dynamics (MD) studies (9-17) have explored the structure of low-dimensional water and predicted a great variety of phases, with results sensitive to modelled conditions and sometimes appearing conflicting. [...]

The contributions of different damage mechanisms in single-layer MoSe2 were studied by investigating different MoSe2/graphene heterostructures by the aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) at 80 keV. The damage cross-sections were determined by direct counting of atoms in the AC-HRTEM images. The contributions of damage mechanisms such as knock-on damage or ionization effects were estimated by comparing the damage rates in different heterostructure configurations, similarly to what has been earlier done with MoS2. The behaviour of MoSe2 was found to be nearly identical to that of MoS2, which is an unexpected result, as the knock-on mechanism should be suppressed in MoSe2 due to the high mass of Se, as compared to S. [ABSTRACT FROM AUTHOR]

The contributions of different damage mechanisms in single-layer MoSe2 were studied by investigating different MoSe2/graphene heterostructures by the aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) at 80 keV. The damage cross-sections were determined by direct counting of atoms in the AC-HRTEM images. The contributions of damage mechanisms such as knock-on damage or ionization effects were estimated by comparing the damage rates in different heterostructure configurations, similarly to what has been earlier done with MoS2. The behaviour of MoSe2 was found to be nearly identical to that of MoS2, which is an unexpected result, as the knock-on mechanism should be suppressed in MoSe2 due to the high mass of Se, as compared to S. [ABSTRACT FROM AUTHOR]

Background: In this retrospective cohort study, we explored the correlation of blood human myxovirus resistance protein A (MxA) level with severity of disease in hospitalized COVID-19 patients., Methods: All 304 patients admitted for COVID-19 in our hospital until 30th of April 2021 were included in this study. MxA was measured from peripheral blood samples in 268 cases. Patients were divided into groups based on their level of MxA on admission. We studied baseline characteristics and severity of disease on admission based on clinical parameters and inflammatory biomarker levels in each group. Severity of disease during hospitalization was determined by the applied level of respiratory support, by the usage of corticosteroids and by the duration of hospitalization., Results: Higher MxA levels on admission were associated with a shorter duration of symptoms before admission, and with more severe disease. Adjusted Odds Ratios for any respiratory support were 9.92 (95%CI 2.11-46.58; p = 0.004) in patients with MxA between 400 μg/L and 799 μg/L (p = 0.004) and 20.08 (95%CI 4.51-89.44; p < 0.001) in patients with MxA ≥ 800 μg/L in comparison with patients with initial MxA < 400 μg/L. The usage of corticosteroids was significantly higher in the high-MxA group (77%) in comparison with the intermediate-MxA group (62%, p = 0.013) and low-MxA group (47%, p < 0.001)., Conclusions: Higher initial levels of MxA were associated with more severe COVID-19. MxA may be a helpful additional biomarker to predict the severity of the disease., (© 2022. The Author(s).)

The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C=C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The "standing up" molecules, covalently anchored to graphene, exhibit two types of oscillatory motion--bending and twisting--caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography.

The ability to manufacture tailored graphene nanostructures is a key factor to fully exploit its enormous technological potential. We have investigated nanostructures created in graphene by swift heavy ion induced folding. For our experiments, single layers of graphene exfoliated on various substrates and freestanding graphene have been irradiated and analyzed by atomic force and high resolution transmission electron microscopy as well as Raman spectroscopy. We show that the dense electronic excitation in the wake of the traversing ion yields characteristic nanostructures each of which may be fabricated by choosing the proper irradiation conditions. These nanostructures include unique morphologies such as closed bilayer edges with a given chirality or nanopores within supported as well as freestanding graphene. The length and orientation of the nanopore, and thus of the associated closed bilayer edge, may be simply controlled by the direction of the incoming ion beam. In freestanding graphene, swift heavy ion irradiation induces extremely small openings, offering the possibility to perforate graphene membranes in a controlled way.

Here, we present a numerical post-processing method for removing the effect of anti-symmetric residual aberrations in high-resolution transmission electron microscopy (HRTEM) images of weakly scattering 2D-objects. The method is based on applying the same aberrations with the opposite phase to the Fourier transform of the recorded image intensity and subsequently inverting the Fourier transform. We present the theoretical justification of the method, and its verification based on simulated images in the case of low-order anti-symmetric aberrations. Ultimately the method is applied to experimental hardware aberration-corrected HRTEM images of single-layer graphene and MoSe₂ resulting in images with strongly reduced residual low-order aberrations, and consequently improved interpretability. Alternatively, this method can be used to estimate by trial and error the residual anti-symmetric aberrations in HRTEM images of weakly scattering objects., (Copyright © 2014 Elsevier B.V. All rights reserved.)

