Interface and Morphology Engineered Amorphous Si for Ultrafast Electrochemical Lithium Storage.

Ultrafast high-capacity lithium-ion batteries are extremely desirable for portable electronic devices, where Si is the most promising alternative to the conventional graphite anode due to its very high theoretical capacity. However, the low electronic conductivity and poor Li-diffusivity limit its rate capability. Moreover, high volume expansion/contraction upon Li-intake/uptake causes severe pulverization of the electrode, leading to drastic capacity fading. Here, interface and morphology-engineered amorphous Si matrix is being reported utilizing a few-layer vertical graphene (VG) buffer layer to retain high capacity at both slow and fast (dis)charging rates. The flexible mechanical support of VG due to the van-der-Waals interaction between the graphene layers, the weak adhesion between Si and graphene, and the highly porous geometry mitigated stress, while the three-dimensional mass loading enhanced specific capacity. Additionally, the high electronic conductivity of VG boosted rate-capability, resulting in a reversible gravimetric capacity of ≈1270 mAh g-1 (areal capacity of ≈37 µAh cm-2) even after 100 cycles at an ultrafast cycling rate of 20C, which provides a fascinating way for conductivity and stress management to obtain high-performance storage devices.

Electrostatic Gating of Monolayer Graphene by Concentrated Aqueous Electrolytes.

Electrostatic gating using electrolytes is a powerful approach for controlling the electronic properties of atomically thin two-dimensional materials such as graphene. However, the role of the ionic type, size, and concentration and the resulting gating efficiency is unclear due to the complex interplay of electrochemical processes and charge doping. Understanding these relationships facilitates the successful design of electrolyte gates and supercapacitors. To that end, we employ in situ Raman microspectroscopy combined with electrostatic gating using various concentrated aqueous electrolytes. We show that while the ionic type and concentration alter the initial doping state of graphene, they have no measurable influence over the rate of the doping of graphene with applied voltage in the high ionic strength limit of 3-15 M. Crucially, unlike for conventional dielectric gates, a large proportion of the applied voltage contributes to the Fermi level shift of graphene in concentrated electrolytes. We provide a practical overview of the doping efficiency for different gating systems.

Complex Strain Scapes in Reconstructed Transition-Metal Dichalcogenide Moiré Superlattices.

We investigate the intrinsic strain associated with the coupling of twisted MoS2/MoSe2 heterobilayers by combining experiments and molecular dynamics simulations. Our study reveals that small twist angles (between 0 and 2°) give rise to considerable atomic reconstructions, large moiré periodicities, and high levels of local strain (with an average value of ∼1%). Moreover, the formation of moiré superlattices is assisted by specific reconstructions of stacking domains. This process leads to a complex strain distribution characterized by a combined deformation state of uniaxial, biaxial, and shear components. Lattice reconstruction is hindered with larger twist angles (>10°) that produce moiré patterns of small periodicity and negligible strains. Polarization-dependent Raman experiments also evidence the presence of an intricate strain distribution in heterobilayers with near-0° twist angles through the splitting of the E2g1 mode of the top (MoS2) layer due to atomic reconstruction. Detailed analyses of moiré patterns measured by AFM unveil varying degrees of anisotropy in the moiré superlattices due to the heterostrain induced during the stacking of monolayers.

Isotope Engineered Fluorinated Single and Bilayer Graphene: Insights into Fluorination Selectivity, Stability, and Defect Passivation.

Tailoring the physicochemical properties of graphene through functionalization remains a major interest for next-generation technological applications. However, defect formation due to functionalization greatly endangers the intrinsic properties of graphene, which remains a serious concern. Despite numerous attempts to address this issue, a comprehensive analysis has not been conducted. This work reports a two-step fluorination process to stabilize the fluorinated graphene and obtain control over the fluorination-induced defects in graphene layers. The structural, electronic and isotope-mass-sensitive spectroscopic characterization unveils several not-yet-resolved facts, such as fluorination sites and CF bond stability in partially-fluorinated graphene (F-SLG). The stability of fluorine has been correlated to fluorine co-shared between two graphene layers in fluorinated-bilayer-graphene (F-BLG). The desorption energy of co-shared fluorine is an order of magnitude higher than the CF bond energy in F-SLG due to the electrostatic interaction and the inhibition of defluorination in the F-BLG. Additionally, F-BLG exhibits enhanced light-matter interaction, which has been utilized to design a proof-of-concept field-effect phototransistor that produces high photocurrent response at a time <200 µs. Thus, the study paves a new avenue for the in-depth understanding and practical utilization of fluorinated graphenic carbon.

