Search

The presence of metal atoms at the edges of graphene nanoribbons (GNRs) opens new possibilities toward tailoring their physical properties. We present here formation and high-resolution characterization of indium (In) chains on the edges of graphene-supported GNRs. The GNRs are formed when adsorbed hydrocarbon contamination crystallizes via laser heating into small ribbon-like patches of a second graphitic layer on a continuous graphene monolayer and onto which In is subsequently physical vapor deposited. Using aberration-corrected scanning transmission electron microscopy (STEM), we find that this leads to the preferential decoration of the edges of the overlying GNRs with multiple In atoms along their graphitic edges. Electron-beam irradiation during STEM induces migration of In atoms along the edges of the GNRs and triggers the formation of longer In atom chains during imaging. Density functional theory (DFT) calculations of GNRs similar to our experimentally observed structures indicate that both bare zigzag (ZZ) GNRs as well as In-terminated ZZ-GNRs have metallic character, whereas in contrast, In termination induces metallicity for otherwise semiconducting armchair (AC) GNRs. Our findings provide insights into the creation and properties of long linear metal atom chains at graphitic edges., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2023.)

We compare the ion-induced electron emission from freestanding monolayers of graphene and MoS_{2} to find a sixfold higher number of emitted electrons for graphene even though both materials have similar work functions. An effective single-band Hubbard model explains this finding by a charge-up in MoS_{2} that prevents low energy electrons from escaping the surface within a period of a few femtoseconds after ion impact. We support these results by measuring the electron energy distribution for correlated pairs of electrons and transmitted ions. The majority of emitted primary electrons have an energy below 10 eV and are therefore subject to the dynamic charge-up effects at surfaces.

Substituting heteroatoms into graphene can tune its properties for applications ranging from catalysis to spintronics. The further recent discovery that covalent impurities in graphene can be manipulated at atomic precision using a focused electron beam may open avenues towards sub-nanometer device architectures. However, the preparation of clean samples with a high density of dopants is still very challenging. Here, we report vacancy-mediated substitution of aluminium into laser-cleaned graphene, and without removal from our ultra-high vacuum apparatus, study their dynamics under 60 keV electron irradiation using aberration-corrected scanning transmission electron microscopy and spectroscopy. Three- and four-coordinated Al sites are identified, showing excellent agreement with ab initio predictions including binding energies and electron energy-loss spectrum simulations. We show that the direct exchange of carbon and aluminium atoms predicted earlier occurs under electron irradiation, although unexpectedly it is less probable than the same process for silicon. We also observe a previously unknown nitrogen-aluminium exchange that occurs at Al─N double-dopant sites at graphene divacancies created by our plasma treatment., Competing Interests: Conflict of interest The authors declare no conflicts of interest.

Heterostructures composed of 2D materials are already opening many new possibilities in such fields of technology as electronics and magnonics, but far more could be achieved if the number and diversity of 2D materials were increased. So far, only a few dozen 2D crystals have been extracted from materials that exhibit a layered phase in ambient conditions, omitting entirely the large number of layered materials that may exist at other temperatures and pressures. This work demonstrates how such structures can be stabilized in 2D van der Waals (vdw) stacks under room temperature via growing them directly in graphene encapsulation by using graphene oxide as the template material. Specifically, an ambient stable 2D structure of copper and iodine, a material that normally only occurs in layered form at elevated temperatures between 645 and 675 K, is produced. The results establish a simple route to the production of more exotic phases of materials that would otherwise be difficult or impossible to stabilize for experiments in ambient., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Herein we report the synthesis of covalently functionalized carbon nano-onions (CNOs) via a reductive approach using unprecedented alkali-metal CNO intercalation compounds. For the first time, an in situ Raman study of the controlled intercalation process with potassium has been carried out revealing a Fano resonance in highly doped CNOs. The intercalation was further confirmed by electron energy loss spectroscopy and X-ray diffraction. Moreover, the experimental results have been rationalized with DFT calculations. Covalently functionalized CNO derivatives were synthesized by using phenyl iodide and n -hexyl iodide as electrophiles in model nucleophilic substitution reactions. The functionalized CNOs were exhaustively characterized by statistical Raman spectroscopy, thermogravimetric analysis coupled with gas chromatography and mass spectrometry, dynamic light scattering, UV-vis, and ATR-FTIR spectroscopies. This work provides important insights into the understanding of the basic principles of reductive CNOs functionalization and will pave the way for the use of CNOs in a wide range of potential applications, such as energy storage, photovoltaics, or molecular electronics.

