Room Temperature On-Surface Synthesis of a Vinylene-Linked Single Layer Covalent Organic Framework.

Conjugated single-layered two-dimensional covalent organic frameworks are flat and extended polymer networks with a unique combination of material properties, giving rise to potential applications in sensing, optoelectronics, and photonics. Despite their great potential, thus far only a few reactions to access such extended conjugated 2D polymers have been reported. Here, the on-surface polymerization of the first vinylene-linked single layered two-dimensional covalent organic framework using reversible Knoevenagel polycondensation under solvothermal conditions is described. Self-assembly of the two monomer building blocks at the solid-liquid interface led to the formation of extended covalent networks at room temperature without the need of additional catalysts or reagents. The described approach grants access to extended conjugated 2D polymers under unprecedentedly mild conditions and paves the way to new hybrid material systems.

Collective States in Molecular Monolayers on 2D Materials.

Collective excited states form in organic two-dimensional layers through Coulomb coupling of the molecular transition dipole moments. They manifest as characteristic strong and narrow peaks in the excitation and emission spectra that are shifted to lower energies compared with the monomer transition. We study experimentally and theoretically how robust the collective states are against homogeneous and inhomogeneous broadening, as well as spatial disorder that occurs in real molecular monolayers. Using a microscopic model for a two-dimensional dipole lattice in real space, we calculate the properties of collective states and their extinction spectra. We find that the collective states persist even for 1-10% random variation in the molecular position and in the transition frequency, with a peak position and integrated intensity similar to those for the perfectly ordered system. We measured the optical response of a monolayer of the perylene derivative MePTCDI on two-dimensional materials. On the wide-band-gap insulator hexagonal boron nitride, it shows strong emission from the collective state with a line width that is dominated by the inhomogeneous broadening of the molecular state. When the semimetal graphene is used as a substrate, however, the luminescence is completely quenched. By combining optical absorption, luminescence, and multiwavelength Raman scattering, we verify that the MePTCDI molecules form very similar collective monolayer states on hexagonal boron nitride and graphene substrates, but on graphene the line width is dominated by nonradiative excitation transfer from the molecules to the substrate. Our study highlights the transition from the localized molecular state of the monomer to a delocalized collective state in the two-dimensional molecular lattice that is entirely based on Coulomb coupling between optically active excitations of the electrons and molecular vibrations. The excellent properties of organic monolayers make them promising candidates for components of soft-matter optoelectronic devices.

At Least 10-fold Higher Lubricity of Molecularly Thin D2O vs H2O Films at Single-Layer Graphene-Mica Interfaces.

Interfacial water is a widespread lubricant down to the nanometer scale. We investigate the lubricities of molecularly thin H2O and D2O films confined between mica and graphene, via the relaxation of initially applied strain in graphene employing Raman spectroscopy. Surprisingly, the D2O films are at least 1 order of magnitude more lubricant than H2O films, despite the similar bulk viscosities of the two liquids. We propose a mechanism based on the known selective permeation of protons vs deuterons through graphene. Permeated protons and left behind hydroxides may form ion pairs clamping across the graphene sheet and thereby hindering the graphene from sliding on the water layer. This explains the lower lubricity but also the hindering diffusivity of the water layer, which yields a high effective viscosity in accordance with findings in dewetting experiments. Our work elucidates an unexpected effect and provides clues to the behavior of graphene on hydrous surfaces.

Reversible Switching of Charge Transfer at the Graphene-Mica Interface with Intercalating Molecules.

Understanding and controlling charge transfer through molecular nanostructures at interfaces is of paramount importance, particularly for electronic devices but also for contact electrification or in bioelectronics. We investigate the influence of intercalation and exchange of molecularly thin layers of small molecules (water, ethanol, 2-propanol, and acetone) on charge transfer at the well-defined interface between an insulator (muscovite mica) and a conductor (graphene). Raman spectroscopy is used to probe the charge carriers in graphene. While a molecular layer of water blocks charge transfer between mica and graphene, a layer of the organic molecules allows for it. The exchange of molecular water layers with ethanol layers switches the charge transfer very efficiently from off to on and back. We propose a charge transfer model between occupied mica trap states and electronic states of graphene, offset by the electrostatic potentials produced by the molecular dipole layers, as supported by molecular dynamics simulations. Our work demonstrates how intercalation of molecules of volatile liquids can reversibly affect charge transfer at interfaces. This implies its strong impact on the function of hybrid inorganic-organic electronic devices in different ambients and potential applications, including sensors and actuators.