Oxidative dehydrogenation of cyclohexene on atomically precise subnanometer Cu4-nPdn (0 ≤ n ≤ 4) tetramer clusters: the effect of cluster composition and support on performance.

The pronounced effects of the composition of four-atom monometallic Cu and Pd and bimetallic CuPd clusters and the support on the catalytic activity and selectivity in the oxidative dehydrogenation of cyclohexene are reported. The ultra-nanocrystalline diamond supported clusters are highly active and dominantly produce benzene; some of the mixed clusters also produce cyclohexadiene, which are all clusters with a much suppressed combustion channel. The also highly active TiO2-supported tetramers solely produce benzene, without any combustion to CO2. The selectivity of the zirconia-supported mixed CuPd clusters and the monometallic Cu cluster is entirely different; though they are less active in comparison to clusters with other supports, these clusters produce significant fractions of cyclohexadiene, with their selectivity towards cyclohexadiene gradually increasing with the increasing number of copper atoms in the cluster, reaching about 50% for Cu3Pd1. The zirconia-supported copper tetramer stands out from among all the other tetramers in this reaction, with a selectivity towards cyclohexadiene of 70%, which far exceeds those of all the other cluster-support combinations. The findings from this study indicate a positive effect of copper on the stability of the mixed tetramers and potential new ways of fine-tuning catalyst performance by controlling the composition of the active site and via cluster-support interactions in complex oxidative reactions under the suppression of the undesired combustion of the feed.

Electrical Contact Resistance of Large-Area Graphene on Pre-Patterned Cu and Au Electrodes.

Contact resistance between electrically connected parts of electronic elements can negatively affect their resulting properties and parameters. The contact resistance is influenced by the physicochemical properties of the connected elements and, in most cases, the lowest possible value is required. The issue of contact resistance is also addressed in connection with the increasingly frequently used carbon allotropes. This work aimed to determine the factors that influence contact resistance between graphene prepared by chemical vapour deposition and pre-patterned Cu and Au electrodes onto which graphene is subsequently transferred. It was found that electrode surface treatment methods affect the resistance between Cu and graphene, where contact resistance varied greatly, with an average of 1.25 ± 1.54 kΩ, whereas for the Au electrodes, the deposition techniques did not influence the resulting contact resistance, which decreased by almost two orders of magnitude compared with the Cu electrodes, to 0.03 ± 0.01 kΩ.

The Effects of Ultrasound Treatment of Graphite on the Reversibility of the (De)Intercalation of an Anion from Aqueous Electrolyte Solution.

Low cycling stability is one of the most crucial issues in rechargeable batteries. Herein, we study the effects of a simple ultrasound treatment of graphite for the reversible (de)intercalation of a ClO4- anion from a 2.4 M Al(ClO4)3 aqueous solution. We demonstrate that the ultrasound-treated graphite offers the improved reversibility of the ClO4- anion (de)intercalation compared with the untreated samples. The ex situ and in situ Raman spectroelectrochemistry and X-ray diffraction analysis of the ultrasound-treated materials shows no change in the interlayer spacing, a mild increase in the stacking order, and a large increase in the amount of defects in the lattice accompanied by a decrease in the lateral crystallite size. The smaller flakes of the ultrasonicated natural graphite facilitate the improved reversibility of the ClO4- anion electrochemical (de)intercalation and a more stable electrochemical performance with a cycle life of over 300 cycles.

Nano-optical Visualization of Interlayer Interactions in WSe2/WS2 Heterostructures.