Single atoms and few-atom nanoclusters are of high interest in catalysis and plasmonics, but pathways for their fabrication and placement remain scarce. We report here the self-assembly of room-temperature-stable single indium (In) atoms and few-atom In clusters (2-6 atoms) that are anchored to substitutional silicon (Si) impurity atoms in suspended monolayer graphene membranes. Using atomically resolved scanning transmission electron microscopy (STEM), we find that the symmetry of the In structures is critically determined by the three- or fourfold coordination of the Si "anchors". All structures are produced without electron-beam induced materials modification. In turn, when activated by electron beam irradiation in the STEM, we observe in situ the formation, restructuring, and translation of the Si-anchored In structures. Our results on In-Si-graphene provide a materials system for controlled self-assembly and heteroatomic anchoring of single atoms and few-atom nanoclusters on graphene.

Structural engineering is the first step toward changing properties of materials. While this can be at relative ease done for bulk materials, for example, using ion irradiation, similar engineering of 2D materials and other low-dimensional structures remains a challenge. The difficulties range from the preparation of clean and uniform samples to the sensitivity of these structures to the overwhelming task of sample-wide characterization of the subjected modifications at the atomic scale. Here, we overcome these issues using a near ultrahigh vacuum system comprised of an aberration-corrected scanning transmission electron microscope and setups for sample cleaning and manipulation, which are combined with automated atomic-resolution imaging of large sample areas and a convolutional neural network approach for image analysis. This allows us to create and fully characterize atomically clean free-standing graphene with a controlled defect distribution, thus providing the important first step toward atomically tailored two-dimensional materials.

Cluster superlattice membranes consist of a two-dimensional hexagonal lattice of similar-sized nanoclusters sandwiched between single-crystal graphene and an amorphous carbon matrix. The fabrication process involves three main steps, the templated self-organization of a metal cluster superlattice on epitaxial graphene on Ir(111), conformal embedding in an amorphous carbon matrix, and subsequent lift-off from the Ir(111) substrate. The mechanical stability provided by the carbon-graphene matrix makes the membrane stable as a free-standing material and enables transfer to other substrates. The fabrication procedure can be applied to a wide variety of cluster materials and cluster sizes from the single-atom limit to clusters of a few hundred atoms, as well as other two-dimensional layer/host matrix combinations. The versatility of the membrane composition, its mechanical stability, and the simplicity of the transfer procedure make cluster superlattice membranes a promising material in catalysis, magnetism, energy conversion, and optoelectronics.

The wide range of actual and potential applications of nanoparticles, highlight the necessity of a reliable production method for both quality and quantity of the products. Mechanical attrition is one of the first well-known techniques used to produce nanoparticles. However, these approaches have been restricted to produce uniform particles below the critical size of 15 nm because of the attrition balance limit. This paper introduces the magnetite-silicate raw material of a Kiruna-type ore deposit as a novel precursor, which enables the production of small iron oxide nanoparticles below the critical size by mechanical attrition. X-ray fluorescence (XRF), powder X-ray diffractometry (pXRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used for characterization of the precursor and obtained nanoparticles. The results indicate that the particles with a mean diameter of 10.7(2.7) nm consist of mainly less than one crystallite. The significant size reduction below the attrition balance limit can be attributed to the quartz content of the raw material, which operated as supporting micro-balls for transferring the energy during the milling process.

The growing family of 2D materials led not long ago to combining different 2D layers and building artificial systems in the form of van der Waals heterostructures. Tailoring of heterostructure properties postgrowth would greatly benefit from a modification technique with a monolayer precision. However, appropriate techniques for material modification with this precision are still missing. To achieve such control, slow highly charged ions appear ideal as they carry high amounts of potential energy, which is released rapidly upon ion neutralization at the position of the ion. The resulting potential energy deposition is thus limited to just a few atomic layers (in contrast to the kinetic energy deposition). Here, we irradiated a freestanding van der Waals MoS 2 /graphene heterostructure with 1.3 keV/amu xenon ions in high charge states of 38, which led to nanometer-sized pores that appear only in the MoS 2 facing the ion beam, but not in graphene beneath the hole. Reversing the stacking order leaves both layers undamaged, which we attribute to the high conductivity and carrier mobility in graphene acting as a shield for the MoS 2 underneath. Our main focus is here on monolayer MoS 2 , but we also analyzed areas with few-layer structures and observed that the perforation is limited to the two topmost MoS 2 layers, whereas deeper layers remain intact. Our results demonstrate that in addition to already being a valuable tool for materials processing, the usability of ion irradiation can be extended to mono- (or bi)layer manipulation of van der Waals heterostructures when the localized potential energy deposition of highly charged ions is also added to the toolbox.