Influence of interface hydration on sliding of graphene and molybdenum-disulfide single-layers.

Humidity influences friction in layered materials in peculiar ways. For example, while water improves the lubricating properties of graphite, it deteriorates those of molybdenum disulfide (MoS2). The reasons remain debated, not the least due to the difficulty in experimentally comparing dry and hydrated interface frictions. Here we show that the hydration of interfaces between a mica substrate and single-layers of graphene and MoS2 with a molecularly thin water layer affects strain transfer from the substrate to the 2D materials. For this, we strain the substrate and detect strain in graphene and MoS2 by changes in Raman and photoluminescence spectra, respectively. Strain relaxation in graphene changes from stick-slip in dry contact, to viscous when hydrated. In contrast, there is no viscous relaxation in MoS2 regardless of hydration. Our work provides a novel approach for better understanding the impact of hydration on friction in layered materials.

Non-monotonous Wetting of Graphene-Mica and MoS2-Mica Interfaces with a Molecular Layer of Water.

Hydration of interfaces with a layer of water is a ubiquitous phenomenon, which has important implications for numerous natural and technologically important processes. Nevertheless, at the nanoscale, the understanding of the wetting process is still limited, since it is experimentally difficult to follow. Here, graphene and monolayers of MoS2 deposited on dry mica are used to investigate wetting of the two-dimensional (2D) material-mica interfaces with a molecularly thin layer of water employing scanning force microscopy in different modes. Wetting occurs non-monotonously in time and space for both types of interfaces. It starts at relative humidities (RH) of 10-17% for graphenes and 8-9% for MoS2 and concludes with a homogeneous layer at 25-30 and 15-20%, respectively. Investigation of the process at the graphene-mica interface indicates that up to about 25% RH, initially a highly compliant and unstable layer of water spreads, which subsequently stabilizes by developing labyrinthine nanostructures. Moreover, these nanostructures exhibit distinct mechanical deformability and dissipation, which is ascribed to different densities of the confined water layer. The laterally structured morphology is explained by the interplay of counteracting long-range dipole-dipole repulsion and short-range line tension, with the latter causing at least in part by the mechanical deformation of the 2D material. The proposed origins of the interactions are common for thin layers of polar molecules at interfaces, implying that the lateral structuring of thin wetting layers at submonolayer concentrations may also be a quite general phenomenon.

Microstructure and Elastic Constants of Transition Metal Dichalcogenide Monolayers from Friction and Shear Force Microscopy.

Optical and electrical properties of 2D transition metal dichalcogenides (TMDCs) grown by chemical vapor deposition (CVD) are strongly determined by their microstructure. Consequently, the visualization of spatial structural variations is of paramount importance for future applications. This study demonstrates how grain boundaries, crystal orientation, and strain fields can unambiguously be identified with combined lateral force microscopy and transverse shear microscopy (TSM) for CVD-grown tungsten disulfide (WS2 ) monolayers, on length scales that are relevant for optoelectronic applications. Further, angle-dependent TSM measurements enable the fourth-order elastic constants of monolayer WS2 to be acquired experimentally. The results facilitate high-throughput and nondestructive microstructure visualization of monolayer TMDCs and insights into their elastic properties, thus providing an accessible tool to support the development of advanced optoelectronic devices based on such 2D semiconductors.

Twinned Growth of Metal-Free, Triazine-Based Photocatalyst Films as Mixed-Dimensional (2D/3D) van der Waals Heterostructures.

Design and synthesis of ordered, metal-free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed-dimensional (2D/3D) metal-free van der Waals (vdW) heterostructures based on triazine (C3 N3 ) linkers grow as large area, transparent yellow-orange membranes on copper surfaces from solution. The membranes have an indirect band gap (Eg,opt = 1.91 eV, Eg,elec = 1.84 eV) and are moderately porous (124 m2 g-1 ). The material consists of a crystalline 2D phase that is fully sp2 hybridized and provides structural stability, and an amorphous, porous phase with mixed sp2 -sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one-pot reaction mixture: unprecedented for metal-free frameworks and a direct consequence of on-catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal-free, light-induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h-1 g-1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of "wet" chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties.

Strongly enhanced Raman scattering of Cu-phthalocyanine sandwiched between graphene and Au(111).

Graphene and flat gold have both been argued to enhance Raman scattering of molecular adsorbates through a chemical mechanism. Here we show that these two effects can add to each other. For Cu-phthalocyanine in between graphene and Au(111) on mica a Raman enhancement up to 68-fold has been observed.

Reconstructing interaction potentials in thin films from real-space images.