The interplay between excitons and phonons governs the optical and electronic properties of transition metal dichalcogenides (TMDs). Even though a number of linear and nonlinear optical-, electron-, and photoelectron-based approaches have been developed and/or adopted to characterize excitons and phonons in single/few-layer TMDs and their heterostructures, no existing method is capable of directly probing ultralow-frequency and interlayer phonons on the nanoscale. To this end, we developed ultralow-frequency tip-enhanced Raman spectroscopy, which allows spectrally and spatially resolved chemical and structural nanoimaging of WSe2/WS2 heterostructures. In this work, we apply this method to analyze phonons in nanobubbles that are sustained in these heterobilayers. Our method is capable of directly probing interlayer (de)coupling using our novel structurally sensitive nano-optical probe and the interplay between excitons and interlayer/intralayer phonons through correlation analysis of the recorded spectral images.

Approach to map nanotopography of cell surface receptors.

Cells communicate with their environment via surface receptors, but nanoscopic receptor organization with respect to complex cell surface morphology remains unclear. This is mainly due to a lack of accessible, robust and high-resolution methods. Here, we present an approach for mapping the topography of receptors at the cell surface with nanometer precision. The method involves coating glass coverslips with glycine, which preserves the fine membrane morphology while allowing immobilized cells to be positioned close to the optical surface. We developed an advanced and simplified algorithm for the analysis of single-molecule localization data acquired in a biplane detection scheme. These advancements enable direct and quantitative mapping of protein distribution on ruffled plasma membranes with near isotropic 3D nanometer resolution. As demonstrated successfully for CD4 and CD45 receptors, the described workflow is a straightforward quantitative technique to study molecules and their interactions at the complex surface nanomorphology of differentiated metazoan cells.

Localized Spectroelectrochemical Identification of Basal Plane and Defect-Related Charge-Transfer Processes in Graphene.

It is well-known that structural defects play a decisive role in electrochemical behavior of atomically thin materials, where all the defects are directly accessible by the electrolyte. However, the vast majority of experimental techniques do not allow disentanglement of the processes at the edges/defects from those at the intact basal plane. Therefore, to address this issue, we introduce a localized spectroelectrochemical method featuring a microdroplet electrochemical cell with simultaneous Raman spectroscopy monitoring. The electrochemical and spectral responses of the basal planes of monolayer graphene samples with varying levels of disorder were compared. Two contributions, stemming from the intact and defective areas on the surface, respectively, were discovered both in the Raman G band shifts and cyclic voltammetry using the hexaammineruthenium complex. Consequently, two independent electron transfer processes of slower and faster rates coexist in one sample, but they are restricted to the defect-free and defect-rich areas, respectively.

Two-Dimensional CVD-Graphene/Polyaniline Supercapacitors: Synthesis Strategy and Electrochemical Operation.

Nanocomposites of graphene materials and conducting polymers have been extensively studied as promising materials for electrodes of supercapacitors. Here, we present a graphene/polyaniline heterostructure consisting of a CVD-graphene and polyaniline monolayer and its electrochemical operation in a supercapacitor. The synthesis employs functionalization of graphene by p-phenylene sulfonic groups and oxidative polymerization of anilinium by ammonium persulfate under reaction conditions, providing no bulk polyaniline. Scanning electron microscopy, atomic force microscopy, and Raman spectroscopy showed the selective formation of polyaniline on the graphene. In situ Raman spectroelectrochemistry and cyclic voltammetry (both in a microdroplet setup) confirm the reversibility of polyaniline redox transitions and graphene electrochemical doping. After an increase within the initial 200 cycles due to the formation of benzoquinone-hydroquinone defects in polyaniline, the specific areal capacitance remained for 2400 cycles with ±1% retention at 21.2 µF cm-2, one order of magnitude higher than the capacitance of pristine graphene.

In Situ Raman Microdroplet Spectroelectrochemical Investigation of CuSCN Electrodeposited on Different Substrates.

Systematic in situ Raman microdroplet spectroelectrochemical (Raman-µSEC) characterization of copper (I) thiocyanate (CuSCN) prepared using electrodeposition from aqueous solution on various substrates (carbon-based, F-doped SnO2) is presented. CuSCN is a promising solid p-type inorganic semiconductor used in perovskite solar cells as a hole-transporting material. SEM characterization reveals that the CuSCN layers are homogenous with a thickness of ca. 550 nm. Raman spectra of dry CuSCN layers show that the SCN- ion is predominantly bonded in the thiocyanate resonant form to copper through its S-end (Cu-S-C≡N). The double-layer capacitance of the CuSCN layers ranges from 0.3 mF/cm2 on the boron-doped diamond to 0.8 mF/cm2 on a glass-like carbon. In situ Raman-µSEC shows that, independently of the substrate type, all Raman vibrations from CuSCN and the substrate completely vanish in the potential range from 0 to -0.3 V vs. Ag/AgCl, caused by the formation of a passivation layer. At positive potentials (+0.5 V vs. Ag/AgCl), the bands corresponding to the CuSCN vibrations change their intensities compared to those in the as-prepared, dry layers. The changes concern mainly the Cu-SCN form, showing the dependence of the related vibrations on the substrate type and thus on the local environment modifying the delocalization on the Cu-S bond.