We study the atomic scale microstructure of nonstoichiometric two-dimensional (2D) transition metal dichalcogenide MoSe2-x by employing aberration-corrected high-resolution transmission electron microscopy. We show that a Se-deficit in single layers of MoSe2 grown by molecular beam epitaxy gives rise to a dense network of mirror-twin-boundaries (MTBs) decorating the 2D-grains. With the use of density functional theory calculations, we further demonstrate that MTBs are thermodynamically stable structures in Se-deficient sheets. These line defects host spatially localized states with energies close to the valence band minimum, thus giving rise to enhanced conductance along straight MTBs. However, electronic transport calculations show that the transmission of hole charge carriers across MTBs is strongly suppressed due to band bending effects. We further observe formation of MTBs during in situ removal of Se atoms by the electron beam of the microscope, thus confirming that MTBs appear due to Se-deficit, and not coalescence of individual grains during growth. At a very high local Se-deficit, the 2D sheet becomes unstable and transforms to a nanowire. Our results on Se-deficient MoSe2 suggest routes toward engineering the properties of 2D transition metal dichalcogenides by deviations from the stoichiometric composition.

Crystallographic defects play a key role in determining the properties of crystalline materials. The new class of two-dimensional materials, foremost graphene, have enabled atomically resolved studies of defects, such as vacancies,1-4 grain boundaries,(5-7) dislocations,(8,9) and foreign atom substitutions.(10-14) However, atomic resolution imaging of implanted self-interstitials has so far been reported neither in any three-dimensional nor in any two-dimensional material. Here, we deposit extra carbon into single-layer graphene at soft landing energies of ∼ 1 eV using a standard carbon coater. We identify all the self-interstitial dimer structures theoretically predicted earlier,(15-17) employing 80 kV aberration-corrected high-resolution transmission electron microscopy. We demonstrate accumulation of the interstitials into larger aggregates and dislocation dipoles, which we predict to have strong local curvature by atomistic modeling, and to be energetically favorable configurations as compared to isolated interstitial dimers. Our results contribute to the basic knowledge on crystallographic defects and lay out a pathway into engineering the properties of graphene by pushing the crystal into a state of metastable supersaturation.

We report the formation and characterization of boron nitride atomic chains. The chains were made from hexagonal boron nitride sheets using the electron beam inside a transmission electron microscope. We find that the stability and lifetime of the chains are significantly improved when they are supported by another boron nitride layer. With the help of first-principles calculations, we prove the heteroatomic structure of the chains and determine their mechanical and electronic properties. Our study completes the analogy between various boron nitride and carbon polymorphs, in accordance with earlier theoretical predictions.

Irradiation with high-energy ions has been widely suggested as a tool to engineer properties of graphene. Experiments show that it indeed has a strong effect on graphene's transport, magnetic and mechanical characteristics. However, to use ion irradiation as an engineering tool requires understanding of the type and detailed characteristics of the produced defects which is still lacking, as the use of high-resolution transmission microscopy (HRTEM)--the only technique allowing direct imaging of atomic-scale defects--often modifies or even creates defects during imaging, thus making it impossible to determine the intrinsic atomic structure. Here we show that encapsulating the studied graphene sample between two other (protective) graphene sheets allows non-invasive HRTEM imaging and reliable identification of atomic-scale defects. Using this simple technique, we demonstrate that proton irradiation of graphene produces reconstructed monovacancies, which explains the profound effect that such defects have on graphene's magnetic and transport properties. This finding resolves the existing uncertainty with regard to the effect of ion irradiation on the electronic structure of graphene.

By combining first-principles and classical force field calculations with aberration-corrected high-resolution transmission electron microscopy experiments, we study the morphology and energetics of point and extended defects in hexagonal bilayer silica and make comparison to graphene, another two-dimensional (2D) system with hexagonal symmetry. We show that the motifs of isolated point defects in these 2D structures with otherwise very different properties are similar, and include Stone-Wales-type defects formed by structural unit rotations, flower defects and reconstructed double vacancies. The morphology and energetics of extended defects, such as grain boundaries have much in common as well. As both sp(2)-hybridised carbon and bilayer silica can also form amorphous structures, our results indicate that the morphology of imperfect 2D honeycomb lattices is largely governed by the underlying symmetry of the lattice.

By combining ion beam experiments and atomistic simulations we study the production of defects in graphene on Ir(111) under grazing incidence of low energy Xe ions. We demonstrate that the ions are channeled in between graphene and the substrate, giving rise to chains of vacancy clusters with their edges bending down toward the substrate. These clusters self-organize to a graphene nanomesh via thermally activated diffusion as their formation energy varies within the graphene moiré supercell.