Showing papers by "Jani Kotakoski published in 2021"

Atomic-Level Structural Engineering of Graphene on a Mesoscopic Scale.

Abstract: 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.

Single Indium Atoms and Few-Atom Indium Clusters Anchored onto Graphene via Silicon Heteroatoms.

Abstract: 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.

Chemistry at graphene edges in the electron microscope

Abstract: Transmission electron microscopy (TEM) and scanning TEM (STEM) are indispensable tools for materials characterization. However, during a typical (S)TEM experiment, the sample is subject to a number of effects that can change its atomic structure. Of these, perhaps the least discussed are chemical modifications due to the non-ideal vacuum around the sample. With single-layer graphene, we show that even at relatively low pressures typical for many instruments, these processes can have a significant impact on the sample structure. For example, pore growth becomes up to two orders of magnitude faster at a pressure of ca. 10^{-6} mbar as compared to ultra-high vacuum (UHV; 10^{-10} mbar). Even more remarkably,the presence of oxygen at the sample also changes the observed atomic structure: When imaged in UHV, nearly 90% of the identifiable graphene edge configurations have the armchair structure, whereas armchair and zigzag structures are nearly equally likely to occur when the oxygen partial pressure in the column is higher. Our results both bring attention to the role of the often neglected vacuum composition of the microscope column, and show that control over it can allow atomic-scale tailoring of the specimen structure.

Highly efficient bilateral doping of single-walled carbon nanotubes

Abstract: A boost in the development of flexible and wearable electronics facilitates the design of new materials to be applied as transparent conducting films (TCFs). Although single-walled carbon nanotube (SWCNT) films are the most promising candidates for flexible TCFs, they still do not meet optoelectronic requirements demanded for their successful industrial integration. In this study, we proposed and thoroughly investigated a new approach that comprises simultaneous bilateral (outer and inner surface) SWCNT doping after their opening by thermal treatment at 400 °C under an ambient air atmosphere. Doping by a chloroauric acid (HAuCl4) ethanol solution allowed us to achieve the record value of equivalent sheet resistance of 31 ± 4 Ω sq−1 at a transmittance of 90% in the middle of the visible spectrum (550 nm). The strong p-doping was examined by open-circuit potential (OCP) measurements and confirmed by ab initio calculations demonstrating a downshift of the Fermi level of around 1 eV for the case of bilateral doping.

Carbon Nano-onions: Potassium Intercalation and Reductive Covalent Functionalization.

Abstract: 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.

The morphology of doubly-clamped graphene nanoribbons

Abstract: Understanding the response of micro/nano-patterned graphene to mechanical forces is instrumental for applications such as advanced graphene origami and kirigami. Here, we analyze free-standing nanoribbons milled into single-layer graphene by focused ion beam processing. Using transmission electron microscopy, we show that the length L of the structures determines their morphology. Nanoribbons with L below 300 nm remain mainly flat, whereas longer ribbons exhibit uni-axial crumpling or spontaneous scrolling, a trend that is well reproduced by molecular dynamics simulations. We measure the strain of the ribbons as well as their crystallinity by recording nanometer-resolved convergent beam electron diffraction maps, and show that the beam tails of the focused ion beam cause significant amorphization of the structures adjacent to the cuts. The expansive or compressive strain in the structures remains below 4%. Our measurements provide experimental constraints for the stability of free-standing graphene structures with respect to their geometry, providing guidelines for future applications of patterned graphene.

Atomic and electronic structure of graphene

Abstract: This chapter introduces the atomic and electronic structure of graphene to provide the reader the necessary basics for following the later chapters with advanced topics. Overviews of deviation of real-life samples from the ideal structures and of most important experiments on electronic properties are also provided.

Direct visualization of local deformations in suspended few-layer graphene membranes by coupled in situ atomic force and scanning electron microscopy

Abstract: Suspended membranes of two-dimensional (2D) materials are of interest for many applications. Much of their characterization relies on scanning probe microscopy (SPM) techniques such as atomic force microscopy (AFM) or scanning tunneling microscopy (STM). Unlike rigid samples, the suspended atomically thin 2D membranes are, however, flexible and do not remain mechanically undisturbed during SPM measurements. Local deformations can occur at the location of the scanning tip and thus result in measurements that misrepresent actual membrane topography and nanomechanical properties. Exact levels of such SPM tip-induced deformations in 2D membranes remain largely unknown, as they are to date only indirectly accessible via dual probe microscope concepts that either are not mechanically independent (e.g., SPM-SPM setups resulting in complicated imaging crosstalk) or suffer from intrinsically limited lateral resolution (e.g., optical far-field techniques as the second probe). Circumventing these shortcomings, we here demonstrate that by coupling an AFM with a scanning electron microscope (SEM) as the second, mechanically independent probe, we can directly and in situ visualize by SEM at high resolution 2D membrane deformations that result from controllable AFM tip manipulations in the nN range. Employing few-layer graphene as model membranes, we discuss the experimental realization of our coupled in situ AFM-SEM approach.

Highly Efficient Bilateral Doping of Single-Walled Carbon Nanotubes

Abstract: A boost in the development of flexible and wearable electronics facilitates the design of new materials to be applied as transparent conducting films (TCFs). Although single-walled carbon nanotube (SWCNT) films are the most promising candidates for flexible TCFs, they still do not meet optoelectronic requirements demanded their successful industrial integration. In this study, we proposed and thoroughly investigated a new approach that comprises simultaneous bilateral (outer and inner surfaces) SWCNT doping after their opening by thermal treatment at 400 C under an ambient air atmosphere. Doping by a chloroauric acid (HAuCl$_{4}$) ethanol solution allowed us to achieve the record value of sheet resistance of 31 $\pm$ 4 $\Omega$/sq at a transmittance of 90% in the middle of visible spectra (550 nm). The strong p-doping was examined by open-circuit potential (OCP) measurements and confirmed by ab initio calculations demonstrating a downshift of Fermi level around 1 eV for the case of bilateral doping.

Towards Exotic Layered Materials: 2D Cuprous Iodide

Abstract: Heterostructures composed of two-dimensional (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 is 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 in other temperatures and pressures. Here, we demonstrate how these structures can be stabilized in 2D van der Waals stacks under room temperature via growing them directly in graphene encapsulation by using graphene oxide as the template material. Specifically, we produce 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. Our results establish a route to the production of more exotic phases of materials that would otherwise be difficult or impossible to stabilize for experiments in ambient.