Strain and Charge Doping Fingerprints of the Strong Interaction between Monolayer MoS2 and Gold.

Gold-mediated exfoliation of MoS2 has recently attracted considerable interest. The strong interaction between MoS2 and Au facilitates preferential production of centimeter-sized monolayer MoS2 with near-unity yield and provides a heterostructure system noteworthy from a fundamental standpoint. However, little is known about the detailed nature of the MoS2-Au interaction and its evolution with the MoS2 thickness. Here, we identify the specific vibrational and binding energy fingerprints of this interaction using Raman and X-ray photoelectron spectroscopy, which indicate substantial strain and charge doping in monolayer MoS2. Tip-enhanced Raman spectroscopy reveals heterogeneity of the MoS2-Au interaction at the nanoscale, reflecting the spatial nonconformity between the two materials. Micro-Raman spectroscopy shows that this interaction is strongly affected by the roughness and cleanliness of the underlying Au. Our results elucidate the nature of the MoS2-Au interaction and guide strain and charge doping engineering of MoS2.

Strong and efficient doping of monolayer MoS2 by a graphene electrode.

The efficient manipulation of the optoelectronic properties of layered semiconductors is essential for future applications of these unique materials. Here, we demonstrate that single-layer, large-area graphene can serve as a conductive spacer between an electrolyte solution and single-layer MoS2. In situ Raman and photoluminescence (PL) spectroscopies were employed to monitor the charge transfer from graphene to MoS2. The Raman G and 2D bands were used to quantify the carrier concentration in graphene. The high efficiency of the charge transfer via graphene in a broad carrier concentration range of ±2.1 × 1013 cm-2 was documented by the extreme sensitivity of the MoS2 Raman mode to the electron-doping (shift rate of ∼2.5 cm-1/1 × 1013 cm-2 electron concentration) and the high sensitivity of the PL yield, which drops by more than one and two orders of magnitude in the hole and electron doping regimes, respectively. The easy implementation, and the lithography-free effectiveness of the setup, in terms of the achievable carrier concentration range and the charge-transfer efficiency, could be an asset in near-future research and in the development of optoelectronic devices.

Superlattice in collapsed graphene wrinkles.

Topographic corrugations, such as wrinkles, are known to introduce diverse physical phenomena that can significantly modify the electrical, optical and chemical properties of two-dimensional materials. This range of assets can be expanded even further when the crystal lattices of the walls of the wrinkle are aligned and form a superlattice, thereby creating a high aspect ratio analogue of a twisted bilayer or multilayer - the so-called twisted wrinkle. Here we present an experimental proof that such twisted wrinkles exist in graphene monolayers on the scale of several micrometres. Combining atomic force microscopy and Raman spectral mapping using a wide range of visible excitation energies, we show that the wrinkles are extremely narrow and their Raman spectra exhibit all the characteristic features of twisted bilayer or multilayer graphene. In light of a recent breakthrough - the superconductivity of a magic-angle graphene bilayer, the collapsed wrinkles represent naturally occurring systems with tuneable collective regimes.

Mastering the Wrinkling of Self-supported Graphene.

We present an approach that allows for the preparation of well-defined large arrays of graphene wrinkles with predictable geometry. Chemical vapor deposition grown graphene transferred onto hexagonal pillar arrays of SiO2 with sufficiently small interpillar distance forms a complex network of two main types of wrinkle arrangements. The first type is composed of arrays of aligned equidistantly separated parallel wrinkles propagating over large distances, and originates from line interfaces in the graphene, such as thin, long wrinkles and graphene grain boundaries. The second type of wrinkle arrangement is composed of non-aligned short wrinkles, formed in areas without line interfaces. Besides the presented hybrid graphene topography with distinct wrinkle geometries induced by the pre-patterned substrate, the graphene layers are suspended and self-supporting, exhibiting large surface area and negligible doping effects from the substrate. All these properties make this wrinkled graphene a promising candidate for a material with enhanced chemical reactivity useful in nanoelectronic applications.