Here, a scalable floating catalyst chemical vapor deposition (FCCVD) method is developed for the production of single-walled carbon nanotubes (SWCNTs) with a controlled structure. For the first time, water is used as the growth promoter in the FCCVD process to modulate the growth of SWCNTs. At an optimum water concentration of ca. 115 ppm, the water-assisted FCCVD process synthesizes SWCNTs with a significantly narrow chirality distribution. In particular, the proportion of (9,8) and (8,7) semiconducting tubes was dramatically enhanced to 45% with 27% of the (9,8) tube in the end product. This is attributed to the changes in both the SWCNT diameter and the chiral angle. The experiment results and accurate quantum chemical molecular dynamics simulations show that the addition of water affects the nucleation and the size distribution of nanoparticle catalysts, thus resulting in the growth of SWCNTs with a highly uniform structure. This direct and continuous water-assisted FCCVD provides the possibility for the mass production of high-quality SWCNTs with a controlled structure.

Dynamic surface modification of suspended graphene at high temperatures was directly observed with in situ scanning transmission electron microscopy (STEM) measurements. The suspended graphene devices were prepared on a SiN membrane substrate with a hole so that STEM observations could be conducted during Joule heating. Current-voltage characteristics of suspended graphene devices inside the STEM chamber were measured while monitoring and controlling the temperature of graphene by estimating the electrical power of the devices. During the in situ STEM observation at high temperatures, residual hydrocarbon adsorbents that had remained on graphene effectively evaporated creating large, atomically clean graphene areas. At other places, dynamic changes in the shape, position, and orientation of adsorbents could be directly observed. The temperature of the suspended graphene sample was estimated to reach up to 2000 K during the experiment, making graphene an efficient high-temperature micrometer-sized electron-transparent hot plate for future experiments in microscopes.

We demonstrate the growth of overlapping grain boundaries in continuous, polycrystalline hexagonal boron nitride (h-BN) monolayer films via scalable catalytic chemical vapor deposition. Unlike the commonly reported atomically stitched grain boundaries, these overlapping grain boundaries do not consist of defect lines within the monolayer films but are composed of self-sealing bilayer regions of limited width. We characterize this overlapping h-BN grain boundary structure in detail by complementary (scanning) transmission electron microscopy techniques and propose a catalytic growth mechanism linked to the subsurface/bulk of the process catalyst and its boron and nitrogen solubilities. Our data suggest that the overlapping grain boundaries are comparatively resilient against deleterious pinhole formation associated with grain boundary defect lines and thus may reduce detrimental breakdown effects when polycrystalline h-BN monolayer films are used as ultrathin dielectrics, barrier layers, or separation membranes.

Layered two-dimensional (2D) materials display great potential for a range of applications, particularly in electronics. We report the large-scale synthesis of thin films of platinum diselenide (PtSe 2 ), a thus far scarcely investigated transition metal dichalcogenide. Importantly, the synthesis by thermally assisted conversion is performed at 400 °C, representing a breakthrough for the direct integration of this material with silicon (Si) technology. Besides the thorough characterization of this 2D material, we demonstrate its promise for applications in high-performance gas sensing with extremely short response and recovery times observed due to the 2D nature of the films. Furthermore, we realized vertically stacked heterostructures of PtSe 2 on Si which act as both photodiodes and photovoltaic cells. Thus, this study establishes PtSe 2 as a potential candidate for next-generation sensors and (opto-)electronic devices, using fabrication protocols compatible with established Si technologies.

Electron beam of a transmission electron microscope can be used to alter the morphology of graphene nanoribbons and create atomically sharp edges required for applications of graphene in nanoelectronics. Using density-functional-theory-based simulations, we study the radiation hardness of graphene edges and show that the response of the ribbons to irradiation is not determined by the equilibrium energetics as assumed in previous experiments, but by kinetic effects associated with the dynamics of the edge atoms after impacts of energetic electrons. We report an unexpectedly high stability of armchair edges, comparable to that of pristine graphene, and demonstrate that the electron energy should be below ~50 keV to minimize the knock-on damage., (© 2011 American Chemical Society)