We demonstrate that an inverse Monte Carlo approach allows one to reconstruct effective interaction potentials from real-space images. The method is exemplified on monomolecular ethanol-water films imaged with scanning force microscopy, which provides the spatial distribution of the molecules. Direct Monte Carlo simulations with the reconstructed potential allow for obtaining characteristics of the system which are unavailable in the experiment, such as the heat capacity of the monomolecularly thin film, and for a prediction of the critical temperature of the demixing transition.

Delamination of graphite oxide in a liquid upon cooling.

Graphite oxide (GO) in liquid acetonitrile undergoes a transition from an ordered phase around ambient temperature to a gel-like disordered phase at temperatures below 260 K, as demonstrated by in situ X-ray diffraction. The stacking order of GO layers is restored below the freezing point of acetonitrile (199 K). The reversible swelling transition between a stacked crystalline phase and an amorphous delaminated state observed upon cooling provides an unusual example of increased structural disorder at lower temperatures. The formation of the gel-like phase is attributed to the thermo-responsive conformational change of individual GO flakes induced by stronger solvation. Scanning force microscopy demonstrates that GO flakes deposited onto a solid substrate from acetonitrile dispersions at a temperature below 260 K exhibit corrugations and wrinkling which are not observed for the flakes deposited at ambient temperature. The thermo-responsive transition between the delaminated and stacked phases reported here can be used for sonication-free dispersion of graphene oxide, micro-container applications, or the preparation of new composite materials.

Morphology, mechanical stability, and protective properties of ultrathin gallium oxide coatings.

Ultrathin gallium oxide layers with a thickness of 2.8 ± 0.2 nm were transferred from the surface of liquid gallium onto solid substrates, including conjugated polymer poly(3-hexylthiophene) (P3HT). The gallium oxide exhibits high mechanical stability, withstanding normal pressures of up to 1 GPa in contact mode scanning force microscopy imaging. Moreover, it lowers the rate of photodegradation of P3HT by 4 orders of magnitude, as compared to uncovered P3HT. This allows us to estimate the upper limits for oxygen and water vapor transmission rates of 0.08 cm(3) m(-2) day(-1) and 0.06 mg m(-2) day(-1), respectively. Hence, similar to other highly functional coatings such as graphene, ultrathin gallium oxide layers can be regarded as promising candidates for protective layers in flexible organic (opto-)electronics and photovoltaics because they offer permeation barrier functionalities in conjunction with high optical transparency.

Biantennary oligoglycines and glyco-oligoglycines self-associating in aqueous medium.

Oligoglycines designed in a star-like fashion, so-called tri- and tetraantennary molecules, were found to form highly ordered supramers in aqueous medium. The formation of these supramers occurred either spontaneously or due to the assistance of a mica surface. The driving force of the supramer formation is hydrogen bonding, the polypeptide chain conformation is related to the folding of helical polyglycine II (PG II). Tri- and tetraantennary molecules are capable of association if the antenna length reach 7 glycine (Gly) residues. Properties of similar biantennary molecules have not been investigated yet, and we compared their self-aggregating potency with similar tri- and tetraantennary analogs. Here, we synthesized oligoglycines of the general formula R-Gly n -Х-Gly n -R (X = -HN-(СН2) m -NH-, m = 2, 4, 10; n = 1-7) without pendant ligands (R = H) and with two pendant sialoligands (R = sialic acid or sialooligosaccharide). Biantennary oligoglycines formed PG II aggregates, their properties, however, differ from those of the corresponding tri- and tetraantennary oligoglycines. In particular, the tendency to aggregate starts from Gly4 motifs instead of Gly7. The antiviral activity of end-glycosylated peptides was studied, and all capable of assembling glycopeptides demonstrated an antiviral potency which was up to 50 times higher than the activity of peptide-free glycans.

Hydration of bilayered graphene oxide.

The hydration of graphene oxide (GO) membranes is the key to understand their remarkable selectivity in permeation of water molecules and humidity-dependent gas separation. We investigated the hydration of single GO layers as a function of humidity using scanning force microscopy, and we determined the single interlayer distance from the step height of a single GO layer on top of one or two GO layers. This interlayer distance grows gradually by approximately 1 Å upon a relative humidity (RH) increase in the range of 2 to ∼80%, and the immersion into liquid water increases the interlayer distance further by another 3 Å. The gradual expansion of the single interlayer distance is in good agreement with the averaged distance measured by X-ray diffraction on multilayered graphite oxides, which is commonly explained with an interstratification model. However, our experimental design excludes effects connected to interstratification. Instead we determine directly if insertion of water into GO occurs strictly by monolayers or the thickness of GO layers changes gradually. We find that hydration with up to 80% RH is a continuous process of incorporation of water molecules into single GO layers, while liquid water inserts as monolayers. The similarity of hydration for our bilayer and previously reported multilayered materials implies GO few and even bilayers to be suitable for selective water transport.