Wrinkled Few-Layer Graphene as Highly Efficient Load Bearer.

Multilayered graphitic materials are not suitable as load-bearers due to their inherent weak interlayer bonding (for example, graphite is a solid lubricant in certain applications). This situation is largely improved when two-dimensional (2D) materials such as a monolayer (SLG) graphene are employed. The downside in these cases is the presence of thermally or mechanically induced wrinkles which are ubiquitous in 2D materials. Here we set out to examine the effect of extensive large wavelength/amplitude wrinkling on the stress transfer capabilities of exfoliated simply supported graphene flakes. Contrary to common belief we present clear evidence that this type of "corrugation" enhances the load-bearing capacity of few-layer graphene as compared to "flat" specimens. This effect is the result of the significant increase of the graphene/polymer interfacial shear stress per increment of applied strain due to wrinkling and paves the way for designing affordable graphene composites with highly improved stress-transfer efficiency.

Tuning the electronic properties of monolayer and bilayer transition metal dichalcogenide compounds under direct out-of-plane compression.

The band-gap modulation of atomically thin semiconductor transition metal dichalcogenides (MX2; M = Mo or W, X = S or Se) under direct out-of-plane compression is systematically studied by means of the density functional theory (DFT) formalism including spin-orbit coupling (SOC) and dispersion correction (D3). The out-of-plane compared with other regimes stress regime significantly reduces the pressure threshold at which the semimetal state is achieved (2.7-3.1 and 1.9-3.2 GPa for mono- and bilayer systems, respectively). Structural, electronic and bonding properties are investigated for a better understanding of the electronic transitions achieved with compression. A notable relationship with the formal ionic radius (M4+ and X2-) is obtained. On one hand, the monolayer systems with the smallest transition metal radius (Mo4+ < W4+) reach the semimetal state at lower stress, on the other hand, for bilayer specimens the transition to semimetal is observed earlier for compounds with the smallest chalcogenide radius (S2- < Se2-). Moreover, the appearance of non-covalent interaction (NCI) domains in the semimetal state confirms that the out-of-plane compression promotes the interaction between sulfur atoms in the single layered systems and reduces the interlayer space in bilayer configurations. Our predictions, supported by experimental evidences in the case of monolayered MoS2, demonstrate new alternative methods for tuning the electronic properties of transition metal dichalcogenides under direct out-of-plane compression.

Graphene wrinkling induced by monodisperse nanoparticles: facile control and quantification.

Controlled wrinkling of single-layer graphene (1-LG) at nanometer scale was achieved by introducing monodisperse nanoparticles (NPs), with size comparable to the strain coherence length, underneath the 1-LG. Typical fingerprint of the delaminated fraction is identified as substantial contribution to the principal Raman modes of the 1-LG (G and G'). Correlation analysis of the Raman shift of the G and G' modes clearly resolved the 1-LG in contact and delaminated from the substrate, respectively. Intensity of Raman features of the delaminated 1-LG increases linearly with the amount of the wrinkles, as determined by advanced processing of atomic force microscopy data. Our study thus offers universal approach for both fine tuning and facile quantification of the graphene topography up to ~60% of wrinkling.

Graphene Mechanics: Current Status and Perspectives.

The mechanical properties of 2D materials such as monolayer graphene are of extreme importance for several potential applications. We summarize the experimental and theoretical results to date on mechanical loading of freely suspended or fully supported graphene. We assess the obtained axial properties of the material in tension and compression and comment on the methods used for deriving the various reported values. We also report on past and current efforts to define the elastic constants of graphene in a 3D representation. Current areas of research that are concerned with the effect of production method and/or the presence of defects upon the mechanical integrity of graphene are also covered. Finally, we examine extensively the work related to the effect of graphene deformation upon its electronic properties and the possibility of employing strained graphene in future electronic applications.