Triazine-based graphitic carbon nitride: a two-dimensional semiconductor.

Graphitic carbon nitride has been predicted to be structurally analogous to carbon-only graphite, yet with an inherent bandgap. We have grown, for the first time, macroscopically large crystalline thin films of triazine-based, graphitic carbon nitride (TGCN) using an ionothermal, interfacial reaction starting with the abundant monomer dicyandiamide. The films consist of stacked, two-dimensional (2D) crystals between a few and several hundreds of atomic layers in thickness. Scanning force and transmission electron microscopy show long-range, in-plane order, while optical spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations corroborate a direct bandgap between 1.6 and 2.0 eV. Thus TGCN is of interest for electronic devices, such as field-effect transistors and light-emitting diodes.

Statistics of time-dependent rupture of single ds-DNA.

Double-stranded (ds-) DNA molecules were stretched and ruptured on molecularly modified graphite surfaces with a scanning force microscope (SFM) exerting a force parallel to the surface. The stretching force was either large enough to break the molecule immediately or compensated by the elastic restoring force of the DNA backbone, which stabilized the molecular length. However, the size-stabilized molecules broke gradually from longer molecules to shorter ones with time. The breakage of different lengths of stabilized molecules was recorded in order to study time-dependent mechanical properties of the molecules under constant forces. From these data, a relatively high rate constant, k0 = (2.2 ± 0.1) × 10(-7) s(-1), was calculated. Moreover, we found a nonlinear stress-strain dependence of DNA on the surface which we attributed to DNA conformational transition. Assuming that the structural transition on the surface is similar to that in solution we estimated the forces needed to stretch the molecules and thereby verify the estimation of the activation energy barrier.

Exfoliation of crystalline 2D carbon nitride: thin sheets, scrolls and bundles via mechanical and chemical routes.

The carbon nitride poly(triazine imide) with intercalated bromide ions is a layered, graphitic material of 2D covalently bonded molecular sheets with an exceptionally large gallery height of 3.52 Å due to the intercalated bromide anions. The material can be cleaved both mechanically and chemically into thin sheets and scrolls analogous to the carbon-only systems graphite and graphene.

Porous organic cage crystals: characterising the porous crystal surface.

The characterisation of porous crystalline solids often relies on single crystal X-ray diffraction, which does not give direct information about the surface of the material. Here, crystals of a porous organic cage, CC3-R, are investigated by atomic force microscopy and shown to possess two distinct gas-solid interfaces, proving that the bulk crystal structure is preserved at the porous crystal surface.

Reversible dewetting of a molecularly thin fluid water film in a soft graphene-mica slit pore.

The behavior of water and other molecular liquids confined to the nanoscale is of fundamental importance, e.g., in biology, material science, nanofluidics, and tribology. Direct microscopic imaging of wetting dynamics in subnanometer pores is however challenging. We will show in the following that a molecularly thin water film confined between mica and graphene is fluid. Ambient humidity allows to control the wetting and dewetting of the film. We follow these processes in space and time using scanning force microscopy imaging of the graphene conforming to the film. At sufficiently high humidity a continuous molecularly thin water film wets the interface between the graphene and mica. At lower humidities the film dewets with fractal depressions exhibiting dimensions around 1.7 and depths comparable to the size of a water molecule. The soft graphene cover offers a previously unexplored semihydrophilic slit pore of self-adjustable size, which enables high-resolution imaging of confined molecularly thin fluid films, and bears the potential for the fabrication of novel nanofluidic devices.

Consecutive conformational transitions and deaggregation of multiple-helical poly(diacetylene)s.

The polymerization of diacetylene macromonomers based on oligopeptide-polymer conjugates yields conjugated polymers with multiple-helical quaternary structures. These polymers exhibit a rich dynamic folding behavior upon the addition of protic cosolvents. Thus, a helix-helix transition under helix-sense inversion was followed by a reversible helix-coil transition. Both transitions involved changes in the aggregation state of the multiple-helical superstructures. The resemblance of the observed consecutive and cooperative conformational transitions to those of biopolymers underlines the importance of supramolecular self-assembly as a pathway toward biofunctional materials with optoelectronic activity.